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

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.