Peripheral Modification and Basicity of (Phthalocyaninato)- copper(II) according to the Electronic Spectroscopy and Quantum Chemical Calculation Data

摘要

Singly, doubly, and triply protonated forms of terra- and octacarboxy (phthalocyaninato)copper(II) derivatives were identified and characterized by electronic absorption spectra and PM3 quantum chemical calculations. Molecules of carboxy-substituted phthalocyanine copper(II) complexes have a distorted nonplanar structure with specific charge distribution over meso-nitrogen atoms. Singly, doubly, and triply protonated complexes at the meso-nitrogen atoms and carboxy groups exist as mixtures of isomers, which is reflected in splitting of the Q band in the electronic absorption spectra and reduction of its symmetry. The formation of bifurcated hydrogen bonds O ···H~+···N_(meso)0 and O ··· H~+ ··· O between the neighboring substituents was revealed.