Tetrapyrazinoporphyrazines and their metal derivatives. Part I: Synthesis and basic structural information

Tetrapyrazinoporphyrazines (TPyzPzs), the heterocyclic azaanalogs of the phthalocyanine macrocycle, are known since 1937 and were intensively studied especially in the last fifteen years. Due to advances in the synthesis, peripherally substituted TPyzPzs and their innumerable metal derivatives have become one of the most easily accessible phthalocyanine analogues. External substituents endow these species with solubility in organic solvents or water, influence aggregation behavior, determine spectral, electrochemical, coordination, acid-base, catalytic and photochemical properties. Moreover, by the building of new exocyclic coordination sites, they enable formation of multimetallic porphyrazines. Aspects concerning the synthesis of precursors, TPyzPz macrocycles and their metal derivatives and the related available structural information are illustrated and discussed in detail in this review including also low symmetry species, oligomeric and polymeric TPyzPzs and higher TPyzPz homologues with fused benzene and heteroaromatic rings. (C) 2015 Elsevier B.V. All rights reserved.