No abstract

The photochemistry and photophysics of six axially substituted silicon phthalocyanines are reported and show the importance of the axial groups in the photochemistry of these compounds. The fluorescence quantum yields are especially affected by the axial ligand. A very good correlation was found for the experimentally determined fluorescence lifetimes and the theoretically determined lifetimes using the Strickler-Berg equation for the unaggregated molecules.

The effects of formation of cyclodextrin inclusion complexes on the photochemical and photophysical properties of zinc phthalocyanine ( ZnPc ) and various peripherally substituted zinc phthalocyanines as well as zinc naphthalocyanine ( ZnNPc ) are investigated. The cyclodextrins employed were the hydroxypropyl-γ-cyclodextrin and unsubstituted β-cyclodextrin. Job's plots were employed to confirm the stoichiometry of the inclusion complexes and showed 2:1 and 4:1 (cyclodextrin:phthalocyanine) inclusion behavior. The phthalocyanine inclusion complexes showed larger singlet oxygen quantum yield (ϕΔ) values when compared to the free phthalocyanines before inclusion, for complexes 1 (zinc naphthalocyanine), 2 (zinc tetranitrophthalocyanine) and 4 (zinc tetra-tert-butylphenoxyphthalocyanine). The fluorescence quantum yields generally remained unchanged following inclusion.

The synthesis of two phthalocyanine-porphyrin covalently linked heteromolecules are described. Intramolecular energy transfer is investigated and quantified in terms of the quantum yield of energy transfer and found to be highly effective in both molecules. The photophysical properties of both molecules are modified greatly by the presence of the porphyrin moieties on the phthalocyanine core.

A number of octaphenoxyphthalocyaninato silicon complexes containing a variety of axial ligands, represented by (OPh) 8 PcSi(X) 2 (where X = chloro 3, hydroxy 4, (4-carboxybenzene) acetato 5, isonicatinato 6, propionato 7, nitrophenoxy 8 and dimethylaminoxy 9) have been synthesized using a convenient route starting with the 4,5-diphenoxy-1,2-dicyanobenzene. 1 H NMR and UV/vis spectra, and the cyclic voltammetry of the complexes are reported. The complexes are obtained in high yield and are soluble in many organic solvents. Cyclic voltammetry revealed two reduction couples and one oxidation couple for these complexes. Analysis of the cyclic voltammograms showed that compounds 6 and 8 were easier to oxidize and more difficult to reduce than the rest. Also cyclic voltammetry data suggested that electron transfer was not governed only by diffusion.