1.8 Aims of this project

The underlying theme of the work described in this thesis is the creation of ordered structures from porphyrins with an emphasis on self assembly using coordination chemistry. The objectives can be summarized,

1) To create large (nm sized) structures from small components using axial ligand coordination to metalloporphyrins.

Hard/soft binding preferences and steric effects will be explored to enable more than one recognition process to operate independently with a view towards assembly of multiporphyrin heterometallic assemblies.

2) Characterization of the above systems in solution using NMR spectroscopy as the principal tool. Single crystal X-ray crystallography will be used for solid state characterization, with the caveat that the diffraction quality crystals obtained need not be representative either of the bulk solid or the solution structure.

3) To develop syntheses of metalloporphyrins and porphyrin-binding ligands with thiol or disulfide functional groups with which to prepare monolayers on gold surfaces, ultimately with a view to exploration of porphyrin coordination chemistry on surfaces. At the time of commencement of this work there were relatively few reports in the literature on this topic.

4) Characterization of the porphyrin and ligand monolayers using a multitechnique approach in order to understand the composition and packing of molecules. This information is valuable, both to ensure that the layers are of the desired constitution, and to aid interpretation of future binding experiments.


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