1,2,5‐Chalcogenadiazole‐Annulated Tripyrazinoporphyrazines: Synthesis, Spectral Characteristics, and Influence of the Heavy Atom Effect on Their Photophysical Properties

Abstract

A series of low‐symmetry ZnII, MgII, and metal‐free porphyrazine derivatives with one 1,2,5‐chalcogenadiazole ring (with S, Se or Te) and three pyrazines bearing tert‐butylsulfanyls were synthesized. The absorption maxima of ZnII complexes lay at 660, 674, and 707 nm for S, Se, and Te, respectively, indicating increasing contribution of the 1,2,5‐chalcogenadiazole rings to the π‐electronic system. Photophysical studies revealed that introduction of Se as a chalcogen and ZnII as a central metal causes an increase in the singlet oxygen quantum yield, reaching a value of 0.81, whereas the combination of S and MgII gives only 0.39. This takes place on the account of the fluorescence quantum yields that differ significantly from 0.072 (ZnII+Se) to 0.51 (MgII+S). These results demonstrated the two‐dimensional heavy atom effect combining the role of the chalcogen (first dimension) as well as the central metal (second dimension). Attempts to prepare oxygen‐containing isologues led to the formation of an unexpected side product.

Heterocyclic Subphthalocyanine Analogue – Boron(III) Subporphyrazine with Fused 1,2,5-Thiadiazole Rings

“…[18] Porphyrazines with annulated 1,2,5-chalcogenadiazole rings are known as strongly electron-deficient phthalocyanine analogues [19][20][21] which can be considered as perspective functional materials for design of organic electronic devices. Thus, tetra(1,2,5-thiadiazolo) porphyrazine, [(SN 2 ) 4 PAH 2 ], and its metal complexes [(SN 2 ) 4 PAM] (M=Zn II , V IV O, and Fe II ) were used as n-type organic semiconductors in the prototypes of field-effect transistors and photovoltaic cells by Awaga and co-workers [22] and in our works.…”

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

“…Porphyrazines combining three fused tert-butylsulfanyl substituted pyrazine fragments in combination with one 1,2,5-chalcogenadiazole ring ([(SeN 2 )TriPyz3PzM] and [(SeN 2 )TriPyz73PzM]) have been recently reported (Chart 34) [191,287]. Tripyrazinoporphyrazines [(Ph 2 Dz)TriPyz3PzM] with 1,4-diazepine [191], or [(HIm)TriPyz24PzM] with imidazole [288] rings were also briefly preliminarily reported.…”

Design and theoretical study of D–A–pi–A' organic sensitizers with [1,2,5]oxa-, thia- or selenadiazoloazine fragment

“…In our study we use both traditional building blocks reviewed previously by us and by other authors and extended list of donor groups that includes some new previously unexplored fragments. Based on our recent investigations and the works of other researchers 7,[14][15][16][17][18][19][20][21][22][23][24] six variants of A-fragments (A-block) which have showed good characteristics were selected for the present study: [1,2,5]thiadiazolo [3,4-c] [3,4-c]pyridazine. The general formula for these derivatives is represented in Scheme 1.…”