Twisted Intramolecular Charge Transfer State of a "Push-Pull" Emitter.

The excited state Raman spectra of 4-dicyanomethylene-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran (DCM) in the locally-excited (LE) and the intramolecular charge transfer (ICT) states have been separately measured by time-resolved stimulated Raman spectroscopy. In a polar dimethylsulfoxide solution, the ultrafast ICT of DCM with a time constant of 1.0 ps was observed in addition to the vibrational relaxation in the ICT state of 4-7 ps. On the other hand, the energy of the ICT state of DCM becomes higher than that of the LE state in a less polar chloroform solution, where the initially-photoexcited ICT state with the LE state shows the ultrafast internal conversion to the LE state with a time constant of 300 fs. The excited-state Raman spectra of the LE and ICT state of DCM showed several major vibrational modes of DCM in the LE and ICT conformer states coexisting in the excited state. Comparing to the time-dependent density functional theory simulations and the experimental results of similar push-pull type molecules, a twisted geometry of the dimethylamino group is suggested for the structure of DCM in the S1/ICT state.