James Edward Redman
Chapter 1 presents an overview of the strategies used by chemists to assemble complex structures from simple components, with an emphasis on the use of metal containing building blocks. Self assembled structures composed of multiple porphyrins are discussed.
Chapter 2 presents the synthesis and characterization of a number of rhodium porphyrin coordination compounds with mono- and bidentate ligands, including dendritic structures assembled using complementary rhodium and tin coordination chemistries. The coordination chemistry of rhodium porphyrin with hydrazine, sulfur and selenium based ligands is presented. 1H NMR and X-ray crystallography were used as the principal methods for solution and solid state characterization respectively.
Chapter 3 describes the syntheses of porphyrins with appended thiols or disulfides with a view to formation of self assembled monolayers on gold surfaces. Porphyrins with a macrocyclic disulfide containing ‘strap’ were prepared and their atropisomerization investigated. The preparation of porphyrin binding ligands with thiol of disulfide tethers is also described.
Chapter 4 presents the characterization of adlayers of the compounds described in the preceding chapter on gold surfaces. Water contact angle measurements, X-ray photoelectron spectroscopy, scanning tunnelling microscopy and electrochemical techniques were utilized for this purpose.
Chapter 5 provides experimental details of compound syntheses and sample preparation. Spectroscopic data of compounds are listed when these have not been presented elsewhere in the text.