Subphthalocyanine azaanalogues – Boron(III) subporphyrazines with fused pyrazine fragments

Сyclotrimerization of pyrazine-2,3-dicarbonitrile and its phenyl substituted derivative in the presence of BCl3 in p-xylene leads to azaanalogues of subphthalocyanine dye. Non-substituted tripyrazinosubporphyrazine [Pyz3sPABCl] was formed only in trace amounts allowing only limited spectral study in...

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Bibliographic Details
Published in:	Dyes and pigments Vol. 162; pp. 888 - 897
Main Authors:	Stuzhin, Pavel A., Skvortsov, Ivan A., Zhabanov, Yuriy A., Somov, Nikolai V., Razgonyaev, Oleg V., Nikitin, Ivan A., Koifman, Oskar I.
Format:	Journal Article
Language:	English
Published:	Elsevier Ltd 01-03-2019
Subjects:	DFT calculations Pyrazine fused subporphyrazines Spectral-luminescence properties Subphthalocyanines X-ray structure Pyrazine fused subporphyrazines Subphthalocyanines X-ray structure DFT calculations Spectral-luminescence properties
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Summary:	Сyclotrimerization of pyrazine-2,3-dicarbonitrile and its phenyl substituted derivative in the presence of BCl3 in p-xylene leads to azaanalogues of subphthalocyanine dye. Non-substituted tripyrazinosubporphyrazine [Pyz3sPABCl] was formed only in trace amounts allowing only limited spectral study in solution. Hexaphenyl substituted derivative [Ph6Pyz3sPABCl] was isolated as chlorboron(III) complex and fully characterized by 1H, 13C, 11B NMR, IR, electronic absorption and emission spectroscopy, cyclovoltammetry and its structure was established by single crystal X-ray diffraction. Pyrazine fused subporphyrazines exhibit strong absorption bands at 300–310 and 530–550 nm. The phenyl substituted derivative [Ph6Pyz3sPABCl] has an additional intense charge transfer band at 390 nm and can be reversibly reduced at −0.81 V (vs Ag/AgCl in MeCN). The influence of pyrazine rings on the geometrical and electronic structural features and spectral properties of subporphyrazine dye was also studied using DFT and TD DFT methods. Experimental and theoretical results evidence that fusion of pyrazine rings leads to stabilization of the frontier π-molecular orbitals and endows the macrocycle with enhanced electron deficiency. Pyrazine fused subporphyrazines can be considered as perspective dyes intensively absorbing in the 300–600 nm range for applications as n-type materials in organic electronics. [Display omitted] •Azaanalogues of subphthalocyanines – tripyrazinosubporphyrazines were prepared.•Fusion of pyrazine rings enhances the electron deficiency of the subporphyrazine core.•The Q band is shifted hypsochromically as compared to subphthalocyanine.•The intense CT transition at ∼390 nm is observed for phenyl substituted derivative.
ISSN:	0143-7208 1873-3743
DOI:	10.1016/j.dyepig.2018.11.006