On the mechanism of vibrational control of light-induced charge transfer in donor-bridge-acceptor assemblies

Milan Delor, Theo Keane, Paul A. Scattergood, Igor V. Sazanovich, Gregory M. Greetham, Michael Towrie, Anthony J H M Meijer, Julia A. Weinstein

Research output: Contribution to journalArticle

63 Citations (Scopus)

Abstract

Nuclear-electronic (vibronic) coupling is increasingly recognized as a mechanism of major importance in controlling the light-induced function of molecular systems. It was recently shown that infrared light excitation of intramolecular vibrations can radically change the efficiency of electron transfer, a fundamental chemical process. We now extend and generalize the understanding of this phenomenon by probing and perturbing vibronic coupling in several molecules in solution. In the experiments an ultrafast electronic-vibrational pulse sequence is applied to a range of donor-bridge-acceptor Pt(II) trans-acetylide assemblies, for which infrared excitation of selected bridge vibrations during ultraviolet-initiated charge separation alters the yields of light-induced product states. The experiments, augmented by quantum chemical calculations, reveal a complex combination of vibronic mechanisms responsible for the observed changes in electron transfer rates and pathways. The study raises new fundamental questions about the function of vibrational processes immediately following charge transfer photoexcitation, and highlights the molecular features necessary for external vibronic control of excited-state processes.

Original languageEnglish
Pages (from-to)689-695
Number of pages7
JournalNature Chemistry
Volume7
Issue number9
DOIs
Publication statusPublished - 22 Sep 2015

Fingerprint

Charge transfer
Infrared radiation
Electrons
Photoexcitation
Excited states
Experiments
Molecules

Cite this

Delor, Milan ; Keane, Theo ; Scattergood, Paul A. ; Sazanovich, Igor V. ; Greetham, Gregory M. ; Towrie, Michael ; Meijer, Anthony J H M ; Weinstein, Julia A. / On the mechanism of vibrational control of light-induced charge transfer in donor-bridge-acceptor assemblies. In: Nature Chemistry. 2015 ; Vol. 7, No. 9. pp. 689-695.
@article{4e918f694b294c8da12226d0812485a6,
title = "On the mechanism of vibrational control of light-induced charge transfer in donor-bridge-acceptor assemblies",
abstract = "Nuclear-electronic (vibronic) coupling is increasingly recognized as a mechanism of major importance in controlling the light-induced function of molecular systems. It was recently shown that infrared light excitation of intramolecular vibrations can radically change the efficiency of electron transfer, a fundamental chemical process. We now extend and generalize the understanding of this phenomenon by probing and perturbing vibronic coupling in several molecules in solution. In the experiments an ultrafast electronic-vibrational pulse sequence is applied to a range of donor-bridge-acceptor Pt(II) trans-acetylide assemblies, for which infrared excitation of selected bridge vibrations during ultraviolet-initiated charge separation alters the yields of light-induced product states. The experiments, augmented by quantum chemical calculations, reveal a complex combination of vibronic mechanisms responsible for the observed changes in electron transfer rates and pathways. The study raises new fundamental questions about the function of vibrational processes immediately following charge transfer photoexcitation, and highlights the molecular features necessary for external vibronic control of excited-state processes.",
author = "Milan Delor and Theo Keane and Scattergood, {Paul A.} and Sazanovich, {Igor V.} and Greetham, {Gregory M.} and Michael Towrie and Meijer, {Anthony J H M} and Weinstein, {Julia A.}",
year = "2015",
month = "9",
day = "22",
doi = "10.1038/nchem.2327",
language = "English",
volume = "7",
pages = "689--695",
journal = "Nature Chemistry",
issn = "1755-4330",
publisher = "Nature Publishing Group",
number = "9",

}

Delor, M, Keane, T, Scattergood, PA, Sazanovich, IV, Greetham, GM, Towrie, M, Meijer, AJHM & Weinstein, JA 2015, 'On the mechanism of vibrational control of light-induced charge transfer in donor-bridge-acceptor assemblies', Nature Chemistry, vol. 7, no. 9, pp. 689-695. https://doi.org/10.1038/nchem.2327

On the mechanism of vibrational control of light-induced charge transfer in donor-bridge-acceptor assemblies. / Delor, Milan; Keane, Theo; Scattergood, Paul A.; Sazanovich, Igor V.; Greetham, Gregory M.; Towrie, Michael; Meijer, Anthony J H M; Weinstein, Julia A.

In: Nature Chemistry, Vol. 7, No. 9, 22.09.2015, p. 689-695.

Research output: Contribution to journalArticle

TY - JOUR

T1 - On the mechanism of vibrational control of light-induced charge transfer in donor-bridge-acceptor assemblies

AU - Delor, Milan

AU - Keane, Theo

AU - Scattergood, Paul A.

AU - Sazanovich, Igor V.

AU - Greetham, Gregory M.

AU - Towrie, Michael

AU - Meijer, Anthony J H M

AU - Weinstein, Julia A.

PY - 2015/9/22

Y1 - 2015/9/22

N2 - Nuclear-electronic (vibronic) coupling is increasingly recognized as a mechanism of major importance in controlling the light-induced function of molecular systems. It was recently shown that infrared light excitation of intramolecular vibrations can radically change the efficiency of electron transfer, a fundamental chemical process. We now extend and generalize the understanding of this phenomenon by probing and perturbing vibronic coupling in several molecules in solution. In the experiments an ultrafast electronic-vibrational pulse sequence is applied to a range of donor-bridge-acceptor Pt(II) trans-acetylide assemblies, for which infrared excitation of selected bridge vibrations during ultraviolet-initiated charge separation alters the yields of light-induced product states. The experiments, augmented by quantum chemical calculations, reveal a complex combination of vibronic mechanisms responsible for the observed changes in electron transfer rates and pathways. The study raises new fundamental questions about the function of vibrational processes immediately following charge transfer photoexcitation, and highlights the molecular features necessary for external vibronic control of excited-state processes.

AB - Nuclear-electronic (vibronic) coupling is increasingly recognized as a mechanism of major importance in controlling the light-induced function of molecular systems. It was recently shown that infrared light excitation of intramolecular vibrations can radically change the efficiency of electron transfer, a fundamental chemical process. We now extend and generalize the understanding of this phenomenon by probing and perturbing vibronic coupling in several molecules in solution. In the experiments an ultrafast electronic-vibrational pulse sequence is applied to a range of donor-bridge-acceptor Pt(II) trans-acetylide assemblies, for which infrared excitation of selected bridge vibrations during ultraviolet-initiated charge separation alters the yields of light-induced product states. The experiments, augmented by quantum chemical calculations, reveal a complex combination of vibronic mechanisms responsible for the observed changes in electron transfer rates and pathways. The study raises new fundamental questions about the function of vibrational processes immediately following charge transfer photoexcitation, and highlights the molecular features necessary for external vibronic control of excited-state processes.

UR - http://www.scopus.com/inward/record.url?scp=84939814843&partnerID=8YFLogxK

U2 - 10.1038/nchem.2327

DO - 10.1038/nchem.2327

M3 - Article

VL - 7

SP - 689

EP - 695

JO - Nature Chemistry

JF - Nature Chemistry

SN - 1755-4330

IS - 9

ER -