Qian Bao-Chen, Zhu Xiao-Qing, Shen Guang-Bin
College of Medical Engineering, Jining Medical University, Jining 272000, China.
Department of Chemistry, Nankai University, Tianjin 300071, China.
Molecules. 2025 Feb 25;30(5):1053. doi: 10.3390/molecules30051053.
Thermodynamic cards of three classic NADH models (XH), namely 1-benzyl-1,4-dihydronicotinamide (BNAH), Hantzsch ester (HEH), and 10-methyl-9,10-dihydroacridine (AcrH), as well as their photoexcited states (XH*: BNAH*, HEH*, AcrH*) releasing hydrides in nine elementary steps in acetonitrile are established. According to these thermodynamic cards, the thermodynamic reducing abilities of XH* are remarkably enhanced upon photoexcitation, rendering them thermodynamically highly potent electron, hydrogen atom, and hydride donors. The application of these thermodynamic cards to imine reduction is demonstrated in detail, revealing that photoexcitation enables XH* to act as better hydride donors, transforming the hydride transfer process from thermodynamically unfeasible to feasible. Most intriguingly, AcrH* is identified as the most thermodynamically favorable electron, hydride, and hydrogen atom donor among the three classic NADH models and their photoexcited states. The exceptional thermodynamic properties of XH* in hydride release inspire further investigation into the excited wavelengths, excited potentials, and excited state stabilities of more organic hydrides, as well as the discovery of novel and highly effective photoexcited organic hydride reductants.
建立了三种经典NADH模型（XH），即1-苄基-1,4-二氢烟酰胺（BNAH）、汉茨酯（HEH）和10-甲基-9,10-二氢吖啶（AcrH）及其光激发态（XH*：BNAH*、HEH*、AcrH*）在乙腈中九个基本步骤释放氢化物的热力学卡片。根据这些热力学卡片，XH的光激发使其热力学还原能力显著增强，使其成为热力学上高效的电子、氢原子和氢化物供体。详细展示了这些热力学卡片在亚胺还原中的应用，表明光激发使XH能够作为更好的氢化物供体，将氢化物转移过程从热力学不可行转变为可行。最有趣的是，在三种经典NADH模型及其光激发态中，AcrH被确定为热力学上最有利的电子、氢化物和氢原子供体。XH在氢化物释放方面的特殊热力学性质激发了对更多有机氢化物的激发波长、激发电位和激发态稳定性的进一步研究，以及新型高效光激发有机氢化物还原剂的发现。
