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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

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金晶, 董绍楠, 侯晓霞, 张婧, 毕树平. 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[J]. 环境化学, 2016, 35(6): 1125-1133. doi: 10.7524/j.issn.0254-6108.2016.06.2015100601
引用本文: 金晶, 董绍楠, 侯晓霞, 张婧, 毕树平. 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[J]. 环境化学, 2016, 35(6): 1125-1133. doi: 10.7524/j.issn.0254-6108.2016.06.2015100601
shu
JIN Jing, DONG Shaonan, HOU Xiaoxia, ZHANG Jing, BI Shuping. Density functional theory studies on the static structures and water exchange reaction of aluminum-8-hydroxyquinoline complexes[J]. Environmental Chemistry, 2016, 35(6): 1125-1133. doi: 10.7524/j.issn.0254-6108.2016.06.2015100601
Citation: JIN Jing, DONG Shaonan, HOU Xiaoxia, ZHANG Jing, BI Shuping. Density functional theory studies on the static structures and water exchange reaction of aluminum-8-hydroxyquinoline complexes[J]. Environmental Chemistry, 2016, 35(6): 1125-1133. doi: 10.7524/j.issn.0254-6108.2016.06.2015100601
shu

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

  • 1.

    南京大学化学化工学院, 南京, 210023

  • 基金项目:

    国家自然科学基金(21177054)资助.

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

  • 1.

    School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023, China

  • Fund Project: Supported by the National Natural Science Foundation of China(21177054).

  • 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B3LYP 6-311+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.
    Abstract: 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 B3LYP 6-311+G(d, p) level based on gas phase-polarizable continuum model (GP-PCM); (2) The 27Al 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.
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  • 收稿日期:  2015-10-06
  • 刊出日期:  2016-06-15
金晶, 董绍楠, 侯晓霞, 张婧, 毕树平. 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[J]. 环境化学, 2016, 35(6): 1125-1133. doi: 10.7524/j.issn.0254-6108.2016.06.2015100601
引用本文: 金晶, 董绍楠, 侯晓霞, 张婧, 毕树平. 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[J]. 环境化学, 2016, 35(6): 1125-1133. doi: 10.7524/j.issn.0254-6108.2016.06.2015100601
shu
JIN Jing, DONG Shaonan, HOU Xiaoxia, ZHANG Jing, BI Shuping. Density functional theory studies on the static structures and water exchange reaction of aluminum-8-hydroxyquinoline complexes[J]. Environmental Chemistry, 2016, 35(6): 1125-1133. doi: 10.7524/j.issn.0254-6108.2016.06.2015100601
Citation: JIN Jing, DONG Shaonan, HOU Xiaoxia, ZHANG Jing, BI Shuping. Density functional theory studies on the static structures and water exchange reaction of aluminum-8-hydroxyquinoline complexes[J]. Environmental Chemistry, 2016, 35(6): 1125-1133. doi: 10.7524/j.issn.0254-6108.2016.06.2015100601
shu

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

  • 1. 南京大学化学化工学院, 南京, 210023
  • 收稿日期:  2015-10-06
基金项目:

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B3LYP 6-311+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.

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