Directing the path of light-induced electron transfer at a molecular fork using vibrational excitation.

Journal article


Delor, Milan, Archer, Stuart A., Keane, Theo, Meijer, Anthony J. H. M., Sazanovich, Igor V., Greetham, Gregory M., Towrie, Michael and Weinstein, Julia A. 2017. Directing the path of light-induced electron transfer at a molecular fork using vibrational excitation. Nature Chemistry. https://doi.org/10.1038/nchem.2793
AuthorsDelor, Milan, Archer, Stuart A., Keane, Theo, Meijer, Anthony J. H. M., Sazanovich, Igor V., Greetham, Gregory M., Towrie, Michael and Weinstein, Julia A.
Abstract

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
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.

KeywordsSpectroscopy; Organometallic chemistry; Physical Chemistry; Optoelectronics
Year2017
JournalNature Chemistry
PublisherSpringer
ISSN1755-4330
1755-4349
Digital Object Identifier (DOI)https://doi.org/10.1038/nchem.2793
Web address (URL)http://hdl.handle.net/10545/623056
hdl:10545/623056
Publication dates19 Jun 2017
Publication process dates
Deposited18 Oct 2018, 15:06
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Archived with thanks to Nature Chemistry

ContributorsUniversity of Sheffield and Research Complex at Harwell
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