The excited-state symmetry-breaking charge transfer (SBCT) dynamics in quadrupolar or octupolar molecules without clear infrared markers is usually hard to be tracked directly. In this work, on the basis of the evolut...The excited-state symmetry-breaking charge transfer (SBCT) dynamics in quadrupolar or octupolar molecules without clear infrared markers is usually hard to be tracked directly. In this work, on the basis of the evolution of instantaneous emission dipole moment obtained by femtosecond transient fluorescence spectroscopy, we presented a real-time characterization of the solvent-induced SBCT dynamics in an octupolar triphenylamine derivative. While the emission dipole moment of the octupolar trimer in weakly polar toluene changes little during the excited-state relaxation, it exhibits a fast reduction in a few picoseconds in strongly polar tetrahydrofuran. In comparison with the uorescence dynamics of dipolar monomer, we deduced that the emitting state of the octupolar trimer in strongly polar solvent, which undergoes solvent-induced structural uctuation, changes from exciton-coupled octupolar to excitation localized dipolar symmetry. In weakly polar solvent, the octupolar symmetry of the trimer is largely preserved during the solvation stabilization.展开更多
基金supported by the National Natural Science Foundation of China (No.21673252, No.21333012, No.21672211, and No.21773252, No.21827803)the Strategic Priority Research Program of the Chinese Academy of Sciences (No.XDB12020200)
文摘The excited-state symmetry-breaking charge transfer (SBCT) dynamics in quadrupolar or octupolar molecules without clear infrared markers is usually hard to be tracked directly. In this work, on the basis of the evolution of instantaneous emission dipole moment obtained by femtosecond transient fluorescence spectroscopy, we presented a real-time characterization of the solvent-induced SBCT dynamics in an octupolar triphenylamine derivative. While the emission dipole moment of the octupolar trimer in weakly polar toluene changes little during the excited-state relaxation, it exhibits a fast reduction in a few picoseconds in strongly polar tetrahydrofuran. In comparison with the uorescence dynamics of dipolar monomer, we deduced that the emitting state of the octupolar trimer in strongly polar solvent, which undergoes solvent-induced structural uctuation, changes from exciton-coupled octupolar to excitation localized dipolar symmetry. In weakly polar solvent, the octupolar symmetry of the trimer is largely preserved during the solvation stabilization.
