5. Experimental

Instrumentation

NMR spectra were recorded on Bruker DRX 500 (500.1 MHz for 1H, 125.7 MHz for 13C), AM 400 or DRX 400 (400.1 MHz for 1H, 100.6 MHz or 13C), DPX 250 or AC 250 (250.1 MHz for 1H, 62.9 MHz for 13C) instruments. Chemical shifts are quoted in parts per million with respect to TMS. Mass spectra were recorded on Kratos MS-50 (FAB), VG BioQ (ES), Kratos MS890 (FAB, EI), Kratos Kompact MALDI IV, Bruker BioApex II (ES), Micromass Quattro (ES) and Micromass Q-TOF (ES) instruments. Solution and solid state infrared spectra were recorded on a Perkin Elmer Paragon 1000 FTIR spectrometer at 4cm-1 resolution or better.

Reflection - adsorption infrared spectra were recorded at ThermoUnicam (Cambridge) on a Mattson Infinity Series FTIR spectrometer with an external sample module fitted with a liquid nitrogen cooled MCT detector and SpectraTech variable angle reflection accessory set to 83. 2048 scans were recorded at a resolution of 4 cm-1.

X-ray photoelectron spectroscopy was performed with a VG ESCALAB 200D instrument at ICI Runcorn Heath. Unmonochromated Mg Ka radiation was used with a photoelectron takeoff angle of 90. Binding energies were calibrated to the Au 4f7/2 peak at 83.98 eV. Spectral acquisition and processing was controlled with the Eclipse software. Alternatively spectra were recorded on a Scienta ESCA300 spectrometer at Daresbury Laboratory.

Contact mode atomic force microscopy was carried out with either a Digital Instruments (DI) Nanoscope III or East Coast Scientific microscope. Oxide sharpened silicon nitride cantilevers (DI) with a nominal force constant of 0.12 Nm-1 were used to acquire the images of appendix 4.

Scanning tunnelling microscopy was performed with an Omicron Micro H/LH microscope with SCALA control system and software at the School of Physics and Astronomy, University of Birmingham. A mechanically cut Pt/Ir tip was used. The gold on mica sample was affixed to the steel sample plate by spot welding with Ta foil. Imaging at above room temperature was performed in a vacuum chamber at a pressure of < 5 10-7 mbar.

Contact angles and electrochemical measurements were carried out at the Laboratory of Supramolecular Chemistry and Technology, University of Twente.

Advancing and receding water contact angles were recorded with a Krss contact angle goniometer using the sessile drop method. Angles were calculated by the G40 software (Krss) by automatic analysis of images of the drop as it was slowly advanced or receded on the sample.

Electrochemistry was carried out in a 3 electrode cell in which the gold sample comprised the working electrode with a geometric area of 0.44 cm2. A Pt disc was used as a counter electrode with a Hg/Hg2SO4 reference electrode with KCl salt bridge solution (Radiometer). Potentials are quoted with respect to this electrode. Experiments were controlled by an Autolab potentiostat and frequency response analyser (EcoChemie BV) interfaced to a computer running the GPES 4.5 and FRA software. The differential double layer capacitance was measured by cyclic voltammetry in 0.1 M NaClO4 aqueous solution, scanning over the range -0.3 - 0.4 V at rates of 0.1, 0.2 and 0.5 Vs-1. The capacitance was calculated as the sum of the current at 0.35 V in both scan directions divided by 2 scan rate geometric electrode area. Heterogeneous electron transfer between the modified electrodes and the external redox couple Fe(CN)63-/4- was measured by cyclic voltammetry in a solution 1 mM in both K3Fe(CN)6 and K4Fe(CN)6 and 0.1 M in K2SO4 scanning over the range 0 - 7 V at 0.1 Vs-1. The solution was purged with N2 prior to measurement. Faradaic impedance spectra were recorded using the same electrolyte solution. A sinusoidal excitation of 5 mV was applied to the open cell potential of 0.2 V. Impedance was measured at 40 frequencies between 0.1 Hz and 10 kHz. The spectra were analysed with the program Equivalent Circuit (B. A. Boukamp, University of Twente).

All glassware and glass slides used for preparation of monolayer were cleaned by one of two procedures. Procedure 1) Rinsing in acetone, sonication for 45 min in a 2 % solution of Decon 75, extensive rinsing with distilled water, sonication (45 min) in HPLC grade isopropanol, followed by sonication in ultrapure water for a further 45 min then drying under a stream of nitrogen or 2) Immersion in freshly prepared piranha solution (conc. H2SO4/30 % H2O2, 7/3) (caution - reacts violently with organic material. Contact with metals may cause rapid decomposition) followed by rinsing extensively with distilled water and finally with ultrapure water.

Preparation of gold substrates

Gold (99.99 %) was supplied by Birmingham Metals or Goodfellow Ltd.

(i) For RAIRS and microcontact printing. Substrates for reflection adsorption IR spectroscopy were prepared by Mr. R. Nelson by thermal evaporation of ~50 Cr and ~1000 of gold onto glass microscope slides using an Edwards evaporator. Substrates for microcontact printing were prepared in the same way, except using a silicon wafer instead of glass slides. The wafer was cleaved with a diamond stylus after evaporation of the gold.

(ii) For XPS. Gold substrates were prepared using a Balzers evaporator. Freshly cleaved mica was preheated to 300 C for 20 h in vacuo. 1000 Au was evaporated at a rate of 10 s-1 onto the heated mica, which was annealed for 6 h at 300 C followed by cooling in vacuo. The pressure in the chamber prior to evaporation was typically ~1 10-7 mbar. Substrates for STM were prepared similarly but using a home built evaporator.

(iii) For contact angle and electrochemical measurements. Gold substrates prepared by electron beam evaporation of Ti (5 nm) and Au (200 nm) onto 25 mm diameter glass discs were supplied by H. Krabbe (University of Twente). These were stored under nitrogen in Fluoroware containers and cleaned prior to use by treatment with oxygen plasma for 5 min followed by soaking in EtOH for 10 min.462

Typical monolayer preparations. Freshly evaporated or plasma cleaned gold substrates were immersed into a solution of thiol or disulfide at a concentration of 0.1 - 1 mM for ~12 h at room temperature. THF was used as a solvent for porphyrins. EtOH was used for non-porphyrin compounds. Care was taken to minimize exposure of the porphyrin solutions to light. After incubation samples were rinsed extensively with the same solvents before blowing dry with a stream of nitrogen.

Microcontact printing was carried out using a PDMS stamp prepared by Dr. W. T. S. Huck. After application of a 10 mM solution of mercaptoundecanoic acid in EtOH to the stamp using a filter paper, followed by blowing dry with nitrogen, the stamp was placed in contact with a gold substrate for several seconds. After removal of the stamp the sample was immersed into a solution of another thiol/disulfide (1 mM) for 4 min, before rinsing and blowing dry.

UV/visible titrations. For measurement of binding constants of sulfur/selenium ligands to 118, a 3.0 mL aliquot of a 4 mM solution of 118MeOH in DCM/MeOH (200 mL MeOH per 100 mL of solvent) at 25 C was titrated with 10 mL aliquots of a 75 mM solution of ligand in the same solvent mixture. The cuvette was magnetically stirred for ~30 s prior to recording each spectrum. Spectra were analysed with the program Specfit.257

1H NMR titrations. Typically a solution of 118MeOH (4 mg) in CDCl3 (600 mL) was titrated with 5 mL aliquots of a solution of ligand in CDCl3 at a concentration of 72 mM. Spectra were acquired at room temperature. CDCl3 was stored over anhydrous K2CO3 in a refrigerator.

Prior to binding studies, EtSH, Me2S and Me2Se2 were filtered through neutral alumina, DMSO was filtered through CaH2 then neutral alumina, Ph2S and Ph2SO were distilled with a Kugelrohr apparatus.

X-ray crystallography. Diffraction data were collected on a Rigaku R-Axis IIc or Nonius Kappa CCD device. Data for small crystal were collected at the Daresbury SRS, Station 9.8 using a Bruker AXS SMART CCD area-detector, or at the ESRF (Grenoble). Structures were solved with either SHELXS-97 or SIR92.463-465 Refinement was carried out with SHELXL-97.463

Synthesis

THF, hexane, EA and Et2O were distilled before use. When stated as anhydrous, solvents were distilled from an appropriate drying agent immediately prior to use. Et3N was freshly distilled from CaH2, or stored over KOH pellets. 3-Picoline was distilled from KOH pellets under N2. Technical grade thionyl chloride was purified by distillation from triphenyl phosphite. Ultrapure water was obtained from a Millipore or Elgastat water purification system. Melting points were determined on a Gallenkamp melting point apparatus and are uncorrected.

Merck or Fluorochem 60 mesh silica gel was used for column chromatography. Merck silica was used for preparations involving rhodium porphyrins unless stated otherwise.

Benzyl-5-methyl-4-hexyl-3-methyl-pyrrole-2-carboxylate, trimethylsilyl-acetylene, 3,5-diiodobenzyl alcohol and 4-pyridyl-trimethyl-stannane were provided by Mr. C. Sporikou. 3-Trimethylsilylethynyl-benzaldehyde and 3,5-di-tert-butyl-benzaldehyde were provided by Dr. S. L. Darling. All other chemicals were purchased as reagent grade or better and used without further purification unless specified otherwise.

General procedure for porphyrin synthesis

The general porphyrin synthesis procedure is illustrated for 117. Other symmetrical porphyrins were prepared by substituting an alternative aldehyde for benzaldehyde. Unsymmetrical porphyrins were prepared by a statistical reaction using an equimolar mixture of two aldehydes. The purification of each compound is described separately.

116 (1.00 g, 1.64 mmol) and Pd/C (10 %, 0.10 g) were mixed then THF (50 mL) and Et3N (2 mL) added. The mixture was degassed then stirred under an atmosphere of H2 for 1 h. After filtration through celite, the solvents were removed and the grey solid (5,5'-carboxy-3,3'-dihexyl-4,4'-dimethyl-2,2'-dihydropyrrin) dried in vacuo. To this was added by cannula cold (~0 C) degassed TFA (20 mL). After stirring for 10 min at 0 C and 30 min at rt, with periodic exposure to vacuum to remove evolved CO2, the yellow solution was cooled to -20 C. A degassed solution of benzaldehyde (166 mL, 1.63 mmol) in THF (50 mL) was added and the solution stirred under N2 for 3 h allowing the temperature to increase from -20 C to -10 C. DDQ (0.48 g, 2.11 mmol) was added and the green solution stirred for 15 min at rt. Et3N (40 mL) was added cautiously, followed by CHCl3 (200 mL). The brown solution was washed with water (100 mL portions) until the aqueous washings were colourless, the organic phase dried (MgSO4), and evaporated. The resulting dark coloured solids were dried in vacuo.

General procedure for Zn metallation of porphyrins

Zn metallation was carried out by boiling a solution of free-base porphyrin in chloroform and ~5 % MeOH with excess Zn(OAc)22H2O or Zn(OAc)2 for several minutes. The solution was filtered, washed with water, dried (MgSO4) and evaporated.

General procedure for Ni metallation of porphyrins

The free-base porphyrin in mixed CHCl3/MeOH solvent was refluxed under N2 with excess (>5 eq) Ni(OAc)24H2O overnight. After cooling the solution was filtered, washed with water, dried (MgSO4) and evaporated.


5-Acetoxymethyl-4-hexyl-3-methyl-1H-pyrrole-2-carboxylic acid benzyl ester (115)228

Pb(OAc)4 (28.35 g, 64 mmol) was added gradually with stirring over a 15 min period to a solution of benzyl-5-methyl-4-hexyl-3-methyl-pyrrole-2-carboxylate (20 g, 64 mmol) in glacial acetic acid (200 mL). After stirring for 2 h at rt under argon, the solvent was evaporated to produce an orange solid. The solids were extracted with CHCl3 (250 mL), filtered to remove undissolved material, the solution was washed with water (5 100 mL), dried (MgSO4), and evaporated to a brown solid. Recrystallization from MeOH afforded the pure product as a white solid (10.2 g, 43 %). Rf 0.7 (hexane/EA, 3/1).

1H NMR (250 MHz, CDCl3): d 9.02 (br s, 1H, NH), 7.44 - 7.28 (m, 5H, Ar), 5.30 (s, 2H, CH2Ph), 5.00 (s, 2H, CH2OAc), 2.41 (t, J = 7 Hz, 2H, hex H1), 2.27 (s, 3H, O2CCH3), 2.05 (s, 3H, CH3), 1.44 - 1.28 (m, 8H, hex H2-5), 0.87 (t, J = 7 Hz, 3H, hex H6); Anal. Calcd for C22H29NO4: C 71.13, H 7.87, N 3.77. Found: C 71.28, H 7.89, N 3.92.

5,5'-Dibenzyloxycarbonyl-3,3'-dihexyl-4,4'-dimethyl-2,2'-dihydropyrrin (116)228

Conc. HCl (4 mL) was added to a solution of 115 (10.24 g, 27 mmol) in warm MeOH (70 mL) and refluxed under argon for 3 h. After cooling to rt, water (70 mL) was added and the solution extracted with DCM (3 120 mL). The combined organic extracts were washed with satd. Na2CO3 (50 mL), dried (MgSO4) and evaporated to an orange solid. Recrystallization twice from MeOH yielded the pure product as pale yellow needles (6.77 g, 40 %). Rf 0.55 (hexane/EA, 3/1).

1H NMR (250 MHz, CDCl3): d 8.99 (s, 2H, NH), 7.35 - 7.23 (m, 10H, Ar), 5.22 (s, 4H, CO2CH2), 3.79 (s, 2H, CH2), 2.35 (t, J = 7 Hz, 4H, hex H1), 2.26 (s, 6H, CH3), 1.35 - 1.25 (m, 16H, hex H2-5), 0.87 (t, J = 7 Hz, 6H, hex H6); Anal. Calcd for C39H50N2O4: C 76.69, H 8.25, N. 4.59. Found: C 76.72, H 8.30, N 4.74.

2,8,12,18-Tetrahexyl-3,7,13,17-tetramethyl-5,15-diphenyl-porphyrin (117)

Purified by passing through a short silica column, eluted with hexane/EA (10/1), followed by recrystallization twice from CHCl3 layered with MeOH. Purple needles (489 mg, 70 %). Rf 0.75 (hexane/EA, 5/1).

Crystals were for structure determination were grown from toluene solution layered with MeOH, or from CHCl3 layered with a solution of 4-bromophenol in MeOH.

1H NMR (400 MHz, CDCl3): d 10.23 (s, 2H meso), 7.57 (d, J = 7 Hz, 4H, Ar), 7.81-7.71 (m, 6H, Ar), 3.97 (t, J = 8 Hz, 8H, hex H1), 2.48 (s, 12H, CH3), 2.18 (m, 8H, hex H2), 1.72 (m, 8H, hex H3), 1.48 (m, 8H, hex H4), 1.34 (m, 8H, hex H5), 0.89 (t, J = 7 Hz, 12H, hex H6), -2.40 (s, 2H, NH); 13C NMR (100.6 MHz, CDCl3): d 145.1, 143.3, 142.4, 141.4, 136.2, 133.0, 128.2, 127.6, 117.9, 96.9, 33.3, 32.0, 30.0, 26.8, 22.8, 14.6, 14.1; UV/vis (DCM): lmax 400, 506, 540, 574, 626 nm; FAB MS: m/z [M+H]+ calcd 855.6299, found 855.6302; IR (CCl4): nmax 2957 (s), 2929 (s), 1467 (m), 1444 (m) cm1; Anal. Calcd for C60H78N4: C 84.26, H 9.19, N 6.55. Found C 84.04, H 9.17, N 6.45.

2,8,12,18-Tetrahexyl-3,7,13,17-tetramethyl-5,15-diphenyl-porphyrinato rhodium(III) iodide (118)

117 (200 mg, 0.23 mmol) and anhydrous NaOAc (96 mg, 1.17 mmol) were dissolved in DCM (anhydrous, 50 mL). The solution was degassed, and to this was added a solution of Rh2(CO)4Cl2 (160 mg, 4.12 mmol) in degassed DCM (20 mL) dropwise over 80 min. After stirring for 150 min at rt under N2, iodine (147 mg, 0.58 mmol) was added and stirring continued for a further 30 min. The solution was washed with aqueous KI (30 mL), and water (100 mL portions) until the washings were colourless. The organic phase was dried (MgSO4) and evaporated to a brown solid. Column chromatography (hexane/DCM, 1/1) afforded the product as a deep orange solid (225 mg, 89 %). Rf 0.6 (hexane/DCM, 1/1)

The product could be obtained as black crystals of the MeOH complex by recrystallization from DCM or CHCl3 layered with MeOH. Crystals of 118MeOH for structure determination were obtained from a DCM solution layered with MeOH. Crystals of unsolvated 118 were obtained from a solution of 118 in DCM layered with ethylene glycol.

1H NMR (400 MHz, CDCl3): d 10.29 (s, 2H, meso), 8.13 (d, J = 7 Hz, 2H, Ar), 7.94 (d, J = 7 Hz, 2H, Ar), 7.80 - 7.67 (m, 6H, Ar), 4.04 (m, 4H, hex H1), 3.87 (m, 4H, hex H1), 2.47 (s, 12H, CH3), 2.17 (m, 8H, hex H2), 1.73 (m, 8H, hex H3), 1.48 (m, 8H, hex H4), 1.38 (m, 8H, hex H5), 0.90 (t, J = 7 Hz, 12H, hex H6); 13C NMR (100.6 MHz, CDCl3): d 144.4, 142.5, 141.5, 141.3, 138.9, 133.2, 133.0, 128.4, 127.7, 127.4, 121.2, 100.7, 33.1, 32.0, 30.0, 26.9, 22.8, 15.5, 14.1; UV/vis (DCM): lmax 402, 548, 522 nm; FIB MS: m/z [M+H]+ calcd 1105.4062, found 1105.4150; IR (CCl4): nmax 2930 (m), 2930 (m) cm1. Anal. Calcd for C60H76N4RhICH3OH: C 65.70, H 7.23, N 5.02. Found: C 65.23, H 7.19, N 5.02.

118 NH3 complex (119)

Method 1

The compound was prepared unintentionally by the use of Fluorochem silica during the purification of 118. A mixture of 118 and 119 was obtained which could be converted to solely 119 by warming with a slurry of Fluorochem silica in CHCl3. After filtration and evaporation of the solvent pure 5 was obtained as an orange solid.

Method 2

A solution of 118 (5 mg, 4.6 mmol) in DCM (1 mL) was treated with vapour from aqueous NH3 solution for 30 min at rt. The solvent was evaporated by blowing with N2, and the product obtained quantitatively after drying in vacuo.

Crystals for structure determination were obtained from a toluene solution layered with MeOH.

1H NMR (400 MHz, CDCl3): d 10.23 (s, 2H, meso), 8.14 (d, J = 7 Hz, 2H, Ar), 7.98 (d, J = 7 Hz, 2H, Ar), 7.78 - 7.68 (m, 6H, Ar), 4.00 (m, 4H, hex H1), 3.89 (m, 4H, hex H1), 2.45 (s, 12H, CH3), 2.22 (m, 8H, hex H2), 1.80 (m, 8H, hex H3), 1.55 (m, 8H, hex H4), 1.43 (m, 8H, hex H5), 0.95 (t, J = 7 Hz, 12H, hex H6), -5.77 (s, 3H, NH3); 13C NMR (100.6 MHz, CDCl3): d 144.1, 142.8, 140.5, 140.1, 138.6, 134.0, 132.8, 128.3, 127.8, 127.2, 119.3, 98.8, 33.4, 32.0, 30.3, 27.1, 22.8, 15.6, 14.2; UV/vis (DCM): lmax 360, 420, 532, 562 nm; MALDI MS: m/z [M - NH3]+ 1084; IR (CCl4): nmax 3381 (w), 2957 (s), 2930 (s), 2858 (m) cm1; Anal. Calcd for C60H79IN5Rh: C 65.51, H 7.24, N 6.37. Found: C 65.70, H 7.43, N 6.03.

Rh meso oxoporphyrin (120)

120 was isolated in small (~1 mg) quantities during chromatography of 119 prepared inadvertently by method 1. 120 is visible as a fast moving bright yellow band on the column. Crystals for structure determination were obtained from a CDCl3 solution layered with MeOH.

1H NMR (400 MHz, CDCl3): d 7.35 (m, 6H, Ar), 7.15 (m, 2H, Ar), 5.02 (s, 1H, meso), 1.82 (m, 4H), 1.74 (m, 4H), 1.42 (s), 1.43 (s), 1.26 - 1.13 (br m), 0.89 - 0.80 (m), 0.68 (s, 6H), 0.49 (s, 6H); 13C NMR (100.6 MHz, CDCl3): d 154.2, 150.2, 146.9, 146.6, 146.2, 144.7, 140.4, 136.2, 135.1, 129.2, 128.2, 31.5, 31.4, 30.6, 29.7, 29.4, 29.2, 29.0, 24.0, 23.9, 22.5, 14.1, 14.0, 13.2, 12.1; UV/vis (DCM): lmax262, 280, 400, 484 nm; MALDI MS: m/z [M - 2I]+ 972.5.

(118)2 4,4'-Bipyridine complex (121)

To a stirred solution of 4,4'-bipyridine (50 mg, 0.32 mmol) in THF (0.5 mL) was added 118 (40 mg, 0.037 mmol) in THF (1 mL). After stirring for 3 h at room temperature, the solvent was evaporated and the residue chromatographed on silica eluted with DCM/hexane (1/1) to afford the product as an orange solid (32 mg, 75 %). Rf 0.33 (hexane/DCM, 1/1).

Crystals for structure determination were obtained from a mixed DCM/CHCl3 solution layered with MeOH.

1H NMR (400 MHz, CDCl3): d 9.97 (s, 4H, meso), 7.92 (d, J = 8 Hz, 4H, Ar), 7.70 (m, 8H, Ar), 7.60 (m, 8H, Ar), 4.11 (d, J = 7 Hz, 4H, bpy Hb), 3.76 (m, 16H, hex H1), 2.30 (s, 24H, CH3), 1.99 (m, 16H, hex H2), 1.59 (m, 16H, hex H3), 1.37 (m, 16H, hex H4), 1.25 (m, 16H, hex H5), 0.79 (t, J = 7 Hz, 24 H, hex H6), 0.39 (d, J = 7 Hz, 4H, bpy Ha); 13C NMR (100.6 MHz, CDCl3): d 144.6, 143.9, 142.6, 140.4, 139.6, 138.4, 133.8, 132.7, 128.2, 127.7, 127.0, 119.1, 117.5, 98.6, 33.2, 31.9, 30.0, 26.9, 22.7, 15.4, 14.1; UV/vis (DCM): lmax 358, 420, 532, 560 nm; Anal. Calcd for C130H160N10Rh2I2 C 67.23, H 6.94, N 6.03. Found: C 67.12, H 6.89, N 5.92.

5,15-Bis(4-methoxycarbonyl-phenyl)-2,8,12,18-tetrahexyl-3,7,13,17-tetramethyl porphyrinato rhodium(III) iodide (122)

5,15-Bis(4-methoxycarbonyl-phenyl)-2,8,12,18-tetrahexyl-3,7,13,17-tetramethyl porphyrin, obtained as a symmetrical side product from the preparation of unsymmetrical porphyrins, was metallated using an analogous procedure to the synthesis of 118. The product was obtained as an orange solid (144 mg, 58 %) after chromatography on Merck silica eluted with DCM. A sample for analysis was recrystallized from DCM layered with MeOH. Rf 0.46 (DCM).

1H NMR (400 MHz, CDCl3): d 10.30 (s, 2H, meso), 8.46 (m, 2H, Ar), 8.39 (m, 2H, Ar), 8.28 (m, 2H, Ar), 8.05 (m, 2H, Ar), 4.13 (s, 6H, OCH3), 4.02 (m, 4H, hex H1), 3.87 (m, 4H, hex H1), 2.46 (s, 12H, CH3), 2.15 (m, 8H, hex H2), 1.74 (m, 8H, hex H3), 1.48 (m, 8H, hex H4), 1.39 (m, 8H, hex H5), 0.91 (t, J = 7 Hz, 12H, hex H6); 13C NMR (100.6 MHz, CDCl3): d 167.3, 147.5, 144.8, 141.2, 140.7, 138. 4, 133.5, 133.2, 130.2, 128.8, 128.6, 119.5, 100.5, 52.4, 33.1, 31.9, 30.0, 26.9, 22.7, 15.9, 14.1; UV/vis (DCM): lmax 404, 522, 550 nm; MALDI MS: m/z [M-I]+ 1072; IR (CCl4): nmax 1728 (s) cm1; Anal. Calcd for C64H80O4N4RhI CH3OH: C 63.41, H 6.88, N 4.55. Found: C 62.99, H 6.87, N 4.38.

2,8,12,18-Tetrahexyl-3,7,13,17-tetramethyl-5,15-diphenyl-porphyrinato rhodium(III) methyl (123)

To a degassed solution of 121 (10 mg, 4.3 mmol) in dry THF (2 mL) was added MeLi (0.5 mL, 1.6 M in Et2O). After stirring for several seconds EA (0.5 mL) was added. The solvent was evaporated and the residues chromatographed on silica gel eluted with hexane/DCM (4/1). The product was obtained as an air stable orange solid (7.1 mg, 85 %). Rf 0.44 (hexane/DCM, 4/1).

Crystals for structure determination were obtained from a DCM solution layered with MeOH.

1H NMR (250 MHz, CDCl3): d 10.04 (s, 2H, meso), 8.08 (d, J = 7 Hz, 2H, Ar), 7.97 (d, J = 6 Hz, 2H, Ar), 7.73 (m, 6H, Ar), 3.86 (m, 8H, hex H1), 2.38 (s, 12H, CH3), 2.15 (m, 8H, hex H2), 1.72 (m, 8H, hex H3), 1.51 - 1.29 (m, 16H, hex H4,5), 0.90 (t, J = 7 Hz, 12H, hex H1), -6.06 (d, J = 3 Hz, 3H, CH3); 13C NMR (100.6 MHz, CDCl3): d 143.0, 142.9, 140.6, 140.2, 137.3, 2 133.3, 128.1, 127.4, 120.2, 99.4, 33.1, 32.0, 30.0, 26.7, 22.7, 15.3, 14.1; UV/vis (DCM): lmax 402, 516, 548 nm; FIB MS: m/z [M]+ 973.7; IR (CCl4): nmax 2958 (s), 2930 (s), 2859 (s), 1467 (m), 1445 (m) cm1.

118 Pyridine complex (124)

To a stirred solution of 118 (20 mg, 0.018 mmol) in CHCl3 (1 mL) was added pyridine (50 ml). After several minutes the solvent and excess pyridine were removed under reduced pressure to afford the product as an orange solid in quantitative yield.

Crystals for structure determination were obtained from a toluene solution layered with MeOH.

1H NMR (400 MHz, CDCl3): d 10.18 (s, 2H, meso), 8.03 (t, J = 8 Hz, 4H, Ar), 7.78 (m, 2H, Ar), 7.70 (m, 4H, Ar), 5.93 (tt, J = 7, 1 Hz, 1H, pyr Hg), 4.98 (t, J = 7 Hz, 2H, pyr Hb), 3.92 (m, 8H, hex H1), 2.45 (s, 12H, CH3), 2.17 (m, 8H, hex H2), 1.71 (m, 8H, hex H3), 1.48 (m, 8H hex H4), 1.37 (m, 8H, hex H5), 0.89 (t, J = 7 Hz, 12H, hex H6), 0.81 (d, J = 6 Hz, 2H, pyr H a); 13C NMR (100.6 MHz, CDCl3): d 144.5, 144.0, 143.0, 140.1, 139.8, 138.4, 134.3, 133.9, 133.1, 128.2, 127.7, 127.1, 121.2, 119.2, 98.8, 33.2, 32.0, 30.1, 27.0, 22.8, 15.6, 14.1; UV/vis (DCM): lmax 358, 422, 532, 560 nm; Anal. Calcd for C65H81N5RhI: C 67.18, H 7.02, N 6.03. Found: C 66.56, H 6.91, N 5.57.

4,4'-Bipyrimidine (125)262

A solution of BuLi (2 mL, 1.6 M in hexane) was added dropwise to a solution of 2,2,6,6-tetramethylpiperidine (0.55 mL, 3.24 mmol) in THF (20 mL) at -30 C. After stirring at 0 C for 30 min, followed by cooling to -79 C, to this was added dropwise pyrimidine (220 mL, 2.79 mmol) in THF (5 mL). Stirring was continued at -79 C for 1 h, after which HCl (5 mL, saturated in THF/EtOH, 1/1) was added dropwise to form a brown precipitate. After warming to rt, satd. NaHCO (25 mL) was added to dissolve the solids. The solution was extracted with DCM (3 50 mL) and the combined organic extracts dried (MgSO4) and evaporated to a cream solid. Column chromatography on silica eluted with EA/DCM (3/2) afforded the product as a white solid (109 mg, 49 %). Rf 0.33 (EA/DCM, 3/2).

1H NMR (250 MHz, CDCl3): d 9.35 (d, J = 1 Hz, 2H, H3), 8.96 (d, J = 5 Hz, 2H, H6), 8.43 (dd, J = 5, 1 Hz, 2H, H5); Anal. Calcd for C8H6N4: C 60.75, H 3.82, N 35.42. Found: C 60.17, H 3.70, N 34.78.

(118)2 4,4'-Bipyrimidine (126)

This was prepared in an identical manner to 121, using 125 instead of 4,4'-bipyridine. Purified by column chromatography on silica eluting with hexane/DCM (4/3 gradient to 1/1). Orange solid (33 mg, 77 %). Rf 0.47 (hexane/DCM, 1/1).

Crystals for structure determination were obtained from CHCl3/DCM solution layered with MeOH.

1H NMR (400 MHz, CDCl3): d 9.99 (s, 4H, meso), 7.90 (d, J = 7 Hz, 4H, Ar), 7.74 (m, 8H, Ar), 7.61 (m, 8H, Ar), 4.98 (dd, 2H, J = 6, 1 Hz, bpm H6), 3.82 (m, 8H, hex H1), 3.71 (m, 8H, hex H1), 2.31 (s, 24H, CH3), 2.00 (m, 16H, hex H2), 1.57 (m, 16H, hex H3), 1.37 (m, 16H, hex H4), 1.25 (m, 16H, hex H5), 1.07 (s, 2H, bpm H3), 0.79 (t, J = 7 Hz, 24H, hex H6), 0.67 (d, J = 6 Hz, 2H, bpm H5); 13C NMR (100.6 MHz, CDCl3): d 155.2, 152.7, 144.1, 142.4, 139.9, 139.6, 138.6, 133.8, 132.8, 128.3, 127.8, 127.1, 119.2, 113.9, 33.1, 31.9, 30.0, 26.9, 22.7, 15.4, 14.0; UV/vis (DCM): lmax 358, 418, 530, 560 nm; Anal. Calcd for C128H158N12Rh2I2: C 66.14, H 6.85, N 7.23. Found: C 65.94, H 6.80, N 7.08.

