The dynamics of the excited states of 3- and 4-aminofluoren-9-ones (3AF and 4AF, respectively) are investigated in different kinds of solvents by using a subpicosecond time-resolved absorption spectroscopic technique. They undergo hydrogen-bonding interaction with protic solvents in both the ground and excited states. However, this interaction is more significant in the lowest excited singlet (S(1)) state because of its substantial intramolecular charge-transfer character. Significant differences in the spectroscopic characteristics and temporal dynamics of the S(1) states of 3AF and 4AF in aprotic and protic solvents reveal that the intermolecular hydrogen-bonding interaction between the S(1) state and protic solvents plays an important role in its relaxation process. Perfect linear correlation between the relaxation times of the S(1) state and the longitudinal relaxation times (tau(L)) of alcoholic solvents confirms the prediction regarding the solvation process via hydrogen-bond reorganization. In the case of weakly interacting systems, the relaxation process can be well described by a dipolar solvation-like process involving rotation of the OH groups of the alcoholic solvents, whereas in solvents having a strong hydrogen-bond-donating ability, for example, methanol and trifluoroethanol, it involves the conversion of the non-hydrogen-bonded form to the hydrogen-bonded complex of the S(1) state. Efficient radiationless deactivation of the S(1) state of the aminofluorenones by protic solvents is successfully explained by the energy-gap law, by using the energy of the fully solvated S(1) state determined from the time-resolved spectroscopic data.
The dynamics of the excited states of 1-aminofluoren-9-one (1AF) and 1-(N,N-dimethylamino)-fluoren-9-one (1DMAF) are investigated by using steady-state absorption and fluorescence as well as subpicosecond time-resolved absorption spectroscopic techniques. Following photoexcitation of 1AF, which exists in the intramolecular hydrogen-bonded form in aprotic solvents, the excited-state intramolecular proton-transfer reaction is the only relaxation process observed in the excited singlet (S(1)) state. However, in protic solvents, the intramolecular hydrogen bond is disrupted in the excited state and an intermolecular hydrogen bond is formed with the solvent leading to reorganization of the hydrogen-bond network structure of the solvent. The latter takes place in the timescale of the process of solvation dynamics. In the case of 1DMAF, the main relaxation pathway for the locally excited singlet, S(1)(LE), or S(1)(ICT) state is the configurational relaxation, via nearly barrierless twisting of the dimethylamino group to form the twisted intramolecular charge-transfer, S(1)(TICT), state. A crossing between the excited-state and ground-state potential energy curves is responsible for the fast, radiationless deactivation and nonemissive character of the S(1)(TICT) state in polar solvents, both aprotic and protic. However, in viscous but strong hydrogen-bond-donating solvents, such as ethylene glycol and glycerol, crossing between the potential energy surfaces for the ground electronic state and the hydrogen-bonded complex formed between the S(1)(TICT) state and the solvent is possibly avoided and the hydrogen-bonded complex is weakly emissive.
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