The Geometry of the Excited Charge Transfer States: Flattening or Twisting?

Numerous molecules built of an electron acceptor and electron donor units linked together by single bond exhibit a peculiar behavior in their low-lying electronically excited states. N,N-diethylaminoacetophenone and 4-acetyl-4'-dimethylamino-biphenyl, having acetophenone as the acceptor and differentiated by the donors groups $N(CH_3)_2$ and dimethylaniline, respectively, were selected as the subject of study. To recognize the excited state relaxation paths the stationary and time-resolved spectroscopy in absorption and emission was applied. Experimental results indicate that after excitation in polar solvents N,N-diethylaminoacetophenone reduces to minimum the overlap between π-electron systems of the donor and acceptor groups relaxing to the twisted internal charge-transfer state; contrary to that, flattening of the 4-acetyl-4'-dimethylamino-biphenyl skeleton generates increase in the overlap of the π-electron systems.