Charge transfer heterocomplexes based on oppositely charged macroheterocycles

Abstract

Heterocomplexes based on anionic metal phthalocyanines and cationic porphyrins or their metal complexes were prepared in DMSO. The ratios of the initial macroheterocycles were determined by titrimetric method. The ratio of the initial compounds in the heterocomplexes containing carboxyl-substituted metal phthalocyanines and metal-free porphyrin is 2:1, respectively. However, the phthalocyanine:porphyrin ratio is 1:1 in the heterocomplexes consisting of metal phthalocyanines and cobalt porphyrin. The structures of the investigated heterocomplexes based on differently charged structural blocks were optimized using the ORCA 6.0 program by the DFT/M06L/def2-TZVP method. All the heterocomplexes exhibit a donor-acceptor nature of the interaction of macrocycles, in which metal phthalocyanine acts as an electron acceptor, and porphyrin or its metal complex behaves as a donor.