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

Autor:	Katayama T; Japan Synchrotron Radiation Research Institute Kouto 1-1-1, Sayo Hyogo 679-5198 Japan.; RIKEN SPring-8 Center 1-1-1 Kouto, Sayo Hyogo 679-5148 Japan tetsuo@spring8.or.jp., Choi TK; XFEL Division, Pohang Accelerator Laboratory Jigok-ro 127-80 Pohang 37673 Republic of Korea., Khakhulin D; European XFEL Holzkoppel 4, Schenefeld 22869 Germany., Dohn AO; Science Institute, University of Iceland 107 Reykjavík Iceland giale@hi.is.; DTU Physics, Technical University of Denmark Kongens Lyngby Denmark., Milne CJ; European XFEL Holzkoppel 4, Schenefeld 22869 Germany., Vankó G; Wigner Research Centre for Physics, Hungarian Academy of Sciences H-1525 Budapest Hungary., Németh Z; Wigner Research Centre for Physics, Hungarian Academy of Sciences H-1525 Budapest Hungary., Lima FA; European XFEL Holzkoppel 4, Schenefeld 22869 Germany., Szlachetko J; SOLARIS National Synchrotron Radiation Centre, Jagiellonian University PL-30392 Kraków Poland., Sato T; European XFEL Holzkoppel 4, Schenefeld 22869 Germany., Nozawa S; Institute of Materials Structure Science, High Energy Accelerator Research Organization (KEK) 1-1 Oho Tsukuba Ibaraki 305-0801 Japan.; Department of Materials Structure Science, School of High Energy Accelerator Science, The Graduate University for Advanced Studies 1-1 Oho Tsukuba Ibaraki 305-0801 Japan., Adachi SI; Institute of Materials Structure Science, High Energy Accelerator Research Organization (KEK) 1-1 Oho Tsukuba Ibaraki 305-0801 Japan.; Department of Materials Structure Science, School of High Energy Accelerator Science, The Graduate University for Advanced Studies 1-1 Oho Tsukuba Ibaraki 305-0801 Japan., Yabashi M; RIKEN SPring-8 Center 1-1-1 Kouto, Sayo Hyogo 679-5148 Japan tetsuo@spring8.or.jp., Penfold TJ; Chemistry-School of Natural and Environmental Sciences, Newcastle University Newcastle Upon-Tyne NE1 7RU UK., Gawelda W; Departamento de Química, Universidad Autónoma de Madrid, Campus Cantoblanco 28047 Madrid Spain.; IMDEA-Nanociencia, Campus Cantoblanco C/Faraday 9 28049 Madrid Spain.; Faculty of Physics, Adam Mickiewicz University 61-614 Poznań Poland., Levi G; Science Institute, University of Iceland 107 Reykjavík Iceland giale@hi.is.
Jazyk:	angličtina
Zdroj:	Chemical science [Chem Sci] 2023 Feb 01; Vol. 14 (10), pp. 2572-2584. Date of Electronic Publication: 2023 Feb 01 (Print Publication: 2023).
DOI:	10.1039/d2sc06600a
Abstrakt:	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. Competing Interests: The authors declare no competing interests. (This journal is © The Royal Society of Chemistry.)
Databáze:	MEDLINE
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