4,4'-Bipyrimidine rhenium tricarbonyl chloride (127)266

Re(CO)5Cl (181 mg, 0.50 mmol) and 125 (79 mg, 0.50 mmol) were refluxed in degassed toluene (25 mL) under N2 for 2 h. After cooling to room temperature the brown precipitate was collected and washed with Et2O (10 mL). The Et2O washings were discarded and the residues washed with CHCl3 (100 mL). Hexane was added to the filtrate to precipitate the product as an orange solid (51 mg, 22 %).

1H NMR (250 MHz, DMSO-d6): 9.79 (d, 2H, J = 1 Hz, H2), 9.44 (d, J = 5 Hz, 2H, H6), 8.99 (dd, J = 5, 1 Hz, 2H, H5); 13C NMR (62.9 MHz, DMSO-d6): 196.6, 161.5, 161.0, 160.7, 121.0; FAB MS: m/z [M]+ 464.1; Anal. Calcd for C11H6O3N4ReCl: C 28.48, H 1.30, N 12.08. Found: C 28.74, H 1.35, N 11.63.

4,4'-Bipyrimidine molybdenum tetracarbonyl (128)265

Mo(CO)6 (0.33 g, 1.2 mmol) and 125 (50 mg, 0.32 mmol) were refluxed in degassed THF (5 mL) under Ar for 24 h. The solution turned from yellow to green then deep blue over several minutes. After filtration through celite the solvent was evaporated to afford a dark purple solid which was recrystallized from CHCl3/hexane then chromatographed on a short silica column eluted with hexane/DCM (7/3) to afford the product as a black solid (32 mg, 28 %). Rf 0.31 (DCM/EA, 7/3).

1H NMR (250 MHz, Acetone-d6): 9.76 (d, J = 1 Hz, 2H, H2), 9.22 (d, J = 5 Hz, 2H, H6), 8.77 (dd, J = 5, 1 Hz, 2H, H5); Anal. Calcd for C12H6O4N4Mo: C 39.36, H 1.65, N 15.30. Found: C 39.56, H 1.77, N 15.10.

N,N'-Dimethyl-1,4,5,8-naphthalenetetracarboxylic diimide (129)268

Methylamine (100 mL, 40 % aq) was added to naphthalene tetracarboxylic acid hydrate (31.0 g, 0.10 mol). The solution was warmed to boiling and sonicated briefly, then evaporated under reduced pressure to afford a brown solid. To this was added N-methyl pyrrolidinone (500 mL) and heated to 150 C for 2 h. After cooling to 80 C the solution was filtered to collect the product which was washed with MeOH until the washings were colourless. After drying the product was used without further purification. Pink needles (16.1 g, 54 %).

Anal. Calcd for C16H10N2O4: C 65.31, H 3.43, N 9.52. Found: C 64.94, H 3.46, N 9.65.

1,3,6,8-Tetrahydro-2,7-dimethyl-2,7-diazapyrene (130)271

LiAlH4 (14.7 g, 0.39 mol) was added to a solution of AlCl3 (17.2 g, 0.13 mol) in THF (300 mL) at 0 C. To this was added 129 (16.1 g, 55 mmol) in portions over several minutes. The green solution was stirred at rt for 30 min, then refluxed for 4 h. After cooling the solution was poured into a mixture of THF (500 mL) and ice (100 mL). The resulting slurry was filtered, and the brown filtrate concentrated to 50 mL to produce a brown precipitate of 130 which was collected. The residues were washed with THF (3 100 mL) and after concentration, further 130 precipitated. The residues were further extracted with boiling CHCl3 (4 500 mL). After evaporation of the solvent a further portion of 130 was obtained as a yellow solid (combined mass 8.89 g, 68 %).

1H NMR (400 MHz, CDCl3): 7.12 (s, 4H, Ar), 3.88 (s, 8H, CH2N), 2.57 (s, 6H, CH3).

2,7-Diazapyrene (131)269

Pd/C (2.0 g, 10 % Pd) and 130 (2.0 g, 8.4 mmol) were ground together and packed into a Schlenk tube which was evacuated then placed under N2. The tube was heated to ~300 C for 1 h, with periodic exposure to vacuum. After cooling to rt, HCl (20 mL, 3 N) was added and the solids removed by filtration through celite. The green filtrate was basified by addition of NaOH (10 %) to produce a brown precipitate, which was filtered, washed with water and dried in vacuo. The product was purified by passage through a column of basic alumina (toluene/DCM 1/1, 3 % Et3N), followed by sublimation (140 C, 0.05 mmHg), then chromatography on silica (CHCl3/MeOH, 20/1). Pale yellow solid (32 mg, 2 %). Rf 0.33 (CHCl3/MeOH, 20/1).

1H NMR (400 MHz, CDCl3): d 9.51 (s, 4H, H2), 9.21 (s, 4H, H3).

(118)2 Diazapyrene complex (132)

118 (21 mg, 19 mmol) and 131 (2.0 mg, 9.8 mmol) were mixed and CDCl3 (1.0 mL) added (to allow for acquisition of the NMR spectrum of the reaction mixture). After stirring for 3 h the solvent was evaporated and the residue purified by chromatography on silica gel (hexane/DCM,1/1 gradient to DCM) to afford an orange solid (10 mg, 44 %). Rf 0.30 (hexane/DCM, 1/1).

Crystals for structure determination were grown from a CHCl3 solution layered with hexane.

1H NMR (400 MHz, CDCl3): d 10.04 (s, 4H, meso), 7.98 (d, J = 7 Hz, 4H, Ar), 7.65 (m, 12H, Ar), 7.52 (m, 4H, Ar), 5.64 (s, 4H, dap H3), 3.86 (m, 8H, hex H1), 3.71 (m, 8H, hex H1), 2.30 (s, 24H, CH3), 2.01 (m, 16H, hex H2), 1.57 (m, 16H, hex H3), 1.33 (m, 16H, hex H4), 1.21 (m, 16H, hex H5), 1.08 (s, 4H, dap H2), 0.76 (t, J = 7 Hz, 24H, hex H6); 13C NMR (100.6 MHz, CDCl3): d 143.9, 142.6, 2 140.0, 139.7, 138.4, 133.8, 132.6, 128.2, 127.7, 127.0, 124.2, 122.0, 121.6, 119.2, 98.7, 33.1, 31.8, 29.9, 26.8, 22.6, 15.4, 14.0; UV/vis (DCM): lmax 342, 420, 532, 560 nm; Anal. Calcd for C134H160N10Rh2I2: C 67.90, H 6.80, N 5.91. Found: C 67.98, H 6.28, N 5.50.

5,5'-Dimethyl-2,2'-bipyridine (133)274,275

NiAl alloy (71 g) was added portionwise over several minutes to a stirred solution of NaOH (90.7 g, 2.3 mol) in ice cold water (340 mL) (cautionfoaming). After the addition was complete the suspension was heated on a steam bath for 30 min. An additional portion of water (340 mL) was added and the supernatant liquid decanted off. The grey solids were washed with water (5 300 mL) then dried in vacuo by heating with a steam bath for 90 min. After cooling to rt, the activated Ni catalyst was placed under N2. 3-Picoline (90 mL, 0.92 mol) was added dropwise to the catalyst ensuring air did not enter the apparatus until the addition was complete. The picoline was refluxed over the catalyst under dry air for 48 h, after which the catalyst was removed by filtration and rinsed with toluene (100 mL). The filtrate was evaporated to a brown solid which was extracted with boiling 60/80 petroleum ether (250 mL). The extracts were filtered hot, then a further portion of 60/80 petroleum ether (750 mL) added. After swirling with activated charcoal for 5 min, and filtration through celite, the solution was evaporated to yellow solids which were recrystallized from boiling EtOH to afford the product as pale yellow crystals (18.1 g, 21 %).

1H NMR (250 MHz, CDCl3): d 8.47 (d, J = 2 Hz, 2H, H6), 8.22 (d, J = 8 Hz, 2H, H3), 7.59 (dd, J = 8, 2 Hz, 2H, H4), 2.36 (s, 6H, CH3); Anal. Calcd for C12H12N2: C 78.23, H 6.56, N 15.21. Found: C 78.15, H 6.56, N 15.23.

5,5'-Dicarboxy-2,2'-bipyridine (134)276

133 (10.54 g, 57 mmol) was added portionwise to stirred conc. H2SO4 (125 mL) maintaining the temperature in the range 5 - 10 C. To the cooled solution (ice bath) was added finely divided CrO3 (32.8 g, 0.33 mol) portionwise over 90 min. The solution was allowed to warm to rt over 150 min, after which conc. H2SO4 (50 mL) was added followed by heating to 56 C for 18 h. Water (300 mL) was added (caution exothermic) and the resulting slurry poured into iced water (700 mL). After allowing the solids to settle, the green supernatant was decanted and celite (20 g) and water (500 mL) added to the remaining suspension. The solids were filtered onto a pad of celite, which was washed with water (200 mL). The celite was resuspended in water (1 L) and the pH adjusted to 8.5 using NaOH (10 % aq) and HCl (3 N). After filtration the yellow filtrate was acidified to pH 2 with HCl (3 N) to form a white precipitate which was collected and washed with water (50 mL), acetone (50 mL) and Et2O (50 mL). After drying overnight in an oven (70 C) the product was obtained as a white powder (12.2 g, 87 %) and used without further purification.

5,5'-Dicarboxyethyl-2,2'-bipyridine (135)277

134 (4.0 g, 16 mmol) was refluxed in EtOH (200 mL) and conc. H2SO4 (70 mL) for 21 h. After cooling to room temperature the solution was poured into water (1 L) to form a white precipitate. The pH was adjusted to 8 by addition of conc. NH3 and the precipitates collected by filtration and washed with water. After drying in vacuo and recrystallization from EtOH the product was obtained as almost colourless needles (2.66 g, 54 %).

1H NMR (400 MHz, CDCl3): d 9.29 (dd, J = 2, 1 Hz, 2H, H6), 8.57 (dd, J = 8, 1 Hz, 2H, H3), 8.43 (dd, J = 8, 2 Hz, 2H, H4), 4.15 (q, J = 7 Hz, 4H, CH2O), 1.44 (t, J = 7 Hz, 6H, CH3); Anal. Calcd for C16H16N2O4: C 63.99, H 5.37, N 9.33. Found: C 63.65, H 5.32, N 9.29.

5,5'-Dicarboxamide-2,2'-bipyridine (136)273

A solution of 135 (2.66 g, 8.86 mmol) in EtOH (90 mL) and ethylene glycol (90 mL) was saturated with NH3 and stirred at 95 C under an NH3 atmosphere for 2 d. The gelatinous white precipitate was collected by filtration and washed with ethylene glycol (20 mL) and hot EtOH (20 mL). The filtrate was retained. The solids were resuspended in EtOH (30 mL), filtered and dried in an oven. As 1H NMR indicated the presence of starting material the solids were recombined with the filtrate from the initial filtration. An additional portion of EtOH (40 mL) was added, the mixture was saturated with NH3 and refluxed for 1 d under NH3. After cooling to rt the precipitate was filtered, washed with EtOH and dried in an oven (80 C) to obtain the product as a white powder (1.16 g, 54 %) which was used without purification.

5,5'-Dicyano-2,2'-bipyridine (137)278

A mixture of 136 (0.20 g, 0.83 mmol) and P4O10 (0.5 g) was heated in a sublimator under vacuum. The white hygroscopic solids that sublimed were mixed with P4O10 (0.5 g) and sublimed again to obtain a small quantity (17 mg) of product which was further purified by passage through a short silica plug eluted with CHCl3 to afford the product as a white solid (8 mg, 5 %).

1H NMR (400 MHz, CDCl3): d 8.96 (dd, J = 2, 1 Hz, 2H, H6), 8.63 (dd, J = 8, 1 Hz, 2H, H3), 8.14 (dd, J = 8, 2 Hz, 2H, H4); 13C NMR (100.6 MHz, CDCl3): d 156.9, 152.1, 140.5, 121.6, 116.5, 110.7.

(118)2 DABCO (139)

Prepared by titration of a solution of 118 (3.95 mg, 3.5 mmol) in CDCl3 (600 mL) with DABCO in CDCl3. After titration the sample was loaded onto a silica column and eluted with hexane/DCM (1/1). The porphyrin containing eluent was evaporated, redissolved in DCM and layered with MeOH to obtain crystals of 139 for structure determination.

1H NMR (400 MHz, CDCl3): d 9.70 (s, 4H, meso), 7.75 (m, 8H, Ar), 7.66 (t, J = 7 Hz, 4H, Ar), 7.59 (t, J = 7 Hz, 4H, Ar), 7.37 (d, J = 7 Hz, 4H, Ar), 3.67 (m, 16H, hex H1), 2.21 (s, 24H, CH3), 1.82 (m, 16H, hex H2), 1.57 (m, 16H, hex H3), 1.43 (m, 32H, hex H4,5), 0.93 (t, J = 7 Hz, 24H, hex H6), -6.05 (s, 12H, NCH2).

Isonicotinic acid undecyl ester (140)

Isonicotinic acid (0.50 g, 4.1 mmol), SOCl2 (280 mL) and pyridine (0.67 g) were heated to 100 C under N2 for 1 h. 1-Undecanol (0.75 mL, 3.6 mmol) was added and the mixture stirred at 100 C for a further 3 h after which water (10 mL) was added and the mixture basified by addition of NaOH (10 % aq). The red solution was extracted with Et2O (3 30 mL), dried (MgSO4) and evaporated to a red oil. The product was precipitated as a salt from Et2O solution by addition of conc. H2SO4. The yellow solids were filtered and washed with Et2O, placed in a separating funnel and shaken with a mixture of CHCl3 (30 mL), water (10 mL) and satd. Na2CO3 (10 mL) until all the solids had dissolved. The organic phase was dried (MgSO4) and evaporated to a red oil which was eluted through a silica gel plug with hexane/EA (3/1) to afford the product as a colourless oil after removal of the solvent. (0.69 g, 69 %). Rf 0.40 (hexane/EA, 3/1).

1H NMR (250 MHz, CDCl3): d 8.72 (d, J = 5.0 Hz, 2H, pyr H2,6), 7.78 (dd, J = 5, 2 Hz, 2H, pyr H3,5), 4.29 (t, J = 7 Hz, 2H, OCH2), 1.72 (m, 2H, CH2), 1.60 - 1.21 (m, 16H, (CH2)8), 0.82 (t, J = 7 Hz, 3H, CH3); 13C NMR (62.9 MHz, CDCl3): d 165.1, 150.6, 137.6, 122.8, 65.9, 31.9, 2 29.5, 29.3, 29.2, 28.5, 25.9, 22.6, 14.1; FAB MS: m/z [M+H]+ calcd 278.2120, found 278.2125; IR (CCl4): nmax 2956 (m), 2927 (s), 2855 (m), 1732 (s), 1279 (s) cm1; Anal. Calcd for C17H27O2N: C 73.61, H 9.81, N 5.05. Found: C 73.96, H 9.80, N 5.06.

2,8,12,18-Tetrahexyl-3,7,13,17-tetramethyl-5,15-diphenyl-porphyrinato tin(IV) dichloride (142)

SnCl2 (0.10 g, 0.53 mmol) and 117 (80 mg, 94 mmol) were refluxed in pyridine (5 mL) under air for 7 h. and allowed to cool to rt. Water (20 mL) was added and the red precipitate filtered onto celite and washed with MeOH (50 mL). The porphyrin was extracted from the celite with CHCl3 (70 mL), and the organic solution washed with HCl (3 N, 2 20 mL) and water (2 20 mL), dried (Na2SO4) and evaporated to a red solid which was used without further purification (95 mg, 97 %).

1H NMR (400 MHz, CDCl3): d 10.60 (s, 2H, meso), 8.16 (m, 4H, Ar), 7.86 (m, 2H, Ar), 7.80 (m, 4H, Ar), 4.06 (t, J = 8 Hz, 8H, hex H1), 2.57 (s, 12H, CH3), 2.30 (m, 8H, hex H2), 1.85 (m, 8H, hex H3), 1.58 (m, 8H, hex H4), 1.44 (m, 8H, hex H5), 0.97 (t, J = 7 Hz, 12H, hex H6); 13C NMR (100.6 MHz, CDCl3): d 144.4, 143.8, 142.8, 141.5, 139.6, 133.3, 129.1, 128.0, 119.4, 96.9, 33.1, 31.9, 30.2, 27.0, 22.7, 15.2, 14.1; UV/vis (DCM): lmax 418, 548, 582 nm; Anal. Calcd for C60H76N4SnCl2: C 69.10, H 7.35, N 5.37. Found C 69.09, H 7.36, N 5.20.

2,8,12,18-Tetrahexyl-3,7,13,17-tetramethyl-5,15-diphenyl-porphyrinato tin(IV) dihydroxide (143)

Activity I basic alumina (10 g) was shaken with water (2 mL) until homogenous. To this was added 142 (91 mg, 73 mmol) in CHCl3 (10 mL). Light was excluded and the suspension stirred for 1 d at rt. The suspension was filtered through celite which was washed with CHCl3 (100 mL) to remove all porphyrin. The filtrate was evaporated to afford the product as a purple solid which was used without further purification (89 mg, 100 %).

1H NMR (500 MHz, CDCl3): d 10.51 (s, 2H, meso), 8.17 (m, 4H, Ar), 7.85 (m, 2H, Ar), 7.78 (t, J = 7 Hz, 4H, Ar), 4.03 (t, J = 8 Hz, 8H, hex H1), 2.52 (s, 12H, CH3), 2.28 (m, 8H, hex H2), 1.83 (m, 8H, hex H3), 1.55 (m, 8H, hex H4), 1.44 (m, 8H, hex H5), 0.96 (t, J = 7 Hz, 12H, hex H6), -7.84 (s, 2H, OH); 13C NMR (100.6 MHz, CDCl3): d 2 144.2, 143.1, 142.3, 139.3, 133.3, 128.8, 127.9, 119.4, 97.2, 33.2, 31.9, 30.1, 29.7, 26.9, 22.8, 15.1, 14.2; UV/vis (DCM): lmax 416, 548 nm; MALDI MS: m/z [M-OH]+ 989; IR (CCl4): nmax 3644 (w), 2958 (s), 2930 (s), 2858 (s) cm1; Anal. Calcd for C60H78N4SnO2: C 71.64, H 7.81, N 5.57. Found: C 71.18, H 7.90, N 5.39.

5-(4-Methoxycarbonyl-phenyl)-15-(4-pyridyl)-2,8,12,18-tetrahexyl-3,7,13,17-tetramethyl porphyrin (147)

Prepared using the standard porphyrin synthesis procedure from 4-formyl-pyridine and 4-formyl-methyl-benzoate. After purification by column chromatography on silica eluted with DCM/EA (10/1) the product was obtained as a dark purple solid (67 mg, 7 %). Rf 0.52 (DCM/EA, 10/1).

1H NMR (500 MHz, CDCl3): d 10.26 (s, 2H, meso), 9.02 (d, J = 5 Hz, 2H, pyr Ha), 8.44 (d, J = 8 Hz, 2H, Ar), 8.18 (d, J = 8 Hz, 2H, Ar), 8.06 (d, J = 5 Hz, 2H, pyr Hb), 4.14 (s, 3H, OCH3), 3.97 (m, 8H, hex H1), 2.51 (s, 6H, CH3), 2.46 (s, 6H, CH3), 2.18 (m, 8H, hex H2), 1.73 (m, 8H, hex H3), 1.47 (m, 8H, hex H4), 1.37 (m, 8H, hex H5), 0.90 (t, J = 7 Hz, 12H, hex H6), -2.39 (br s, 2H, NH); 13C NMR (100.6 MHz, CDCl3): d 167.3, 150.8, 149.0, 147.3, 144.7, 2 144.0, 143.8, 141.7, 141.5, 136.0, 135.3, 133.1, 130.2, 128.8, 128.5, 117.0, 114.5, 97.4, 52.4, 2 33.3, 32.0, 2 30.0, 26.8, 22.7, 15.0, 14.8, 14.1; UV/vis (DCM): lmax 408, 506, 574, 626 nm; ES MS: m/z [M+H]+ calcd 914.6312, found 914.6320; IR (CCl4): nmax 2956 (s), 2930 (s) 2858 (m), 1728 (s) cm1.

5-(4-Carboxy-phenyl)-15-(4-pyridyl)-2,8,12,18-tetrahexyl-3,7,13,17-tetramethyl porphyrin (148)

A solution of 147 (40 mg, 44 mmol) and KOH (100 mg, 1.8 mmol) in a mixture of THF (13.5 mL) and water (125 mL) was heated to 40 C for 1 d. Tlc indicated the presence of starting material. KOH (38 mg) and water (100 mL) were added and stirring was continued at the same temperature overnight. Addition of a further portion of water (100 mL) and heating at reflux for 1 h was required to complete the reaction. After cooling to rt, HCl (3 N, 50 mL) was added and the solution extracted with CHCl3 (2 50 mL). The green organic layer was washed with water (3 100 mL), dried (MgSO4) and evaporated to a brown solid. Column chromatography on silica eluted with DCM/EA (10/1) gradient to DCM/MeOH (10/1) afforded the product as a purple solid (27 mg, 69 %).

1H NMR (500 MHz, CD3OD + CDCl3): d 10.21 (s, 2H, meso), 8.90 (br d, 2H, pyr Ha), 8.40 (d, 2H, J = 8 Hz, Ar), 8.11 (d, 2H, J = 8 Hz, Ar), 8.07 (d, J =5 Hz, 2H, pyr Hb), 3.91 (br, 8H, hex H1), 2.44 (s, 6H, CH3), 2.40 (s, 6H, CH3), 2.12 (m, 8H, hex H2), 1.67 (m, 8H, hex H3), 1.41 (m, 8H, hex H4), 1.31 (m, 8H, hex H5), 0.84 (t, J = 7 Hz, 12H, hex H6); 13C NMR (100.6 MHz, CD3OD + CDCl3): d 168.9, 151.5, 148.4, 147.0, 144.6, 144.1, 143.8, 143.7, 141.7, 141.4, 136.1, 135.1, 133.0, 130.5, 129.1, 128.8, 117.3, 114.0, 97.4, 2 33.2, 31.9, 29.9, 26.7, 22.6, 14.9, 14.7, 14.0; UV/vis (DCM): lmax 408, 506, 540, 574 nm; ES MS: m/z [M+H]+ calcd 900.6156, found 900.6166.

4-Trimethylsilylethynyl-benzaldehyde (152)466

A mixture of 4-bromobenzaldehyde (5.0 g, 27 mmol), Pd(OAc)2 (0.36 g, 1.6 mmol), PPh3 (0.56 g, 2.1 mmol), trimethylsilylacetylene (5.8 mL, 41 mmol) and Et3N (dry, 50 mL) was degassed and refluxed under Ar for 6 h. After cooling overnight the black solution was poured into water (300 mL) and extracted with DCM (4 100 mL). The combined organic extracts were dried (MgSO4), and evaporated to a brown oil. Column chromatography on silica gel eluting with hexane/EA (10/1) followed by recrystallization from cold (-79 C) hexane afforded the product as pale yellow crystals (3.12 g, 57 %). Rf 0.43 (hexane/EA, 10/1).

1H NMR (250 MHz, CDCl3): d 9.99 (s, 1H, CHO), 7.81 (d, J = 8 Hz, 2H, Ar), 7.59 (d, J = 8 Hz, 2H, Ar), 0.26 (s, 9H, SiCH3); Anal. Calcd for C12H14OSi: C 71.24, H 6.97. Found: C 71.24, H 6.99.

3,5-Diiodobenzaldehyde (153)467

To a solution of 3,5-diiodobenzyl alcohol (2.7 g, 7.5 mmol) in THF (10 mL) and DCM (5 mL) was added PCC (3.0 g, 13.9 mmol) suspended in DCM (10 mL). The solution was stirred for 2 h at rt, after which Et2O (75 mL) was added. The brown precipitate was removed by filtration through celite, which was washed with a portion of Et2O (50 mL). The combined filtrates were evaporated to a yellow solid, which was redissolved in hexane/EA mixture and evaporated onto silica gel. The silica was loaded onto a short column and eluted with hexane/EA (20/1) to afford the product as yellow crystals. (2.1 g, 78 %).

1H NMR (500 MHz, CDCl3): d 9.83 (s, 1H, CHO), 8.29 (s, 1H, H4), 8.14 (s, 2H, H2,6).

5-(4-Trimethylsilylethynyl-phenyl)-15-(4-pyridyl)-2,8,12,18-tetrahexyl-3,7,13,17-tetramethyl porphyrin (154)

Synthesized according to the standard procedure, and isolated by chromatography on silica, eluted with DCM/EA (15/1 gradient to 10/1). Further purification was carried out using a second column eluted with DCM/EA (15/1) and recrystallization from CHCl3 layered with MeOH. Deep red crystals (0.31 g, 13 %). Rf 0.35 (DCM/EA, 15/1).

1H NMR (400 MHz, CDCl3): d 10.25 (s, 2H, meso), 9.02 (d, J = 6 Hz, 2H, pyr Ha), 8.07 (d, J = 6 Hz, 2H, pyr Hb), 8.02 (d, J = 8 Hz, 2H, Ar), 7.87 (d, J = 8 Hz, 2H, Ar), 3.97 (m, 8H, hex H1), 2.51 (s, 6H, CH3), 2.50 (s, 6H, CH3), 2.18 (m, 8H, hex H2), 1.73 (m, 8H, hex H3), 1.48 (m, 8H, hex H4), 1.37 (m, 8H, hex H5), 0.90 (t, J = 7 Hz, 12 H, hex H6), -2.42 (s, 2H, NH).

5-(4-Ethynyl-phenyl)-15-(4-pyridyl)-2,8,12,18-tetrahexyl-3,7,13,17-tetramethyl porphyrin (155)468

To a solution of 154 (250 mg, 0.26 mmol) in THF (10 mL) and water (100 mL) was added TBAF (1 M in THF, 290 mL, 0.29 mmol). After stirring for 50 min at rt a precipitate had formed. After this time water (50 mL) was added and the suspension extracted with CHCl3 (2 50 mL). The combined organic phase was washed with water and dried (MgSO4). The solvent was evaporated and the resulting solids recrystallized from CHCl3 layered with MeOH to afford the product as purple fibres (214 mg, 93 %).

1H NMR (400 MHz, CDCl3): d 10.25 (s, 2H, meso), 9.03 (d, J = 4 Hz, 2H, pyr Ha), 8.08 (d, J = 4 Hz, 2H, pyr Hb), 8.05 (d, J = 8 Hz, 2H, Ar), 7.90 (d, J = 8 Hz, 2H, Ar), 3.98 (t, J = 8 Hz, 8H, hex H1), 3.34 (s, 1H, CCH), 2.52 (s, 6H, CH3), 2.51 (s, 6H, CH3), 2.19 (m, 8H, hex H2), 1.73 (m, 8H, hex H3), 1.47 (m, 8H, hex H4), 1.36 (m, 8H, hex H5), 0.90 (t, J = 7 Hz, 12H, hex H6), -2.42 (s, 2H, NH).

5-(4-Methoxycarbonyl-phenyl)-15-(3,5-diiodo-phenyl)-2,8,12,18-tetrahexyl-3,7,13,17-tetramethyl porphyrin (156)

Prepared according to the standard procedure from 153 and 4-formyl-methyl-benzoate. The product was isolated by chromatography on silica eluted with hexane/EA/CHCl3 (20/1/1) with a gradient to hexane/EA (10/1). Recrystallization from CHCl3 layered with MeOH afforded the product as purple crystals (0.45 g, 16 %). Rf 0.33 (hexane/CHCl3/EA, 20/1/1).

1H NMR (500 MHz, CDCl3): d 10.25 (s, 2H, meso), 8.53 (s, 1H, ArH4), 8.46 - 8.44 (m, 4H, Ar), 8.18 (d, J = 8 Hz, 2H, Ar), 4.14 (s, 3H, OCH3), 3.98 (m, 8H, hex H1), 2.59 (s, 6H, CH3), 2.46 (s, 6H, CH3), 2.19 (m, 8H, hex H2), 1.74 (m, 8H, hex H3), 1.48 (m, 8H, hex H4), 1.38 (m, 8H, hex H5), 0.91 (m, 12H, hex H6), -2.45 (s, 1H, NH), -2.48 (s, 1H, NH); 13C NMR (100.6 MHz, CDCl3): d 167.4, 147.3, 146.2, 145.0, 144.6, 144.5, 144.0, 143.8, 141.7, 141.6, 141.1, 136.0, 135.5, 133.1, 130.1, 128.8, 117.0, 114.3, 97.5, 93.8, 52.5, 2 33.3, 32.0, 30.1, 30.0, 2 26.8, 22.8, 22.7, 15.5, 14.9, 14.2, 14.1; UV/vis (DCM): lmax 410, 508, 542, 574, 626 nm; ES MS: m/z [M]+ 1165; IR (CCl4): nmax 2956 (s), 2930 (s), 2858 (s), 1728 (s) cm1; Anal. Calcd for C62H78N4O2I2: C 63.80, H 6.74, N 4.80. Found: C 63.80, H 6.68, N 4.70.

5-(4-Methoxycarbonyl-phenyl)-15-(3,5-diiodo-phenyl)-2,8,12,18-tetrahexyl-3,7,13,17-tetramethyl porphyrinato nickel(II) (157)

156 was nickel metallated according to the standard procedure. The product was recrystallized from CHCl3 layered with MeOH. Fibrous red crystals (91 mg, 87 %).

1H NMR (500 MHz, CDCl3): d 9.46 (s, 2H, meso), 8.41 (m, 1H, ArH4), 8.33 (d, J = 8 Hz, 2H, ArCO2), 8.22 (d, J = 1 Hz, 2H, ArH2), 7.96 (d, J = 8 Hz, 2H, ArCO2), 4.08 (s, 3H, CO2CH3), 3.66 (m, 8H, hex H1), 2.33 (s, 6H, CH3), 2.20 (s, 6H, CH3), 2.00 (m, 8H, hex H2), 1.62 (m, 8H, hex H3), 1.45 (m, 8H, hex H4), 1.36 (m, 8H, hex H5), 1.82 (m, 12H, hex H6); 13C NMR (100.6 MHz, CDCl3): d 167.2, 146.3, 145.3, 2 144.7, 144.5, 141.2, 140.0, 139.8, 139.7, 139.6, 138.6, 138.1, 133.2, 130.0, 128.7, 115.6, 113.0, 96.8, 93.6, 52.3, 2 32.8, 31.9, 29.8, 29.7, 2 26.3, 2 22.7, 16.0, 15.5, 2 14.1; UV/vis (DCM): lmax 408, 528, 564 nm; LSI MS: m/z [M]+ 1225; IR (CCl4): nmax 2956 (s), 2930 (s), 2860 (m), 1728 (s), 1274 (s) cm1; Anal. Calcd for C62H76N4O2I2Ni: C 60.95, H 6.27, N 4.59. Found: C 61.02, H 6.32, N 4.68.

Me ester fb wedge (158)

AsPh3 (26 mg, 85 mmol), Pd2(dba)3 (12 mg, 13 mmol), 155 (75 mg, 86 mmol) and 156 (50 mg, 43 mmol) were mixed and DCM (dry, 3 mL) and Et3N (dry, 3 mL) added. The mixture was degassed and stirred under Ar at rt for 36 h. DCM (50 mL) was added to the red suspension. The solution was washed with water (3 30 mL), dried (MgSO4) and evaporated to a red solid. After column chromatography on a short (10 cm) silica column eluted with CHCl3/MeOH (50/1) and precipitation from CHCl3 solution by addition of MeOH the product was obtained as a red solid (85 mg, 75 %). Rf 0.41 (CHCl3/MeOH, 50/1).

1H NMR (400 MHz, CDCl3): d 10.33 (s, 2H, meso), 10.26 (s, 4H, meso), 9.01 (d, J = 6 Hz, 4H, pyr Ha), 8.53 (s, 3H, Ar), 8.46 (d, J = 8 Hz, 2H, Ar), 8.21 (d, J = 8 Hz, 2H, Ar), 8.11 (d, J = 8 Hz, 4H, Ar), 8.06 - 8.02 (m, 8H, Ar), 4.15 - 3.98 (m, 27H, OCH3, hex H1), 2.87 (s, 6H, CH3), 2.57 (s, 12H, CH3), 2.51, 2.50 (both s, 18H, CH3), 2.35 - 2.14 (m, 24H, hex H2), 1.89 - 1.32 (m, 72H hex H3-5), 1.00 - 0.88 (m, 36H, hex H6), -2.29, -2.33, -2.40 (br s, total 6H, NH); 13C NMR (100.6 MHz, CDCl3): d 167.4, 150.8, 149.0, 147.4, 145.1, 145.0, 144.6, 144.0, 143.9, 143.8, 143.7, 143.3, 142.8, 141.8, 2 141.7, 141.5, 136.2, 2 135.9, 135.3, 134.6, 133.2, 133.1, 133.0, 131.1, 130.1, 128.8, 128.5, 123.3, 123.0, 117.4, 116.9, 115.9, 114.4, 97.4, 90.8, 89.8, 52.4, 33.4, 33.3, 32.1, 2 32.0, 30.1, 2 30.0, 26.9, 26.8, 2 22.8, 22.7; UV/vis (DCM): 412, 508, 542, 574, 626 nm; MALDI MS: m/z [M]+ 2670.

Acid fb wedge (159)

KOH (100 mg, 1.8 mmol) and 158 (36 mg, 13 mmol) were stirred in a mixture of THF (10 mL) and water (100 mL) at 40 C for 32 h to form a red suspension. Additional portions of KOH (25 mg, 0.45 mmol), water (200 mL) and THF (10 mL) were added and the mixture refluxed for 18 h under N2. After cooling, water (30 mL) and CHCl3 (50 mL) were added and HCl (3 N) added until the organic layer became green. The organic phase was separated and washed with water (3 30 mL), dried (MgSO4) and evaporated to a red solid. Column chromatography on silica eluting with CHCl3 gradient to CHCl3/MeOH (20/1) followed by precipitation from CHCl3 solution by addition of hexane afforded the product as a deep purple solid (15 mg, 42 %). Rf 0.50 (CHCl3/MeOH, 10/1).

1H NMR (400 MHz, CDCl3): d 10.35 (s, 2H, inner meso), 10.26 (s, 4H, outer meso), 9.04 (d, J = 4 Hz, 4H, pyr Ha), 8.58 (d, J = 8 Hz, 2H, Ar), 8.53 (s, 3H, Ar), 8.28 (d, J = 8 Hz, 2H, Ar), 8.12 - 8.03 (m, 12H, Ar), 4.11, 3.99 (br m, 24H, hex H1), 2.87 (s, 6H, CH3), 2.57 (s, 12H, CH3), 2.54 (s, 6H, CH3), 2.51 (s, 12H, CH3), 2.35 - 2.14 (m, 24H, hex H2), 1.89 - 1.68 (m, 24H, hex H3), 1.62 (m, 48H, hex H4,5), 1.00 - 0.88 (m, 36H, hex H6), -2.33 (br, NH). 13C NMR (125.7 MHz, CDCl3): d 148.7, 145.0, 144.6, 144.0, 143.9, 143.8, 143.8, 142.8, 141.7, 141.5, 136.2, 135.9, 135.2, 133.3, 133.1, 131.1, 129.3, 128.5, 123.3, 122.9, 117.4, 114.2, 97.3, 90.7, 89.7, 33.2, 2 32.0, 31.9, 30.1, 29.9, 26.7, 22.8, 2 22.7, 15.6, 15.0, 14.9, 14.1 (2 peaks). UV/vis (DCM): 412, 508, 540, 574 nm; ES MS: m/z [M]+ 2657.

Me ester Ni/fb wedge (160)

Prepared analogously to 158 but substituting 156 with 157. The product was purified by silica gel chromatography eluting with DCM/EA (10/1), followed by a second column eluted with CHCl3/MeOH (50/1). The product was obtained as a red solid (99 mg, 89 %). Rf 0.34 (CHCl3/MeOH, 50/1).

1H NMR (400 MHz, CDCl3): d 10.27 (s, 4H, fb meso), 9.51 (s, 2H, Ni meso), 8.98 (d, J = 6 Hz, 4H, pyr Ha), 8.44 (d, J = 2 Hz, 1H, Ar), 8.36 (d, J = 8 Hz, 2H, Ar), 8.31 (d, J = 2 Hz, 2H, Ar), 8.08 (d, J = 8 Hz, 4H, Ar), 8.01 (m, 10H, Ar), 4.11 (s, 3H, OCH3), 3.99 (m, 16H, hex H1), 3.77 (t, J = 7 Hz, 4H, hex H1), 3.66 (t, J = 8 Hz, 4H, hex H1), 2.62 (s, 6H, CH3), 2.56 (s, 12H, CH3), 2.49 (s, 12H, CH3), 2.24 - 2.01 (m, 30H, CH3, hex H2), 1.79 - 1.34 (m, 72H, hex H3-5), 1.02 - 0.90 (m, 36H, hex H6), -2.39 (s, 4H, NH); 13C NMR (125.7 MHz, CDCl3): d 167.3, 150.7, 149.0, 146.4, 145.0, 144.5, 144.4, 143.9, 143.7, 142.8, 142.3, 141.7, 141.5, 140.4, 139.9, 2 139.7, 138.5, 136.2, 135.9, 135.2, 134.5, 133.2, 133.0, 131.0, 129.9, 128.6, 128.4, 123.1, 122.9, 117.4, 115.4, 114.6, 114.3, 97.3, 96.7, 90.7, 89.7, 52.3, 33.3, 33.0, 32.8, 2 31.9, 2 29.9, 29.8, 26.8, 26.4, 26.3, 22.8, 22.7, 16.2, 15.5, 14.9, 14.2, 14.1; UV/vis (DCM): 412, 508, 570 nm; MALDI MS: m/z [M]+ 2727.

Acid Ni/fb acid wedge (161)

A mixture of KOH (10 mL) and 160 (42 mg, 15 mmol) was refluxed in THF (10 mL) and water (500 mL) under N2 for 13 h. After cooling to rt, water (30 mL) was added to produce a red precipitate. DCM (50 mL) was added followed by dropwise addition of HCl (3 N) until the precipitate had been solubilized. The red organic layer was washed with water (3 30 mL), dried and evaporated to a red solid. After chromatography on a short (5 cm) silica column eluted with toluene/MeOH (100/1 gradient to 10/1) the product was obtained as a red solid (38 mg, 90 %). Rf 0.15 (toluene/MeOH, 10/1).

1H NMR (400 MHz, CDCl3): d 10.27 (s, 4H, fb meso), 9.54 (s, 2H, Ni meso), 9.04 (d, J = 4 Hz, 4H, pyr Ha), 8.43 (m, 3H, Ar), 8.30 (d, J = 1 Hz, 2H, Ar), 8.11 - 8.00 (m, 14H, Ar), 3.99 (br, 16H, fb hex H1), 3.79 (br, 4H, Ni hex H1), 3.70 (br, 4H, Ni hex H1), 2.61 (s, 6H, Ni CH3), 2.57 (s, 12H, fb CH3), 2.51 (s, 12H, fb CH3), 2.29 (s, 6H, Ni CH3), 2.19 (m, 16H, fb hex H2), 2.07 (m, 8H, Ni hex H2), 1.78 - 1.63 (m, 24H, hex H3), 1.57 - 1.33 (m, 48H, hex H4,5), 0.99 (t, J = 7 Hz, 6H, Ni hex H6), 0.95 (t, J = 7 Hz, 6H, Ni hex H6), 0.91 (t, J = 7Hz, 24H, fb hex H6), -2.3 (br, NH); 13C NMR (100.6 MHz, CDCl3): d 170.3, 151.4, 148.4, 146.6, 145.0, 144.6, 144.4, 144.0, 143.9, 143.7, 142.7, 142.5, 141.8, 141.5, 140.4, 140.0, 139.7, 138.6, 138.5, 136.2, 135.9, 135.2, 133.4, 133.0, 131.1, 129.2, 128.6, 123.2, 123.0, 117.5, 115.6, 114.6, 114.1, 97.4, 96.8, 90.8, 89.7, 33.4, 33.1, 32.9, 2 32.0, 30.0, 29.9, 29.7, 29.4, 26.8, 26.4, 22.9, 2 22.8, 16.3, 15.6, 15.0, 14.9, 14.3, 2 14.2. UV/vis (DCM): 412, 508, 570, 626 nm; MALDI MS: m/z [M]+ 2712.

(118)2 NH2NH2 (166)

Hydrazine monohydrate (0.5 mL, 10 mmol) in water (10 mL) was added to a mixture of a solution of 118 (10 mg, 9.2 mmol) in DCM (1 mL) and water (5 mL). After 150 min at rt an additional portion of DCM (20 mL) was added and the organic layer separated, washed with water (2 30 mL) and dried (MgSO4). Evaporation of the solvent afforded the product as an orange solid (5 mg, 49 %).

Crystals of 166 for structure determination were obtained from a solution of 166 and 118 N2H4 in toluene layered with MeOH.

1H NMR (400 MHz, CDCl3): d 9.37 (s, 4H, meso), 7.84 (m, 8H, Ar), 7.55 (m, 8H, Ar), 7.25 (m, Ar), 3.72 (m, 16H, hex H1), 2.24 (s, 24H, CH3), 2.04 (m, 16H, hex H2), 1.84 (m, 16H, hex H3), 1.63 (m, 16H, hex H4), 1.52 (m, 16H, hex H5), 1.05 (t, J = 7 Hz, 24H, hex H6), -11.03 (s, 4H, NH2); 13C NMR (100.6 MHz, CDCl3): d 143.5, 141.6, 138.6, 138.0, 137.8, 133.0, 132.9, 128.5, 127.6, 127.3, 118.3, 96.8, 33.4, 31.9, 30.5, 27.0, 22.9, 15.1, 14.2; UV/vis (DCM): lmax 360, 408, 528, 558 nm. IR (CCl4): nmax 3287 (w), 3230 (w), 3147 (w) 2957 (s), 2930 (s), 2858 (m), 1466 (m) cm1.

(118)2 NHMeNHMe (167)

A solution of 168 (10 mg, 8.7 mmol) in DCM/hexane (1/1) was passed through a silica column. The solvent was evaporated to afford the product as an orange solid (7.1 mg, 73 %).

Crystals for structure determination were obtained from a DCM solution layered with MeOH.

1H NMR (400 MHz, CDCl3): d 9.64 (s, 4H, meso), 7.79 (m, 12H, Ar), 7.53 (m, 8H, Ar), 4.17 (m, 4H, hex H1), 4.05 (m, 4H, hex H1), 3.79 (m, 8H, hex H1), 2.32 (s, 12H, CH3), 2.29 (s, 12H, CH3), 1.96 (m, 4H, hex H2), 1.85 (m, 12H, hex H2), 1.65 (m, 16H, hex H3), 1.47 - 1.33 (m, 32H, hex H4,5), 0.93, 0.90 (2 t, J = 7 Hz, 24H, hex H6), -7.32 (d, J = 6 Hz, 6H, NHCH3), -9.40 (t, J = 6 Hz, 2H, NHCH3).

118 NHMeNHMe (168)

To a solution of 118MeOH (12.2 mg, 11 mmol) in DCM (20 mL) was added N,N'-dimethyl hydrazine dihydrochloride (17.3 mg, 0.13 mmol) in water (20 mL). NaOH (10 %, 2 drops) was added and the mixture shaken. The organic phase was separated, dried (MgSO4) and evaporated to an orange solid (10.6 mg, 85 %).

1H NMR (400 MHz, CDCl3): d 10.28 (s, 2H, meso), 8.10 (m, 2H, Ar), 8.04 (m, 2H, Ar), 7.76 (m, 6H, Ar), 4.03 (m, 4H, hex H1), 3.91 (m, 4H, hex H1), 2 2.48 (s, 12H, CH3), 2.21 (m, 8H, hex H2), 1.77 (m, 8H, hex H3), 1.52 (m, 8H, hex H4), 1.41 (m, 8H, hex H5), 2 0.92 (t, J = 7 Hz, hex H6), -0.66 (s, 3H, NHCH3), -3.27 (d, J = 6 Hz, 3H, RhNHCH3), -4.09 (s, 1H, NHCH3), -4.90 (q, J = 5 Hz, 1H, RhNHCH3); 13C NMR (100.6 MHz, CDCl3): d 2 144.3, 142.7, 140.5, 140.4, 140.1, 140.0, 138.8, 138.7, 133.8, 133.0, 128.3, 127.7, 127.3, 119.5, 98.9, 34.3, 33.8, 2 33.3, 32.0, 2 30.1, 2 27.0, 22.7, 15.5, 14.1.

(118)2 NHMeNH2 (169)

Prepared by titration of a solution of 118MeOH (4.2 mg, 3.8 mmol) with methyl hydrazine in CDCl3. After the titration the sample was eluted through a silica column with hexane/DCM (1/1) and evaporated to an orange solid. This was dissolved in DCM and layered with MeOH to obtain crystals for structure determination.

1H NMR (400 MHz, CDCl3): d 9.47 (s, 2H, meso), 9.43 (s, 2H, meso), 7.93 (d, J = 7 Hz, 2H, Ar), 7.82 (m, 8H, Ar), 7.52 (m, 8H, Ar), 7.33 (d, J = 4 Hz, 2H, Ar), 4.03 (m, 4H, hex H1), 3.89 (m, 4H, hex H1), 3.75 (m, 4H, hex H1), 3.66 (m, 4H, hex H1), 2.33 (s, 6H, CH3), 2 2.27 (2 s, 18H, CH3), 2.17 - 1.34 (m, 64H, hex H2-5), 0.96 (m, 24H, hex H6), -7.79 (d, J = 6 Hz, 3H, NHCH3), -10.00 (d, J = 12 Hz, 2H, NH2), -10.34 (m, 1H, NHCH3).

(118)2 NH2NMe2 (170)

Prepared by titration of a solution of 118MeOH (4.0 mg, 3.6 mmol) with N,N-dimethyl hydrazine in CDCl3.

Material for crystal growth was prepared by passing a solution of 118 (5.2 mg, 4.8 mmol) and N,N-dimethyl hydrazine (1 mL, 13 mmol) in DCM (0.5 mL) and hexane (0.5 mL) through a silica column. Porphyrin was washed from the column with DCM/hexane (1/1) and the solvent evaporated. X-ray quality crystals were obtained from a DCM solution layered with MeOH.

1H NMR (400 MHz, CDCl3): d 9.77 (s, 2H, meso), 0.37 (s, 2H, meso), 7.80 (m, 12H, Ar), 7.62 (m, 6H, Ar), 7.37 (d, J = 7 Hz, 2H, Ar), 4.04 (m, 8H, hex H1), 3.76 (m, 8H, hex H1), 2.38 (s, 12H, CH3), 2.29 (s, 12H, CH3), 1.85 (m, 16H, hex H2), 1.63 (m, 16H, hex H3), 1.50 - 1.30 (m, 32H, hex H4,5), 0.93 (t, J = 7 Hz, 12H, hex H6), 0.88 (t, J = 7 Hz, 12H, hex H6), -7.83 (s, 6H, NCH3), -10.24 (s, 2H, NH2).

118 EtSH (171)

To a solution of 118 (10 mg, 9.2 mmol) in CHCl3 (1 mL) was added EtSH (10 mL, 0.14 mmol). After stirring for several minutes the solvent was evaporated and the residues dried in vacuo to afford 171 as an orange solid in quantitative yield.

1H NMR (250 MHz, CDCl3): d 10.21 (s, 2H, meso), 8.04 (m, 4H, Ar), 7.72 (m, 6H, Ar), 3.95 (m, 8H, hex H1), 2.47 (s, 12H, CH3), 2.19 (m, 8H, hex H2), 1.76 (m, 8H, hex H3), 1.56 - 1.31 (m, 16H, hex H4,5), 0.91 (t, J = 7 Hz, 12H, hex H6), -1.29 (t, J = 7 Hz, 3H, CH3CH2S), -2.86 (m, 2H, CH2S), -4.29 (t, J = 7 Hz, 1H, SH).

118 DMSO (172)

Prepared by titration of a solution of 118 in CDCl3 with DMSO in CDCl3.

Crystals for structure determination were grown by layering a solution of 118 in DCM with a mixture of DMSO and MeOH.

1H NMR (250 MHz, CDCl3): d 10.28 (s, 2H, meso), 8.12 (d, J = 7 Hz, 2H, Ar), 7.95 (d, J = 8 Hz, 2H, Ar), 7.73 (m, 6H, Ar), 3.95 (m, 8H, hex H1), 2.47 (s, 12H, CH3), 2.17 (m, 8H, hex H2), 1.75 (m, 8H, hex H3), 1.55 - 1.30 (m, 16H, hex H4,5), 0.90 (t, J = 7 Hz, 12H, hex H6), -2.23 (s, 6H, CH3S).

118 Me2S (173)

To a solution of 118 (11 mg, 10 mmol) in DCM (1 mL) was added Me2S (10 mL). After stirring for 20 min, the solution was chromatographed on silica gel eluted with DCM. The orange eluent was collected and evaporated to afford 172 as an orange solid (1.3 mg, 11 %).

1H NMR (400 MHz, CDCl3): d 10.21 (s, 2H, meso), 8.10 (d, J = 7 Hz, 2H, Ar), 7.97 (d, J = 8 Hz, 2H, Ar), 7.78 (m, 2H, Ar), 7.70 (m, 4H, Ar), 3.99 (m, 4H, hex H1), 3.88 (m, 4H, hex H1), 2.45 (s, 12H, CH3), 2.17 (m, 8H, hex H2), 1.74 (m, 8H, hex H3), 1.49 (m, 8H, hex H4), 1.38 (m, 8H, hex H5), 0.89 (t, J = 7 Hz, 12H, hex H6), -3.12 (d, J = 1 Hz, 6H, CH3S).

Isonicotinic acid 11-bromo-undecyl ester (174)

Isonicotinic acid (0.50 g, 4.1 mmol) was refluxed in thionyl chloride (10 mL) under an argon atmosphere for 3 h. Excess thionyl chloride was removed by distillation and the resulting oil dried in vacuo. To this was added 11-bromo-1-undecanol (0.90 g, 3.6 mmol) in DCM (10 mL). The solution was refluxed for 1 h under argon. After cooling to room temperature, CHCl3 (20 mL) was added and the solution washed with satd. Na2CO3, dried (MgSO4) and the solvent evaporated. The crude product was dissolved in Et2O (30 mL), filtered to remove yellow insoluble material, and the filtrate was acidified by dropwise addition of conc. H2SO4. The resulting precipitates were filtered, washed repeatedly with Et2O, then shaken with CHCl3 (20 mL), water (5 mL) and satd. Na2CO3. The organic phase was separated, washed with dil. Na2CO3 (10 mL), dried (MgSO4) and evaporated to a cream solid (0.97 g, 76 %). Rf 0.30 (hexane/EA, 3/1).

1H NMR (250 MHz, CDCl3): d 8.75 (dd, J = 4, 2 Hz, 2H, pyr H2), 7.82 (dd, J = 4, 2 Hz, 2H, pyr H3), 4.33 (t, J = 7 Hz, 2H, OCH2), 3.38 (t, J = 7 Hz, 2H, CH2Br), 1.88 - 1.73 (m, 4H, CH2), 1.42 - 1.27 (m, 14H, CH2); 13C NMR (62.9 MHz, CDCl3):d 165.1, 150.6, 137.6, 122.8, 65.9, 39.94, 32.8, 2 29.4, 29.2, 28.7, 28.5, 28.1, 25.9; FAB MS: m/z [M+H]+ calcd 356.1225, found 356.1224; IR (CCl4): nmax 2930 (s), 2856 (s), 1732 (s), 1279 (s), 1121 (m) cm1; Anal. Calcd for C17H26NO2Br: C 57.31, H 7.36, N 3.93. Found C 57.54, H 7.33, N 3.82.

Isonicotinic acid 11-thioacetyl-undecyl ester (175)

A solution of 174 (0.97 g, 2.7 mmol) and potassium thioacetate (0.34 g, 3.0 mmol) in PEG 400 (1.6 mL) was stirred at 50 C under nitrogen for 3 h. To this was added water (10 mL) and CHCl3 (20 mL). The organic layer was separated and washed with water (10 mL), dried (MgSO4) and evaporated to a brown oil which solidified on standing. After column chromatography on silica eluted with hexane/EA (3/1) the product was obtained as a cream coloured solid (0.76 g, 79 %). Rf 0.25 (hexane/EA, 3/1).

1H NMR (250 MHz, CDCl3): d 8.74 (dd, J = 4, 2 Hz, 2H, pyr H2), 7.81 (dd, J = 4, 2 Hz, pyr H3), 4.32 (t, J = 6.7 Hz, 2H, OCH2), 2.82 (t, J = 7 Hz, 2H, SCH2), 2.28 (s, 3H, CH3), 1.74 (m, 2H, CH2), 1.53 (m, 2H, CH2), 1.39 - 1.25 (m, 14H, CH2); 13C NMR (100.6 MHz, CDCl3): d 196.0, 165.2, 150.6, 137.6, 122.8, 65.9, 30.6, 29.5, 29.4, 29.4, 29.2, 2 29.1, 28.8, 28.6, 25.9, 25.8; ES MS: m/z [M+H]+ 352; IR (CCl4): nmax 2928 (s), 2856 (m), 1732 (s), 1694 (s), 1279 (s) cm1; Anal. Calcd for C19H29O3SN: C 64.92, H 8.32, N 3.98. Found: C 64.94, H 8.30, N 3.94; mp 47 - 49 C.

Nicotinic acid 11-bromo-undecyl ester (176)

Prepared analogously to 174 except using nicotinic acid. Cream solid (0.82 g, 64 %). Rf 0.30 (hexane/EA, 3/1).

1H NMR (250 MHz, CDCl3): d 9.20 (dd, J = 2, 1 Hz, 1H, pyr H2), 8.75 (dd, J = 5, 2 Hz, 1H, pyr H6), 8.27 (dt, J = 8, 2 Hz, 1H, pyr H4), 7.36 (m, 1H, pyr H5), 4.32 (t, J = 7 Hz, 2H, OCH2), 3.37 (t, J = 7 Hz, 2H, CH2Br), 1.89 - 1.70 (m, 4H, CH2), 1.42 - 1.19 (m, 14H, CH2); 13C NMR (100.6 MHz, CDCl3): d 165.3, 153.3, 150.9, 137.0, 126.4, 123.3, 65.6, 34.2, 32.8, 29.4, 2 29.4, 29.2, 28.7, 28.6, 28.2, 26.0, 25.8; EI MS: m/z [M-Br]+ calcd 276.1963, found 276.1971; IR (CCl4): nmax 2930 (s), 2856 (s), 1727 (s), 1284 (s) cm1; Anal. Calcd for C17H26NO2Br: C 57.31, H 7.36, N 3.93. Found C 57.46, H 7.41, N 3.89.

Nicotinic acid 11-thioacetyl-undecyl ester (177)

Prepared analogously to 175, except starting from 176.White crystalline solid (0.76 g, 73 %). Rf 0.25 (hexane/EA, 3/1).

1H NMR (250 MHz, CDCl3) d 9.21 (d, J = 1 Hz, 1H, pyr H2), 8.75 (dd, J = 5, 2 Hz, 1H, pyr H6), 8.28 (dt, J = 8, 2 Hz, 1H, pyr H4), 7.37 (m, 1H, pyr H5), 4.33 (t, J = 7 Hz, 2H, OCH2), 2.84 (t, J = 7 Hz, 2H, SCH2), 2.30 (s, 3H, CH3), 1.76 (m, 2H, CH2), 1.54 (m, 2H, CH2), 1.44 - 1.26 (m, 14H, CH2); 13C NMR (100.6 MHz, CDCl3): d 196.0, 165.4, 153.3, 150.9, 137.0, 126.4, 123.3, 65.6, 30.6, 29.5, 29.5, 29.4, 29.2, 29.1, 29.1, 28.8, 28.6, 26.0; ES MS: m/z [M+H]+ 352; IR (CCl4): nmax 2930 (s), 2856 (s), 1726 (s), 1694 (s) cm1; Anal. Calcd for C19H29O3SN: C 64.92, H 8.32, N 3.98. Found: C 64.50, H 8.36, N 3.99; mp 42 - 43 C.

11-Mercapto undecanol (178)351

A solution of 11-bromoundecanol (2.00 g, 7.96 mmol) and thiourea (0.73 g, 9.59 mmol) in EtOH (25 mL) was degassed then refluxed under N2 for 18 h. After cooling to rt, NaOH (10 % aq, 20 mL) was added, the solution degassed then refluxed for 2 h under N2. After cooling, HCl (3 N, 40 mL) was added and the solution extracted with DCM (4 30 mL). The combined extracts were washed with satd. NaHCO3 (20 mL), dried (MgSO4) and evaporated to afford the product as a white solid which was used without purification (1.49 g, 92 %). Rf 0.33 (hexane/EA, 5/1).

1H NMR (250 MHz, CDCl3): d 3.62 (t, J = 7 Hz, 2H, OCH2), 2.50 (t, J = 7 Hz, 2H, SCH2), 1.64 - 1.26 (m, 20H, (CH2)9, SH, OH).

Disulfanyl bis-(11-undecanol) (179)338,352

NaBO3H2O (0.98 g, 9.8 mmol) and 178 (1.00 g, 4.9 mmol) were stirred in MeOH (15 mL) and water (2.5 mL) for 220 min at rt. The solvent was evaporated and water (50 mL) added. The suspension was extracted with CHCl3 (2 100 mL), the combined extracts washed with satd. Na2CO3 (20 mL), dried (MgSO4) and evaporated to yield the product as a white solid which did not require further purification (0.92 g, 92 %).

1H NMR (250 MHz, CDCl3): d 3.63 (br m, 4H, OCH2), 2.67 (t, J = 7 Hz, 4H, SCH2), 1.63 (m, 4H, CH2), 1.56 (m, 4H, CH2), 1.39 - 1.24 (m, 30H, (CH2)7, OH); Anal. Calcd for C22H46O2S2: C 64.97, H 11.40. Found: C 65.16, H 11.29.

Disulfanyl bis(11-undecyl-isonicotinate) (180)

Isonicotinic acid (0.91 g, 7.4 mmol), DMAP (60 mg, 0.50 mmol) and 179 (1.00 g, 2.5 mmol) were mixed and DCM (10 mL) added. To this suspension was added a solution of EDC (1.42 g, 7.4 mmol) in a mixture of DCM (10 mL) and DMF (10 mL) over 1 min. The suspension was stirred for 16 h at rt during which time it cleared. Further portions of EDC (0.47 g, 2.4 mmol) and isonicotinic acid (0.30 g, 2.4 mmol) were added. Stirring was continued for an additional 4 h, after which DCM (30 mL) was added and the solution washed with water (50 mL), satd. NaHCO3 (30 mL), dried (MgSO4) and evaporated onto silica gel which was loaded onto a silica column. Elution with hexane/EA (1/1) furnished the product as a white solid (1.25 g, 84 %). Rf 0.42 (hexane/EA, 1/1).

Crystals for structure determination were obtained from a DCM solution layered with MeOH.

1H NMR (500 MHz, CDCl3): d 8.76 (d, J = 5 Hz, 4H, pyr H2), 7.82 (d, J = 5 Hz, 4H, pyr H3), 4.33 (t, J = 6.7 Hz, 4H, OCH2), 2.66 (t, J = 7.3 Hz, 4H, SCH2), 1.76 (m, 4H, CH2), 1.65 (m, 4H, CH2), 1.43 - 1.27 (m, 28H, (CH2)7); 13C NMR (62.9 MHz, CDCl3): d 165.2, 150.6, 137.6, 122.8, 65.9, 39.1, 29.4, 29.2, 28.6, 28.5, 25.9; FAB MS: m/z [M+H]+ calcd 617.3447, found 617.3423; IR (CCl4): nmax 2928 (s), 2855 (m), 1732 (s), 1279 (s) cm1; Anal. Calcd for C34H52N2O4S2: C 66.20, H 8.50, N 4.54. Found: C 66.29, H 8.54, N 4.61; mp 40 - 42 C.

Disulfanyl bis(11-undecyl-nicotinate) (181)

Prepared analogously to 180 except using nicotinic acid. White solid (1.27 g, 84 %). Rf 0.49 (hexane/EA, 1/1).

1H NMR (250 MHz, CDCl3): d 9.21 (dd, J = 2, 1 Hz, 2H, pyr H2), 8.75 (dd, J = 5, 2 Hz, 2H, pyr H6), 8.27 (dt, J = 8, 2 Hz, 2H, pyr H4), 7.37 (ddd, J = 8, 5, 1 Hz, 2H, pyr H5), 4.33 (t, J = 7 Hz, 4H, OCH2), 2.65 (t, J = 7 Hz, 4H, CH2S), 1.78 (m, 4H, CH2), 1.67 (m, 4H, CH2), 1.40 - 1.27 (m, 28H, (CH2)7); 13C NMR (62.9 MHz, CDCl3): d 165.3, 153.3, 150.9, 137.0, 126.3, 123.2, 65.6, 39.1, 29.5, 29.2, 28.6, 28.5, 26.0; FAB MS: m/z [M+H]+ calcd 617.3447, found 617.3389; IR (CCl4): nmax 2927 (s), 2855 (s), 1727 (s), 1591 (m), 1284 (s), 1121 (m) cm1; Anal. Calcd for C34H52N2O4S2: C 66.20, H 8.50, N 4.54. Found: C 66.16, H 8.52, N 4.50; mp 63 - 65 C.

12-Thioacetyl-dodecanoic acid (182)

12-Bromododecanoic acid (1.50 g, 5.37 mmol) and KSCOCH3 (1.23 g, 10.8 mmol) were stirred in PEG 400 (10 mL) at 40 C for 1 h under N2. Water (50 mL) was added and the yellow suspension extracted with Et2O (2 100 mL). The combined organic extracts were washed with brine (25 mL), dried (MgSO4) and evaporated to a cream solid. Recrystallization from boiling hexane afforded the product as a white powder (1.20 g, 81 %). Rf 0.37 (hexane/EA, 3/1).

