Time-dependent density functional theory study on the electronic excited-state hydrogen bonding of the chromophore coumarin 153 in a room-temperature ionic liquid

In the present work, in order to investigate the electronic excited-state intermolecular hydrogen bonding between the chromophore coumarin 153 (C153) and the room-temperature ionic liquid N,N-dimethylethanolammonium formate (DAF), both the geometric structures and the infrared spectra of the hydrogen-bonded complex C153–DAF+ in the excited state were studied by a time-dependent density functional theory (TDDFT) method. We theoretically demonstrated that the intermolecular hydrogen bond C1 = O1···H1–O3 in the hydrogen-bonded C153–DAF+ complex is significantly strengthened in the S1 state by monitoring the spectral shifts of the C=O group and O–H group involved in the hydrogen bond C1 = O1···H1–O3. Moreover, the length of the hydrogen bond C1 = O1···H1–O3 between the oxygen atom and hydrogen atom decreased from 1.693 Å to 1.633 Å upon photoexcitation. This was also confirmed by the increase in the hydrogen-bond binding energy from 69.92 kJ mol−1 in the ground state to 90.17 kJ mol−1 in the excited state. Thus, the excited-state hydrogen-bond strengthening of the coumarin chromophore in an ionic liquid has been demonstrated theoretically for the first time.