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Solution Structure of One‐Electron Reduced and Oxidized Molecules with Twisted Donor and Acceptor Moieties
Author(s) -
Hopf Henning,
Kreutzer Martin,
Mlynek Cornelia,
Scholz Markus,
Gescheidt Georg
Publication year - 1994
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19940770524
Subject(s) - chemistry , dithiol , moiety , acceptor , molecule , radical ion , crystallography , ion , electron paramagnetic resonance , photochemistry , electron acceptor , charge (physics) , stereochemistry , nuclear magnetic resonance , organic chemistry , physics , quantum mechanics , condensed matter physics
The solution structures of the radical anion and the radical cation of the donor‐acceptor molecules 3,4‐di(1,3‐dithiol‐2‐ylidene)‐4‐phenylbut‐1‐ene‐1,1‐dicarbonitrile ( 1 ) and 3,4‐di(1,3‐dithiol‐2‐ylidene)‐4‐phenylbut‐1‐ene‐1,1,2‐tricarbonitrile ( 2 ) are discussed based on cyclovoltammetric and ESR/ENDOR measurements. It is shown that the spin population of the radical anions is limited to the di‐ and tricyanoethene moiety and the coplanar 1,3‐dithiole at C(3), whereas that of the radical cations resides mainly inside the two 1,3‐dithiole rings. The energies of the long‐wave bands in the electronic‐absorption spectra of 1 and 2 correspond to the differences between the oxidation and reduction potentials and thus point to a charge‐transfer character of these transitions.