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

• Published in: Coordination chemistry reviews 2016-02, Vol.309, p.107-179
• Main Authors: Donzello, Maria Pia, Ercolani, Claudio, Novakova, Veronika, Zimcik, Petr, Stuzhin, Pavel A.
• Format: Article
• Language: English
• Subjects: Annulated porphyrazines; Azaphthalocyanines; Mono/multinuclear complexes; Pyrazine-2,3-dicarbonitriles; Synthesis and structure; Tetrapyrazinoporphyrazines
• ISSN: 0010-8545; 1873-3840
• DOI: 10.1016/j.ccr.2015.09.006

Peripherally substituted tetrapyrazinoporphyrazines and their metal derivatives (TPyzPzs) are among the most easily accessible phthalocyanine analogues. As described here in detail, TPyzPzs can be prepared basically from their o-dicyano precursors or by modifying peripherally the TPyzPz macrocycle. The synthetic procedures, general properties of precursors and TPyzPz macrocycles together with the related structural information are illustrated and discussed in this review. •Tetrapyrazinoporphyrazines (TPyzPzs) are among the most easily accessible phthalocyanine analogues.•This review reports on detailed synthetic procedures of precursors, TPyzPz macrocycles and their metal derivatives.•Peripheral changes can lead to formation of multiply charged or multimetallic TPyzPzs.•Single crystal X-ray work provides information on the structure of precursors and macrocycles. 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.