物理化学学报 >> 1987, Vol. 3 >> Issue (03): 298-305.doi: 10.3866/PKU.WHXB19870314

研究论文 上一篇    下一篇

同系列电子给体与同系列电子受体CT络合作用的研究 Ⅱ. 几何匹配效应

蒋明谦; 胡惟孝*   

  1. 中国科学院化学研究所, 北京
  • 收稿日期:1985-12-25 修回日期:1986-08-08 发布日期:1987-06-15
  • 通讯作者: 胡惟孝

INVESTIGATION OF CT-COMPLEXATION AMONG HOMOLOGOUS ELECTRON DONORS AND HOMLOGOUS ACCEPTORS Ⅱ. GEOMETRICAL MATCH EFFECT

Chiang Mingchien; Hu Weixiao*   

  1. Institute of Chemistry; Academia Sinica; Beijing; China
  • Received:1985-12-25 Revised:1986-08-08 Published:1987-06-15
  • Contact: Hu Weixiao

摘要: 在研究弱的CT络合物中给体与受体的相对取向时, 认为应更多地考虑分子间的静电作用, 并根据晶体结构分析结果, 提出头并头的几何匹配棋型。用此模型来分析分子间的作用能, 并由平衡常数的测定结果表明, 当同系列给体与同一受体相作用时, 随着同系序数的增加, 由于几何匹配效应, 络合物的基态稳定性不是单调变化的, 而是呈现两头小中间大的现象。在红外光谱中, 某些吸收峰相对强度的变化也有类似的现象。

Abstract: During the investigation of the relative orientation between donor and acceptor in weak CT-complexes, it has been noticed that the electrostatic action between molecules should be considered much more. Based on the analysis of thin crystal structures, a “head-to-head” geometrically matching model has been proposed. From the analysis of the energy of action between donor and acceptor using this model and the measurement of the equilibrium constants, it has been found that when homologous donors act with sameacceptor, because of the geometrical match effect, the stability of the ground state of the complex does not change monotoneously with the asending serial number of donor wheras the stabilities at the ends of the given donor series are smaller and the largest stability presents in middle.
In IR spectra, a similar trends of relative intensity of some adsorption peaks been observed.