1H NMR (250 MHz, CDCl3): d 2.85 (t, J = 7 Hz, 2H, SCH2), 2.33, 2.31 (t and s, J = 7 Hz, 5H, CH2CO2 and CH3), 1.64 - 1.49 (m, 4H, CH2), 1.25 (br m, 14H, (CH2)7); 13C NMR (62.9 MHz, CDCl3): d 196.1, 179.8, 34.0, 30.6, 29.5, 2 29.4, 29.3, 29.2, 2 29.1, 29.0, 28.8, 24.6; FAB MS: m/z [M+H]+ calcd 275.1681, found 275.1682. IR (CCl4): nmax 3028 (br m), 2928 (s), 2856 (m), 1710 (s), 1684 (s) cm1; Anal. Calcd for C14H26O3S: C 61.28, H 9.55. Found: C 61.55, H 9.53.

rac-12-Thioacetyl-dodecanoic acid 1-aza-bicyclo[2.2.2]oct-3-yl ester (183)

To a solution of DMAP (63 mg, 0.52 mmol), EDC (1.18 g, 6.20 mmol) and 182 (1.40 g, 5.17 mmol) in DCM at 0 C (anhydrous, 10 mL) was added racemic 3-quinuclidinol (789 mg, 6.20 mmol) in DCM (10 mL) dropwise over 4 min. The solution was stirred at rt for 14 h, then the solvent evaporated. Water (30 mL) was added and the solution extracted with EA (3 50 mL). The combined organic extracts were washed with brine (30 mL), dried (MgSO4) and evaporated to a white paste. This was chromatographed on silica eluted with CHCl3/MeOH (9/1). The product fractions were redissolved in hexane, filtered and the solvent evaporated to yield a colourless oil which solidified on standing (1.04 g, 53 %). Rf 0.3 (CHCl3/MeOH, 9/1).

1H NMR (250 MHz, CDCl3): d 4.77 (m, 1H, OCH), 3.21 (m, 1H), 2.88 - 2.61 (m, 7H), 2.29 (m, 5H, CH2S, CH2CO2), 1.96 (m, 1H), 1.80 (m, 1H), 1.61 - 1.46 (m, 6H), 1.35 - 1.24 (m, 15H); 13C NMR (62.9 MHz, CDCl3):d 196.0, 173.6, 71.0, 55.6, 47.4, 46.5, 34.5, 30.6, 29.5, 29.4, 29.2, 2 29.1, 28.8, 25.2, 25.0, 24.6, 19.6; FAB MS: m/z [M+H]+ calcd 384.2572, found 384.2565; IR (CCl4): nmax 2929 (s), 2855 (m), 1732 (s), 1694 (s) cm1; Anal. Calcd for C21H37NO3S: C 65.76, H 9.72, N 3.65. Found: C 65.96, H 9.76, N 3.89.

(R) (-) 12-Thioacetyl-dodecanoic acid 1-aza-bicyclo[2.2.2]oct-3-yl ester ((R)(-) 183)

Prepared using the same procedure as the racemic compound, but using (R) (-) 3-quinuclidinol. White solid (0.91 g, 46 %).

Anal. Calcd for C21H37NO3S: C 65.76, H 9.72, N 3.65. Found: C 65.49, H 9.78, N 3.66.

rac-12-Mercapto-dodecanoic acid 1-aza-bicyclo[2.2.2]oct-3-yl ester (184)

Sodium methoxide (217 mg, 3.10 mmol) and 183 were placed under N2 and degassed MeOH (10 mL) added by cannula. The solution was stirred at rt for 30 min. Satd. NH4Cl (5 mL) was added, followed by water (45 mL) to form an emulsion which was extracted with EA (3 50 mL). The combined extracts were washed with brine (20 mL), dried MgSO4 and evaporated to an oil which was purified by chromatography on silica eluted with CHCl3/MeOH (10/1). The resulting white solids were dissolved in hot hexane, filtered and the solvent removed to afford the product as a white solid (536 mg, 62 %). Rf 0.43 (CHCl3/MeOH, 10/1).

1H NMR (250 MHz, CDCl3): d 4.78 (m, 1H, OCH), 3.22 (m, 1H), 2.89 - 2.61 (m, 6H), 2.50 (q, J = 7 Hz, 2H, CH2S), 2.30 (t, J = 7 Hz, CH2CO2), 1.98 (m, 1H), 1.81 (m, 1H), 1.70 - 1.49 (m, 6H), 1.38 - 1.25 (br m, 16H); 13C NMR (62.9 MHz, CDCl3): d 173.6, 70.9, 55.5, 47.4, 46.5, 34.5, 34.0, 29.4, 29.2, 29.1, 29.0, 28.3, 25.2, 25.0, 24.6, 24.5, 19.5; FAB MS: m/z [M+H]+ calcd 342.2467, found 342.2472; IR (CDCl3): nmax 2930 (s), 2856 (s), 1721 (s) cm1; Anal. Calcd for C19H35O2NS: C 66.81, H 10.33, N 4.10. Found: C 66.81, H 10.29, N 4.10.

(R) (-) 12-Mercapto-dodecanoic acid 1-aza-bicyclo[2.2.2]oct-3-yl ester ((R) (-) 184)

Prepared using the same method as the racemic compound, except using enantiomerically pure 183.

Anal. Calcd for C19H35O2NS: C 66.81, H 10.33, N 4.10. Found: C 66.68, H 10.37, N 4.13.

Nicotinic acid undecyl ester (185)

Prepared analogously to 140 but using nicotinic acid. Colourless oil (0.77 g, 75 %). Rf 0.40 (hexane/EA, 3/1).

1H NMR (250 MHz, CDCl3): d 9.13 (dd, J = 2, 1 Hz, 1H, pyr H2), 8.66 (dd, J = 5, 2 Hz, 1H, pyr H6), 8.18 (dt, J = 8, 2 Hz, 1H, pyr H4), 7.27 (ddd, J = 8, 5, 1 Hz, 1H, pyr H5), 4.24 (t, J = 7 Hz, 2H, OCH2), 1.67 (m, 2H, CH2), 1.36 - 1.16 (m, 16H, (CH2)8). 0.77 (t, J = 7 Hz, 3H, CH3); 13C NMR (62.9 MHz, CDCl3): d 165.3, 153.3, 150.9, 136.9, 126.3, 123.2, 65.5, 31.9, 2 29.5, 29.3, 29.2, 28.6, 26.0, 22.6, 14.1; FAB MS: m/z [M+H]+ calcd 278.2120, found 278.2104; IR (CCl4): nmax 2956 (m), 2927 (s), 2855 (m), 1727 (s), 1283 (s) cm1; Anal. Calcd for C17H27O2N: C 73.61, H 9.81, N 5.05. Found: C 73.70, H 9.84, N 5.11.

rac-Dodecanoic acid 1-aza-bicyclo[2.2.2]oct-3-yl ester (186)

To a solution of racemic 3-quinuclidinol (200 mg, 1.57 mmol) and Et3N (0.25 mL) in DCM (anhydrous, 2 mL) was added decanoyl chloride (290 mL, 1.40 mmol). The solution was stirred for 4 h, during which time a white precipitate formed. The solution was washed with satd. NaHCO3 (2 10 mL), brine (10 mL) and evaporated to a yellow paste. The product was columned on silica eluted with CHCl3/MeOH (10/1) to afford an inhomogenous material which was dissolved in hexane, filtered, and the solvent evaporated to afford the product as a colourless oil (110 mg, 28 %). Rf 0.32 (CHCl3/MeOH, 10/1).

1H NMR (250 MHz, CDCl3): d 4.76 (m, 1H, OCH), 3.21 (m, 1H), 2.89 - 2.53 (m, 5H), 2.28 (t, J = 7 Hz, 2H, CH2CO2), 1.96 (m, 1H), 1.80 (m, 1H), 1.67 - 1.55 (m, 4H), 1.39 - 1.23 (br m, 13H), 0.85 (t, J = 7 Hz, 3H, CH3); 13C NMR (62.9 MHz, CDCl3): d 173.6, 70.9, 55.5, 47.3, 46.4, 34.5, 31.8, 29.4, 29.2, 29.1, 25.2, 25.0, 24.5, 22.6, 19.5, 14.1; ES MS: m/z [M+H]+ calcd 282.2428, found 282.2412; IR (CCl4): nmax 2954 (s), 2930 (s), 2872 (m), 2856 (m), 1732 (s) cm1; Anal. Calcd for C17H31O2N: C 72.55, H 11.10, N 4.98. Found: C 72.48, H 11.00, N 5.01.

3,3'-Dimethyl-4,4'-bipyridine (187)363

3-Picoline (9.7 mL, 0.16 mol) and chlorotrimethylsilane (12.5 mL, 0.10 mol) were added to THF (anhydrous, 50 mL). Sodium dispersion (30 wt % in toluene, 10 mL, + 25 mL THF) was added maintaining the temperature below 25 C with an ice bath. After stirring for 6 h at rt under N2 the solvent was evaporated. The brown tar was extracted with boiling toluene (4 50 mL), and the extracts filtered. The toluene was evaporated and the residues dissolved in a mixture of acetone (75 mL) and water (75 mL). Solid KMnO4 was added portionwise until a purple colour persisted. A brown precipitate of MnO2 was filtered onto celite, and glucose was added to the filtrate to discharge the purple colour. The solution was filtered a further two times, the volume reduced by evaporation, then basified to pH 14 by addition of NaOH (10 % aq). The solution was extracted with CHCl3 (4 50 mL), the combined extracts dried (Na2SO4) and evaporated to a yellow oil. This was extracted with boiling hexane, then EA (several mL) added to the hexane extract. Concentration of this solution afforded the product as white crystals which were collected by filtration (930 mg, 6 %).

1H NMR (250 MHz, CDCl3): d 8.54 (s, 2H, H2), 8.49 (d, J = 5 Hz, 2H, H6), 7.00 (d, J = 5 Hz, 2H, H5), 2.05 (s, 6H, CH3).

4,4'-Bipyridine-3,3'-dicarboxylic acid (188)363

To a solution of 187 (914 mg, 4.96 mmol) in water (50 mL) at 90 C was added KMnO4 (1.57 g, 9.94 mmol) portionwise over 20 min. The solution was stirred for 35 min at 90 C, after which a further portion of KMnO4 (1.57 g, 9.94 mmol) was added over 15 min. The solution was stirred for 210 min at 90 C, then KMnO4 (0.79 g, 5 mmol) added. After stirring for a further 4 h at 90 C, the brown suspension was filtered through celite, and the residues washed with boiling water (150 mL). The filtrate was concentrated to 10 mL and the pH adjusted to 4 by dropwise addition of HCl (3 N) to afford a cloudy suspension. After standing in a refrigerator overnight the solid product was collected by filtration. An additional portion of product was obtained as colourless crystals by further concentration of the mother liquor and cooling to 0 C for several hours. (346 mg, 29 %). The product was used without further purification.

Crystals suitable for structure determination were obtained from an aqueous solution.

4-Chloro-pyridine-3-carboxylic acid (189)368

4-chloropyridine was prepared by extraction of a solution of the hydrochloride salt (4.50 g, 0.03 mol) in satd. Na2CO3 (50 mL) with Et2O (4 50 mL). The combined Et2O layers were washed with brine (20 mL), dried (MgSO4) and concentrated to several mL.

LDA was prepared by addition of BuLi (15 % in hexane, 21 mL, ~34 mmol) to a solution of iPrNH2 (4.6 mL, 33 mL) in THF (anhydrous, 50 mL) at -79 C under N2. The solution was stirred for 30 min, allowing to warm to 0 C.

To a solution of the 4-chloropyridine in THF (300 mL) at -79 C was added the LDA, also at -79 C. After stirring for 20 min at -79 C, CO2 was bubbled through the solution for 15 min, which was then allowed to warm to rt over 18 h. Several NaOH pellets were added, the THF evaporated and NaOH (2.5 M, 200 mL) added. The solution was extracted with DCM (2 50 mL), and the organic extracts discarded. The aqueous layer was acidified with conc. HCl, concentrated on the rotary evaporator until crystals formed. The crystals were filtered, and washed with water to afford the product as a cream powder (4.39 g, 93 %) which was used immediately.

4-Chloro-pyridine-3-carboxylic acid methyl ester (190)368

To a solution of 189 (4.38 g, 28 mmol), DMAP (0.50 g, 4.1 mmol), MeOH (5 mL) in DMF (40 mL) at 0 C was added DCC (13.8 g, 67 mmol) in DMF (20 mL) over 5 min. The solution was stirred under N2 allowing to warm to rt over 4 h. A white precipitate was filtered off and the filtrate evaporated under reduced pressure. The residues were distilled (0.01 mmHg, 64 - 75 C) to obtain a colourless solid which was further purified by chromatography on silica eluting with hexane/EA (3/1) to afford the product as a pale yellow solid (1.33 g, 28 %) which was stored at -20 C. Rf 0.24 (hexane/EA, 3/1).

1H NMR (250 MHz, CDCl3): d 9.03 (s, 1H, H2), 8.57 (d, J = 5 Hz, 1H, H6), 7.40 (d, J = 5 Hz, 1H, H5), 3.96 (s, 3H, CH3); 13C NMR (62.9 MHz, CDCl3): d 164.3, 152.7, 152.3, 144.1, 125.9, 52.7; EI MS: m/z [M]+ calcd 171.0087, found 171.0084; IR (CDCl3): nmax 2955 (w), 1730 (s), 1295 (s), 1277 (s) cm1.

4,4'-Bipyridine-3-carboxylic acid methyl ester (191)

A solution of 4-pyridyl-trimethyl-stannane (1.87 g, 7.73 mmol) and 190 (1.06 g, 6.18 mmol) in toluene (anhydrous, 100 mL) was added to LiCl (0.66 g, 16 mmol) and Pd(PPh3)4. The solution was degassed and heated at 110 C under N2 in the dark for 42 h. After cooling and filtration the solution was evaporated to a yellow oil which solidified on standing. The product was chromatographed on silica eluted with EA, and recrystallized from boiling hexane to afford white needles (0.93 g, 70 %). NMR indicated a minor impurity which could not be removed by further recrystallization from water or hexane. Rf 0.19 (EA).

1H NMR (250 MHz, CDCl3): d 9.14 (s, 1H), 8.79 (d, J = 5 Hz, 1H), 8.68 (m, 2H), 7.26 - 7.22 (m, 3H), 3.73 (s, 3H, CH3); 13C NMR (62.9 MHz, CDCl3): d 166.1, 152.5, 151.4, 149.7, 147.8, 146.6, 125.4, 124.4, 122.7, 52.4; ES MS: m/z [M+H]+ calcd 215.0811, found 215.0821; Anal. Calcd for C12H10N2O2: C 67.28, H 4.70, N 13.08. Found C 66.76, H 4.66, N 12.76.

4,4'-Bipyridine-3-carboxylic acid (192)

NaOH (149 mg, 4.48 mmol) and 191 (900 mg, 4.21 mmol) were refluxed in water (2 mL) for 150 mL. After cooling to rt the pH was adjusted to 4 by addition of HCl (3 N) to form a white precipitate of product which was collected by filtration. Recrystallization from boiling MeOH afforded the product as a white powder (302 mg, 36 %).

1H NMR (400 MHz, CD3OD + CDCl3): d 9.14 (s, 1H, H2), 8.71 (d, J = 5 Hz, 1H, H6), 8.64 (dd, J = 5, 1 Hz, 2H, H2',6'), 7.53 (dd, J = 5, 1 Hz, 2H, H3',5'), 7.22 (dd, J = 5, 1 Hz, 1H, H5); 13C NMR (62.9 MHz, CD3OD + CDCl3): d 166.3, 152.7, 152.1, 151.6, 146.9, 144.7, 125.6, 124.9, 124.3.

4,4'-Bipyridyl-3-carboxylic acid 11-(11-hydroxy-undecyldisulfanyl)-undecyl ester (193)

Disulfanyl bis[11-undecyl-(4,4'-bipyridine-3-carboxylate)] (194)

A suspension of 192 (151 mg, 7.54 mmol), 179 (153 mg, 0.38 mmol), DMAP (9 mg, 0.07 mmol) and EDC (174 mg, 0.91 mmol) in DCM (4 mL) was stirred at rt for 2 d. After this time the suspension was evaporated on to silica gel and loaded on a column which was eluted with hexane/EA (1/1) to elute unreacted 179, followed by a gradient to EA then EA/MeOH (9/1) to elute the products.

Data for 193. White solid (60 mg). Rf 0.53 (EA).

1H NMR (250 MHz, CDCl3): d 9.13 (s, 1H, bpy H2), 8.78 (d, J = 5 Hz, 1H, bpy H6), 8.67 (m, 2H, bpy H2',6'), 7.64 (m, 3H, bpy H3',5', bpy H5), 4.11 (t, J = 7 Hz, 2H, CO2CH2), 3.63 (t, J = 7 Hz, 2H, OCH2), 2.66 (t, J = 7 Hz, 4H, SCH2), 1.71 - 1.22 (m, ~36H. CH2); ES MS: m/z [M+Na]+ calcd 611.3317, found 611.3358.

Data for 194. White solid (91 mg, 31 %) Rf 0.35 (EA).

1H NMR (250 MHz, CDCl3): d 9.11 (s, 2H, bpy H2), 8.76 (d, J = 5Hz, 2H, bpy H6), 8.66 (m, 4H, bpy H2',6'), 7.22 (m, 6H, bpy H3',5', bpy H5), 4.09 (t, 4H, J = 7 Hz, CO2CH2), 2.64 (t, J = 7 Hz, 4H, SCH2), 1.63 (m, 4H, CH2), 1.47 - 1.11 (m, 16H, CH2); 13C NMR (62.9 MHz, CDCl3): d 165.8, 152.4, 151.4, 149.7, 147.5, 146.8, 125.8, 124.3, 122.7, 65.8, 39.1, 29.4, 29.4, 29.2, 29.1, 28.5, 28.2, 25.8; ES MS: m/z [M+H]+ calcd 771.3978, found 771.4014.

Thioacetic acid S-(11-bromo-undecyl) ester (195)

To a solution of potassium thioacetate (0.72 g, 6.4 mmol) in PEG 400 (5 mL) was added 1,11-dibromo-undecane (1.5 mL, 6.4 mmol). The solution was stirred under dry air at room temperature for 4.5 h. CHCl3 (50 mL) was added and the solution washed with water (50 mL, 30 mL), dried (MgSO4) and evaporated to a two phase oil. The portion of this mixture soluble in hexane/Et2O (20/1) was loaded on to a silica column which was eluted with this solvent to yield the desired product as a colourless oil (0.61 g, 31 %). Rf 0.27 (hexane/Et2O, 5/1).

1H NMR (500 MHz, CDCl3): d 3.37 (t, J = 7 Hz, 2H, CH2Br), 2.83 (t, J = 7 Hz, 2H, SCH2), 2.28 (s, 3H, COCH3), 1.81 (m, 2H, CH2), 1.54 (m, 2H, CH2), 1.38 (m, 2H, CH2), 1.37 - 1.24 (m, 12H, (CH2)6); 13C NMR (62.9 MHz, CDCl3): d 195.8, 33.8, 32.7, 30.5, 2 29.3, 2 29.0, 28.7, 28.6, 28.1; FAB MS: m/z [M+H]+ calcd 309.0871, found 309.0888; IR (CCl4): nmax 2928 (s), 2885 (s), 1694 (s), 1465 (m), 1353 (m), 1135 (m) cm1.

2,8,12,18-Tetrahexyl-5,15-bis(3-hydroxyphenyl)-3,7,13,17-tetramethyl porphyrin (196)

2,8,12,18-Tetrahexyl-5-(3-hydroxyphenyl)-15-phenyl-3,7,13,17-tetramethyl porphyrin (197)

Prepared according to the standard procedure, except MeOH was used as solvent for the 3-hydroxybenzaldehyde. The three porphyrin products were separated chromatographically on silica gel eluted with hexane/EA (5/1).

Crystals of 196 and 197 for structure determination were grown by hexane vapour diffusion into EA solutions.

Data for 196: Rf 0.15 (hexane/EA, 5/1)

1H NMR (400 MHz, CDCl3 + DMSO-d6): d 10.08 (s, 2H, meso), 8.94 (s, 2H, ArOH), 7.39 (m, 6H, Ar), 7.14 (m, 2H, Ar), 3.84 (t, J = 8 Hz, 8H, hex H1), 2.47 (s, 12H, CH3), 2.04 (m, 8H, hex H2), 1.59 (m, 8H, hex H3), 1.37 (m, 8H, hex H4), 1.22 (m, 8H, hex H5), 0.77 (t, J = 7 Hz, 12H, hex H6), -2.64 (s, 2H, NH); 13C NMR (100.6 MHz, THF-d8): d 158.4, 145.9, 144.4, 143.8, 142.2, 136.9, 129.4, 125.3, 121.5, 119.0, 116.1, 97.3, 34.4, 33.0, 30.94, 27.4, 23.7, 14.8, 14.5; UV/vis (DCM): lmax 408, 506, 538, 572 nm; FAB MS: m/z [M+H]+ calcd 887.6203, found 887.6274; IR (CCl4): nmax 3604 (m), 2957 (s), 2928 (s), 2858 (m), 1593 (m), 1467 (m), 1444 (m), 1154 (m) cm1; Anal. Calcd for C60H78O2N4: C 81.22, H 8.86, N 6.31. Found C 80.62, H 8.96, N 6.21.

Data for 197: Rf 0.43 (hexane/EA, 5/1)

1H NMR (400 MHz, CDCl3): d 10.22 (s, 2H, meso), 8.06 (d, J = 7 Hz, 2H, Ar), 7.75 (m, 3H, Ar), 7.59 (d, 1H, J = 7 Hz, Ar), 7.52 (t, J = 8 Hz, 1H, Ar), 7.29 (d, J = 1 Hz, 1H, Ar), 7.15 (m, 1H, Ar), 5.3 (br s, OH), 3.96 (t, J = 8 Hz, 8H, hex H1), 2.51 (s, 6H, CH3), 2.47 (s, 6H, CH3), 2.15 (m, 8H, hex H2), 1.72 (m, 8H, hex H3), 1.47 (m, 8H, hex H4), 1.29 (m, 8H, hex H5), 0.90 (t, J = 7 Hz, 12H, CH3), -2.41 (br, NH); 13C NMR (100.6 MHz, CDCl3): d 154.9, 145.1, 144.9, 143.6, 143.3, 142.3, 141.4, 136.3, 136.1, 133.0, 128.7, 128.2, 127.6, 120.3, 118.0, 117.2, 115.1, 97.0, 33.3, 32.0, 30.0, 26.8, 22.8, 14.6, 14.5, 14.1; FAB MS: m/z [M+H]+ calcd 871.6254, found 871.6318.

3-(11-Hydroxy-undecyloxy)-benzaldehyde (198)

Typical procedure. 3-Hydroxybenzaldehyde (5.00 g, 41 mmol), 11-bromoundecanol (6.85 g, 27 mmol) and Cs2CO3 (14.4 g, 44 mmol) were stirred in DMF (anhydrous, 36 mL) under N2 for 3 d at rt. Water (50 mL) was added to the dark suspension, which was extracted with Et2O (2 100 mL). The combined extracts were washed with brine (30 mL), dried (MgSO4) and evaporated to an orange oil which was redissolved in EtOH (several mL). Water (200 mL) was added, followed by cooling in a refrigerator to precipitate a pink solid which was collected by filtration. The solids were dissolved in Et2O (70 mL), washed with NaOH (10 %, 3 20 mL), dried (MgSO4) and evaporated to afford the product as a pink solid (7.30 g, 92 %). This was used without further purification, although could be recrystallized from hexane/EA mixture. Rf 0.19 (hexane/EA, 3/1).

1H NMR (250 MHz, CDCl3): d 9.96 (s, 1H, CHO), 7.42 (m, 2H, Ar), 7.37 (m, 1H, Ar), 7.16 (m, 1H, Ar), 4.00 (t, J = 7 Hz, 2H, ArOCH2), 3.63 (br t, J = 6 Hz, 2H, CH2OH), 1.79 (m, 2H, CH2), 1.56 (m, 2H, CH2), 1.50 - 1.29 (m, 15H, CH2, OH); 13C NMR (62.9 MHz, CDCl3): d 192.2, 159.7, 137.8, 130.0, 123.3, 122.0, 112.8, 68.3, 63.1, 32.8, 3 29.5, 29.4, 29.3, 29.1, 26.0, 25.7; FAB MS: m/z [M+H]+ calcd 293.2117, found 293.2146; IR (CCl4): nmax 3638 (w), 2929 (s), 2855 (s), 2724 (w), 1702 (s), 1599 (m), 1262 (s) cm1; Anal. Calcd for C18H28O3: C 73.93, H 9.65. Found: C 73.86, H 9.66; mp 41 - 42 C.

3-(11-p-Toluenesulfonyloxy-undecyloxy)-benzaldehyde (199)

To a solution of 198 (7.30 g, 25.0 mmol) and Et3N (5.3 mL) in DCM (anhydrous, 25 mL) at 0 C under N2 was added dropwise TsCl (12.2 g, 37.5 mmol) in DCM (anhydrous, 25 mL) over 30 min. After stirring at rt for 17 h under N2, additional portions of TsCl (1.00 g, 3.07 mmol) and Et3N (1.0 mL) were added. Stirring was continued for a further 5 h. The pink solution was washed with water (4 20 mL), dried over MgSO4 and evaporated onto silica gel which was loaded onto a silica column. The column was eluted first with hexane/EA/CHCl3 (10/1/1) to elute unreacted starting materials, then with hexane/EA (3/1) to elute the product which was obtained as a white crystalline solid (9.40 g, 84 %). Rf 0.46 (hexane/EA, 3/1).

1H NMR (400 MHz, CDCl3): d 9.96 (s, 1H, CHO), 7.78 (d, J = 8 Hz, 2H, Ts), 7.43 (m, 2H, Ar), 7.37 (d, J = 2 Hz, 1H, Ar), 7.33 (d, J = 8 Hz, 2H, Ts), 7.16 (m, 1H, ArH), 4.01, 4.00 (2 t, J = 7 Hz, 4H, ArOCH2, CH2OSO2), 2.44 (s, 3H, CH3), 1.79 (m, 2H, CH2), 1.62 (m, 2H, CH2), 1.44 (m, 2H, CH2), 1.35 - 1.22 (m, 12H, (CH2)6); 13C NMR (62.9 MHz, CDCl3): d 192.1, 159.7, 144.5, 137.7, 133.2, 129.9, 129.7, 127.8, 123.2, 121.9, 112.7, 70.6, 68.2, 29.4, 2 29.3, 29.0, 28.8, 28.7, 25.9, 25.3, 21.6; FAB MS: m/z [M+H]+ calcd 447.2205, found 447.2228; IR (CCl4): nmax 2928 (s), 2956 (m), 2725 (w), 1703 (s), 1599 (m), 1371 (s), 1261 (s), 1189 (s), 1178 (s) cm1; Anal. Calcd for C25H34O5S: C 67.24, H 7.67. Found: C 67.06, H 7.70; mp 55 - 57 C.

3-(11-Thioacetyl-undecyloxy)-benzaldehyde (200)

199 (9.40 g, 21.0 mmol) was finely ground and PEG 400 (65 mL) added. The mixture was sonicated and stirred at 50 C until dissolution was complete. To this was added KSCOCH3 (3.13 g, 27.4 mmol). The solution was stirred under N2 at 40 - 50 C for 75 min. Water (300 mL) was added to form a white precipitate which was solubilized by shaking with Et2O (200 mL). The organic phase was separated, and the aqueous layer extracted with further portions of Et2O (6 100 mL). The combined Et2O extracts were washed with brine (50 mL), dried (MgSO4) and evaporated to a pale yellow solid which was recrystallized from hexane to afford the pure product as a white powder (6.27 g, 85 %). Rf 0.43 (hexane/CHCl3/EA, 10/1/1).

1H NMR (250 MHz, CDCl3): d 9.96 (s, 1H, CHO), 7.45 (m, 2H, Ar), 7.37 (m, 1H, Ar), 7.16 (m, 1H, Ar), 4.00 (t, J = 7 Hz, 2H, OCH2), 2.85 (t, J = 7 Hz, 2H, CH2S), 2.30 (s, 3H, SCOCH3), 1.79 (m, 2H, CH2), 1.58 - 1.27 (m, 16H, (CH2)8); 13C NMR (62.9 MHz, CDCl3): d 196.0, 192.1, 159.7, 137.7, 129.9, 123.2, 121.9, 112.7, 68.2, 30.6, 29.4, 29.3, 29.1, 28.7, 25.9; FAB MS: m/z [M+H]+ calcd 351.1979, found 351.1994; IR (CCl4): nmax 2928 (s), 2854 (m), 1697 (s), 1262 (s) cm1; Anal. Calcd for C20H30O3S: C 68.53, H 8.63. Found: C 68.50, H 8.60; mp 42 - 44 C.

3-(12-Hydroxy-dodecyloxy)-benzaldehyde (201)

Prepared from 3-hydroxybenzaldehyde and 12-bromododecanol using the same procedure as 204. Pale pink solid (1.57 g, 94 %).

1H NMR (250 MHz, CDCl3): d 9.95 (s, 1H, CHO), 7.44 (m, 2H, Ar), 7.36 (d, J = 3 Hz, 1H, Ar), 7.15 (m, 1H, Ar), 3.99 (t, J = 7 Hz, 2H, ArOCH2), 3.62 (t, J = 7 Hz, 2H, CH2OH), 1.79 (m, 2H, CH2), 1.60 - 1.27 (m, 19H, (CH2)9, OH); 13C NMR (62.9 MHz, CDCl3): d 192.2, 159.7, 137.8, 130.0, 123.3, 122.0, 112.8, 68.3, 63.1, 29.5, 29.4, 29.3, 29.1, 26.0, 25.7; EI MS: m/z [M]+ calcd 306.2200, found 306.2195; IR (CCl4): nmax 3444 (w), 3036 (w), 2930 (s), 2856 (s), 1732 (s), 1280 (s) cm1; Anal. Calcd for C19H30O3: C 74.47, H 9.87. Found: C 74.46, H 9.85.

3-(12-p-Toluenesulfonyloxy-dodecyloxy)-benzaldehyde (202)

Prepared (from 201) and purified analogously to 199. Pale yellow solid (2.14 g, 94 %). Rf 0.53 (hexane/EA, 3/1).

