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Distorted Porphyrins with High Stability: Synthesis and Characteristic Electronic Properties of Mono‐ and Di‐Nuclear Tricarbonyl Rhenium Tetraazaporphyrin Complexes
Author(s) -
Wang Mengfei,
Murata Kei,
Ishii Kazuyuki
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202005042
Subject(s) - chemistry , rhenium , ligand (biochemistry) , tap water , metal , photochemistry , acceptor , polar , crystallography , inorganic chemistry , organic chemistry , receptor , biochemistry , physics , astronomy , environmental engineering , engineering , condensed matter physics
Abstract Mono‐ and di‐nuclear tricarbonyl Re(I) tetraazaporphyrin complexes ( Re 1 TAP and Re 2 TAP ) are investigated and compared with Re(I) phthalocyanine complexes ( Re 1 Pc and Re 2 Pc ). Although Re 2 Pc is unstable in polar solvents, and easily undergoes demetallation reaction, the coordination of the TAP ligand significantly improves the tolerance toward polar solvents, affording more stability to Re 2 TAP . Additionally, the incorporation of [Re(CO) 3 ] + unit(s) and the TAP ligand results in remarkable positive shifts in both oxidation and reduction potentials. Consequently, the more positive oxidation potentials of the ReTAP complexes significantly increase the tolerance toward oxidation, while the reduction potential indicates that Re 2 TAP is suitable for a soluble electron acceptor. In contrast to Re 1 Pc and Re 2 Pc , Re 1 TAP and Re 2 TAP show unique broad Q bands, which can be attributed to the admixture of the π‐π* and metal‐to‐ligand charge transfer characters, owing to the lowered π orbital energy in the TAP complexes. This study is useful for controlling electronic properties and realizing high stability in Pc analogues.