高等学校化学学报 ›› 2003, Vol. 24 ›› Issue (10): 1869.

• 论文 • 上一篇    下一篇

2,3-二芳基马来酸酐环合反应机理的计算研究

王骐1, 刘跃1,2, 刘颖2   

  1. 1. 哈尔滨工业大学光电子技术研究所, 可调谐激光技术国家级重点实验室, 哈尔滨 150001;
    2. 哈尔滨师范大学化学系, 哈尔滨 150080
  • 收稿日期:2002-12-03 出版日期:2003-10-24 发布日期:2003-10-24
  • 通讯作者: 刘跃(1958年出生),男,博士,教授,主要从事计算物理和计算化学研究.E-mail:yuesd@up369.com E-mail:yuesd@up369.com
  • 基金资助:

    黑龙江省教育厅科学技术研究基金(批准号:10531081,10511033)资助

Computational Studies on Electrocyclic Reaction Mechanism of 2,3-Diaryl Maleic Anhydrides

WANG Qi1, LIU Yue1,2, LIU Ying2   

  1. 1. National Key Laboratory of Tunable Laser Technology, Institute of Opto-Electronics, Harbin Institute of Technology, Harbin 150001, China;
    2. Department of Chemistry, Harbin NormaLUniversity, Harbin 150080, China
  • Received:2002-12-03 Online:2003-10-24 Published:2003-10-24

摘要: 在B3LYP/6-311+G(d,p)//HF/3-21G水平上研究了2,3-二芳基马来酸酐环合反应机理.2,3-二芳基马来酸酐环合反应有两条反应途径:(1)反应过程中涉及的各种构型始终保持反式,即中心成环碳原子上的取代基团甲基或氢原子位于分子平面的异侧,这些构型具有C2对称性;(2)反应过程中涉及的各种构型始终保持顺式,即中心成环碳原子上的取代基团甲基或氢原子位于分子平面的同一侧面,这些构型可具有Cs对称性.二芳基乙烯类化合物环合反应的位垒计算结果与Woodward-Hoffman原理一致,计算结果支持在环合碳原子上引入甲基能改善反应的热不可逆反应性能的实验结果.电荷分析表明,在环合碳原子上引入甲基,能增加二芳基乙烯类化合物体系对氧的稳定性,与实验结果一致.2,3-二芳基马来酸酐化合物的闭环结构的LUMO和HOMO能隙小于开环结构的能隙,说明闭环结构的最大吸收波长大于开环结构的最大吸收波长,与实验结果一致.

关键词: 密度泛函方法, 二芳基马来酸酐, 光致变色

Abstract: Electrocyclic reaction mechanism of 2,3-diaryl maleic anhydrides was studied at B3LYP/6-311+G(d,p)//HF/3-21Glevel.There are two reaction paths for the mechanism.One keeps all the species in trans forms with a strict C2symmetry throughout the reaction path; and the other keeps all the species in cis forms with a strict Cs symmetry.The results are consistent with Woodward-Hoffman principle.The results also support the experimental result that the thermal irreversible property is improved when the hydrogen atoms on the central carbons involved in the bond forming process of the electrocyclic reaction are changed to methyl groups.There is less negative charge on central carbons involved in the electrocyclic reaction for 2,3-bis(2,4-dimethylthiophen-3-yl)maleic anhydride than for 2,3-bis(4-methylthiophen-3-yl)maleic anhydride, conforming the experimental result that the former compound is more stable to oxygen.The LUMO and HOMO energy gaps conform with experimental result that the maximum absorption wavelength for the closed-ring form of bis(methylthiophen-3-yl)maleic anhydride is longer than that of the open-ring form.

Key words: Density function calculation method, Diaryl maleic anhydrides, Photochromism

中图分类号: 

TrendMD: