新型异三聚体超分子的密度泛函计算及其晶体结构、热性能研究

化学学报 ›› 2004, Vol. 62 ›› Issue (14): 1265-1271. 下一篇

新型异三聚体超分子的密度泛函计算及其晶体结构、热性能研究

赵朴素^1,2, 卑凤利¹, 杨绪杰¹, 汪信¹, 陆路德², 建方方³, 汪庆祥³

1. 南京理工大学材料化学研究室, 南京, 210094;
2. 淮阴师范学院化学系, 淮安, 223001;
3. 青岛科技大学新材料与功能配合物实验室, 青岛, 266042

投稿日期:2004-01-05 修回日期:2004-03-31 发布日期:2014-02-17
通讯作者: 赵朴素,E-mail:zhaopusu@163.com;Tel:0532-4022948;Fax:0532-4022948 E-mail:zhaopusu@163.com
基金资助:
国家自然科学基金(No.50372028),江苏省高校自然科学研究指导性计划(No.03KJD150053)资助项目.

Density Functional Theory Study, Crystal Structure and Thermal Stability of a Novel Heterotrimer Supramolecule

ZHAO Pu-Su^1,2, BEI Feng-Li¹, YANG Xu-Jie¹, WANG Xin¹, LU Lu-De², JIAN Fang-Fang³, WANG Qing-Xiang³

1. Materials Chemistry Laboratory, Nanjing University of Science and Technology, Nanjing 210094;
2. Department of Chemistry, Huaiyin Teachers' College, Huai'an 223001;
2. New Materials & Function Coordination Chemistry Laboratory, Qingdao University of Science and Technology, Qingdao 266042

Received:2004-01-05 Revised:2004-03-31 Published:2014-02-17

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摘要/Abstract

运用密度泛函B3LYP方法,在6-31G^*水平上设计优化了丁二酮肟与苯甲酸通过四重氢键构筑的异三聚体超分子.此异三聚体的总能量比三个单体总能量之和低144.0816 kJ/mol,四重氢键的平均键能约为36.0204 kJ/mol,属中高强度;298.15 K时吉布斯自由能变化△G_T=-41.70 kJ/mol,显示形成三聚体的反应可自发进行.在此设想指导下,实验合成出相关异三聚体,并得到了晶体结构,与预测的结构极为相似.热性能分析显示,此三聚体不是三个单体的简单叠加,而是一个不同于其单体的全新化合物.理论计算数据与实验结果的一致性,证明了理论计算的预见性.

关键词: 氢键, 异三聚体, 超分子, 密度泛函, 晶体结构, 热稳定性

A novel quadruple hydrogen bonded heterotrimer supramolecule of benzoic acid and dimethylglyoxime has been designed and completely optimized using density functional theory (DFT)B3LYP/6-31G^* method.The calculated results show that the total energy of the heterotrimer is much lower than the sum of energies of three monomers, the average strength of the quadruple hydrogen bonds is about 36.0204 kJ/mol and the change of Gibbs free energy for the aggregation from monomer to the trimer ΔG_T=-41.70 kJ/mol at 298.15 K, which implies the spontaneous process of formation of the trimer.Under the guidance of the DFT calculations, the heterotrimer was synthesized successfully and its crystal structure was obtained.The crystal structure resembles closely the predicted structure.Thermal stability analysis indicates that the heterotrimer is a new material and it is not the ordinary superposition of the original monomers.The calculations are in good agreement with the experimental results.It demonstrates the reliability of theoretical calculation as well as the feasibility of construction of supramolecule in laboratory.

Key words: hydrogen bond, heterotrimer, supramolecule, density functional theory, crystal structure, thermal stability

引用此文

赵朴素, 卑凤利, 杨绪杰, 汪信, 陆路德, 建方方, 汪庆祥. 新型异三聚体超分子的密度泛函计算及其晶体结构、热性能研究[J]. 化学学报, 2004, 62(14): 1265-1271.

ZHAO Pu-Su, BEI Feng-Li, YANG Xu-Jie, WANG Xin, LU Lu-De, JIAN Fang-Fang, WANG Qing-Xiang. Density Functional Theory Study, Crystal Structure and Thermal Stability of a Novel Heterotrimer Supramolecule[J]. Acta Chimica Sinica, 2004, 62(14): 1265-1271.

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