Complexes of zinc(II) tetra-(15-crown-5)-phthalocyaninate with axially coordinates N-donor ligands as potential components of photosensitive materials of telecommunication range

Abstract

The methods of electron absorption spectroscopy and 1H NMR were used to study the processes of interactions between zinc tetra-(15-crown-5)-phthalocyaninate and a number of N-donor ligands, including 1,4-diazabicyclo[2.2.2]octane, 4-dimethylaminopyridine, 3-aminopyridine, imidazole, 2-amino-5-methylpyridine, 2-methyla-4-aminopyridine, 2,3-diaminopyridine, pyrazine. A new effective method for synthesizing zinc tetra-15-crown-5-phthalocyaninate was developed that allowed one to obtain the complex at a yield of greater than 80% under simple conditions in 2 h. The structure of associates was studied in detail using the example of interactions between zinc tetra-15-crown-5-phthalocyaninate and 1,4-diazabicyclo[2.2.2]octane. 1H NMR studies in a wide temperature range of 213–323 K (−60 to +50°C), as well as quantum-chemical calculations, allowed us to establish the formation of two types of associates of phthalocyanine and 1,4-diazabicyclo[2.2.2]octane with the composition of 1: 1 and 2: 1. Up to a temperature of 253 K, the 1: 1 and 2: 1 associates are in equilibrium with a high rate of interconversion.