Ground and excited state dipole moments of planar vs. twisted p-N,N-(dimethylamino)benzonitrile systems: maximum charge transfer for minimum overlap

Electric field induced change in the absorption spectrum (electrochromism) has been employed to obtain the ground and excited state dipole moments of planar and sterically hindered (twisted) p-N,N-(dimethylamino)benzonitriles in dioxane solution. These studies support the twisted intramolecular charge transfer (TICT) hypothesis and provide additional insight to the TICT concept. The charge transfer nature of the excited state has been found to directly depend on the torsional angle of the N,N-dimethylamino group with respect to the benzonitrile moiety. It is suggested that solvent coupling is essential to initiate twisting by affecting the intramolecular degrees of freedom and the existence of the highly dipolar excited state is a result of such twisting of the donor-acceptor bond. Theoretical calculations have been performed to explain the observed changes in dipole moment values.