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Density functional theory study of silole‐fused tetramethyleneethane biradicals with orbital interactions
Author(s) -
Kano Yusuke,
Mizuno Kazuhiko,
Ikeda Hiroshi
Publication year - 2011
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.1891
Subject(s) - chemistry , density functional theory , atomic orbital , singlet state , molecular orbital , band gap , computational chemistry , molecular physics , chemical physics , atomic physics , condensed matter physics , molecule , quantum mechanics , electron , physics , organic chemistry , excited state
The geometries, energy gap between singlet and triplet states (S–T gap), electronic transitions, and molecular orbitals of the diphenyl derivative of the silole‐fused tetramethyleneethane (TME) (3,4‐dimethylenesilole) biradical 7 •• were determined by using the density functional theory method at the unrestricted Becke, three‐parameter, Lee–Yang–Parr/cc‐pVDZ level. In a manner similar to that of the parent TME biradical, the S–T gap of 7 •• is small. The wavelengths of electronic transitions of 3 7 •• ( λ ET = 450 nm) are calculated to be different from that of 1 7 •• ( λ ET = 673 nm). These differences are attributed to interactions between orbitals of the two allyl radical moieties, especially, the existence of double σ*–π* conjugation, that is, π*–σ*–π* conjugation, that takes place in the silole subunit. Copyright © 2011 John Wiley & Sons, Ltd.