1H NMR (250 MHz, CDCl3): d 9.96 (s, 1H, CHO), 7.78 (d, J = 8 Hz, 2H, Ts), 7.44 (m, 2H, Ar), 7.37 (d, J = 3 Hz, 1H, Ar), 7.33 (d, J = 8 Hz, 2H, Ts), 7.15 (m, 1H, Ar), 4.00 (m, 4H, SO3CH2, ArOCH2), 2.44 (s, 3H, CH3), 1.79 (m, 2H, CH2), 1.62 (m, 2H, CH2), 1.47 - 1.22 (m, 16H, (CH2)8); 13C NMR (100.6 MHz, CDCl3): d 193.6, 131.3, 131.1, 129.2, 124.7, 123.3, 114.1, 72.0, 69.6, 30.8, 30.7, 30.5, 2 30.2, 27.3, 26.7; ES MS: m/z [M+Na]+ calcd 483.2181, found 483.2184; IR (CDCl3): nmax 2929 (s), 2856 (m), 1697 (s), 1599 (m) cm1; Anal. Calcd for C26H36O5S: C 67.80. Found: C 67.55, H 7.84.

3-(12-Thioacetyl-dodecyloxy)-benzaldehyde (203)

Prepared (from 202) analogously to 200. Purified by column chromatography on silica eluted with hexane/EA (5/1) to afford the product as a white solid (869 mg, 62 %). Rf 0.49 (hexane/EA, 5/1).

1H NMR (250 MHz, CDCl3): d 9.96 (s, 1H, CHO), 7.43 (m, 2H, Ar), 7.37 (d, J = 2 Hz, 1H, Ar), 7.16 (m, 1H, Ar), 4.00 (t, J = 7 Hz, 2H, OCH2), 2.85 (t, J = 7 Hz, 2H, SCH2), 2.31 (s, 3H, CH3), 1.79 (m, 2H, CH2), 1.61 - 1.26 (m, 18H, (CH2)9); 13C NMR (62.9 MHz, CDCl3): d 196.0, 192.2, 159.7, 137.8, 130.0, 123.2, 121.9, 112.8, 68.3, 30.6, 29.5, 29.4, 29.3, 2 29.1, 28.8, 26.0; ES MS: m/z [M+Na]+ calcd 387.1970, found 387.1992; IR (CDCl3): nmax 2929 (s), 2856 (m), 1682 (s), 1599 (m); Anal. Calcd for C21H32O3S: C 69.19, H 8.85. Found: C 69.12, H 8.87.

4-(11-Hydroxy-undecyloxy)-benzaldehyde (204)

Cs2CO3 (14.4 g, 44 mmol), 4-hydroxybenzaldehyde (5.0 g, 41 mmol) and 11-bromoundecanol (6.85 g, 27.3 mmol) were mixed and DMF (36 mL) added. The suspension was degassed by exposure to vacuum, then stirred under N2 for 60 h. Water (50 mL) was added to produce a precipitate. This mixture was extracted with Et2O (3 200 mL) and the combined extracts washed with NaOH (10 %, 2 50 mL), brine (50 mL), dried (MgSO4) and evaporated to afford the product as a white solid which was used without further purification (7.97 g, 100 %). The product could be recrystallized from hexane/EA mixture if desired. Rf 0.14 (hexane/EA, 3/1).

1H NMR (250 MHz, CDCl3): d 9.86 (s, 1H, CHO), 7.81 (d, J = 9 Hz, 2H, ArH3,5), 6.97 (d, J = 9 Hz, 2H, ArH2.6), 4.02 (t, J = 7 Hz, 2H, ArOCH2), 3.63 (t, J = 6 Hz, 2H, CH2OH), 1.80 (m, 2H, CH2), 1.58 - 1.29 (m, 17H, (CH2)8, OH); 13C NMR (62.9 MHz, CDCl3): d 190.8, 164.2, 131.9, 129.7, 114.7, 68.4, 63.0, 32.7, 30.8, 29.5, 29.4, 29.3, 29.2, 29.0, 25.9, 25.7; FAB MS: m/z [M+H]+ calcd 293.2117, found 293.2111; IR (CCl4): nmax 3636 (w), 2929 (s), 2855 (m), 1700 (s), 1601(s), 1258 (s), 1160 (s) cm1; Anal. Calcd for C18H28O3: C 73.93, H 9.65. Found: 73.91, H 9.71; mp 63 - 65 C.

4-(11-p-Toluenesulfonyloxy-undecyloxy)-benzaldehyde (205)

Prepared (from 204) and purified using an analogous method to 199. Cream solid (10.17 g, 83 %). Rf 0.23 (hexane/EA, 3/1).

1H NMR (250 MHz, CDCl3): d 9.86 (s, 1H, CHO), 7.82 (m, 4H, Ar, Ts), 7.33 (d, J = 8 Hz, 2H, Ts), 6.97 (d, J = 9 Hz, 2H, Ar), 4.01 (m, 4H, CH2OSO2, ArOCH2), 2.43 (s, 3H, CH3), 1.79 (m, 2H, CH2), 1.62 (m, 2H, CH2), 1.46 - 1.22 (m, 14H, (CH2)7); 13C NMR (62.9 MHz, CDCl3): d 190.8, 164.3, 144.6, 133.3, 132.0, 129.8, 127.9, 114.7, 70.7, 68.4, 2 29.4, 2 29.3, 29.0, 28.9, 28.8, 25.9, 25.3, 21.6; FAB MS: m/z [M+H]+ calcd 447.2205, found 447.2200; IR (CDCl3): nmax 2929 (s), 2856 (m), 1686 (s), 1600 (s), 1577 (m), 1176 (s) cm1; Anal. Calcd for C25H34O5S: C 67.24, H 7.67, S 7.18. Found: C 67.24, H 7.70, S 6.88.

4-(11-Thioacetyl-undecyloxy)-benzaldehyde (206)

Prepared (from 205) and purified using an analogous method to 200. White solid (6.73 g, 84 %). Rf 0.28 (hexane/CHCl3/EA, 10/1/1).

1H NMR (250 MHz, CDCl3): d 9.89 (s, 1H, CHO), 7.84 (d, J = 9 Hz, 2H, Ar), 6.99 (d, J = 9 Hz, 2H, Ar), 4.04 (t, J = 7 Hz, 2H, OCH2), 2.87 (t, J = 7 Hz, 2H, SCH2), 2.33 (s, 3H, CH3), 1.82 (m, 2H, CH2), 1.56 - 1.29 (m, 16H, (CH2)8); 13C NMR (62.9 MHz, CDCl3): d 196.0, 190.8, 164.2, 132.0, 129.7, 114.7, 68.4, 30.6, 29.5, 29.3, 2 29.1, 28.8, 25.9; FAB MS: m/z [M+H]+ calcd 351.1994, found 351.1982; IR (CDCl3): nmax 2930 (s), 2855 (m), 1685 (s), 1600 (s), 1577 (m); Anal. Calcd for C20H30O3S: C 68.53, H 8.63. Found: C 68.41, H 8.68.

2-(11-Hydroxy-undecyloxy)-benzaldehyde (207)

To a suspension of Cs2CO3 (9.80 g, 27.8 mmol) and 11-bromoundecanol (5.00 g, 19.9 mmol) in DMF (anhydrous, 30 mL) was added salicyladehyde (3.2 mL, 30 mmol). The solution was degassed and stirred under N2 at rt for 3 d. Water (200 mL) was added and the mixture extracted with Et2O (5 50 mL). The combined organic extracts were washed with brine (2 30 mL), dried (MgSO4) and evaporated to an oil. This was shaken with water (200 mL) and the resulting emulsion cooled in a refrigerator for 2 h to cause solidification. The cream solids were filtered, washed with water (50 mL) and dried in vacuo. Recrystallization from hexane/EA mixture afforded the product as pale yellow crystals after 4 d standing in a refrigerator (4.85 g, 83 %). Rf 0.22 (hexane/EA, 3/1).

1H NMR (400 MHz, CDCl3): d 10.50 (d, J = 1 Hz, 1H, CHO), 7.81 (dd, J = 2, 8 Hz, 1H, Ar), 7.51 (m, 1H, Ar), 6.97 (m, 2H, Ar), 4.05 (t, J = 6 Hz, 2H, ArOCH2), 3.62 (t, J = 7 Hz, 2H, CH2OH), 1.82 (m, 2H, CH2), 1.54 (m, 2H, CH2), 1.47 (m, 2H, CH2), 1.28 (br m, 13H, (CH2)6, OH); 13C NMR (62.9 MHz, CDCl3): d 190.0, 161.6, 135.9, 128.2, 124.9, 120.4, 112.5, 68.5, 63.0, 32.8, 2 29.5, 2 29.4, 29.3, 29.1, 26.0, 25.7;EI MS: m/z [M]+ calcd 292.2038, found 292.2036; IR (CCl4): nmax 3636 (w), 2929 (s), 2856 (s), 1693 (s), 1599 (s), 1457 (s), 1242 (s) cm1; Anal. Calcd for C18H28O3: C 73.92, H 9.65. Found: C 74.16, H 9.61; mp 30 - 32 C.

2-(11-p-Toluenesulfonyloxy-undecyloxy)-benzaldehyde (208)

Prepared (from 207) and purified analogously to 199. Rf 0.38 (hexane/EA, 3/1). Yellow solid (2.66 g, 87 %).

1H NMR (250 MHz, CDCl3): d 10.50 (d, J = 1 Hz, 1H, CHO), 7.82 (dd, J = 8, 2 Hz, 1H, Ar), 7.78 (d, J = 9 Hz, 2H, Ar), 7.52 (m, 1H, Ar), 7.33 (d, J = 8 Hz, 2H, Ts), 6.98 (m, 2H, Ar), 4.04 (m, 4H, SO3CH2, ArOCH2), 2.44 (s, 3H, CH3), 1.84 (m, 2H, CH2), 1.62 (m, 2H, CH2), 1.29 - 1.08 (m, 14H, (CH2)7); 13C NMR (62.9 MHz, CDCl3): d 189.9, 161.6, 144.6, 135.9, 133.3, 129.8, 128.2, 127.9, 124.9, 120.4, 112.5, 70.7, 68.5, 29,4, 3 29.3, 29.1, 28.9, 28.8, 26.0, 25.3, 21.6; FAB MS: m/z [M+H]+ calcd 447.2205, found 447.2209; IR (CDCl3): nmax 2929(s), 2856 (s), 1686 (s), 1599 (s), 1177 (s) cm1; Anal. Calcd for C25H34O5S: C 67.24, H 7.67, S 7.18. Found: C 66.92, H 7.66, S 6.98.

2-(11-Thioacetyl-undecyloxy)-benzaldehyde (209)

Prepared from 208 analogously to 200. Column chromatography on silica eluted with hexane/EA/CHCl3 (10/1/1) afforded the product as a colourless oil (1.31 g, 71 %). Rf 0.30 (hexane/EA/CHCl3, 10/1/1).

1H NMR (250 MHz, CDCl3): d 10.51 (d, J = 1 Hz, 1H, CHO), 7.82 (dd, J = 8, 2 Hz, 1H, Ar), 7.52 (m, 1H, Ar), 6.98 (m, 2H, Ar), 4.06 (t, J = 6 Hz, 2H, OCH2), 2.85 (t, J = 7 Hz, 2H, SCH2), 2.31 (s, 3H, COCH3), 1.84 (m, 2H, CH2), 1.58 - 1.27 (m, 16H, (CH2)8); 13C NMR (62.9 MHz, CDCl3): d 189.9, 161.6, 135.9, 128.2, 124.9, 120.4, 112.5, 68.5, 30.6, 29.5, 29.3, 2 29.1, 28.8, 26.0; FAB MS: m/z [M+H]+ calcd 351.1974, found 351.1994; IR (CDCl3): nmax 2929 (s), 2856 (m), 1685 (s), 1599 (s) cm1; Anal. Calcd for C20H30O3S: C 68.53, H 8.63. Found: C 68.35, H 8.64.

2,8,12,18-Tetrahexyl-5-[3-(11-thioacetyl-undecyloxy)-phenyl]-15-phenyl-3,7,13,17-tetramethyl porphyrin (210)

Prepared according to the standard procedure using a statistical reaction with benzaldehyde and 200. The desired product was separated by repeated column chromatography on silica eluted with hexane/CHCl3/EA (20/1/1 and 40/1/1). Red viscous oil (661 mg, 32 %). Rf 0.39 (hexane/CHCl3/EA, 20/1/l).

1H NMR (400 MHz, CDCl3): d 10.23 (s, 2H, meso), 8.06 (d, J = 7 Hz, 2H, Ar), 7.70 (m, 6H, Ar), 7.33 (dt, J = 8, 1 Hz, 1H, Ar), 4.10 (t, J = 7 Hz, 2H, OCH2), 3.98 (m, 8H, hex H1), 2.81 (t, J = 7 Hz, 2H, SCH2), 2.57 (s, 6H, CH3), 2.47 (s, 6H, CH3), 2.28 (s, 3H, SCOCH3), 2.17 (m, 8H, hex H2), 1.85 (m, 2H, CH2), 1.72 (m, 8H, hex H3), 1.49 - 1.25 (m, hex H4,5, (CH2)8), 0.89 (m, 12H, hex H6), -2.42 (s, 2H, NH); 13C NMR (100.6 MHz, CDCl3): d 196.0, 158.7, 145.1, 145.0, 143.4, 2 143.3, 142.4, 141.4, 136.3, 136.2, 133.0, 128.5, 128.3, 127.6, 125.9, 119.4, 118.0, 117.8, 115.1, 97.0, 68.4, 33.3, 32.0, 30.6, 2 30.0, 2 29.5, 2 29.1, 28.8, 26.8, 26.1, 22.8, 14.6, 14.5, 14.2; UV/vis (DCM): lmax 408, 506, 540, 574, 626 nm; ES MS: m/z [M+H]+ calcd 1099.7796, found 1099.7809; IR (CCl4): nmax 2929 (s), 2857 (m), 1694 (m), 1595 (m), 1467 (m) cm1. Anal. Calcd for C73H102O2N4S: C 79.73, H 9.35, N 5.09. Found: C 79.78, H 9.48, N 5.15.

2,8,12,18-Tetrahexyl-5,15-bis[3-(11-thioacetyl-undecyloxy)-phenyl]-3,7,13,17-tetramethyl porphyrin (211)

Prepared according to the standard procedure from 200. Purification by chromatography on silica eluted with hexane/EA (10/1) followed by recrystallization twice from CHCl3 layered with MeOH afforded the product as purple crystals (2.30 g, 70 %). Rf 0.51 (hexane/EA, 10/1).

1H NMR (400 MHz, CDCl3): d 10.23 (s, 2H, meso), 7.63 (m, 6H, Ar), 7.33 (dt, J = 8, 1 Hz, 2H, Ar), 4.10 (t, J = 7 Hz, 4H, OCH2), 3.98 (t, J = 8 Hz, 8H, hex H1), 2.81 (t, J = 7 Hz, 4H, SCH2), 2.57 (s, 12H, CH3), 2.28 (s, 6H, SCOCH3), 2.18 (m, 8H, hex H2), 1.85 (m, 4H, CH2), 1.73 (m, 8H, hex H3), 1.55 - 1.24 (m, hex H4,5, 48H, (CH2)8), 0.89 (t, J = 7 Hz, 12H, hex H6), -2.44 (s, 2H, NH); 13C NMR (100.6 MHz, CDCl3): d 196.0, 158.7, 145.0, 143.5, 143.3, 141.5, 136.3, 128.5, 125.9, 119.4, 117.8, 115.1, 97.0, 68.5, 33.4, 32.1, 30.6, 30.1, 29.6, 2 29.5, 29.2, 29.1, 28.8, 26.9, 26.1, 22.8, 14.5, 14.2; UV/vis (DCM): lmax 408, 506, 540, 572 nm; FAB MS: m/z [M+H]+ calcd 1343.9298, found 1343.9393; IR (CCl4): nmax 2928 (s), 2856 (s), 1694 (s), 1595 (m), 1467 (m), 1137 (m) cm1. Anal. Calcd for C86H126N4O4S2: C 76.85, H 9.45, N 4.17. Found: C 76.89, H 9.53, N 4.20.

2,8,12,18-Tetrahexyl-5,15-bis[3-(12-thioacetyl-dodecyloxy)-phenyl]-3,7,13,17-tetramethyl porphyrin (212)

Prepared from 203 according to the standard procedure. Multiple ( 3) column chromatography on silica eluted with hexane/EA (10/1) followed by recrystallization from CHCl3 layered with MeOH afforded the product as a purple solid (828 mg, 52 %). Rf 0.42 (hexane/EA, 10/1).

1H NMR (250 MHz, CDCl3): d 10.29 (s, 2H, meso), 7.67 (m, 6H, Ar), 7.38 (d, J = 8 Hz, 2H, Ar), 4.15 (t, J = 7 Hz, 4H, OCH2), 4.04 (t, J = 8 Hz, 8H, hex H1), 2.86 (t, J = 7 Hz, 4H, SCH2), 2.63 (s, 12H, CH3), 2.33 (s, 6H, SCOCH3), 2.25 (m, 8H, hex H2), 1.90 (m, 4H, CH2), 1.79 (m, 8H, hex H3), 1.59 - 1.29 (m, 52H, hex H4,5, (CH2)9), 0.96 (t, J = 7 Hz, 12H, hex H6), -2.36 (s, 2H, NH); 13C NMR (100.6 MHz, CDCl3): d 106.1, 158.7, 145.0, 143.5, 143.2, 141.5, 136.3, 128.6, 125.9, 119.4, 117.9, 115.1, 97.0, 68.5, 33.4, 32.1, 30.7, 30.1, 29.6, 2 29.5, 2 29.2, 28.9, 26.9, 26.1, 22.8, 14.6, 14.2; UV/vis (DCM): lmax 408, 506, 540, 574, 624 nm; MALDI MS: m/z [M]+ 1371; IR (CDCl3): nmax 2929 (s), 2856 (s), 1685 (s), 1596 (s) cm1; Anal. Calcd for C88H130N4O4S2: C 77.03, H 9.55, N 4.08. Found: C 77.12, H 9.69, N 4.18.

2,8,12,18-Tetrahexyl-5,15-bis[3-(11-thioacetyl-undecyloxy)-phenyl]-3,7,13,17-tetramethyl porphyrinato zinc(II) (213)

211 was Zn metallated according to the standard procedure. An attempt at recrystallization from CHCl3 layered with MeOH afforded 213 as a pink oil which was dried in vacuo (1.79 g, 97 %).

1H NMR (400 MHz, CDCl3): d 10.18, 10.15 (2 s, 2H, meso), 7.68 (m, 6H, Ar), 7.39 (m, 2H, Ar), 4.15 (m, 4H, OCH2), 3.98 (m, 8H, hex H1), 2.75 (m, 4H, SCH2), 2.60, 2.59 (2 s, 12H, CH3), 2.23 (m, 14H, hex H2, COCH3), 1.90 (m, 4H, CH2), 1.81 (m, 8H, hex H3), 1.58 - 1.29 (m, 48H, hex H4,5, (CH2)8), 0.98 (t, J = 7 Hz, hex H6); 13C (100.6 MHz, CDCl3): d 195.9, 158.6, 2 147.6, 146.4, 146.3, 144.9, 2 143.4, 2 138.1, 128.4, 126.3, 119.8, 119.7, 2 119.2, 115.0, 97.5, 68.4, 33.4, 32.1, 2 30.5, 30.1, 2 29.5, 29.4, 2 29.1, 28.8, 26.8, 26.1, 22.8, 2 15.1, 14.2; MALDI MS: m/z [M]+ 1406. UV/vis (DCM): lmax 410, 538, 574 nm; Anal. Calcd for C86H124N4O2S2Zn: C 73.39, H 8.88, N 3.98. Found: C 73.40, H 8.96, N 4.09.

2,8,12,18-Tetrahexyl-5,15-bis[3-(11-thioacetyl-undecyloxy)-phenyl]-3,7,13,17-tetramethyl porphyrinato nickel(II) (214)

211 was Ni metallated according to the standard procedure. An attempt at recrystallization from CHCl3 layered with MeOH afforded 214 as a red oil which was dried in vacuo (669 mg, 84 %).

1H NMR (250 MHz, CDCl3): d 9.43 (s, 2H, meso), 7.51 (m, 4H, Ar), 7.35 (s, 2H, Ar), 7.21 (m, 2H, Ar), 4.02 (t, J = 7 Hz, 4H, OCH2), 3.65 (t, J = 8 Hz, 8H, hex H1), 2.82 (t, J = 7 Hz, 4H, SCH2), 2.30, 2.29 (2 s, 18 H, CH3, SCOCH3), 2.00 (m, 8H, hex H2), 1.81 (m, 2H, CH2), 1.67 - 1.25 (m, 56H, hex H3-5, (CH2)8), 0.90 (t, J = 7 Hz, 12H, hex H1); 13C NMR (100.6 MHz, CDCl3): d 196.0, 158.5, 143.9, 142.4, 140.3, 139.4, 139.0, 128.3, 126.0, 119.3, 116.3, 115.0, 108.0, 68.3, 32.8, 31.9, 30.6, 29.8, 29.5, 29.3, 2 29.1, 28.8, 26.3, 26.0, 22.7, 15.1, 14.2; MALDI MS: m/z [M+H]+ 1399; IR (CDCl3): nmax 2930 (s), 2857 (m), 1685 (m), 1597 (m) cm1; Anal. Calcd for C86H124N4O4S2Ni: C 73.74, H 8.92, N 4.00. Found: C 73.46, H 8.93, N 4.33.

2,8,12,18-Tetrahexyl-5-[3-(11-thioacetyl-undecyloxy)-phenyl]-15-phenyl-3,7,13,17-tetramethyl porphyrinato zinc(II) (215)

210 was Zn metallated according to the standard procedure. The product was obtained as a viscous oil which was used without further purification (51 mg, 94 %).

1H NMR (500 MHz, CDCl3): d 10.14 (s, 2H, meso), 8.07 (m, 2H, Ar), 7.79 (m, 1H, Ar), 7.73 (m, 2H, Ar), 7.69 (d, J = 7 Hz, 1H, Ar), 7.63 (m, 2H, Ar), 7.35 (d, J = 8 Hz, 1H, Ar), 4.11 (t, J = 7 Hz, 2H, OCH2), 3.94 (m, 8H, hex H1), 2.74 (t, J = 7 Hz, 2H, SCH2), 2.55 (s, 6H, CH3), 2.43 (s, 6H, CH3), 2.21 (s, 3H, COCH3), 2.17 (m, 8H, hex H2), 1.86 (m, 2H, CH2), 1.75 (m, 8H, hex H3), 1.49 - 1.25 (m, 32H, hex H4,5, (CH2)8), 0.93 (t, J = 7 Hz, 12H, hex H6); 13C NMR (100.6 MHz, CDCl3): d 195.9, 158.6, 147.7, 147.6, 146.4, 144.9, 143.8, 143.4, 2 138.1, 136.6, 133.3, 128.3, 128.0, 127.5, 126.3, 119.7, 119.3, 119.2, 115.0, 97.5, 68.4, 33.3, 32.0, 30.5, 30.1, 30.0, 29.5, 3 29.4, 29.1, 2 28.8, 28.2, 26.7, 26.0, 22.8, 2 15.1, 14.1; UV/vis (DCM): lmax 410, 538, 574 nm; FAB MS: m/z [M+H]+ calcd 1161.6937, found 1161.6930; IR (CCl4): nmax 2029 (s), 2867 (s), 1694 (m), 1597 (m) cm1.

2,8,12,18-Tetrahexyl-5-[3-(11-thioacetyl-undecyloxy)-phenyl]-15-phenyl-3,7,13,17-tetramethyl porphyrinato nickel(II) (216)

210 was Ni metallated according to the standard conditions. After chromatography on silica eluted with hexane/EA (10/1) the product was obtained as a red viscous oil (51 mg, 97 %). Rf 0.63 (hexane/EA, 10/1).

1H NMR (400 MHz, CDCl3): d 9.44 (s, 2H, meso), 7.85 (d, J = 7 Hz, 2H, Ar), 7.68 - 7.61 (m, 3H, Ar), 7.50 (m, 2H, Ar), 7.36 (s, 1H, Ar), 7.24 (m, 1H, Ar), 4.03 (t, J = 7 Hz, 2H, OCH2), 3.66 (m, 8H, hex H1), 2.84 (t, J = 7 Hz, 2H, SCH2), 2.32 (s, 6H, CH3), 2.30 (s, 3H, COCH3), 2.23 (s, 6H, CH3), 2.01 (m, 8H, hex H2), 1.82 (m, 2H, CH2), 1.64 - 1.27 (m, 40H, hex H3-5, (CH2)8); 13C NMR (125.7 MHz, CDCl3): d 196.0, 158.4, 2 143.9, 142.4, 141.3, 140.3, 140.2, 139.3, 2 138.9, 133.0, 128.3, 128.0, 127.4, 125.9, 119.2, 116.4, 116.3, 114.9, 96.3, 68.3, 32.7, 31.8, 30.6, 29.7, 29.5, 2 29.4, 29.3, 29.1, 29.0, 28.8, 26.2, 26.0, 22.7, 15.2, 15.1, 14.1; UV/vis (DCM): lmax 408, 528, 562 nm; MALDI MS: m/z [M]+ 1154.

2,8,12,18-Tetrahexyl-5,15-bis[4-(11-thioacetyl-undecyloxy)-phenyl]-3,7,13,17-tetramethyl porphyrin (217)

Prepared from 206 using the standard porphyrin synthesis procedure. The product was purified by passage through a silica column eluted with hexane/toluene/EA (10/1/1). Multiple recrystallizations ( 6) from CHCl3 layered with MeOH afforded the product as purple needles (2.07 g, 63 %). Rf 0.09 (DCM/CHCl3, 10/1).

Crystals for structure determination were obtained from a DCM solution layered with MeOH.

1H NMR (400 MHz, CDCl3): d 10.20 (s, 2H, meso), 7.91 (d, 4H, J = 8 Hz, Ar), 7.25 (d, J = 8 Hz, Ar), 4.25 (t, J = 7 Hz, 4H, OCH2), 3.97 (t, J = 8 Hz, 8H, hex H1), 2.89 (t, J = 7 Hz, 4H, SCH2), 2.53 (s, 12H, CH3), 2.32 (s, 6H, SCOCH3), 2.16 (m, 8H, hex H2), 1.99 (m, 4H, CH2), 1.74 - 1.31 (m, 56H, hex H3-5, (CH2)8), 0.88 (t, J = 7 Hz, 12H, hex H6), -2.44 (s, 2H, NH); 13C NMR (100.6 MHz, CDCl3): d 196.1, 159.5, 145.6, 143.1, 141.4, 136.3, 134.5, 133.8, 117.7, 113.7, 96.8, 68.4, 33.3, 32.0, 30.7, 30.0, 29.7, 2 29.6, 29.5, 29.2, 28.9, 26.8, 26.3, 22.8, 14.8, 14.1; UV/vis (DCM): lmax 410, 508, 540, 572 nm; ES MS: m/z [M+Na]+ calcd 1365.9113, found 1365.9123; IR (CDCl3): nmax 2930 (s), 2856 (s), 1686 (m), 1514 (s) cm1.

2,8,12,18-Tetrahexyl-5,15-bis[2-(11-thioacetyl-undecyloxy)-phenyl]-3,7,13,17-tetramethyl porphyrin (218)

Prepared from 209 according to the standard procedure. The porphyrin was separated from the crude material by chromatography on silica eluted with hexane/EA/CHCl3 (20/1/1) gradient to hexane/EA (10/1) and recrystallization from CHCl3 layered with MeOH. This afforded a purple solid (1.26 g, 52 %) consisting of a mixture of atropisomers which could not be separated.

2,2'-Methylene-1H-bis-pyrrole (219)380

Paraformaldehyde (1.73 g, 57.6 mmol) was placed under Ar in a Schlenk tube and warmed with a heat gun until vapour was evolved. The vapour was transferred by cannula to stirred pyrrole (freshly distilled from CaH2 and degassed,130 mL). During this transfer TFA (445 mL, 6.0 mmol) was added to the pyrrole by syringe. After complete transfer of the formaldehyde the solution was stirred for 15 min at rt, then poured into degassed NaOH (0.1 M, 50 mL). The mixture was extracted with EA (300 mL), the organic extract washed with brine (50 mL), dried (Na2SO4) and evaporated on to silica. Chromatography on silica eluted with hexane/EA (4/1) afforded the product as pale cream crystals (2.14 g, 25 %). Rf 0.32 (hexane/EA, 4/1).

1H NMR (250 MHz, CDCl3): d 7.79 (br s, 2H, NH), 6.65 (m, 2H), 6.16 (m, 2H), 6.04 (m, 2H), 3.97 (s, 2H, CH2); 13C NMR (62.9 MHz, CDCl3): d 129.1, 117.3, 108.4, 106.4, 26.4; Anal. Calcd for C9H10N2: C 73.94, H 6.89, N 19.16. Found: C 73.54, H 6.87, N 19.16.

5,15-Bis[3-(11-thioacetyl-undecyloxy)-phenyl] porphyrin (220)

To a degassed solution of 219 (718 mg, 4.91 mmol) and 200 (1.72 g, 4.91 mmol) in DCM (anhydrous, 50 mL) was added BF3OEt2 (180 mL, 1.46 mmol). After stirring for 45 min under N2, DDQ (1.1 g, 4.8 mmol) was added and stirring continued for 15 min. The black suspension was filtered through celite and the solvent evaporated. After filtration of a CHCl3 solution through two short silica plugs, and chromatography on silica eluted with hexane/DCM (1/1 gradient to 3/7) the product was obtained as a purple foam (299 mg, 13 %). Rf 0.13(hexane/DCM, 1/1).

1H NMR (250 MHz, CDCl3): d 10.31 (s, 2H, meso), 9.39 (d, J = 5 Hz, 4H, Hb), 9.13 (d, J = 5 Hz, 4H, Hb), 7.84 (m, 4H, Ar), 7.68 (t J = 8 Hz, 2H, Ar), 7.35 (m, 2H, Ar), 4.18 (t, J = 7 Hz, 4H, OCH2), 2.82 (t, J = 7 Hz, 4H, SCH2), 2.29 (s, 6H, SCOCH3), 1.90 (m, 4H, CH2), 1.52 (m, 8H, CH2), 1.40 - 1.26 (br m, 12 H, (CH2)6), -3.14 (s, 2H, NH); 13C NMR (100.6 MHz, CDCl3): d 196.1, 157.8, 147.1, 145.3, 142.7, 131.6, 131.1, 127.8, 121.4, 119.0, 114.1, 105.2, 68.4, 30.6, 3 29.5, 2 29.1, 28.8, 26.2; UV/vis (DCM): lmax 402, 502, 536, 574 nm; ES MS: m/z [M+H]+ calcd 951.4911, found 951.4886; IR (CDCl3): nmax 2930 (s), 2856 (m), 1685 (s), 1597 (m) cm1; Anal. Calcd for C58H70N4O4S2: C 73.23, H 7.42, N 5.89. Found: C 73.10, H 7.46, N 5.73.

2,8,12,18-Tetrahexyl-5,15-bis[4-(11-thioacetyl-undecyloxy)-phenyl]-3,7,13,17-tetramethyl porphyrinato rhodium(III) iodide (221)

217 was Rh metallated according to the same procedure used for preparation of 118. Column chromatography on silica (Merck) eluted with hexane/EA (5/1) afforded the product as an orange solid (72 mg, 62 %). Rf 0.53 (hexane/EA, 5/1).

