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
Weinstein, Julia A.

Issue Date
2017-06-19
Metadata
Show full item recordAbstract
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.Citation
Delor, M. et al. (2017) ‘Directing the path of light-induced electron transfer at a molecular fork using vibrational excitation’, Nature Chemistry, 9 (11), pp. 1099–1104. doi: 10.1038/nchem.2793Publisher
SpringerJournal
Nature ChemistryDOI
10.1038/nchem.2793Additional Links
http://www.nature.com/doifinder/10.1038/nchem.2793Type
ArticleLanguage
enISSN
1755-4330EISSN
1755-4349ae974a485f413a2113503eed53cd6c53
10.1038/nchem.2793