分子内氢键对3,2-羟基吡啶酮衍生物与铀酰螯合影响的理论探究  

Theoretical Exploration of Effect of Intramolecular Hydrogen Bonds on Chelation of 3,2-hydroxypyridinone Derivatives with Uranyl

作　　者：璐瑶 聂长明[1] LU Yao;NIE Changming(School of Chemistry and Chemical Engineering,University of South China,Hengyang,Hunan 421001,China)

机构地区：[1]南华大学化学化工学院,湖南衡阳421001

出　　处：《南华大学学报（自然科学版）》2022年第3期77-82,共6页Journal of University of South China：Science and Technology

基　　金：国家自然科学基金项目(11475079);湖南省自然科学基金项目(2020JJ6049)。

摘　　要：为了探究锕系螯合剂分子内氢键对其配位原子与铀酰成键的影响,通过相对论密度泛函理论计算和波函数分析,研究了两种结构相似但有不同类型分子内氢键的铀酰配合物UO_(2)-Si-5LIO-1-Cm-3,2-HOPO和UO_(2)-Si-5LIO-(Me-3,2-HOPO),分析了分子内氢键对供体表面静电势的影响和对供体与铀酰成键的影响,通过态密度分析揭示了配合物的电子结构。结果表明,螯合剂供体形成的分子内强氢键降低了螯合剂与铀酰的离解能和稳定性,而UO_(2)-Si-5LIO-1-Cm-3,2-HOPO分子内氢键比UO_(2)-Si-5LIO-(Me-3,2-HOPO)弱,具有更高的稳定性。In order to understand the effect of intramolecular hydrogen bond on the bonding of donors to uranyl,two uranyl sequestering agents N,N′-(oxybis(ethane-2,1-diyl))bis(1-(3-hydroxy-2-oxopyridin-1(2H)-yl)silanecarboxamide)(Named as Si-5LIO-1-Cm-3,2-HOPO)and N,N′-(oxybis(ethane-2,1-diyl))bis(1-(3-hydroxy-1-methyl-2-oxo-1,2-dihydropyridin-4-yl)silanecarboxamide)(Named as Si-5LIO-(Me-3,2-HOPO))with similar structures but different types of intramolecular hydrogen bonds were studied by rela-tivistic density functional theory calculations and wave function analysis.The effect of in-tramolecular hydrogen bonding on the electrostatic potential of the donor surface and on the bonding of the donor to the uranyl were analyzed.What is more,the electronic structures of the complexes were also revealed by density of states analysis.The results showed that the strong intramolecular hydrogen bonds of the donor reduced the dissociation energy and stability of bond between chelator and uranyl.The intramolecular hydrogen bond of UO_(2)-5LIO-1-Cm-3,2-HOPO was weaker than that of UO_(2)-Si-5LIO-(Me-3,2-HOPO)and UO_(2)-5LIO-1-Cm-3,2-HOPO had higher stability.

关 键 词：铀酰 锕系促排剂 氢键 羟基吡啶酮 密度泛函理论 

分 类 号：O641.12[理学—物理化学]