1H NMR (400 MHz, CDCl3): d 10.18 (s, 2H, meso), 8.14 (dd, J = 8, 2 Hz, 2H, Ar), 7.65 (dd, J = 8, 2 Hz, 2H, Ar), 7.29 (dd, J = 8, 3 Hz, Ar), 7.23 (dd, J = 8, 3 Hz, Ar), 4.28 (t, J = 7 Hz, 4H, OCH2), 4.07 (m, 4H, hex H1), 3.89 (m, 4H, hex H1), 2.57 (s, 12H, CH3), 2.21 (m, 8H, hex H2), 2.01 (m, 4H, CH2), 1.79 (m, 8H, CH2), 1.64 (m, 4H, CH2), 1.56 - 1.33 (m, 28H, CH2), 1.24 (m, 6H, CH2), 1.09 (br, 4H, CH2), 0.94 (t, J = 7 Hz, 12H, hex H6), 0.8 (br m, 6H, CH2), 0.7 - 0.1 (br, 10H, CH2); 13C NMR (100.6 MHz, CDCl3): d 159.5, 144.7, 140.6, 139.8, 139.5, 135.0, 134.5, 133.5, 119.0, 113.6, 113.4, 99.2, 68.5, 33.5, 32.1, 30.1, 29.7, 29.7, 29.6, 29.5, 29.0, 28.6, 28.0, 27.3, 27.0, 26.9, 26.3, 22.8, 16.0, 14.2; UV/vis (DCM): lmax 362, 428, 354 nm; FIB MS: m/z [M]+ 1574, [M-I]+ 1446; IR (CDCl3): nmax 2928 (s), 2855 (s), 1733 (m), 1684 (m) cm1; Anal. Calcd for C86H124N4O4S2RhI: C 65.71, H 7.95, N 3.56. Found: C 65.57, H 7.94, N 3.61.

221 Pyridine complex (222)

Pyridine (2 drops) was added to an NMR sample of 221 in CDCl3. The solvent was removed and the orange solids dried in vacuo to afford 222.

1H NMR (250 MHz, CDCl3): d 10.15 (s, 2H, meso), 7.88 (m, 4H, Ar), 7.21 (m, 4H, Ar), 5.92 (tt, J = 8, 1 Hz, 1H, pyr Hg), 4.96 (t, J = 7 Hz, 2H, pyr Hb), 4.24 (t, J = 7 Hz, 4H, OCH2), 3.91 (m, 8H, hex H1), 2.89 (t, J = 7 Hz, 4H, SCH2), 2.51 (s, 12H, CH3), 2.33 (s, 6H, COCH3), 2.16 (m, 8H, hex H2), 1.99 (m, 4H, CH2), 1.75 - 1.25 (m, 56H, hex H3-5, (CH2)8), 0.88 (t, J = 7 Hz, 12H, hex H6), 0.78 (d, J = 6 Hz, 2H, pyr Ha); 13C NMR (100.6 MHz, CDCl3): d 196.1, 159.4, 144.5, 143.8, 140.6, 139.7, 138.5, 135.3, 134.7, 134.2, 133.8, 121.1, 118.9, 113.6, 113.2, 98.7, 68.4, 33.2, 32.0, 30.7, 30.1, 2 29.6, 29.2, 28.9, 27.0, 26.3, 22.8, 15.9, 14.1; UV/vis (DCM): lmax 358, 422, 532, 560 nm; IR (CDCl3): nmax 2929 (s), 2856 (m), 1686 (m) cm1.

2,8,12,18-Tetrahexyl-5,15-bis[3-(11-mercapto-undecyloxy)-phenyl]-3,7,13,17-tetramethyl porphyrin (223)

To a solution of 211 (1.00 g, 0.74 mmol) in THF (10 mL) was added mercaptoethanol (0.50 mL, 7.13 mmol) and butylamine (1.0 mL, 10.1 mmol). After degassing the solution was refluxed under N2 for 1 h. Tlc indicated incomplete reaction. Additional portions of butylamine (1.0 mL, 10.1 mmol) and mercaptoethanol (0.50 mL, 7.13 mmol) were added, the solution degassed, and refluxed for 2 h under N2. Et2O (100 mL) was added and the solution washed with water (3 50 mL), brine (30 mL), dried (MgSO4) and evaporated to a red oil. Chromatography on silica gel eluted with hexane/EA/toluene (10/1/1) afforded the product as a viscous purple oil which solidified on standing (785 mg, 84 %). Rf 0.34 (hexane/EA, 15/1). A sample for analysis was obtained by recrystallization from DCM layered with MeOH.

1H NMR (400 MHz, CDCl3): d 10.25 (s, 2H, meso), 7.67 (m, 6H, Ar), 7.35 (m, 2H, Ar), 4.12 (t, J = 7 Hz, 4H, OCH2), 4.00 (t, J = 8 Hz, 8H, hex H1), 2.59 (s, 12H, CH3), 2.47 (q, 4H, J = 7 Hz, SCH2), 2.20 (m, 8H, hex H2), 1.87 (m, 4H, CH2), 1.75 (m, 8H, hex H3), 1.57 - 1.26 (m, 50H, hex H4,5, SH, (CH2)8), 0.91 (t, J = 7 Hz, 12H, hex H6), -2.41 (s, 2H, NH); 13C NMR (100.6 MHz, CDCl3): d 158.7, 145.0, 143.4, 143.3, 141.4, 136.3, 128.5, 125.9, 119.3, 117.8, 115.1, 97.0, 68.4, 34.0, 33.3, 32.0, 30.0, 29.6, 2 29.5, 29.4, 29.l, 28.4, 26.8, 26.1, 24.6, 22.8, 14.5, 14.2; UV/vis (DCM): lmax 408, 506, 542, 572 nm; FIB MS: m/z [M+H]+ 1262; IR (CCl4): nmax 2929 (s), 2857 (s), 1596 (m), 1466 (m) cm1. Anal. Calcd for C82H122O2N4S2: C 78.17, H 9.76, N 4.45. Found: C 78.14, H 9.69, N 4.46.

2,8,12,18-Tetrahexyl-5,15-bis[3-(11-mercapto-undecyloxy)-phenyl]-3,7,13,17-tetramethyl porphyrinato zinc(II) (224)

To a solution of DTT (0.20 g, 1.3 mmol) and 213 (1.79 g, 1.27 mmol) in THF (25 mL) was added BuNH2 (2.0 mL, 20 mmol). The solution was degassed and refluxed under N2 for 150 min. After cooling, Et2O was added and the solution washed with water (3 30 mL), brine (30 mL), dried (MgSO4) and evaporated to a red oil. An attempt was made to purify the product by chromatography, but the material so obtained was not pure by NMR. This was refluxed in degassed THF (20 mL) with DTT (0.10 g) and BuNH2 (4 mL) for 150 min under N2 to ensure complete cleavage of the thioacetyl group. The product was worked up as previously described. Column chromatography on silica eluting with hexane/EA (10/1) followed by a second column eluting with hexane/CHCl3 (4/1) with a gradient to CHCl3 afforded the product as a red oil (1.04 g, 62 %) which solidified on storage at -20 C. It is believed that photosensitized oxidation to polymeric material was responsible for difficulties in purification and a lowered yield. Rf 0.40 (hexane/EA, 10/1).

1H NMR (400 MHz, CDCl3): d 10.17, 10.15 (2 s, 2H, meso), 7.67 (m, 6H, Ar), 7.36 (m, 2H, Ar), 4.11 (m, 4H, OCH2), 3.96 (m, 8H, hex H1), 2.57, 2.56 (2 s, 12H, CH3), 2.38 (q, J = 7 Hz, 4H, SCH2), 2.20 (m, 8H, hex H2), 1.87 (m, 4H, CH2), 1.77 (m, 8H, hex H3), 1.54 - 1.17 (m, 50H, hex H4,5, SH, (CH2)8), 0.95 (t, J = 7 Hz, 12H, hex H6); 13C NMR (100.6 MHz, CDCl3): d 158.6, 147.6, 146.4, 144.9, 143.5, 138.2, 128.4, 126.3, 119.7, 119.2, 115.0, 97.6, 68.4, 34.0, 33.4, 2 32.1, 2 29.5, 29.4, 29.1, 28.4, 26.8, 26.1, 24.6, 22.8, 15.1, 14.2; UV/vis (DCM): lmax 410, 538, 574 nm; ES MS: m/z [M+Na]+ calcd 1343.8036, found 1343.7914; IR (CCl4): nmax 2929 (s), 2857 (s), 1596 (m), 1286 (m) cm1. Anal. Calcd for C82H120O2N4S2Zn: C 74.42, H 9.14, N 4.23. Found: C 74.48, H 9.15, N 4.33.

2,8,12,18-Tetrahexyl-5,15-bis[3-(11-mercapto-undecyloxy)-phenyl]-3,7,13,17-tetramethyl porphyrinato nickel(II) (225)

To a solution of DTT (0.10 g, 6.5 mmol) and 214 (669 mg, 0.48 mmol) in THF (10 mL) was added BuNH2 (2 mL, 20 mmol). The solution was degassed and refluxed under N2 for 210 min. After cooling to rt, Et2O (100 mL) was added and the solution washed with water (3 30 mL), brine (30 mL), dried (MgSO4) and evaporated to a red oil. Chromatography on silica eluted with hexane/EA (10/1) afforded the product as a deep red viscous oil (623 mg, 99 %). Rf 0.5 (hexane/EA, 10/1).

1H NMR (250 MHz, CDCl3): d 9.43 (s, 2H, meso), 7.51 (m, 4H, Ar), 7.35 (s, 2H, Ar), 7.22 (m, 2H, Ar), 4.02 (t, J = 7 Hz, 4H, OCH2), 3.65 (t, J = 8 Hz, 8H, hex H1), 2.47 (q, J = 7 Hz, 4H, SCH2), 2.30 (s, 12H, CH3), 2.00 (m, 8H, hex H2), 1.81 (m, 4H, CH2), 1.67 - 1.25 (m, 58H, hex H3-5, SH, (CH2)8), 0.90 (t, J = 7 Hz, 12H, hex H6); 13C NMR (100.6 MHz, CDCl3): d 158.4, 143.9, 142.4, 140.3, 139.4, 2 138.9, 128.3, 126.0, 119.3, 116.3, 115.0, 96.3, 68.3, 34.0, 32.8, 31.9, 29.8, 2 29.5, 29.4, 29.3, 29.0, 28.3, 26.3, 26.0, 24.6, 22.7, 15.1, 14.1; UV/vis (DCM): lmax 406, 528, 562 nm; MALDI MS: m/z [M]+ 1317; IR (CDCl3): nmax 2929 (s), 2857 (m), 1597 (m), 1467 (m) cm1. Anal. Calcd for C82H120O2N4S2Ni: C 74.80, H 9.19, N 4.26. Found: C 74.44, H 9.07, N 4.52.

2,8,12,18-Tetrahexyl-5,15-bis[3-(12-mercapto-dodecyloxy)-phenyl]-3,7,13,17-tetramethyl porphyrin (226)

Prepared and purified analogously to 225 except starting from 212. Purification by chromatography on silica eluted with hexane/EA (10/1) afforded the product as a purple solid (650 mg, 84 %). Rf 0.42 (hexane/EA, 10/1).

1H NMR (250 MHz, CDCl3): d 10.24 (s, 2H, meso), 7.62 (m, 6H, Ar), 7.34 (d, J = 8 Hz, 2H, Ar), 4.11 (t, J = 7 Hz, 4H, OCH2), 3.99 (t, J = 8 Hz, 8H, hex H1), 2.57 (s, 12H, CH3), 2.46 (q, J = 7 Hz, 4H, SCH2), 2.19 (m, 8H, hex H2), 1.86 (m, 4H, CH2), 1.73 (m, 8H, hex H3), 1.57 - 1.24 (m, 54H, hex H4,5, (CH2)9, SH), 0.89 (0.89, t J = 7 Hz, 12H, hex H6), -2.43 (s, 2H, NH); 13C NMR (100.6 MHz, CDCl3): d 158.7, 145.0, 143.4, 143.3, 141.4, 136.3, 128.5, 125.9, 119.3, 117.8, 115.1, 96.9, 68.4, 34.0, 33.3, 32.0, 30.0, 2 29.5, 29.4, 29.0, 28.4, 26.8, 26.1, 24.6, 22.8, 14.5, 14.1; UV/vis DCM): lmax 408, 506, 540, 574, 626 nm; ES MS: m/z [M+H]+ calcd 1287.9395, found 1287.9385. IR (CCl4): nmax 2928 (s), 2856 (s), 1596 (m) cm1; Anal. Calcd for C84H126N4O2S2: C 78.33, H 9.86, N 4.35. Found: C 78.50, H 9.93, N 4.47.

2,8,12,18-Tetrahexyl-5-[3-(11-mercapto-undecyloxy)-phenyl]-15-phenyl-3,7,13,17-tetramethyl porphyrin (227)

Prepared and purified analogously to 225 except starting from 210. Red viscous oil (459 mg, 82 %). Rf 0.36 (hexane/EA, 10/1).

1H NMR (400 MHz, CDCl3): d 10.23 (s, 2H, meso), 8.06 (m, 2H, Ar), 7.85 - 7.60 (m, 6H, Ar), 7.33 (m, 1H, Ar), 4.10 (t, J = 7 Hz, 2H, OCH2), 3.98 (m, 8H, hex H1), 2.57 (s, 6H, CH3), 2.47 (m, 8H, CH3, SCH2), 2.20 (m, 8H, hex H2), 1.85 (m, 2H, CH2), 1.72 (m, 8H, hex H3), 1.58 - 1.25 (m, 33H, hex H4,5, SH, (CH2)8), 0.89 (2 t, J = 7 Hz, 12H, hex H6), -2.42 (s, 2H, NH); 13C NMR (100.6 MHz, CDCl3): d 158.6, 145.1, 145.0, 143.4, 143.3, 142.3, 141.4, 136.2, 133.0, 128.5, 128.2, 127.6, 125.9, 119.3, 117.9, 117.8, 115.1, 96.9, 68.4, 34.0, 33.3, 32.0, 31.0, 30.0, 29.5, 29.4, 29.1, 28.4, 26.8, 26.1, 24.6, 22.8, 14.6, 14.5, 14.2; UV/vis (DCM): lmax 408, 506, 542, 572, 626 nm; MALDI MS: m/z 1058; IR (CCl4): nmax 2957 (s), 2929 (s), 2857 (s), 1597 (m) cm1.

2,8,12,18-Tetrahexyl-5-[3-(11-mercapto-undecyloxy)-phenyl]-15-phenyl-3,7,13,17-tetramethyl porphyrinato zinc(II) (228)

Prepared analogously to 225 except starting from 215. Purified by chromatography on silica eluted with hexane/EA (10/1) followed by a second column eluted with hexane/CHCl3 (7/3). Red oil (108 mg, 67 %). Rf 0.46 (hexane/EA, 10/1).

1H NMR (400 MHz, CDCl3): d 10.10 (s, 2H, meso), 8.06 (m, 2H, Ar), 7.71 (m, 6H, Ar), 6.11 (m, 1H, Ar), 4.12 (t, J = 7 Hz, 2H, OCH2), 3.92 (m, 8H, hex H1), 2.55 (s, 6H, CH3), 2.42 (s, 6H, CH3), 2.38 (q, J = 7 Hz, 2H, SCH2), 2.17 (m, 8H, hex H2), 1.87 (m, 2H, CH2), 1.76 (m, 8H, hex H3), 1.55 - 1.20 (m, 33H, hex H4,5, SH, (CH2)8), 0.94 (m, 12H, hex H6); 13C NMR (100.6 MHz, CDCl3): d 158.6, 147.7, 147.6, 146.3, 144.9, 143.8, 143.4, 2 138.1, 133.3, 128.4, 128.1, 127.5, 126.3, 119.7, 119.3, 119.2, 115.0, 97.5, 68.4, 34.0, 33.4, 32.0, 31.6, 31.0, 2 30.1, 2 29.5, 29.4, 29.1, 28.4, 27.0, 26.8, 26.1, 25.3, 24.6, 22.8, 15.3, 15.2, 15.1; UV/vis (DCM): lmax 410, 538, 572 nm; FAB MS: m/z [M+Na]+ calcd 1141.6645, found 1141.6643; IR (CCl4): nmax 2956 (s), 2930 (s), 2857 (s), 1597 (m) cm1.

2,8,12,18-Tetrahexyl-5-[3-(11-mercapto-undecyloxy)-phenyl]-15-phenyl-3,7,13,17-tetramethyl porphyrinato nickel(II) (229)

Prepared analogously to 225, starting from 216. Deep red oil (68 mg, 84 %). Rf 0.73 (hexane/EA, 10/1).

1H NMR (500 MHz, CDCl3): d 9.44 (s, 2H, meso), 7.85 (d, J = 7 Hz, 2H, Ar), 7.68 (m, 1H, Ar), 7.62 (m, 2H, Ar), 7.50 (m, 2H, Ar), 7.35 (s, 1H, Ar), 7.23 (d, J = 8 Hz, 1H, Ar), 4.03 (t, J = 7 Hz, 2H, OCH2), 3.66 (m, 8H, hex H1), 2.48 (q, J = 7 Hz, 2H, SCH2), 2.32 (s, 6H, CH3), 2.22 (s, 6H, CH3), 2.08 (m, 8H, hex H2), 1.82 (m, 2H, CH2), 1.65 - 1.55 (m, 10H, m, hex H3, CH2), 1.46 - 1.26 (m, 31H, hex H4,5, SH, (CH2)7), 0.91 (t, J = 7 Hz, 12H, hex H6); 13C NMR (100.6 MHz, CDCl3): d 158.4, 2 143.9, 142.4, 141.4, 140.4, 140.3, 139.4, 139.0, 138.9, 133.1, 128.3, 128.1, 127.4, 126.0, 119.3, 116.4, 116.3, 115.0, 96.3, 68.3, 34.0, 32.8, 31.9, 29.8, 2 29.5, 29.4, 29.3, 29.0, 28.3, 26.3, 26.0, 24.6, 22.7, 15.2, 15.1, 14.1; UV/vis (DCM): lmax 408, 526, 564 nm; MALDI MS: m/z [M]+ 1114; IR (CCl4): nmax 2956 (s), 2929 (s), 2857 (s), 1598 (m) cm1.

5,15-Bis[3-(11-mercapto-undecyloxy)-phenyl] porphyrin (230)

To a solution of 220 (0.30 g, 0.32 mmol) and mercaptoethanol (250 mL) in CHCl3 was added pyrrolidine (250 mL, 3.0 mmol). The solution was degassed and then allowed to stand at rt in a sealed vessel for 390 min after which the solvent was removed under reduced pressure. The product was purified by chromatography on a conventional silica column eluted with hexane/DCM (1/1) gradient to hexane/toluene/EA (10/10/1), followed by chromatography on prepacked flash columns (2) eluted with hexane/DCM (1/1). 230 was obtained as a purple solid (144 mg, 53 %).

1H NMR (250 MHz, CDCl3): d 10.31 (s, 2H, meso), 9.39 (d, J = 5 Hz, 4H, b-H), 9.13 (d, J = 5 Hz, 4H, b-H), 7.85 (m, 4H, Ar), 7.68 (t, J = 8 Hz, 2H, Ar), 7.34 (d, J = 8 Hz, 2H, Ar), 4.18 (t, J = 7 Hz, 4H, OCH2), 2.47 (q, J = 7 Hz, 4H, SCH2), 1.90 (m, 4H, CH2), 1.53 (m, 8H, 2 CH2), 1.42 - 1.25 (m, 26H, (CH2)6, SH), -3.14 (s, 2H, NH); 13C NMR (100.6 MHz, CDCl3): d 157.8, 147.1, 145.2, 142.6, 131.6, 131.1, 127.7, 121.4, 119.0, 114.1, 105.2, 68.3, 34.0, 29.5, 29.4, 29.1, 28.4, 26.1, 24.6; UV/vis (DCM): lmax 406, 502, 536, 574, 630 nm; MALDI MS: m/z [M]+ 867; IR (CDCl3): nmax 2930 (s), 2856 (m), 1596 (m), 1577 (m), 1291 (m) cm1; Anal. Calcd for C54H66N4O2S2: C 74.79, H 7.67, N 6.46. Found: C 74.35, H 7.50, N 6.25.

2,8,12,18-tetrahexyl-5,15-bis(3-methoxyphenyl)-3,7,13,17-tetramethyl porphyrinato zinc(II) (231)

Prepared from 3-methoxybenzaldehyde according to the standard procedure except using MeOH as the solvent for the aldehyde. The crude product was evaporated onto silica and eluted from a column with hexane/EA (10/1). Recrystallization ( 2) from CHCl3 layered with MeOH afforded the free-base porphyrin as black crystals (517 mg, 35 %). Rf 0.40 (hexane/EA, 10/1). Crystals for structure determination were obtained from a CHCl3 solution layered with MeOH.

The porphyrin (449 mg, 0.49 mmol) was Zn metallated according to the standard procedure to afford 231 as a purple solid (430 mg, 90 %). A sample for analysis was recrystallized from DCM layered with MeOH.

Crystals of 231pyridine for structure determination were grown from a solution in toluene and pyridine layered with MeOH.

1H NMR (500 MHz, CDCl3): d 10.19, 10.18 (2 s, 2H, meso), 7.70 (d, J = 7 Hz, 1H, Ar), 7.64 (m, 4H, Ar), 7.35 (m, 2H, Ar), 3.97, 3.95 (t and s, J = 8 Hz, 14H, hex H1, OCH3), 2.54 (s, 12H, CH3), 2.18 (m, 8H, hex H2), 1.75 (m, 8H, hex H3), 1.50 (m, 8H, hex H4), 1.38 (m, 8H, hex H5), 0.92 (t, J = 7 Hz, 12H, hex H6); 13C NMR (100.6 MHz, CDCl3): d 159.1, 147.6, 146.4, 144.9, 143.5, 138.1, 128.4, 126.5, 2 119.1, 114.2, 97.6, 55.6, 33.3, 32.0, 30.0, 26.8, 22.7, 15.0, 14.1; UV/vis (DCM): lmax 410, 538, 674 nm; MALDI MS: m/z [M]+ 977; IR (CCl4): nmax 2957 (s), 2930 (s), 2870 (m), 2858 (m), 1596 (m), 1285 (s) cm-1; Anal. Calcd for C62H80O2N4Zn: C 76.09, H 8.24, N 5.72. Found: C 75.74, H 8.14, N 5.69.

Disulfanyl bis[11-undecyloxy-(3-benzaldehyde)] (232)

200 (3.08 g, 8.79 mmol) was stirred with K2CO3 (1.5 g, 11 mmol) in MeOH (60 mL) under air for 17 h to form a white suspension. The solvent was evaporated and water (50 mL) added. This was extracted with Et2O (3 100 mL), the combined extracts washed with brine (50 mL), dried (MgSO4) and evaporated to a yellow oil. To a two phase mixture of this oil in CHCl3 (100 mL) and water (50 mL) was added a saturated solution of I2 in CHCl3 until a brown colour persisted. The organic phase was washed with dil. sodium thiosulfate (20 mL) and water (50 mL), dried (MgSO4) and evaporated to a yellow solid. This material was chromatographed on silica twice, eluting with hexane/EA (5/1) then hexane/EA (7/1). Fractions containing a trace of impurity were recrystallized from hot hexane, before recombination with the remaining product. 232 was obtained as a pale cream solid (2.26 g, 84 %). Rf 0.42 (hexane/EA, 5/1).

1H NMR (250 MHz, CDCl3): d 9.95 (s, 2H, CHO), 7.43 (m, 4H, Ar), 7.37 (m, 2H, Ar), 7.16 (m, 2H, Ar), 3.99 (t, J = 7 Hz, 4H, CH2), 2.67 (t, J = 7 Hz, 4H, SCH2), 1.79 (m, 4H, CH2), 1.66 (m, 4H, CH2), 1.47 - 1.28 (br m, 28H, (CH2)7); 13C NMR (62.9 MHz, CDCl3): d 192.2, 159.1, 137.8, 130.0, 123.3, 121.9, 112.7, 68.3, 39.2, 29.5, 29.3, 29.2, 29.1, 28.5, 26.0; ES MS: m/z [M+Na]+ calcd 637.3356, found 637.3373; IR (CCl4): nmax 2928 (s), 2855 (s), 2722 (w), 1702 (s), 1598 (m) cm1; Anal. Calcd for C36H54O4S2: C 70.31, H 8.85. Found: C 70.40, H 8.90.

Disulfanyl bis[11-undecyloxy-(2-benzaldehyde)] (233)

Prepared from 209 using a modification of the procedure used for 232. CHCl3 was used instead of Et2O for the extraction step in the work-up. The CHCl3 extracts were reacted with I2, washed with KI (aq), sodium thiosulfate (aq), dried (MgSO4) and evaporated to a yellow oil. Some solid material failed to dissolve during the extraction, and this was treated directly with I2 in CHCl3 which resulted in dissolution. This solution was worked up as described, to afford a black oil. Both portions of oil were combined and chromatography on silica eluted with hexane/EA (6/1) afforded the product as a cream solid (887 mg, 49 %). Rf 0.38 (hexane/EA, 5/1).

1H NMR (400 MHz, CDCl3): d 10.51 (d, J = 1 Hz, 2H, CHO), 7.82 (dd, J = 8, 2 Hz, 2H, Ar), 7.52 (m, 2H, Ar), 6.99 (m, 4H, Ar), 4.07 (t, J = 6 Hz, 4H, OCH2), 2.68 (t, J = 6 Hz, 4H, SCH2), 1.84 (m, 4H, CH2), 1.67 (m, 4H, CH2), 1.48 (m, 4H, CH2), 1.39 - 1.29 (m, 24H, (CH2)6); 13C NMR (62.9 MHz, CDCl3): d 189.9, 161.6, 135.9, 128.2, 124.9, 120.4, 112.5, 68.5, 39.2, 29.5, 29.3, 29.2, 29.1, 28.5, 26.0; ES MS: m/z [M+Na]+ calcd 637.3356, found 637.3339; IR (CDCl3): nmax 2929 (s), 2856 (s), 1686 (s) cm1; Anal. Calcd for C36H54O4S2: C 70.31, H 8.85. Found: C 70.18, H 8.78.

Fb meta strapped porphyrin (234)

Et3N (2 mL) was added to a suspension of Pd/C (10 %, 0.04 g) and 116 (397 mg, 0.65 mmol) in THF (50 mL). After degassing, the mixture was stirred under H2 for 2 h, filtered through celite and evaporated to a grey solid which was dried in vacuo. To this was added TFA (degassed, 15 mL) and stirred under N2 at 0 C for 10 min, followed by 30 min at rt with periodic exposure to vacuum. After cooling to -20 C a solution of 232 (200 mg, 0.33 mmol) in THF (degassed, 100 mL) at 0 C was added by cannula. The solution was cooled to -25 C, and stirred in the dark under N2, allowing to warm to - 7 C over 4 h. DDQ (192 mg, 0.85 mmol) was added, and stirring continued at rt for 20 min. Et3N (30 mL) was added followed by CHCl3 (200 mL). The solution was washed with portions (100 mL) of water until the washings were colourless. The organic phase was dried (MgSO4) and evaporated to a brown tar. Column chromatography on silica eluted with hexane/EA (20/1) afforded a red oil which was chromatographed a second time eluting with hexane/CHCl3/EA (40/1/1) to yield the product as a red foam (215 mg, 53 %). Rf 0.34 (hexane/EA, 10/1).

1H NMR (400 MHz, CDCl3): d 10.25 (s, 2H, meso), 7.83 (d, J = 7 Hz, 2H, Ar), 7.66 (t, J = 8 Hz, 2H, Ar), 7.46 (t, J = 2 Hz, 2H, Ar), 7.33 (dd, J = 8, 2 Hz, 2H, Ar), 4.06 - 3.93 (t, J = 7 Hz, 12H, OCH2, hex H1), 2.58 (s, 12H, CH3), 2.21 (m, 12H, CH2, hex H2), 1.83 (m, 4H, CH2), 1.75 (m, 8H, hex H3), 1.52 - 0.89 (m, 60H, hex H4-6, (CH2)8), -2.42 (s, 2H, NH); 13C NMR (100.6 MHz, CDCl3): d 158.6, 145.0, 143.4, 143.3, 141.4, 136.3, 128.5, 125.7, 119.0, 117.8, 115.8, 97.0, 68.4, 38.6, 33.3, 32.0, 30.0, 29.4, 29.2, 29.0, 28.9, 28.2, 26.9, 25.7, 22.8, 14.5, 14.2; UV/vis (DCM): lmax 406, 506, 540, 574 nm; ES MS: m/z [M+H]+ calcd 1257.8925, found 1257.8930; Anal. Calcd for C82H120O2N4S2: C 78.26, H 9.61, N 4.45. Found: C 78.07, H 9.63, N 4.55.

Zn meta strapped porphyrin (235)

Prepared from 232 using the same procedure as 234 except the product was Zn metallated according to the standard procedure after chromatography. 235 was obtained as a pink foam (356 mg, 41 %).

1H NMR (400 MHz, CDCl3): d 10.18 (s, 2H, meso), 7.84 (d, J = 7 Hz, 2H, Ar), 7.67 (t, J = 8 Hz, 2H, Ar), 7.48 (s, 2H, Ar), 7.36 (d, J = 8 Hz, 2H, Ar), 4.07 (t, J = 7 Hz, 4H, OCH2), 3.97 (m, 8H, hex H1), 2.57 (s, 12H, CH3), 2.20 (m, 8H, hex H2), 2.07 (t, J = 7 Hz, SCH2), 1.85 (m, 12H, hex H3, CH2), 1.54 - 0.94 (m, 60H, hex H4-6, (CH2)8); 13C (100.6 MHz, CDCl3): d 158.6, 147.6, 146.4, 144.8, 143.5, 138.2, 128.3, 126.2, 119.4, 119.2, 115.5, 97.6, 68.4, 38.4, 33.3, 32.0, 30.1, 29.2, 29.1, 2 28.9, 2 28.8, 28.1, 26.8, 25.7, 22.8, 15.1, 14.2; UV/vis (DCM): lmax 344, 410, 538, 574 cm; ES MS: m/z [M+H]+ calcd 1318.7982, found 1318.7958; Anal. Calcd for C82H118O2N4S2Zn: C 74.53, H 9.00, N 4.24. Found: C 74.56, H 9.00, N 4.24.

Zn trans ortho strapped porphyrin (236)

Zn cis ortho strapped porphyrin (237)

Prepared from 233 using the same procedure as for 234 except the solution temperature was maintained in the range -25 - -20 C for 210 min instead of allowing to warm. A mixture of 236 and 237 was separated from the crude product by column chromatography on silica eluted with hexane/EA (20/1) (Rf 0.4). This mixture was Zn metallated according to the standard procedure. The individual atropisomers were separated by preparative tlc on silica plates eluted twice with hexane/EA (40/1). Two major red bands were observed, the upper being 237, the lower being 236.

