Excited-state symmetry breaking in quadrupolar pull-push-pull molecules: dicyanovinyl vs. cyanophenyl acceptors.

ABSTRACT: A significant number of quadrupolar dyes behave as their dipolar analogues when photoexcited in polar environments. This is due to the occurrence of excited-state symmetry breaking (ES-SB), upon which the electronic excitation, initially distributed over the whole molecule, localises preferentially on one side. Here, we investigate the ES-SB properties of two A-D-A dyes, consisting of a pyrrolo-pyrrole donor (D) and either cyanophenyl or dicyanovinyl acceptors (A). For this, we use time-resolved vibrational spectroscopy, comparing IR absorption and femtosecond stimulated Raman spectroscopies. Although dicyanovinyl is a stronger electron-withdrawing group, ES-SB is not observed with the dicyanovinyl-based dye even in highly polar media, whereas it already takes place in weakly polar solvent

SUBMITTER: Verma P 

PROVIDER: S-EPMC10467566 | biostudies-literature | 2023 Aug

REPOSITORIES: biostudies-literature