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Atomic-scale observation of solvent reorganization influencing photoinduced structural dynamics in a copper complex photosensitizer

Lookup NU author(s): Professor Thomas Penfold

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This work is licensed under a Creative Commons Attribution 4.0 International License (CC BY 4.0).


Abstract

Photochemical reactions in solution are governed by a complex interplay between transient intramolecular electronic and nuclear structural changes and accompanying solvent rearrangements. State-of-the-art time-resolved X-ray solution scattering has emerged in the last decade as a powerful technique to observe solute and solvent motions in real time. However, disentangling solute and solvent dynamics and how they mutually influence each other remains challenging. Here, we simultaneously measure femtosecond X-ray emission and scattering to track both the intramolecular and solvation structural dynamics following photoexcitation of a solvated copper photosensitizer. Quantitative analysis assisted by molecular dynamics simulations reveals a two-step ligand flattening strongly coupled to the solvent reorganization, which conventional optical methods could not discern. First, a ballistic flattening triggers coherent motions of surrounding acetonitrile molecules. In turn, the approach of acetonitrile molecules to the copper atom mediates the decay of intramolecular coherent vibrations and induces a further ligand flattening. These direct structural insights reveal that photoinduced solute and solvent motions can be intimately intertwined, explaining how the key initial steps of light harvesting are affected by the solvent on the atomic time and length scale. Ultimately, this work takes a step forward in understanding the microscopic mechanisms of the bidirectional influence between transient solvent reorganization and photoinduced solute structural dynamics.


Publication metadata

Author(s): Katayama T, Choi T-K, Khakhulin D, Dohn AO, Milne CJ, Vankó G, Németh Z, Lima F, Szlachetko J, Sato T, Nozawa S, Adachi S, Yabashi M, Penfold TJ, Gawelda W, Levi G

Publication type: Article

Publication status: Published

Journal: Chemical Science

Year: 2023

Volume: 14

Issue: 10

Pages: 2572-2584

Online publication date: 01/02/2023

Acceptance date: 30/01/2023

Date deposited: 01/02/2023

ISSN (print): 2041-6520

ISSN (electronic): 2041-6539

Publisher: Royal Society of Chemistry

URL: https://doi.org/10.1039/D2SC06600A

DOI: 10.1039/D2SC06600A


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Funding

Funder referenceFunder name
124460
2018-1.2.1-NKP-2018-00012
196070
196279-051
2016/22/E/ST4/00543
217734
BEAGAL18/00092
CEX2020-001039-S
EPSRC
European Regional Development Fund
European XFEL and SACLA Research Support Program
EP/S022058/1EPSRC
Icelandic Research Fund
JP21H04974
Government of Hungary
JP19H05782
JP21K18944
Leverhulme Trust
MINECO
PID2019-108678GB-I00
RPG-2020-268
RPG-2016-103Leverhulme Trust, The
VEKOP-2.3.2-16-2017-00015
SI2/PBG/2020-00003

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