The role played by ethanol in achieving the successive versus simultaneous mechanism of excited-state double proton transfer in dipyrido[2,3-a:3′,2′-i]carbazole

Abstract

The excited-state double proton transfer (ESDPT) process of dipyrido[2,3-a:3',2'-i]carbazole (DPC) in ethanol (EtOH) solvent is investigated using density functional theory (DFT) and time-dependent density functional theory (TDDFT). The computational results provide convincing evidence that proton transfer did not occur spontaneously for the DPC monomer due to the lack of hydrogen bonds. Interestingly, after adding EtOH to DPC, two intermolecular hydrogen bonds were formed in the ground-state, and the intermolecular hydrogen bonds were strengthened in the excited-state, as confirmed by comparing the changes in the primary bond parameters. In addition, the charge transfer was observed in the DPC-EtOH complex compared with the DPC monomer. In particular, a reliable ESDPT process occurs within the system upon photoexcitation, which was monitored by the formation and disappearance of characteristic peaks in the IR spectrum. All results adequately proved that the participation of EtOH exerts a remarkable effect on the ESDPT process. Overall, our work not only comprehensively elaborated the simultaneous mechanism of ESDPT but can also pave the way towards the design and synthesis of novel molecules.