Synthesis, spectral and electrochemical properties of a novel phosphorous(V)-phthalocyanine

Abstract

A novel phosphorous(V)-phthalocyanine, [ P ( tppc )( OH )( O )], where tppc denotes tetrakis{(2′,6′-dimethyl)phenoxy}phthalocyaninate, has been synthesized and its spectral properties in non-aqueous and aqueous media have been investigated. This compound has been found free from aggregation in EtOH whereas forms J-aggregates in CH 2 Cl 2 and acetonitrile, suggesting the presence of chemical interaction between the axial ligand and the surrounding solvent molecules. The most intense absorption band (Q-band) appears at 683 nm in EtOH , however, reaction with CF 3 COOH has given rise to a large red shift of the Q-band without lowering of its C 4 symmetry (evidenced by magnetic circular dichroism spectroscopy), indicating protonation at the axial site. Its fluorescence quantum yield has been determined (0.49 in EtOH ) and has been found much higher than those of the known Sb V or As V derivatives by more than one order of magnitude. The first reduction potential has been determined by cyclic voltammetry (-1.09 V vs. ferrocenium+/ferrocene) in CH 2 Cl 2. It is noteworthy that the Q-band maximum wavelength and the first reduction potential values are normal for conventional phthalocyanines despite the presence of pnictogen(V) in the cavity of the macrocyclic ligand.