0000000000049893
AUTHOR
Zbigniew Hnatejko
Adducts of free-base meso-tetraarylporphyrins with trihaloacetic acids: Structure and photostability
Abstract Four diverse meso-tetraarylporphyrins in the form of diprotonated adducts with trifluoro-, trichloro-, tribromoacetic acids and acetic acid were investigated in benzene solution. Despite similar structural distortion of the chromophore system due to protonation, the respective adducts demonstrated different photostability when exposed to UV irradiation. The trifluoro- and trichloroacetic adducts, and the acetic acid one, showed some common features both molecular and in the mechanism of photodegradation. However, the tribromo-derivative decayed according to a different kinetic scheme, revealing a considerable impact of the bromine atoms upon the pyrrole units of the porphyrin macro…
Spectral studies of zinc octacarboxyphthalocyanine aggregation
The association of zinc octacarboxyphthalocyanine, was studied using UV–vis absorption and fluorescence emission spectroscopy; the effects of dye concentration, pH and solvents on spectra were discussed. Calculations showed that the dye dimerized in aqueous solutions ranging from 5.0 × 10−7 to 5.0 × 10−5 mol/dm3, at 25 °C. The dimerization constant of 106 dm3/mol and the spectral Q band shift of 1185 cm−1 imparted by dimerization indicated strong π–π interactions between phthalocyanine molecules. Red S1 fluorescence of the dye monomer was observed in various solutions which was quenched owing to molecular association and other factors. The strong influence of pH on both aggregation and fluo…
Effect of air-absorbed oxygen and moisture on the chemical stability of photoexcitedMg,ZnandEuphthalocyanines in dimethylformamide
Absorption of oxygen and moisture from air by MPc-DMF systems was studied and related to the molecular stability demonstrated by phthalocyanine complexes (unsubstituted MPc's : MgPc , ZnPc and EuPc2; Pc = phthalocyanine ligand, C32H16N8) subjected to UV irradiation. A lower stability of air-exposed dimethylformamide solutions is observed and is due to a specific affinity for molecular oxygen revealed by the Pc macrocycle. SEM results proved oxygen molecules fixed to the phthalocyanine solids by forces strong enough to sustain desorption under vacuum. Absorption curves determined for MPc-DMF systems also indicate oxygen accommodated by the phthalocyanine moiety. This explains the predominant…