Directing the path of light-induced electron transfer at a molecular fork using vibrational excitation.
|Authors||Delor, Milan, Archer, Stuart A., Keane, Theo, Meijer, Anthony J. H. M., Sazanovich, Igor V., Greetham, Gregory M., Towrie, Michael and Weinstein, Julia A.|
Ultrafast electron transfer in condensed-phase molecular systems is often strongly coupled to intramolecular vibrations that can promote, suppress and direct electronic processes. Recent experiments exploring this phenomenon proved that light-induced electron transfer can be strongly modulated by vibrational excitation, suggesting a new avenue for active control over molecular function. Here, we achieve the first example of such explicit vibrational control through judicious design of a Pt(II)-acetylide charge-transfer Donor-Bridge-Acceptor-Bridge-Donor “fork” system: asymmetric 13C isotopic labelling of one of the two -C≡C-bridges makes the two parallel and otherwise identical Donor→Acceptor electron-transfer pathways structurally distinct, enabling independent vibrational perturbation of either. Applying an ultrafast UVpump(excitation)-IRpump(perturbation)-IRprobe(monitoring) pulse sequence, we show that the pathway that is vibrationally perturbed during UV-induced electron-transfer is dramatically slowed down compared to its unperturbed counterpart. One can thus choose the dominant electron transfer pathway. The findings deliver a new opportunity for precise perturbative control of electronic energy propagation in molecular devices.
Ultrafast electron transfer in condensed-phase molecular systems is often strongly coupled to
|Keywords||Spectroscopy; Organometallic chemistry; Physical Chemistry; Optoelectronics|
|Digital Object Identifier (DOI)||https://doi.org/10.1038/nchem.2793|
|Web address (URL)||http://hdl.handle.net/10545/623056|
|Publication dates||19 Jun 2017|
|Publication process dates|
|Deposited||18 Oct 2018, 15:06|
Archived with thanks to Nature Chemistry
|Contributors||University of Sheffield and Research Complex at Harwell|
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