Data for 236: Purple crystals (116 mg, 14 %).

1H NMR (400 MHz, CDCl3): d 10.15 (s, 2H, meso), 7.83 (dd, J = 7, 2 Hz, 2H, Ar), 7.75 (td, J = 8, 2 Hz, 2H, Ar), 7.37 (t, J = 7 Hz, 2H, Ar), 7.27 (d, J = 8 Hz, 2H, Ar), 4.00 (m, 12H, OCH2, hex H1), 2.88 (t, J = 7 Hz, 4H, SCH2), 2.58 (s, 12H, CH3), 2.23 (m, 8H, hex H2), 1.82 (m, 12H, hex H3, CH2), 1.53 (m, 8H, hex H4), 1.44 (m, 12H, hex H5, CH2), 1.22 (m, 4H, CH2), 1.15 (m, 4H, CH2), 0.96 (m, 16H, hex H6, CH2), 0.73 (br m, 4H, CH2), 0.54 (br m, 4H, CH2), 0.39 (br m, 8H, (CH2)2); 13C NMR (100.6 MHz, CDCl3): d 159.1, 148.0, 142.9, 137.6, 135.0, 133.1, 129.8, 120.6, 115.3, 111.9, 97.1, 67.8, 40.1, 33.6, 32.2, 30.2, 30.0, 29.8, 29.6, 29.5, 29.4, 29.1, 28.8, 28.7, 27.0, 25.4, 22.9, 14.7, 14.3; UV/vis (DCM): lmax 338, 412, 538, 574 nm; MALDI MS: m/z [M]+ 1324; Anal. Calcd for C82H118O2N4S2Zn: C 74.53, H 9.00, N 4.24. Found: C 74.32, H 8.97, N 4.31.

Data for 237: Red foam (217 mg, 25 %).

1H NMR (400 MHz, CDCl3): d 10.14 (s, 2H, meso), 7.74 (m, 4H, Ar), 7.29 (m, 4H, Ar), 3.98 (m, 12H, OCH2, hex H1), 2.55 (s, 12H, CH3), 2.48 (t, J = 7 Hz, 4H, SCH2), 2.21 (m, 8H, hex H2), 1.77 (m, 8H, hex H3), 1.52 (m, 8H, hex H4), 1.43 (m, 12H, hex H5, CH2), 1.14 - 1.03 (m, 8H, (CH2)2), 0.94 (t, J = 7 Hz, 12H, hex H6), 0.89 (m, 4H, CH2), 0.78 (m, 4H, CH2), 0.68 - 0.53 (m, 16H, (CH2)4); 13C NMR (100.6 MHz, CDCl3): d 159.1, 148.0, 146.2, 142.9, 137.7, 134.9, 133.1, 129.7, 120.5, 115.4, 111.7, 97.0, 68.3, 39.4, 33.5, 32.1, 30.1, 29.8, 28.9, 2 28.8, 2 28.6, 27.9, 26.9, 25.4, 22.8, 14.5, 14.2; UV/vis (DCM): lmax 338, 412, 538, 574 nm; MALDI MS: m/z [M]+ 1321; Anal. Calcd for C82H118O2N4S2Zn: C 74.53, H 9.00, N 4.24. Found: C 74.35, H 8.98, N 4.37.

Fb trans ortho strapped porphyrin (238)

A solution of 236 (5.5 mg, 4.1 mmol) in CHCl3 (30 mL) was washed with HCl (3 N, 10 mL), water (3 30 mL), dried (MgSO4) and evaporated to a red solid (4.3 mg, 83 %).

1H NMR (500 MHz, CDCl3): d 10.13 (s, 2H, meso), 7.80 (dd, J = 7, 1 Hz, 2H, Ar), 7.73 (m, 2H, Ar), 7.34 (m, 2H, Ar), 7.28 (m, 2H, Ar), 4.00 (m, 8H, hex H1, OCH2), 3.93 (m, 4H, hex H1), 2.87 (t, J = 7 Hz, SCH2), 2.55 (s, 12H, CH3), 2.16 (m, 8H, hex H2), 1.83 (m, 4H, CH2), 1.70 (m, 8H, hex H3), 1.44 (m, 12H, hex H4, CH2), 1.35 (m, 8H, hex H5), 1.26 (m, 4H, CH2), 1.12 - 1.05 (m, 8H, (CH2)2), 0.88 (m, 16H, hex H6, CH2), 0.58 (m, 4H, CH2), 0.52 (m, 4H, CH2), 0.44 (m, 4H, CH2), -2.31 (s, 2H, NH); ES MS: m/z [M]+ 1258.

Fb cis ortho strapped porphyrin (239)

TFA (several drops) was added to a solution of 237 (125 mg, 95 mmol) in CHCl3 (50 mL). The green solution was washed with water (2 20 mL), Et3N was added until a red colour was observed followed by washing with further portions of water (3 20 mL). The solution was dried (MgSO4) and evaporated to afford the product as a red foam (97 mg, 82 %).

1H NMR (400 MHz, CDCl3): d 10.18 (s, 2H, meso), 7.73 (m, 4H, Ar), 7.29 (m, 4H, Ar), 3.98 (m, 12H, OCH2, hex H1), 2.55 (s, 12H, CH3), 2.49 (t, J = 7 Hz, 4H, SCH2), 2.19 (m, 8H, hex H2), 1.74 (m, 8H, hex H3), 1.50 - 1.34 (m, 20H, hex H4, (CH2)3), 1.09 (m, 8H, hex H5), 0.91 (m, 16H, hex H6, CH2), 0.82 (m, 4H, CH2), 0.72 - 0.63 (m, 16 H, (CH2)4, -2.34 (s, 2H, NH); 13C NMR (100.6 MHz, CDCl3): d 158.9, 145.3, 142.6, 141.1, 135.8, 134.7, 131.5, 129.9, 120.5, 114.0, 111.6, 96.3, 68.3, 39.4, 33.4, 32.0, 30.0, 28.9, 28.8, 2 28.7, 28.6, 27.9, 26.8, 25.5, 22.8, 14.1, 13.8; ES MS: m/z [M]+ 1258.

3,5-Diiodo anisole (240)395

A mixture of 3,5-dinitroanisole (5.00 g, 25.2 mmol) and PtO2 (100 mg) in AcOH was degassed then stirred under H2 at rt for 5 h. After filtration through celite the solution was evaporated under reduced pressure to afford a brown solid (3,5-diamino anisole) which was redissolved in AcOH (13 mL). This was added to conc. H2SO4 (13 mL) and cooled to 0 C.

NaNO2 (4.13 g, 59.9 mmol) was added to conc. H2SO4 (13 mL) at 0 C followed by cold AcOH (25 mL). To this was added the solution of the 3,5-diamino anisole over 10 min, followed by stirring at 0 C for 1 h. This was poured into a rapidly stirred mixture of NaI (18.8 g), I2 (15.6 g) and urea (12.5 g) in CHCl3 (80 mL) and water (150 mL) at rt. After stirring for 1 h, the CHCl3 phase was separated and the aqueous layer extracted with CHCl3 (3 100 mL). The combined organics were washed with water (3 100 mL), satd. NaHCO3 (100 mL), dil. sodium thiosulfate (3 100 mL), water (100 mL), dried (MgSO4) and evaporated to a brown solid. This was recrystallized from hot EtOH to obtain brown crystals which were further purified by column chromatography on silica eluted with hexane to afford 240 as a yellow powder (5.53 g, 61 %). Rf 0.38 (hexane).

1H NMR (250 MHz, CDCl3): d 7.62 (t, J = 1 Hz, 1H, ArH4), 7.20 (d, J = 1 Hz, 2H, ArH2,6), 3.75 (s, 3H, OCH2); 13C NMR (62.9 MHz, CDCl3): d 160.3, 137.5, 123.0, 94.6, 55.6; EI MS: m/z [M]+ 360; Anal. Calcd for C7H6I2O: C 23.36, H 1.68. Found: C 23.67, H 1.66.

3,5-diiodo phenol (241)395

A solution of 240 (5.50 g, 15.3 mmol) in AcOH (23 mL) and HI (47 % aq, 15 mL) was refluxed under N2 in the dark for 2 h. The solution was poured into water (200 mL), extracted with CHCl3 (7 50 mL) and the combined extracts evaporated to a yellow solid. Column chromatography on silica eluted with hexane/EA (5/1) afforded 241 (1.45 g), unreacted 240 (3.03 g) and an unidentified material. The unreacted starting material was treated for 5 h with refluxing HI and AcOH then worked up as described. This material was recrystallized from 60/80 petroleum ether to afford pale yellow needles (1.95 g). (Total yield 64 %). Rf 0.38 (hexane/EA, 5/1).

1H NMR (250 MHz, CDCl3): d 7.62 (t, J = 1 Hz, 1H, ArH4), 7.17 (d, J = 1 Hz, 2H, ArH2,6), 4.78 (br, 1H, OH); 13C NMR (62.9 MHz, CDCl3): d 156.2, 137.9, 124.3, 94.6; EI MS: m/z [M]+ 346; Anal. Calcd for C6H4I2O: C 20.83, H 1.17. Found: C 20.65, H 1.16.

11-(3,5-Diiodo-phenoxy)-undecan-1-ol (242)

A mixture of Cs2CO3 (3.0 g, 8.5 mmol), 241 (3.00 g, 8.67 mmol) and 11-bromo-1-undecanol (2.18 g, 8.68 mmol) in DMF (15 mL) was degassed and stirred under N2 at rt for 60 h. DCM (150 mL) was added and the solution washed with water (2 50 mL), NaOH (10 %, 2 50 mL), dried (MgSO4) and evaporated to a white solid. This was recrystallized from hexane to afford 242 as a white solid (3.06 g). Concentration of the mother liquor afforded more material which was recrystallized from MeOH to yield a further portion of 242 (0.93 g). Both portions had identical tlc and NMR spectra. (Total yield 89 %). Rf 0.20 (hexane/EA/CHCl3, 5/1/1).

Caution - 242 is suspected of being a severe skin irritant.

1H NMR (250 MHz, CDCl3): d 7.60 ( t, J = 1 Hz, 1H, ArH4), 7.19 (d, J = 1 Hz, 2H, ArH2,6), 3.87 (t, J = 6 Hz, 2H, ArOCH2), 3.63 (q, J = 6 Hz, 2H, CH2OH), 1.73 (m, 2H, CH2), 1.56 (m, 2H, CH2), 1.43 - 1.29 (br m, 14H, (CH2)7), 1.19 (t, J = 5 Hz, 1H, OH); 13C NMR (62.9 MHz, CDCl3): d 159.9, 137.3, 123.4, 94.5, 68.5, 63.1, 32.8, 2 29.5, 29.4, 29.2, 29.0, 25.9, 25.7; FIB MS: m/z [M+H]+ calcd 517.0101, found 517.0110; IR (CCl4): nmax 3638 (w), 2930 (s), 2856 (m), 1573 (s), 1546 (s) cm1; Anal. Calcd for C17H26O2I2: C 39.56, H 5.08. Found: C 39.43, H 5.03.

Toluene-4-sulfonic acid 11-(3,5-diiodo-phenoxy)-undecyl ester (243)

To a solution of 242 (3.90 g, 7.56 mmol) and Et3N (1.3 mL) in DCM (anhydrous, 80 mL) at rt was added TsCl (2.96 g, 90.8 mmol) in DCM (50 mL) dropwise. After 20 h TsCl (0.50 g, 1.5 mmol) and Et3N (0.5 mL) were added. A further portion of TsCl (0.5 g, 1.5 mmol) was added after 270 min. After stirring for an additional 22 h, the solution was washed with water (2 50 mL), dried (MgSO4) and evaporated to a yellow oil. Column chromatography on silica eluted with hexane/DCM (1/1) afforded the product as a colourless oil (3.95 g, 78 %). Rf 0.30 (hexane/DCM, 1/1).

1H NMR (250 MHz, CDCl3): d 7.78 (d, J = 8 Hz, 2H, Ts), 7.59 (t, J = 1 Hz, 1H, ArH4), 7.33 (d, J = 8 Hz, 2H, Ts), 7.18 (d, J = 1 Hz, 2H, ArH2,6), 4.01 (t, J = 6Hz, 2H, SO3CH2), 3.87 (t, J = 6 Hz, 2H, ArOCH2), 2.44 (s, 3H, CH3), 1.78 - 1.59 (m, 4H, CH2), 1.46 - 1.22 (br m, 14H, (CH2)7); 13C NMR (62.9 MHz, CDCl3): d 159.9, 144.6, 137.2, 133.2, 129.8, 127.8, 123.4, 94.5, 70.7, 68.4, 29.4, 29.3, 29.2, 2 28.9, 28.8, 25.8, 25.3, 21.6; ES MS: m/z [M+Na]+ calcd 693.0030, found 693.0030; IR (CCl4): nmax 2929 (s), 2856 (m), 1573 (s), 1546 (s), 1189 (s), 1372 (s), 1189 (s), 1179 (s) cm1; Anal. Calcd for C24H32O4I2S: C 43.00, H 4.81. Found: C 43.08, H 4.80.

Thioacetic acid 11-(3,5-diiodo-phenoxy)-undecyl ester (244)

To a solution of 243 (3.77 g, 5.62 mmol) in THF (anhydrous, 10 mL) was added MeOH (anhydrous, 10 mL) followed by KSCOCH3 (771 mg, 6.75 mmol). The solution was degassed and stirred in a sealed flask at rt for 21 h. The solvent was evaporated and the resulting solids redissolved in CHCl3 (100 mL), washed with water (2 50 mL), dried MgSO4 and evaporated to a yellow oil which crystallized on standing. Recrystallization from MeOH afforded 244 as a white powder (2.14 g, 66 %).

1H NMR (250 MHz, CDCl3): d 7.59 (t, J = 1 Hz, 1H, ArH4), 7.18 (d, J = 1 Hz, 2H, ArH2,6), 3.87 (t, J = 6 Hz, 2H, OCH2), 2.85 (t, J = 7 Hz, 2H, SCH2), 2.31 (s, 3H, CH3), 1.73 (m, 2H, CH2), 1.55 (m, 2H, CH2), 1.39 (br m, 14H, (CH2)7); 13C NMR (62.9 MHz, CDCl3): d 196.0, 159.9, 137.3, 123.4, 94.5, 68.5, 30.6, 29.4, 29.2, 2 29.1, 29.0, 28.8, 25.9; EI MS: m/z [M]+ calcd 573.9899, found 573.9903; IR (CCl4): nmax 2930 (s), 2856 (m), 1694 (s) cm1; Anal. Calcd for C19H28O2I2S: C 39.74, H 4.91. Found: C 39.66, H 4.92.

5-(3,5-Di-tert-butyl-phenyl)-15-(3-ethynyl-phenyl)-2,8,12,18-tetrahexyl-3,7,13,17-tetramethyl porphyrin (245)

The porphyrin was prepared according to the standard procedure from 3-trimethylsilylethynyl-benzaldehyde and 3,5-di-tert-butyl benzaldehyde. The crude material was recrystallized from CHCl3 layered with MeOH to afford a mixture of three porphyrins. To a solution of this in THF (40 mL) and water (1 mL) was added TBAF (1 M in THF, 2 mL, 2 mmol). After stirring for 6 min the solution was poured into water (200 mL) to form a red precipitate, and extracted with DCM (100 mL). The red organic layer was washed with water (3 50 mL), dried (MgSO4) and evaporated to a brown solid. Multiple column chromatography on silica eluted with CHCl3/MeOH (20/1) followed by recrystallization from CHCl3 layered with MeOH afforded 245 as purple crystals (343 mg, 14 %). Rf 0.44 (hexane/EA, 20/1).

1H NMR (400 MHz, CDCl3): d 10.25 (s, 2H, meso), 8.26 (s, 1H, Ar), 8.10 (d, J = 7 Hz, 1H, Ar), 7.93 (m, 3H, Ar), 7.81 (t, J = 3 Hz, 1H, Ar), 7.72 (t, J = 8 Hz, 1H, Ar), 3.99 (t, J = 8 Hz, 8H, hex H1), 3.18 (s, 1H, CCH), 2.52 (s, 6H, CH3), 2.47 (s, 6H, CH3), 2.20 (m, 8H, hex H2), 1.74 (m, 8H, hex H3), 1.52 (s, 18H, tBu), 1.48 (m, 8H, hex H4), 1.38 (m, 8H, hex H5), 0.91 (t, J = 7 Hz, hex H6), -2.40, -2.42 (2 s, 2H, NH); 13C NMR (100.6 MHz, CDCl3): d 149.9, 145.3, 144.9, 143.5, 143.2, 142.7, 141.5, 141.4, 141.0, 136.7, 136.5, 135.7, 133.5, 132.0, 127.6, 121.5, 121.1, 119.6, 116.2, 97.0, 83.8, 35.2, 33.3, 32.0, 31.7, 30.0, 26.8, 22.8, 15.0, 14.3, 14.1; UV/vis (DCM): lmax 410, 506, 540, 574 nm; ES MS: m/z [M+H]+ calcd 991.7551, found 991.7526; IR (CCl4): nmax 3310 (m), 2960 (s), 2929 (s), 2859 (s), 1595 (m) cm1.

Zn Porphyrin dyad (246)

A solution of 245 (200 mg, 0.20 mmol), 244 (53 mg, 92 mmol), AsPh3 (62 mg, 0.20 mmol), Pd2(dba)3 (24 mg, 26 mmol) in toluene (anhydrous, 48 mL) and Et3N (anhydrous, 9.6 mL) was degassed and stirred in the dark at rt under Ar for 35 h. The solvent was evaporated and the product chromatographed on silica eluted with hexane/CHCl3/EA (40/1/1). Pure and impure fractions were Zn metallated according to the standard procedure. Mixed fractions were purified by preparative tlc on silica plates eluted with hexane/EA (40/1). After combination of material, 246 was obtained as a pink solid (60 mg, 27 %). Rf 0.30 (hexane/EA, 20/1).

1H NMR (400 MHz, CDCl3): d 10.21 (s, 4H, meso), 8.32 (t, J = 1 Hz, 2H, porph Ar), 8.09 (dt, J = 8, 1 Hz, 2H, porph Ar), 7.98 (m, 6H, porph Ar), 7.86 (t, J = 2 Hz, 2H, porph Ar), 7.75 (t, J = 8 Hz, 2H, porph Ar), 7.43 (t, J = 1 Hz, 1H, ArH4), 7.05 (d, J = 1 Hz, 2H, ArH2,5), 3.99 (m, 16H, hex H1), 3.90 (t, J = 7 Hz, 2H, OCH2), 2.74 (t, J = 7 Hz, 2H, SCH2), 2.54 (s, 12H, CH3), 2.49 (s, 12H, CH3), 2.21 (s and m, 19H, hex H2, COCH3), 1.78 (m, 18H, hex H3, CH2), 1.56 - 1.22 (m, 82H, hex H4,5, (CH2)7, tBu), 0.94, 0.95 (t, J = 7 Hz, 24H, hex H6); 13C NMR (100.6 MHz, CDCl3): d 196.0, 158.9, 149.7, 148.0, 147.6, 2 146.5, 144.2, 143.7, 143.4, 142.4, 138.6, 137.8, 136.4, 133.4, 131.4, 128.0, 127.6, 127.3, 124.5, 122.3, 121.0, 118.0, 117.9, 97.7, 90.0, 88.9, 68.3, 35.2, 33.4, 32.0, 31.7, 30.5, 30.1, 29.8, 29.4, 29.3, 29.1, 28.8, 26.9, 25.9, 22.9, 22.8, 15.7, 15.0, 14.2; UV/vis (DCM): lmax 334, 412, 538, 574 nm; MALDI MS: m/z [M]+ 2428; IR (CCl4): nmax 2959, 2930, 2858, 1694 cm1; Anal. Calcd for C159H210N8O2SZn2: C 78.65, H 8.72, N 4.61. Found: C 78.29, H 8.73, N 4.56.

Zn porphyrin dyad (247)

Prepared analogously to 246 except using 1,3-diiodobenzene instead of 244. Attempts at purification by column chromatography on silica eluted with hexane/EA (30/1) followed by preparative tlc eluted with the same solvent four times yielded a small amount of product of poor purity from which the NMR spectra were obtained.

1H NMR (400 MHz, CDCl3): d 10.19 (s, 4H, meso), 8.29 (s, 2H, Ar), 8.07 (d, J = 8 Hz, 2H, Ar), 7.92 (m, 6H, Ar), 7.81 (m, 2H, Ar), 7.72 (t, J = 8 Hz, 2H, Ar), 7.49 (dd, J = 8, 1 Hz, 2H, ArH4,6), 7.29 (m, 2H, Ar), 3.97 (m, 16H, hex H1), 2.51 (s, 12H, CH3), 2.44 (s, 12H, CH3), 2.18 (m, 16H, hex H2), 1.74 (m, 16H, hex H3), 1.51, 1.49 (s and m, 52H, hex H4, tBu), 1.37 (m, 16H, hex H5), 0.91, 0.90 (t, J = 7 Hz, 24H, hex H6); 13C NMR (100.6 MHz, CDCl3): d 149.7, 147.9, 147.6, 146.5, 146.4, 144.1, 143.7, 143.4, 142.4, 138.6, 137.7, 136.3, 134.7, 133.4, 131.4, 131.3, 128.5, 128.0, 127.6, 123.7, 122.3, 121.0, 117.9, 97.7, 90.4, 88.8, 35.2, 33.3, 32.0, 31.7, 30.0, 29.7, 26.8, 2 22.8, 15.7, 14.9, 14.2; MALDI MS: m/z [M]+ 2186.

Fb porphyrin dyad (248)

Prepared analogously to 246 except using 3,5-diiodobenzyl alcohol instead of 244. Column chromatography twice on silica eluted with hexane/EA/CHCl3 (10/1/1) and hexane/EA (20/1) afforded 248 as a red solid (30 mg, 40 %).

1H NMR (400 MHz, CDCl3): d 10.26 (s, 4H, meso), 8.31 (t, J = 2Hz, 2H, Ar), 8.08 (dt, J = 8, 1 Hz, 2H, Ar), 7.97 - 7.93 (m, 6H, Ar), 7.83 (t, J = 2 Hz, 2H, Ar), 7.75 - 7.71 (m, 3H, Ar), 7.47 (d, J = 1 Hz, 2H, ArH2,6), 4.52 (s, 2H, CH2OH), 4.01 (t, J = 7 Hz, 16H, hex H1), 2.57 (s, 12H, CH3), 2.49 (s, 12H, CH3), 2.21 (m, 16H, hex H2), 1.75 (m, 16H, hex H3), 1.54 - 1.34 (m, 68H, hex H4,5, tBu), 0.92, 0.91 (t, J = 7 Hz, 24H, hex H6), -2.39 (s, 4H, NH); 13C NMR (100.6 MHz, CDCl3): d 149.9, 145.3, 144.9, 143.5, 143.2, 142.8, 2 141.5, 141.0, 136.7, 136.0, 135.8, 133.7, 133.2, 131.6, 129.7, 127.7, 127.6, 123.8, 122.4, 121.2, 119.6, 116.4, 97.0, 90.4, 88.8, 64.3, 35.2, 33.4, 32.0, 31.7, 30.0, 29.8, 26.9, 2 22.8, 15.1, 14.3, 14.2; MALDI MS: m/z [M+H]+ 2089.

Zn porphyrin dyad (249)

248 (30 mg, 14 mmol) was Zn metallated according to the standard procedure. Preparative tlc eluted with hexane/DCM (1/1) was used to remove polar brown material. 249 was obtained as a pink solid (1.91 mg, 6 %). Decomposition of 248 on prolonged storage (> 1 y) may be the cause of the apparently low yield. Rf 0.32 (hexane/DCM, 1/1).

1H NMR (400 MHz, CDCl3): d 10.19 (s, 4H, meso), 8.29 (s, 2H, Ar), 8.07 (d, J = 8 Hz, 2H, Ar), 7.93 (m, 6H, Ar), 7.81 (t, J = 2 Hz, 2H, ArH2,6), 7.71 (m, 3H, Ar), 7.45 (s, 1H, ArH4), 4.55 (d, J = 6 Hz, 2H, CH2OH), 3.96 (m, 16H, hex H1), 2.51 (s, 12H, CH3), 2.43 (s, 12H, CH3), 2.16 (m, 16H, hex H2), 1.73 (m, 16H, hex H3), 1.51 - 1.47 (m, 52H, hex H4, tBu), 1.37 (m, 16H, hex H5), 0.90 (m, 24H, hex H6).

4-Iodobenzaldehyde (250)469

To a solution of NaBH4 (0.65 g, 17 mmol) in THF (anhydrous, 10 mL), pyridine (anhydrous, 10 mL) and DMF (anhydrous, 25 mL) at 0 C was added 4-iodobenzoylchloride (5.33 g, 20 mmol) in THF (5 mL). The solution was stirred at 0 C for 1 min, then hexane/Et2O mixture (4/1, 50 mL) and water (50 mL) added. After stirring for a further 2 min, the mixture was filtered through celite which was washed with hexane/Et2O (4/1, 100 mL). The filtrate was diluted with Et2O (100 mL) and the aqueous phase discarded. The organic phase was washed with brine (100 mL), NaOH (10 %, 100 mL), water (100 mL), dried (MgSO4) and evaporated to a yellow solid. Column chromatography on silica eluted with hexane/EA (10/1) afforded the product as a white powder (1.59 g, 45 %). Rf 0.44 (hexane/EA, 10/1).

1H NMR (250 MHz, CDCl3): d 9.95 (s, 1H, CHO), 7.91 (d, J = 8 Hz, 2H, Ar), 7.58 (d, J = 8 Hz, 2H, Ar).

4-(4-Formyl-phenoxy)-butyric acid ethyl ester (251)470,471

K2CO3 (4.53 g, 32.8 mmol) and 4-hydroxybenzaldehyde (2.00 g, 16.4 mmol) were heated in degassed DMF (50 mL) at 60 C for 80 min under N2. Ethyl-4-bromobutyrate (2.1 mL, 15 mmol) was added and the mixture stirred under N2 at 80 C for 2 d. After cooling to rt and filtration, the solution was evaporated under reduced pressure to yield a purple oil. A solution of this in DCM (50 mL) was washed with HCl (30 mL), water (30 mL), dried (MgSO4) and evaporated. The residue was chromatographed on silica eluted with toluene/EA (9/1) to afford a colourless solid. Recrystallization from hot hexane/EA afforded colourless crystals (0.26 g), believed to be 4-(4-carboxy-phenoxy)-butyric acid ethyl ester. The mother liquor was evaporated to an oil which on silica chromatography eluted with hexane/EA (3/1) yielded 251 as a colourless oil (1.54 g, 44 %). Rf 0.45 (toluene/hexane, 9/1).

1H NMR (250 MHz, CDCl3): d 9.84 (s, 1H, CHO), 7.79 (d, J = 9 Hz, 2H, Ar2,5), 6.95 (d, J = 9 Hz, 2H, hex H3,5), 4.11 (q, J = 7 Hz, 2H, CO2CH2), 4.06 (t, J = 6 Hz, 2H, ArOCH2), 2.49 (t, J = 7 Hz, 2H, CH2CO2), 2.11 (m, 2H, CH2), 1.22 (t, J = 7 Hz, 3H, CH3); 13C NMR (62.9 MHz, CDCl3): 190.7, 172.9, 163.9, 131.9, 130.0, 114.7, 67.1, 60.5, 30.6, 24.4, 14.2; EI MS: m/z [M]+ calcd 236.1055, found 236.1049; IR (CCl4): nmax 2982 (m), 2940 (m), 2875 (w), 2825 (w), 2799 (w), 2734 (w), 1737 (s), 1700 (s), 1602 (s), 1579 (s), 1509(s), 1258 (s), 1160 (s) cm1. Anal. Calcd for C13H16O4: C 66.09, H 6.83. Found: C 65.61, H 6.89.

2,8,12,18-Tetrahexyl-5-[4-(11-thioacetyl-undecyloxy)-phenyl]-15-(4-iodo-phenyl)-3,7,13,17-tetramethyl porphyrin (252)

Prepared according to the standard procedure from 250 and 206. The crude mixture was recrystallized from CHCl3 layered with MeOH to obtain a purple solid. The three porphyrins were separated by repeated column chromatography on silica eluted with either hexane/CHCl3/EA (20/1/1) or CHCl3 with a gradient to CHCl3/EA (20/1). Recrystallization from CHCl3 layered with MeOH afforded 252 as purple fibres (371 mg, 13 %). Rf 0.21 (hexane/CHCl3/EA, 20/1/1).

1H NMR (400 MHz, CDCl3): d 10.22 (s, 2H, meso), 8.06 (d, J = 8 Hz, 2H, Ar), 7.90 (d, J = 8 Hz, 2H, Ar), 7.81 (d, J = 8 Hz, 2H, Ar), 7.25 (d, J = 8 Hz, 2H, Ar), 4.24 (t, J = 7 Hz, 2H, OCH2), 3.97 (t, J = 8 Hz, 8H, hex H1), 2.89 (t, J = 7 Hz, 2H, SCH2), 2.53, 2.51 (s, 12H, CH3), 2.33 (s, 3H, COCH3), 2.17 (m, 8H, hex H2), 1.99 (m, 4H, CH2), 1.72 (m, 8H, hex H3), 1.65 - 1.30 (m, 28H, hex H4,5, (CH2)6), 0.89 (t, J = 7 Hz, 12H, hex H6), -2.45 (s, 2H, NH); 13C NMR (100.6 MHz, CDCl3): d 196.1, 159.5, 145.7, 144.7, 143.5, 143.3, 142.1, 141.6, 141.4, 136.7, 136.6, 135.7, 134.9, 134.4, 133.7, 118.1, 116.0, 113.7, 97.0, 94.0, 68.4, 33.3, 32.0, 30.7, 30.0, 29.7, 2 29.6, 29.2, 28.9, 26.8, 26.3, 22.8, 15.0, 14.8, 14.2; UV/vis (DCM): lmax 406, 508, 542, 574 nm; ES MS: m/z [M+Na]+ calcd 1247.6582, found 1247.6543; IR (CCl4): nmax 2956 (s), 2930 (s), 2856 (s), 1694 (s), 1242 (s) cm1. Anal. Calcd for C73H101O2N4SI: C 71.54, H 8.31, N 4.57. Found: C 71.33, H 8.32, N 4.71.

2,8,12,18-Tetrahexyl-5-[4-(11-thioacetyl-undecyloxy)-phenyl]-15-(4-iodo-phenyl)-3,7,13,17-tetramethyl porphyrinato nickel(II) (253)

252 was Ni metallated according to the standard procedure. After recrystallization from CHCl3 layered with MeOH, 253 was obtained as a dark purple solid (141 mg, 93 %).

