Effect of air-absorbed oxygen and moisture on the chemical stability of photoexcitedMg,ZnandEuphthalocyanines in dimethylformamide

Abstract

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 predominantly oxygen-mediated photolysis, as well as the very short fluorescence lifetimes of metal phthalocyanines. The effect of air-absorbed moisture on the photostability is much less pronounced and practically insignificant for concentrations of H2O lower than 1%. An apparent stabilizing effect of water was observed and elucidated basing on kinetic considerations. The degradation rate of the photoexcited phthalocyanine moiety in air-exposed solutions depends on individual chemical properties and the molecular structure of the complex. EuPc2proved very stable whereas the photostability of ZnPc and MgPc gradually decreased in the course of time.