Supramolecular chemistry of phthalocyanines

This thesis reports our investigation on the supramolecular chemistry of phthalocyanines. The first part of the thesis describes the self-assembly of mixed porphyrin and phthalocyanine systems through axial coordination. The second part complexes between phthalocyanines and reports the formation of some novel inclusion phthalocyanine-cyclodextrin conjugates and porphyrins, beta-cyclodextrin.;Chapter 1 presents an overview of supramolecular chemistry and the general properties of phthalocyanines, focusing on the self-assembly of mixed porphyrin and phthalocyanine systems.;Chapter 2 describes the complexation of bis(pyridinolato) silicon(IV) phthalocyanines to several cobalt(II) porphyrins. As shown by absorption spectroscopy, both 1:1 and 1:2 molecular assemblies can be obtained depending on the relative amount of the two components and the position of the pyridyl ligand. The axially bound 1:1 phthalocyanine-porphyrin arrays have also been isolated and characterized spectroscopically.;Chapter 3 reports an extension of this work. Two novel phthalocyanines with 3 or 4 pyridyl axial substituents have been synthesized. These compounds bind to meso-tetraphenyl zinc porphyrin to form the corresponding tetrakis- and pentakis-mixed tetrapyrrole systems.;Chapter 4 discusses the preparation of several covalently-linked phthalocyanine-cyclodextrin conjugates. These compounds can form inclusion complexes with sulfonated porphyrin in water providing a new strategy to construct mixed phthalocyanine and porphyrin systems.;Chapter 5 reports the interactions of two octacarboxy phthalocyanines with beta-cyclodextrin. Through the formation of inclusion complexes, the latter serves as a disstacking agent reducing the aggregation tendency of these phthalocyanines. This supramolecular approach could be an effective way to generate hydrophilic and non-aggregated phthalocyanines, improving their photosensitising properties in aqueous media.;At the end of this thesis, selected 1H NMR spectra and crystallographic data are given as an Appendix.