Excited-state symmetry breaking in solvent mixtures

Article Article scientifique Article Excited-state symmetry breaking in solvent mixtures eng 2024-02-26 2024-02-26 author Balanikas Vangelis 0000-0002-2811-1525 Department of Physical Chemistry, University of Geneva, CH-1211 Geneva, Switzerland 975535 Département de chimie physique (CHIFI) author Reymond-Joubin Maric Department of Physical Chemistry, University of Geneva, CH-1211 Geneva, Switzerland 836986 author Vauthey Eric 0000-0002-9580-9683 Department of Physical Chemistry, University of Geneva, CH-1211 Geneva, Switzerland 133895 Département de chimie physique (CHIFI) 2447-2452 10.1021/acs.jpclett.4c00213 38407054 1948-7185 https://pubs.acs.org/doi/10.1021/acs.jpclett.4c00213 A large number of multipolar dyes undergo excited-state symmetry breaking (ESSB) in polar media. During this process, electronic excitation, initially distributed evenly over the molecule, localizes, at least partially, on one donor–acceptor branch. To resolve its initial stage, ESSB is investigated with a donor–acceptor–donor dye in binary mixtures of nonpolar and polar solvents using time-resolved infrared absorption spectroscopy. The presence of a few polar molecules around the dye is sufficient to initiate ESSB. Although the extent of asymmetry in a mixture is close to that in a pure solvent of similar polarity, the dynamics are slower and involve translational diffusion. However, preferential solvation in the mixtures leads to a larger local polarity. Furthermore, inhomogeneous broadening of the S1 ← S0 absorption band of the dye is observed in the mixtures, allowing for a photoselection of solutes with different local environments and ESSB dynamics. Dewey 540 Swiss National Science Foundation Applications de la spectroscopie ultrarapide à l'étude de processus photoinduits en phase condensée 184607 CH Projects 38 Département de chimie physique 142 false 686 Groupe Vauthey https://doi.org/10/mgtr The journal of physical chemistry letters 15 9 208f5f18-fd5d-48ec-9802-09257c8fb5bb Article (Accepted version) Public Main_text.pdf 1009255 application/pdf Restricted 2025-02-26 caa48dd0f898d68178cdeca3d88a7e0c28e69d7aef7dfd90315987c0929d65aa 94843e90-db5c-40bd-9ee9-899b124352f5 Article (Published version) Restricted BalanikasJPCL24.pdf 1633159 application/pdf c632d306e5ecaa0b76e0f57d1a6213a409b483714f0b6260ebbe0886d10f5fd0 Vignette Public jz4c00213_0005.webp 186623 image/png openAccess Faculté des sciences / Section de chimie et biochimie / Département de chimie physique

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Excited-state symmetry breaking in solvent mixtures	The journal of physical chemistry letters			2024	247	52

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