铝-8-羟基喹啉配合物静态结构和动态水交换的密度泛函理论研究  

Density functional theory studies on the static structures and water exchange reaction of aluminum-8-hydroxyquinoline complexes

作　　者：金晶[1] 董绍楠 侯晓霞[1] 张婧[1] 毕树平[1] 

机构地区：[1]南京大学化学化工学院,南京210023

出　　处：《环境化学》2016年第6期1125-1133,共9页Environmental Chemistry

基　　金：国家自然科学基金(21177054)资助~~

摘　　要：采用密度泛函理论(DFT)量子化学计算方法对铝-8-羟基喹啉配合物(Al-8-Hq)的静态结构以及水交换反应进行了研究,系统地开展了以下工作:(1)采用GP-PCM(气相模型并考虑本体溶剂效应)在B3LYP6-311+G(d,p)水平优化了Al-8-Hq溶液中可能存在的8种构型,获得了相应的静态结构参数、NPA电荷和能量;(2)采用GIAO方法在HF 6-311+G(d,p)水平下计算了1∶3配合物的27Al NMR化学位移,结果表明采用HF的GP-PCM模型化学位移计算值与实验值一致;(3)通过模拟1∶1/1∶2配合物8个不同位点的动态水交换反应,探讨了水交换反应机制并预测了水交换反应速率.本研究有助于从原子层面加深对Al-8-Hq配合物形态结构以及水交换反应动力学过程的理解和认识.The static structural characteristics and the water exchange reaction for the complexes of aluminum with 8-hydroxyquinoline（ Al-8-Hq） were performed using density functional theory（ DFT） quantum chemistry calculation method. Systematic and comprehensive studies were conducted in this work：（ 1） Eight possible configurations for the Al-8-Hq complexes were optimized to obtain their structural parameters,NPA charges and energies at B3 LYP 6-311 ＋ G（ d,p） level based on gas phase-polarizable continuum model（ GP-PCM）;（ 2） The27 Al NMR chemical shifts were calculated using the GIAO method at the HF / 6-311＋G（ d,p） level for Alq3（ 1∶3 complexes）.The theoretical calculations agreed with the experimental data from literatures;（ 3） By simulating dynamic water exchange reactions of 1∶ 1 and 1∶ 2 Al-8-Hq complexes for eight different sites,the water exchange mechanism was discussed and the logarithm of the water-exchange rate constants（ lgkex） of Al-8-Hq complexes were predicted. This work can promote our understanding for the speciation of Al-8-Hq complexes as well as their micro-dynamic water exchange reaction mechanisms.

关 键 词：铝 8-羟基喹啉(8-Hq) 静态结构 水交换反应 密度泛函理论(DFT) 

分 类 号：O641.4[理学—物理化学]