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Spin–spin coupling between the two unpaired electrons in cross‐conjugated tetrathiafulvalene dication radicals
Author(s) -
Yamauchi Jun,
Aoyama Takuo,
Kanemoto Katsuichi,
Sasaki Shigeru,
Iyoda Masahiko
Publication year - 2000
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/(sici)1099-1395(200004)13:4<197::aid-poc229>3.0.co;2-2
Subject(s) - unpaired electron , chemistry , dication , conjugated system , tetrathiafulvalene , moiety , radical , spin (aerodynamics) , electron paramagnetic resonance , photochemistry , molecular orbital , crystallography , electron , ground state , computational chemistry , molecule , stereochemistry , atomic physics , nuclear magnetic resonance , organic chemistry , polymer , physics , quantum mechanics , aerospace engineering , engineering
Spin–spin interactions were examined for bis(tetrathiafulvalenyl) (TTF) derivatives bridged with a 1,1‐vinyl group (2,2‐diphenyl, 1 : 2,2‐fluorenylidene, 2 ; and 2,2‐dimethyl, 3 ). The chemical oxidation of these cross‐conjugated TTFs using AgClO 4 yielded characteristic seven‐line ESR spectra, indicating the exchange interactions between the unpaired electrons on each TTF moiety. Compounds 2 and 3 , in addition, exhibited fine structures and half‐field resonances in the frozen solutions, which evidence the triplet interaction in the solid state, even with a twisted geometry of the molecular configuration. These findings substantiate the possibility of spin–spin interactions or triplet ground states predicted for some TTF oligomers. Copyright © 2000 John Wiley & Sons, Ltd.