Unveiling the effect of solvent polarity on the excited state intramolecular proton transfer mechanism of new 3-hydroxy-4-pyridylisoquinoline compound.

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The new 3-hydroxy-4-pyridylisoquinoline compound is attractive and promising lead structure in drug discovery. The pronounced sensitivity of its emission property toward solvent polarity effect was presented in experiment (J. Org. Chem, 2019, 84, 3011). Nevertheless, the experiment was lack of solvent polarity effect on the excited state intramolecular proton transfer (ESIPT) mechanism in detail. In this study, the ESIPT process of this molecule in different polarity solvents were comprehensively expounded by density functional theory (DFT) and time-dependent DFT (TDDFT) methods. In order to ensure the accuracy of the experiment and roundly explore in theoretical level, two ESIPT pathways (1 and 2) based on the N1 and N2 forms of studied molecule were proposed, among which the ESIPT pathway 1 was derived from experiment. The calculated electronic spectrum of both N1 and N2 forms were rather comparable with the experiment. The calculated intramolecular hydrogen bond (IHB) parameters and infrared (IR) vibration spectra determined the enhancement of IHBs at the S1 state under different solvents for both N1 and N2 forms. The frontier molecular orbitals (FMOs) analysis proved that the intramolecular charge transfer (ICT) taken place during photoexcitation. The potential energy curves (PECs) at the S0 and S1 states were constructed to illustrate the solvent polarity effect on ESIPT mechanism. According to potential energy barriers (PEBs) on the PECs at S1 state, it is concluded that the ESIPT pathway 1 was forbidden with exceedingly high PEBs (24.585-25.322 kcal/mol), while the ESIPT pathway 2 was feasible with enough low PEBs (0.100-0.510 kcal/mol), which suggested the inconsequence of the experiment. Based on the PEBs of ESIPT pathway 2 in different solvent, the effect of solvent polarity on ESIPT mechanism was depicted. The results are as follows: the S1 state IHB intensity was enhanced with increasing solvent polarity; the extent of ICT was decreased with the increment of solvent polarity; the S1 state PEB was decreased as the solvent polarity increased. Indeed in short, the ESIPT reaction became more and more likely as the solvent polarity enhanced. We believe that this investigation will be useful to the utilization and development of property for such photochemical substances.