Hole transfer equilibrium in rigidly linked bichromophoric molecules

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DOIResolve DOI: http://doi.org/10.1021/jp9922211
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TypeArticle
Journal titleThe Journal of Physical Chemistry A
ISSN1089-5639
Volume103
Issue46
Pages91679173; # of pages: 7
AbstractTwo bichromophoric molecules consisting of anthracene and diphenylpolyene moieties linked by two fused norbornyl bridges undergo photoionization upon ultraviolet (UV) pulsed laser irradiation. The simultaneous observation of the cation radicals of both anthracene and polyene groups points to a rapid (nanosecond or faster) intramolecular hole transfer equilibrium between the two chromophores. The existence of an equilibrium is supported by the results of one- and two-laser transient absorption and electrochemical experiments. Equilibrium constants (293 K) were determined by both transient absorption and cyclic voltammetry measurements and were independent of the method used within experimental error. For A-sp-VB, which contains anthracene and vinyldiphenylbutadiene chromophores, Keq = 4.0 ? 2 (transient absorption) and 3.2 ? 2 (electrochemical), favoring the anthracene cation radical. For A-sp-VS, containing anthracene and vinylstilbene groups, Keq = 70 ? 30 (transient absorption) and 105 ? 50 (electrochemical), favoring the anthracene cation radical.
Publication date
LanguageEnglish
AffiliationNational Research Council Canada; NRC Steacie Institute for Molecular Sciences
Peer reviewedYes
Identifier16891788
NPARC number12327098
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Record identifier0ff80ab7-cfb7-430a-9842-94f9724e9433
Record created2009-09-10
Record modified2017-03-23
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