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

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.