物理化学学报 >> 1996, Vol. 12 >> Issue (09): 780-785.doi: 10.3866/PKU.WHXB19960903

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二苯基-2-吡唑啉等分子内电子转移的研究

郭建新,张启元   

  1. 中国科学院化学研究所，分子动态与稳态结构国家重点实验室，北京 100080
  • 收稿日期:1996-02-22 修回日期:1996-04-20 发布日期:1996-09-15
  • 通讯作者:

Study of the Intramolecular Electron Transfer of Diphenyl-2-pyrazoline Compounds

Guo Jian-Xin,Zhang qi-Yuan   

  1. Institute of Chemistry,Academia Sinica,State Key Lab. for Strucutral Chemistry of Unstable and Stable Species,Beijing 100080
  • Received:1996-02-22 Revised:1996-04-20 Published:1996-09-15
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摘要：

对2-吡唑啉、二苯基-2-吡唑啉及其硝基取代衍生物的基态和第一单重激发态的分子构型及电子结构进行了计算．结果表明，基态时由于N1原子上孤对电子的存在使吡唑啉母体环上诸原子不在同一个平面上，1位和3位取代苯环与母体环非共平面；激发态时，1，o-DPP的1位苯环和3，o-DPP的3位苯环分别与母体环互相垂直．其余分子在激发态时取代苯环与母体环均接近于共平面.电子受激发时，从N1原子转移到苯环上．对于1，o-DPP和3，o-DPP，弛豫后电子不发生再转移．对于其它体系，弛豫后电子再转移到N2－C3之间．

关键词: 2-吡唑啉类化合物, 电子转移, 分子构象, 最低单重激发态

Abstract:

The molecular geometry and the electronic structure of 2-pyrazoline(PZL),1,3-biphenyl-2-pyrazoline (DPP) and their nitro derivatives are calculated. The results show that atoms in PZL ring in ground state are not located in a common plane because of the existence of the lone electron-pair at atom N1, and the benzene rings at 1-position and 3-position deviate off the plane of PZL ring. For the excited states of 1,o-DPP and 3,o-DPP, the corresponding benzene rings are perpendicular to the PZL ring, and the electrons are transfered from N1 to the corresponding benzene rings. For the excited states of other cases, the benzene rings are nearly in the same plane as that of PZL ring, and the electron are transfered from N1 to the position between N2-C3.

Key words: 2-pyrazoline compound;Electron transfer, Molecular structure, The first excited singlet state