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Influence of Topology on the Long‐Range Electron‐Transfer Phenomenon
Author(s) -
Rovira Concepció,
RuizMolina Daniel,
Elsner Olaf,
VidalGancedo Jose,
Bonvoisin Jacques,
Launay JeanPierre,
Veciana Jaume
Publication year - 2001
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 - 10.1002/1521-3765(20010105)7:1<240::aid-chem240>3.0.co;2-h
Subject(s) - diradical , intramolecular force , electron transfer , topology (electrical circuits) , chemistry , electron , divinylbenzene , photochemistry , computational chemistry , stereochemistry , atomic physics , organic chemistry , physics , quantum mechanics , mathematics , combinatorics , excited state , styrene , copolymer , polymer , singlet state
Intramolecular electron‐transfer phenomena in the radical anions derived from the partial reduction of diradicals ( E , E )‐ p ‐divinylbenzene‐ β , β ′‐ylene bis(4‐tetradecachlorotriphenylmethyl) diradical ( 1 ) and ( E , E )‐ m ‐divinylbenzene‐ β , β ′‐ylene bis(4‐tetradecachlorotriphenylmethyl) diradical ( 2 ) have been studied by optical and ESR spectroscopy. The synthetic methodology used allows for complete control of the geometry of diradicals 1 and 2 , which have para and meta topologies, respectively, as well as of their E / Z isomerism. This fact is used to show the influence of the different topologies on the ease of electron transfer, which is larger for the para than for the meta isomer, in which a small or negligible electronic coupling is observed. A related monoradical compound ( E )‐bis(pentachlorophenyl)[4‐(4‐bromophenyl‐tlsb> β ‐styryl)‐2,3,5,6‐tetrachlorophenyl]methyl radical ( 3 ), which has only one such redox site, has also been obtained and studied for comparison purposes.