Solute–Solvent Interactions and Excited-State Symmetry Breaking: Beyond the Dipole–Dipole and the Hydrogen-Bond Interactions

Dereka, Bogdan; Vauthey, Eric

doi:10.1021/acs.jpclett.7b01821

Scientific article

English

Solute–Solvent Interactions and Excited-State Symmetry Breaking: Beyond the Dipole–Dipole and the Hydrogen-Bond Interactions

Contributors

Dereka, Bogdan; Vauthey, Eric

Published in

Journal of Physical Chemistry Letters, vol. 8, no. 16, p. 3927-3932

Publication date

2017

Abstract

Symmetry breaking of the excited state of a linear quadrupolar acceptor-donor-acceptor molecule was investigated using time-resolved infrared spectroscopy in 55 solvents allowing the influence of several solute–solvent interactions to be examined separately. No symmetry breaking was found in nonpolar solvents irrespective of their refractive index, indicating that differences in dispersion interactions between the two arms of the molecule do not suffice to induce an asymmetric distribution of the excitation. However, symmetry breaking was observed in nondipolar but quadrupolar solvents like benzene to an extent that can be as large as that found in medium dipolar solvents like THF. Whereas larger symmetry breaking occurs in the most dipolar solvents, the strongest are observed in protic solvents due to hydrogen bonding. Strong evidence of the formation of halogen bonds in the excited state is also presented, confirming the idea of symmetry-breaking-induced asymmetrical photochemistry.

UNIGE affiliation entities

Faculté des sciences / Section de chimie et biochimie / Département de chimie physique

UNIGE research groups

Groupe Vauthey

Citation (ISO format)

DEREKA, Bogdan, VAUTHEY, Eric. Solute–Solvent Interactions and Excited-State Symmetry Breaking: Beyond the Dipole–Dipole and the Hydrogen-Bond Interactions. In: Journal of Physical Chemistry Letters, 2017, vol. 8, n° 16, p. 3927–3932. doi: 10.1021/acs.jpclett.7b01821

Article (Published version)

Identifiers

PID : unige:96310
DOI : 10.1021/acs.jpclett.7b01821

Journal ISSN

1948-7185

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25/08/2017 11:05:00

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15/03/2023 01:57:17

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15/03/2023 01:57:17

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31/10/2024 07:37:51

Solute–Solvent Interactions and Excited-State Symmetry Breaking: Beyond the Dipole–Dipole and the Hydrogen-Bond Interactions

Contributors

Published in

Publication date

Abstract

UNIGE affiliation entities

UNIGE research groups

Citation (ISO format)

Main files (1)

Identifiers

Journal ISSN

Technical informations

Creation

First validation

Update

Status update

Last indexation