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In this work a selection of octasubstituted phthalocyaninato zinc complexes were synthesized and their photochemistry studied. The substituents included cholesterol (3a), estrone (3b), naphthol (3c) and phenoxy groups substituted with CH₃ (3d), C(CH₃)₃ (at two positions, 3e), C(CH₃)₃ (3f), NO₂ (3g), NH₂ (3h), COH (3i), COOH (3j), and H (3k). In general, complexes containing electron-donating groups attached to the phenoxy ring (e.g. 3e and 3f) were found to be photochemically unstable with photobleaching quantum yields of the order of 10^-3. In the presence of electron-withdrawing groups (3g, 3i, and 3j) the photobleaching quantum yields were of the order of 10^-6 to 10^-5. Singlet oxygen quantum yields (Φ_Δ) ranged from 0.01 to 0.73. The lowest Φ_Δ was observed for the highly aggregated complex 3c. All the complexes showed aggregation at high concentrations. Electrochemical reduction using a thin-layer spectroelectrochemistry cell showed that the complexes become more monomeric following reduction.

The synthesis of a phthalocyanine-porphyrin heteropentamer (zinc(II) tetra(5-phenoxy-10,15,20-triphenylporphyrin)) zinc(II) phthalocyanine, (ZnPc-(ZnTPP)₄), containing four units of zinc tetraphenylporphyrin linked to a central zinc phthalocyanine macrocycle via an ether linkage is reported. The photophysical parameters of the pentamer are reported in toluene and dimethyl sulfoxide (DMSO). The observed differences in the fluorescence behavior of the pentamer in the two solvents is explained in terms of emission from different states; charge transfer state in DMSO and locally excited state in toluene. The rate constants for fluorescence, intersystem crossing, internal conversion, and of charge and energy transfer are reported for the pentamer. Quantum yields for fluorescence, internal conversion, triplet state and of charge and energy transfer are also reported for the pentamer, ZnPc-(ZnTPP)₄ and the mixture of ZnPc and ZnTPP. The latter two parameters are higher in the pentamer compared to a mixture containing ZnPc and ZnTPP.

Photochemical and photophysical measurements were conducted on pentoxy and naphthaloxy appended zinc and magnesium phthalocyanines. We describe in this paper the synthesis as well as unexpected photodegradation behavior of naphthaloxy appended magnesium phthalocyanines. General trends are described for quantum yields of photodegradation, triplet lifetimes and triplet quantum yields as well as singlet oxygen quantum yields of these compounds.

The synthesis, spectral and photophysical properties including fluorescence quenching of the following octa-substituted oxotitanium phthalocyanines are reported: 2,3,9,10,16,17,23,24-octaphenoxyphthalocyaninato titanium(IV) oxide, 2,3,9,10,16,17,23,24-[octakis(4-t-butylphenoxyphthalocyaninato)]titanium(IV) oxide, 2,3,9,10,16,17,23,24-{octakis[(4-benzyloxy)phenoxy]phthalocyaninato}titanium(IV) oxide and 2,3,9,10,16,17,23,24-octaphenylthiophthalocyaninato titanium(IV) oxide. The complexes are characterized by ¹H NMR, IR and UV-vis spectroscopies. Their photophysical properties are presented where moderate fluorescence quantum yields (0.14-0.19) and lifetimes were determined. Varied triplet quantum yields were obtained and the triplet lifetimes (40-100 μs) were short.

Ni(II) and Zn(II) phthalocyanines carrying four or eight branched oligo(ethyleneoxy)-thia groups on peripheral positions have been synthesized from new phthalonitrile derivatives. The new compounds have been characterized by elemental analysis, IR, NMR, mass spectra and electronic spectroscopy. The aggregation behaviors of the phthalocyanine complexes were studied in different solvents and concentrations. General trends are described for photodegradation, singlet oxygen and fluorescence quantum yields, and fluorescence lifetimes of these compounds in dimethylsulfoxide (DMSO). The effects of the substitution on the photophysical and photochemical parameters of the nickel(II) (3a and 4a) and zinc(II) phthalocyanines (4b) are also reported. The octasubstituted zinc(II) complex (3b) is not stable for these measurements. Preliminary investigation of the photophysical and photochemical properties of phthalocyanine complexes are very useful for further PDT applications. The mesogenic properties of these new materials were studied by differential scanning calorimetry (DSC), optical polarized microscopy and X-ray investigations.

Excited state dynamics, particularly intersystem crossing, of a set of meso-substituted porphyrins bearing different electron–donor and acceptor groups was studied by pulse train fluorescence technique. Triplet quantum yield was found to be critically dependent on the nature of meso-substituents in the porphyrin system. Porphyrins with meso methoxyphenyl groups were found to show high triplet quantum yields (${\varphi }_T$ between 0.70 and 0.81). Moreover, the quantity of methoxyphenyl groups and the substitution pattern directly influence ${\varphi }_T$. Alternatively, porphyrins attached to nitrophenyl group possess low triplet quantum yield values (~0.3). The observed structure-properties relationships suggest new ways for tuning the optical properties of porphyrins via chemical modification.

The singlet oxygen quantum yields of photosensitizers in different solvents are very important for photodynamic therapy (PDT). Here, we investigated the singlet oxygen quantum yields of tetrakis (4-carboxyphenyl) porphyrin (TCPP) in various solvents by the iodide method. Results indicate that TCPP has different singlet oxygen formation efficiency in different solvents. When compared to TCPP dissolved in water, TCPP showed higher singlet oxygen yields in methanol and ethanol, but lower singlet oxygen yields in DMF under identical conditions. In particular, TCPP rapidly precipitated in acetone after potassium iodide added in the solution. The salting out effect of TCPP by potassium iodide in acetone was confirmed by re-dissolving the precipitation in water and the characteristic absorption of TCPP was measured. The phenomenon of salting out for TCPP in acetone suggests that acetone is not a good solvent for singlet oxygen generation when evaluated by the iodide method.