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Electron-Transfer Dynamics for a Donor–Bridge–AcceptorComplex in Ionic Liquids.

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Title: Electron-Transfer Dynamics for a Donor–Bridge–AcceptorComplex in Ionic Liquids.
Authors: DeVine, Jessalyn A.1, Labib, Marena2, Harries, Megan E.2, Rached, Rouba Abdel Malak2, Issa, Joseph1, Wishart, James F.3 wishart@bnl.gov, Castner, Edward W.1 ed.castner@rutgers.edu
Source: Journal of Physical Chemistry B. Aug2015, Vol. 119 Issue 34, p11336-11345. 10p.
Subjects: Charge exchange, Ionic liquids, Photoinduced electron transfer, Phenylenediamines, Proline
Abstract: Intramolecular photoinduced electrontransfer from an N,N-dimethyl-p-phenylenediaminedonor bridged by a diproline spacer to a coumarin 343 acceptor wasstudied using time-resolved fluorescence measurements in three ionicliquids and in acetonitrile. The three ionic liquids have the bis[(trifluoromethyl)sulfonyl]amideanion paired with the tributylmethylammonium, 1-butyl-1-methylpyrrolidinium,and 1-decyl-1-methylpyrrolidinium cations. The dynamics in the two-prolinedonor–bridge–acceptor complex are compared to thoseobserved for the same donor and acceptor connected by a single prolinebridge, studied previously by Lee et al. (J. Phys. Chem. C2012, 116, 5197). The increasedconformational freedom afforded by the second bridging proline resultedin multiple energetically accessible conformations. The multiple conformationshave significant variations in donor–acceptor electronic coupling,leading to dynamics that include both adiabatic and nonadiabatic contributions.In common with the single-proline bridged complex, the intramolecularelectron transfer in the two-proline system was found to be in theMarcus inverted regime. [ABSTRACT FROM AUTHOR]
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Abstract:Intramolecular photoinduced electrontransfer from an N,N-dimethyl-p-phenylenediaminedonor bridged by a diproline spacer to a coumarin 343 acceptor wasstudied using time-resolved fluorescence measurements in three ionicliquids and in acetonitrile. The three ionic liquids have the bis[(trifluoromethyl)sulfonyl]amideanion paired with the tributylmethylammonium, 1-butyl-1-methylpyrrolidinium,and 1-decyl-1-methylpyrrolidinium cations. The dynamics in the two-prolinedonor–bridge–acceptor complex are compared to thoseobserved for the same donor and acceptor connected by a single prolinebridge, studied previously by Lee et al. (J. Phys. Chem. C2012, 116, 5197). The increasedconformational freedom afforded by the second bridging proline resultedin multiple energetically accessible conformations. The multiple conformationshave significant variations in donor–acceptor electronic coupling,leading to dynamics that include both adiabatic and nonadiabatic contributions.In common with the single-proline bridged complex, the intramolecularelectron transfer in the two-proline system was found to be in theMarcus inverted regime. [ABSTRACT FROM AUTHOR]
ISSN:15206106
DOI:10.1021/acs.jpcb.5b03320