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Spatial Separation of Molecular Conformers and Clusters
Published on: January 9, 2014
Hydrogen-bonding dynamics in photoinduced electron transfer in a ferrocene-quinone linked dyad with a rigid amide
Shunichi Fukuzumi1, Yutaka Yoshida, Ken Okamoto
1Department of Material and Life Science, Graduate School of Engineering, Osaka University, CREST, Japan Science and Technology Corporation (JST), 2-1, Yamada-oka, Suita, Osaka 565-0871, Japan. fukuzumi@ap.chem.eng.osaka-u.ac.jp
Abstract:
A newly designed ferrocene-quinone dyad with an amide space (Fc-Q) is employed to examine formation of the hydrogen bonding in the one-electron reduced form (Q*-) and the dynamics in the photoinduced electron-transfer reaction from the ferrocene to the quinone moiety. Photoexcitation of the Q moiety in Fc-Q in deaerated PhCN with 388 nm results in intramolecular electron transfer from Fc to the singlet excited state of Q to produce Fc+-Q*- without changing the conformation (<1 ps), followed by hydrogen bond formation with the amide proton of the spacer (tau = approximately 5 ps). The resulting radical ion pair decays via a back electron transfer to the ground state at a longer time scale with a rate constant of 2.6 x 108 s-1.
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