Photoinduced Charge Shifts and Electron Transfer in Viologen-Tetraphenylborate Complexes: Push-Pull Character of the Exciplex

Journal of the American Chemical Society
Willy G SantosMalcolm D E Forbes

Abstract

Viologen-tetraarylborate ion-pair complexes were prepared and investigated by steady-state and time-resolved spectroscopic techniques such as fluorescence and femtosecond transient absorption. The results highlight a charge transfer transition that leads to changes in the viologen structure in the excited singlet state. Femtosecond transient absorption reveals the formation of excited-state absorption and stimulated emission bands assigned to the planar (kobs < 1012 s-1) and twisted (kobs ∼ 1010 s-1) structures between two pyridinium groups in the viologen ion. An efficient photoinduced electron transfer from the tetraphenylborate anionic moiety to the viologen dication was observed less than 1 μs after excitation. This is a consequence of the push-pull character of the electron donor twisted viologen structure, which helps formation of the borate triplet state. The borate triplet state is deactivated further via a second electron transfer process, generating viologen cation radical (V•+).

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Citations

Oct 19, 2017·Chemical Communications : Chem Comm·Tingjuan QianWenping Hu
Mar 28, 2019·Angewandte Chemie·Weijie ChiXiaogang Liu
Dec 22, 2019·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Raffaello Papadakis
Dec 6, 2019·Acta Crystallographica. Section C, Structural Chemistry·Yan ZhangXian Ming Zhang
May 28, 2020·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Hyunhee SoKang Mun Lee
Jun 11, 2019·ACS Applied Materials & Interfaces·Nuo-Hua XieMing-Qiang Zhu
Oct 4, 2019·Journal of the American Chemical Society·M Mustafa CetinJ Fraser Stoddart

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