Wave-Function Symmetry Control of Electron-Transfer Pathways within a Charge-Transfer Chromophore
Aramburu-Trošelj BM, Ramírez-Wierzbicki I, Scarcasale F, Oviedo PS, Baraldo LM, Cadranel A (2020)
Publication Type: Journal article
Publication year: 2020
Journal
Book Volume: 11
Pages Range: 8399-8405
Journal Issue: 19
DOI: 10.1021/acs.jpclett.0c02167
Abstract
Despite a diverse manifold of excited states available, it is generally accepted that the photoinduced reactivity of charge-transfer chromophores involves only the lowest-energy excited state. Shining a visible-light laser pulse on an aqueous solution of the chromophore-quencher [Ru(tpy)(bpy)(μNC)OsIII(CN)5]- assembly (tpy = 2,2';6,2''-terpyridine and bpy = 2,2'-bipyridine), we prepared a mixture of two charge-transfer excited states with different wave-function symmetry. We were able to follow, in real time, how these states undergo separate electron-transfer reaction pathways. As a consequence, their lifetimes differ in 3 orders of magnitude. Implicit are energy barriers high enough to prevent internal conversion within early excited-state populations, shaping isolated electron-transfer channels in the excited-state potential energy surface. This is relevant not only for supramolecular donor/acceptor chemistry with restricted donor/acceptor relative orientations. These energy barriers provide a means to avoid chemical potential dissipation upon light absorption in any molecular energy conversion scheme, and our observations invite to explore wave-function symmetry-based strategies to engineer these barriers.
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Argentina (AR)How to cite
APA:
Aramburu-Trošelj, B.M., Ramírez-Wierzbicki, I., Scarcasale, F., Oviedo, P.S., Baraldo, L.M., & Cadranel, A. (2020). Wave-Function Symmetry Control of Electron-Transfer Pathways within a Charge-Transfer Chromophore. Journal of Physical Chemistry Letters, 11(19), 8399-8405. https://dx.doi.org/10.1021/acs.jpclett.0c02167
MLA:
Aramburu-Trošelj, Bruno M., et al. "Wave-Function Symmetry Control of Electron-Transfer Pathways within a Charge-Transfer Chromophore." Journal of Physical Chemistry Letters 11.19 (2020): 8399-8405.
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