1H NMR (250 MHz, CDCl3): d 9.42 (s, 2H, meso), 7.96 (d, J = 8 Hz, 2H, Ar), 7.68 (d, J = 9 Hz, 2H, Ar), 7.59 (d, J = 8 Hz, 2H, Ar), 7.14 (d, J = 9 Hz, 2H, Ar), 4.18 (t, J = 7 Hz, 2H, OCH2), 3.64 (t, J = 8 Hz, 8H, hex H1), 2.88 (t, J = 7 Hz, 2H, SCH2), 2.32 (s, 3H, COCH3), 2.27, 2.25 (s, 12H, CH3), 1.99 (m, 10H, hex H2, CH2), 1.64 (m, 8H, hex H3), 1.48 - 1.30 (m, 30H, hex H4,5, (CH2)7), 0.90 (t, J = 7 Hz, 12H. hex H6); 13C NMR (100.6 MHz, CDCl3): d 196.1, 159.3, 144.1, 143.9, 141.1, 140.0, 139.6, 139.4, 139.3, 138.4, 136.5, 135.0, 133.8, 133.5, 116.4, 114.7, 113.5, 96.4, 93.8, 68.4, 32.8, 31.9, 30.7, 29.8, 29.6, 2 29.5, 29.2, 28.9, 26.3, 26.2, 22.7, 15.6, 15.4, 14.1; UV/vis (DCM): lmax 408, 528, 564 nm; EI MS: m/z [M+Na]+ calcd 1303.5779, found 1303.5790; IR (CCl4): nmax 2956 (s), 2930 (s), 2858 (s), 1694 (s), 1242 (s) cm1. Anal. Calcd for C73H99O2N4SINi: C 68.38, H 7.78, N 4.37: Found: C 67.92, H 7.68, N 4.20.

2,8,12,18-Tetrahexyl-5-[4-(11-thioacetyl-undecyloxy)-phenyl]-15-(4-iodo-phenyl)-3,7,13,17-tetramethyl porphyrinato zinc(II) (254)

252 was Zn metallated according to the standard procedure to afford 254 as a red solid which was used without purification (104 mg, 99 %).

1H NMR (400 MHz, CDCl3): d 10.09 (s, 2H, meso), 8.07 (d, J = 8 Hz, 2H, Ar), 7.91 (d, J = 8 Hz, 2H, Ar), 7.80 (d, J = 8 Hz, 2H, Ar), 7.27 (d, 2H, Ar), 4.28 (t, J = 7 Hz, OCH2), 3.90 (m, 8H, hex H1), 2.89 (t, J = 7 Hz, SCH2), 2.50 (s, 6H, CH3), 2.45 (s, 6H, CH3), 2.32 (s, 3H, COCH3), 2.15 (m, 8H, hex H2), 2.02 (m, 2H, CH2), 1.76 - 1.34 (m, 40H, hex H3-5, (CH2)8), 0.93 (t, J = 7 Hz, hex H6); 13C NMR (100.6 MHz, CDCl3): d 196.0, 159.4, 148.3, 147.2, 146.5, 146.2, 143.6, 143.5, 143.4, 138.4, 137.5, 136.5, 135.9, 135.2, 134.0, 119.3, 117.4, 97.6, 93.7, 68.4, 33.3, 32.0, 30.6, 30.0, 29.7, 2 29.6, 29.5, 29.2, 28.9, 26.7, 26.2, 22.7, 15.6, 15.4, 14.1; MALDI MS: m/z [M]+ 1286; UV/vis (DCM): lmax 412, 538, 574 nm.

5-[4-(3-Ethoxycarbonyl-propoxy)-phenyl]-15-(4-trimethylsilylethynyl-phenyl)-2,8,12,18-tetrahexyl-3,7,13,17-tetramethyl porphyrin (255)

Prepared according to the standard procedure from 152 and 251. The crude material was recrystallized from CHCl3 layered with MeOH to obtain purple needles. The desired product was separated from this by repeated column chromatography on silica eluted with hexane/EA (15/1 gradient to 10/1). A recrystallization from CHCl3 layered with MeOH afforded 255 as purple fibres (684 mg, 26 %). Rf 0.60 (hexane/EA, 5/1).

1H NMR (400 MHz, CDCl3): d 10.22 (s, 2H, meso), 8.02 (d, J = 8 Hz, 2H, Ar), 7.91 (d, J = 8 Hz, 2H, Ar), 7.87 (d, J = 8 Hz, 2H, Ar), 7.24 (d, 2H, Ar), 4.30, 4.27 (t, J = 6 Hz, q, J = 7 Hz, 4H, ArOCH2, CO2CH2), 3.97 (m, 8H, hex H1), 2.71 (t, J = 7 Hz, 2H, CH2CO2), 2.52, 2.50 (2 s, 12H, CH3), 2.33 (m, 2H, OCH2CH2), 2.18 (m, 8H, hex H2), 1.73 (m, 8H, hex H3), 1.47 (m, 8H, hex H4), 1.37 (m, 11H, hex H5, CH2CH3), 0.90 (t, J = 7 Hz, 12H, hex H6), 0.41 (s, 9H, SiMe3), -2.42 (br s, 2H, NH); 13C NMR (100.6 MHz, CDCl3): d 173.4, 159.2, 145.7, 144.8, 143.4, 143.3, 143.0, 141.5, 141.4, 136.5, 135.9, 134.7, 133.8, 132.9, 131.2, 123.0, 117.9, 116.8, 113.7, 105.4, 97.0, 95.0, 67.2, 60.6, 33.3, 32.0, 31.1, 30.0, 26.8, 24.9, 22.8, 15.0, 14.8, 14.4, 14.1; UV/vis (DCM): lmax 410, 508, 542, 574, 626 nm; ES MS: m/z [M+Na]+ calcd 1103.7144, found 1103.7174; IR (CCl4): nmax 2958 (s), 2930 (s), 2859 (s), 2158 (m), 1737 (s) cm1. Anal. Calcd for C71H96O3SiN4: C 78.84, H 8.95, N 5.18. Found: C 79.33, H 9.11, N 5.26.

5-[4-(3-Ethoxycarbonyl-propoxy)-phenyl]-15-(4-ethynyl-phenyl)-2,8,12,18 tetrahexyl-3,7,13,17-tetramethyl porphyrinato nickel(II) (256)

255 (200 mg, 0.19 mmol) was Ni metallated using the standard procedure. To the product in THF (20 mL) and water (200 mL) was added TBAF (1M in THF, 750 mL, 0.75 mmol). After stirring for 6 min at rt, DCM (100 mL) was added and the solution washed with water (3 40 mL), dried (MgSO4) and evaporated. Recrystallization from CHCl3 layered with MeOH afforded 256 as a red solid (185 mg, 94 %).

1H NMR (400 MHz, CDCl3): d 9.43 (s, 2H, meso), 7.83 (d, J = 8 Hz, 2H, Ar), 7.77 (d, J = 8 Hz, 2H, Ar), 7.70 (d, J = 9 Hz, 2H, Ar), 7.14 (d, J = 9 Hz, 2H, Ar), 4.25 (m, 4H, ArOCH2, CO2CH2), 3.65 (t, J = 8 Hz, 8H, hex H1), 3.27 (s, 1H, CCH), 2.67 (t, J = 7 Hz, 2H, CH2CO2), 2.30 (s and m, 8H, CH3, OCH2CH2), 2.24 (s, 6H, CH3), 2.00 (m, 8H, hex H2), 1.62 (m, 8H, hex H3), 1.45 - 1.32 (m, 19H, hex H3,2, CH3), 0.91 (t, J = 7 Hz, 12H, hex H6); 13C NMR (100.6 MHz, CDCl3): d 173.3, 159.0, 144.1, 143.9, 142.3, 141.0, 140.0, 139.5, 139.4, 139.2, 138.5, 133.9, 133.8, 133.1, 131.2, 121.8, 116.3, 115.3, 113.5, 96.4, 83.9, 77.8, 67.0, 60.5, 32.8, 31.9, 31.0, 29.8, 26.3, 24.8, 22.7, 15.5, 15.4, 14.3, 14.1; UV/vis (DCM): lmax 350, 408, 528, 564 nm; ES MS: m/z [M+Na]+ calcd 1087.5946, found 1087.5992; IR (CCl4): nmax 3310 (m), 2958 (s), 2930 (s), 2858 (m), 2110 (w), 1736 (s) cm1; Anal. Calcd for C68H86N4O3Ni: C 76.61, H 8.13, N 5.26. Found: C 76.59, H 8.16, N 5.38.

5-[4-(3-Ethoxycarbonyl-propoxy)-phenyl]-15-(4-ethynyl-phenyl)-2,8,12,18-tetrahexyl-3,7,13,17-tetramethyl porphyrinato zinc(II) (257)

Prepared and purified analogously to 256 except with initial Zn metallation according to the standard procedure. 257 was obtained as a red solid (175 mg, 86 %).

1H (250 MHz, CDCl3): d 10.10 (s, 2H, meso), 8.03 (d, J = 8 Hz, 2H, Ar), 7.89 (m, 4H, Ar), 7.25 (d, J = 9 Hz, 2H, Ar), 4.32, 4.25 (t, J = 6 Hz and q, J = 7 Hz, 4H, OCH2, CO2CH2), 3.90 (m, 8H, hex H1), 3.33 (s, 1H, CCH), 2.72 (t, J = 7 Hz, 2H, CH2CO2), 2.48 (s, 6H, CH3), 2.43 (s, 6H, CH3), 2.33 (m, 2H, OCH2CH2), 2.15 (m, 8H, hex H2), 1.73 (m, 8H, hex H3), 1.54 - 1.30 (m, 19H, hex H4,5, CH3), 0.91 (t, J = 7 Hz, 12H, hex H6); 13C NMR (62.9 MHz, CDCl3): d 173.4, 159.1, 148.3, 147.2, 146.4, 146.3, 144.7, 143.6, 143.4, 138.3, 137.6, 136.2, 134.0, 133.3, 131.2, 121.7, 119.2, 118.0, 113.5, 97.6, 84.1, 77.8, 67.1, 60.5, 33.3, 32.0, 31.1, 30.0, 29.7, 26.7, 24.9, 22.7, 15.5, 15.4, 14.3, 14.1; UV/vis (DCM): lmax 410, 538, 574 nm; ES MS: m/z [M+Na]+ calcd 1093.5884, found 1093.5971; IR (CCl4): nmax 3307 (m), 2957 (s), 2930 (s), 2859 (s), 2110 (w), 1737 (s) cm1; Anal. Calcd for C68H86N4O3Zn: C 76.13, H 8.08, N 5.22. Found: C 76.05, H 7.95, N 5.19.

Zn Ni porphyrin dyad (258)

A solution of AsPh3 (17 mg, 56 mmol), Pd2(dba)3 (6.4 mg, 7 mmol), 254 (59 mg, 46 mmol) and 256 (49 mg, 46 mmol) in toluene (anhydrous, 13 mL) and Et3N (anhydrous, 2.7 mL) was degassed and allowed to stand at rt in the dark under Ar for 22 h. The solvent was removed under reduced pressure and the red residue purified by column chromatography on silica with hexane/EA (3/1) to elute the starting material and toluene/hexane (9/1) to elute the product. 258 was obtained as a red solid (67 mg, 66 %). Rf 0.33 (toluene/hexane, 9/1).

1H NMR (400 MHz, CDCl3): d 10.16 (s, 2H, Zn meso), 9.47 (s, 2H, Ni meso), 8.15 (d, J = 8 Hz, 2H, Ar), 8.06 (d, J = 8 Hz, 2H, Ar), 7.96 (m, 6H, Ar), 7.72 (d, J = 9 Hz, 2H, Ar), 7.27 (d, J = 9 Hz, 2H, Ar), 7.15 (d, 2H, J = 9 Hz, Ar), 4.26 (m, 6H, OCH2, CO2CH2), 3.96 (br m, 8H, Zn hex H1), 3.68 (m, 8H, Ni hex H1), 2.56 (s, 6H, Zn b-CH3), 2.52 (s, 6H, Zn b-CH3), 2.37 (s, 6H, Ni b-CH3), 2.32 (s, 3H, SCOCH3), 2.29 (s, 6H, Ni b-CH3), 2.19 (m, 8H, hex H2), 2.03 (m, 10H, hex H2, CH2), 1.79 (m, 8H, hex H3), 1.64 (m, 12H, hex H3, 2 CH2), 1.55 - 1.32 (m, 49H, hex H4,5, 7 CH2, CH3), 0.95 - 0.90 (m, 24H, hex H1); 13C NMR (100.6 MHz, CDCl3): d 196.1, 173.4, 159.4, 159.1, 148.4, 147.4, 146.5, 146.3, 144.4, 144.2, 144.0, 143.6, 143.4, 141.9, 141.1, 140.2, 139.6, 139.5, 139.2, 138.6, 138.5, 137.7, 136.0, 134.0, 133.9, 133.8, 133.3, 133.5, 130.8, 123.1, 122.9, 119.3, 118.3, 116.3, 115.6, 113.6, 113.5, 97.6, 96.5, 68.5, 67.1, 60.6, 33.4, 32.8, 32.0, 31.9, 31.0, 30.7, 30.1, 29.8, 2 29.6, 29.2, 28.9, 26.8, 26.3, 24.9, 22.8, 15.6, 15.5, 14.4, 14.2; UV/vis (DCM): lmax 536, 567, 413 nm; ES MS: m/z [M+Na]+ calcd 2246.2648, found 2246.2579; Anal. Calcd for C141H184O5N8SNiZn: C 76.04, H 8.33, N 5.03. Found: C 75.51, H 8.37, N 4.94.

Ni Zn porphyrin dyad (259)

Prepared analogously to 258, from 253 and 257. The product was purified by chromatography on a silica column eluted with hexane/EA (5/1) followed by toluene/hexane (9/1) then recrystallization from CHCl3 layered with MeOH. 259 was obtained as a red solid (108 mg, 74 %).

1H NMR (400 MHz, CDCl3): d 10.17 (s, 2H, Zn meso), 9.46 (s, 2H, Ni meso), 8.15 (d, J = 8 Hz, 2H, Ar), 8.06 (d, J = 8 Hz, 2H, Ar), 7.96 (m, 6H, Ar), 7.71 (d, J = 9 Hz, 2H, Ar), 7.26 (d, 2H, Ar), 7.16 (d, J = 9 Hz, 2H, Ar), 4.33 (t, J = 6 Hz, 2H, ArOCH2), 4.27 (q, J = 7 Hz, 2H, CO2CH2), 4.19 (t, J = 7 Hz, 2H, OCH2), 3.96 (br, 8H, hex H1), 3.68 (m, 8H, hex H1), 2.88 (t, J = 7 Hz, 2H, SCH2), 2.72 (t, J = 7 Hz, 2H, CH2CO2), 2.56 (s, 6H, Zn b-Me), 2.51 (s, 6H, Zn b-Me), 2.37 (s, 6H, Ni b-Me), 2.32 (s, 3H, SCOCH3), 2.30 (s, 6H, Ni b-Me), 2.20 (m, 8H, hex H2), 2.02, 1.95 (m, 10H, hex H2, CH2), 1.76 (m, 8H, hex H3), 1.69 - 1.35 (m, 61H, hex H3, hex H4,5, 9 CH2, CH3), 0.94 (m, 24H, hex H1); 13C NMR (100.6 MHz, CDCl3): d 196.1, 173.4, 159.3, 159.1, 148.3, 147.4, 146.5, 146.4, 144.4, 144.1, 143.9, 143.6, 143.5, 141.9, 141.1, 140.1, 139.6, 139.5, 139.3, 138.6, 138.4, 137.8, 136.3, 134.1, 133.9, 133.5, 133.3, 130.8, 123.1, 123.0, 119.2, 118.3, 116.4, 115.5, 113.5, 97.7, 96.5, 90.7, 68.4, 67.2, 60.6, 33.4, 32.8, 32.0, 31.9, 31.1, 30.7, 30.1, 29.8, 29.6, 29.2, 28.9, 26.8, 26.3, 26.2, 25.0, 22.8, 15.6, 15.5, 14.4, 14.2; UV/vis (DCM): lmax 536, 567, 413 nm; ES MS: m/z [M+Na]+ calcd 2246.2648, found 2246.2643. Anal. Calcd for C141H184O5N8SNiZn: C 76.04, H 8.33, N 5.03. Found: C 75.77, H 8.31, N 5.03.

Disulfanyl bis [11-undecyl-oxycarbonyl-(4-pyridyl-triosmium-mH-decacarbonyl)] (260)

This compound was prepared from 180 by P. Goh using the same procedure as 263. Purification by preparative tlc eluted with hexane/CHCl3/EA (15/1/1) afforded 260 as a yellow solid (28 mg, 15 %). Rf 0.28 (hexane/EA/CHCl3, 15/1/1).

1H NMR (400 MHz, CDCl3): d 8.24 (d, J = 6 Hz, 2H, pyr H6), 7.80 (d, J = 1 Hz, 2H, pyr H3), 7.18 (dd, J = 6, 2 Hz, 2H, pyr H5), 4.28 (t, J = 7 Hz, 4H, OCH2), 2.66 (t, J = 7 Hz, 4H, SCH2), 1.74 (m, 4H, CH2), 1.65 (m, 4H, CH2), 1.38 - 1.27 (m, 14H, (CH2)7), -14.79 (s, 2H m-H); 13C NMR (100.6 MHz, CDCl3): d 183.5, 182.5, 178.4, 176.9, 175.1, 174.5, 174.4, 174.1 173.8, 164.6, 164.4, 155.0, 138.7, 134.5, 120.4, 66.3, 39.2, 29.5, 29.2, 28.5, 25.9; UV/vis (DCM): lmax 232, 320, 394 nm; IR (CCl4): nmax 2927 (m), 2854 (m), 2104 (s), 2064 (s), 2053 (s), 2022 (s), 2010(s), 1991 (s), 1975 (s), 1731 (m) cm1.

5-[3-(11-Thioacetyl-undecyloxy)-phenyl]-15-(4-pyridyl)-2,8,12,18-tetrahexyl-3,7,13,17-tetramethyl porphyrin (261)

Prepared from 200 and 4-formyl-pyridine according to the standard procedure. The product was isolated by chromatography on silica eluted with hexane/EA (5/1 gradient to 3/1) and purified by a second silica column eluted with hexane/EA (5/1). 261 was obtained as a red oil (388 mg, 12 %). Rf 0.41 (hexane/EA, 3/1).

1H NMR (400 MHz, CDCl3): d 10.24 (s, 2H, meso), 9.02 (d, J = 6 Hz, 2H, pyr Ha), 8.08 (d, J = 6 Hz, 2H, pyr Hb), 7.62 (m, 3H, Ar), 7.34 (dt, J = 8, 2 Hz, 1H, Ar), 4.10 (t, J = 7 Hz, 2H, OCH2), 3.98 (t, J = 8 Hz, 8H, hex H1), 2.81 (t, J = 7 Hz, 2H, SCH2), 2.57 (s, 6H, CH3), 2.51 (s, 6H, CH3), 2.17 (m, 8H, hex H2), 1.85 (m, 2H, CH2), 1.72 (m, 8H, hex H3), 2.27 (s, 3H, COCH3), 1.54 - 1.25 (m, 32H, hex H4,5, (CH2)8), 0.89 (t, J = 7 Hz, 12H, hex H6), -2.44 (s, 2H, NH); 13C NMR (100.6 MHz, CDCl3): d 196.0, 158.7, 151.0, 149.0, 145.2, 143.9, 143.5, 143.2, 141.7, 141.4, 136.6, 135.1, 128.6, 125.8, 119.3, 118.4, 115.1, 114.1, 97.3, 68.4, 33.3, 32.0, 31.6, 30.6, 30.0, 29.5, 29.4, 29.1, 28.8, 26.8, 26.1, 22.8, 15.0, 14.5, 14.1; UV/vis (DCM): lmax 408, 506, 540, 574, 626 nm; ES MS: m/z 1100; IR (CCl4): nmax 2929 (s), 2857 (m), 1694 (m), 1594 (m) cm1.

5-[3-(11-Mercapto-undecyloxy)-phenyl]-15-(4-pyridyl)-2,8,12,18-tetrahexyl-3,7,13,17-tetramethyl porphyrin (262)

A solution of 261 (375 mg, 0.32 mmol) and pyrrolidine (30 mL, 0.36 mmol) was refluxed in THF (~5 mL) for 6 h. DCM (20 mL) was added and the solution washed with water (2 10 mL), dried (MgSO4) and evaporated to a red oil. NMR demonstrated that this contained a mixture of starting material and 262, although separation was not attempted due to streaking of the tlc. All of this material was refluxed in degassed DCM (5 mL) and pyrrolidine (100 mL) under N2 for 1 h. The solvent was evaporated and the red oil dried in vacuo. After column chromatography on silica eluted with CHCl3/MeOH (100/1) 262 was obtained as a viscous red oil (164 mg, 48 %). Rf 0.61 (CHCl3/MeOH, 100/1).

1H NMR (400 MHz, CDCl3): d 10.24 (s, 2H, meso), 9.02 (d, J = 6 Hz, 2H, pyr Ha), 8.08 (d, J = 6 Hz, 2H, pyr Hb), 7.62 (m, 3H, Ar), 7.34 (dt, J = 8, 2 Hz, 1H, Ar), 4.11 (t, J = 7 Hz, 2H, OCH2), 3.97 (t, J = 8 Hz, 8H, hex H1), 2.57 (s, 6H, CH3), 2.51 (s, 6H, CH3), 2.45 (q, J = 7 Hz, 2H, SCH2), 2.17 (m, 8H, hex H2), 1.85 (m, 2H, CH2), 1.72 (m, 8H, hex H3), 1.54 - 1.25 (m, 32H, hex H4,5, (CH2)8), 0.89 (t, J = 7 Hz, 12H, hex H6), -2.43 (br s, 2H, NH); 13C NMR (100.6 MHz, CDCl3): d 158.7, 151.0, 149.0, 145.2, 143.9, 143.5, 143.2, 141.7, 141.4, 136.6, 135.2, 128.6, 125.8, 119.3, 118.4, 115.1, 114.1, 97.3, 68.4, 34.0, 33.3, 32.0, 30.0, 29.5, 29.0, 28.3, 26.8, 26.1, 24.6, 22.8, 15.0, 14.5, 14.1; UV/vis (DCM): lmax 406, 506, 540, 574 nm; ES MS: m/z [M+H]+ calcd 1058.7643, found 1058.7669.

5-[3-(11-(Mercapto-triosmium-mH-decacarbonyl)-undecyloxy)-phenyl]-15-(4-pyridyl-triosmium-mH-decacarbonyl)-2,8,12,18-tetrahexyl-3,7,13,17-tetramethyl porphyrin (263)

5-[3-(11-(Mercapto-triosmium-mH-decacarbonyl)-undecyloxy)-phenyl]-15-(4-pyridyl)-2,8,12,18-tetrahexyl-3,7,13,17-tetramethyl porphyrinato zinc(II) (264)

Me3NO2H2O was warmed in vacuo for 2 h. A solution of this in DCM (degassed, 20 mL) was added dropwise over 17 min to a degassed solution of Os3(CO)12 in MeCN (anhydrous, 25 mL) and DCM (anhydrous, 50 mL) at -79 C under N2. The solution was allowed to warm to rt over 2 h. To this was added a solution of 262 (110 mg, 0.10 mmol) in DCM (anhydrous and degassed, 20 mL). After stirring for 11 h under N2 the solvent was evaporated. Chromatography on silica eluted with DCM/CHCl3 (1/1) with a gradient to CHCl3/MeOH (100/1) afforded mixed fractions. The first porphyrin fractions eluted were columned a second time on silica eluted with hexane/DCM (7/3 gradient to 1/1) to afford 263 as a red solid (18 mg, 11 %).

264 was isolated as a pink solid (29 mg) from the remaining material (Rf 0.24, CHCl3/MeOH, 100/1) by preparative tlc on silica plates eluted with DCM/EA (9/1) followed by Zn metallation by the standard procedure.

Data for 263: Rf 0.20 (hexane/DCM, 1/1).

1H NMR (400 MHz, CDCl3): d 10.23 (s, 2H, meso), 8.49 (d, J = 6 Hz, 1H, pyr H), 8.24 (d, J = 6 Hz, 1H, pyr H), 7.62 (m, 3H, Ar), 7.41 (d, J = 6 Hz, 1H, pyr H), 7.34 (dt, J = 7, 2 Hz, 1H, Ar), 4.10 (t, J = 7 Hz, 2H, OCH2), 3.96 (m, 8H, hex H1), 2.78 (s, 3H, CH3), 2.56 (s, 6H, CH3), 2.32 (m, 5H, SCH2, CH3), 2.17 (m, 8H, hex H2), 1.85 (m, 2H, CH2), 1.72 (m, 8H, hex H3), 1.65 - 1.25 (m, 32H, hex H4,5, (CH2)8), 0.90 (t, J = 7 Hz, 12H, hex H6), -2.40 (s, 2H, NH), -14.84 (s, 1H, pyr mH), -17.43 (s, 1H, S mH); 13C NMR (100.6 MHz, CDCl3): d 185.0, 183.0, 180.7, 180.3, 178.2, 177.3, 176.3, 175.3, 175.1, 174.5, 173.7, 170.5, 169.4, 159.0, 158.7, 153.1, 148.6, 145.9, 145.4, 144.5, 143.8, 143.5, 143.4, 143.1, 142.5, 141.7, 141.0, 137.0, 136.5, 135.0, 134.4, 128.7, 126.8, 125.7, 119.2, 118.7, 115.2, 113.1, 97.5, 97.3, 68.4, 55.4, 33.3, 33.0, 32.0, 30.0, 29.5, 29.4, 29.2, 28.5, 26.9, 26.8, 26.1, 22.8, 17.1, 14.5, 14.2, 13.5; UV/vis (DCM): lmax 412, 508, 542, 574, 626, 656 nm; IR (CCl4): nmax 2954 (m), 2929 (s), 2857 (m), 2103 (s), 2064 (s), 2057 (s), 2052 (s), 2021 (s), 2009 (s), 1996 (s), 1987 (s) cm1. Anal. Calcd for C90H99O21N5SOs6: C 39.17, H 3.62, N 2.54. Found: C 39.18, H 3.59, N 2.48.

Data for 264:

1H NMR (250 MHz, CDCl3): d 9.98 (s, 2H, meso), 7.68 (m, 2H, Ar), 7.57 (t, J = 8 Hz, 1H, Ar), 7.30 (d, J = 9 Hz, 1H, Ar), 6.08 (br s, 2H, pyr Hb), 4.08 (t, J = 6 Hz, 2H, OCH2), 3.94 (br, 4H, hex H1), 3.71 (br, 4H, hex H1), 2.54 (s, 6H, CH3), 2.30 (t, J = 8 Hz, 2H, SCH2), 2.13 (br, 4H), 1.96 (br, 4H), 1.79 - 1.18 (m, 44H), 0.85 (m, 18H, hex H6, b-CH3), -17.44 (s, 1H, mH); UV/vis (DCM): lmax 338, 408, 540, 574 nm; IR (CCl4): nmax 2107 (s), 2065 (s), 2057 (s), 2022 (s), 1996 (s), 1987 (s) cm1. Anal. Calcd for C80H97O11N5SZnOs3: C 48.71, H 4.96, N 3.55. Found: C 49.13, H 5.11, N 3.41.

Disulfanyl-bis[5-(3-(11-undecyloxy)-phenyl)-15-(4-pyridyl)-2,8,12,18-tetrahexyl-3,7,13,17-tetramethyl porphyrin] (265)

265 was isolated as a side product during preparation of 262. Polar fractions from the first column were chromatographed a second time eluting with CHCl3/MeOH (100/1) to afford 265 as a red viscous oil (84 mg, 25 %). Rf 0.39 (CHCl3/MeOH, 100/1).

1H NMR (250 MHz, CDCl3): d 10.24 (s, 2H, meso), 9.00 (m, 2H, pyr Ha), 8.05 (m, 2H, pyr Hb), 7.62 (m, 3H, Ar), 7.32 (m, 1H, Ar), 4.09 (t, J = 7 Hz, 2H, OCH2), 3.94 (m, J = 8 Hz, 8H, hex H1), 2.60, 2.56 (t, J = 7 Hz, SCH2, s, CH3, total 8H), 2.49 (s, 6H, CH3), 2.17 (m, 8H, hex H2), 1.85 (m, 2H, CH2), 1.72 (m, 8H, hex H3), 1.63 - 1.25 (m, 32H, hex H4,5, (CH2)8), 0.90 (t, J = 7 Hz, 12H, hex H6), -2.43 (s, 2H, NH); 13C NMR (100.6 MHz, CDCl3): 158.7, 150.9, 149.0, 145.2, 143.9, 143.5, 143.2, 141.7, 141.4, 136.6, 135.1, 128.5, 125.8, 119.3, 118.4, 115.1, 114.1, 97.2, 68.4, 39.1, 33.3, 32.0, 30.0, 29.5, 29.4, 29.2, 28.5, 26.8, 26.1, 22.8, 15.0, 14.5, 14.1; UV/vis (DCM): lmax 408, 506, 540, 574, 626 nm; MALDI MS: m/z [M]+ 2114; IR (CDCl3): nmax 2956 (m), 2930 (s), 2857 (s), 1596 (m) cm1.

Zn Rh porphyrin dyad (266)

264 (17 mg, 8.6 mmol) and 118 (10 mg, 9.2 mmol) were mixed and CHCl3 (1 mL) added. After 15 min the solvent was evaporated by N2 blowing. Column chromatography on silica eluted with hexane/DCM (1/1) afforded 266 as a red solid (17 mg, 63 %). Rf 0.33 (hexane/DCM, 1/1).

1H NMR (400 MHz, CDCl3): d 10.34 (s, 2H, Rh meso), 9.91 (s, 2H, Zn meso), 8.20 (d, J = 8 Hz, 2H, Ar), 8.15 (d, J = 7 Hz, 2H, Ar), 7.76 (m, 6H, Ar), 7.53 (m, 2H, Ar), 7.45 (s, 1H, Ar), 7.28 (dt, J = 8, 2 Hz, 1H, Ar), 5.77 (d, J = 7 Hz, 2H, pyr Hb), 4.14 (m, 4H, Rh hex H1), 3.99 (m, 6H, Rh hex H1, OCH2), 3.81 (t, J = 8 Hz, 4H, Zn hex H1), 3.61 (t, J = 8 Hz, 4H, Zn hex H1), 2.56 (s, 12H, Rh b-CH3), 2.43 (s, 6H, Zn b-CH3), 2.27 (m, 10H, 5 CH2), 2.03 (m, 4H, 2 CH2), 1.83 (m, 14H, 7 CH2), 1.67 - 1.22 (m, 56H, 28 CH2), 1.18 (d, J = 6 Hz, 2H, pyr Ha), 0.88 (m, 24H, hex H6), 0.68 (s, 6H, Zn b-CH3), -17.44 (s, 1H, mH); UV/vis (DCM): lmax 358, 412, 534, 564 nm; IR (CDCl3): nmax 2956 (s), 2929 (s), 2857 (m), 2107 (s), 2066 (s), 2057 (s), 2022 (s), 1996 (s) cm1; Anal. Calcd for C140H173O11N9RhISZnOs3: C 55.03, H 5.71, N 4.13. Found: C 54.94, H 5.72, N 4.03.

 


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