化学学报 ›› 1978, Vol. 36 ›› Issue (2): 89-106. 上一篇    下一篇

论文

同系物分子结构与物理化学性能间的定量关系——Ⅲ.联苯链物与骈苯链物电子光谱中的同系线性规律

蒋明谦   

  1. 中国科学院化学研究所
  • 投稿日期:1977-08-16 发布日期:2013-06-03

A QUANTITATIVE RELATIONSHIP BETWEEN MOLECULAR STRUCTURES AND PHYSICOCHEMICAL PROPERTIES OF HOMOLOGOUS COMPOUNDS——Ⅲ.THE RULE OF HOMOLOGOUS LINEARITY FOR THE ELECTRONIC SPECTRA OF POLYPHENYLS AND CONDENSED AROMATIC COMPOUNDS

CHIANG MING-CHIEN   

  1. Institute of Chemistry, Academia Sinica
  • Received:1977-08-16 Published:2013-06-03

本文讨论了联苯链物和骈苯链物电子吸收光谱中的同系线性规律.在这些类型的化合物中,只有具有共同的通式和同数的芳六(合)组的系列,才是真正的同系化合物.对于符合这两个条件的同系列,同系线性规律完全适用于它们各吸收带的各次峰,关联情况一般都很良好.并且,同系线性关系的精确程度高于Hueckel分子轨道法的同类线性关系.在骈苯化合物的四个系列中,α带、p带和β带内的各次峰,都各自成为一组邻同系峰.每组的同系直线,在其位置、斜率和与其他线组的间隔方面,都有各自的特征.每带内各峰之间的关系,都符合近似的迭合规律;但各带之间不存在类似的迭合关系.这表明一个吸收带各峰所依存的结构因素可能是基本上相同的,而不同的吸收带所依存的结构因素是不相同的.各带各组同系直线的特征,为同系物电子光谱吸收峰的分类和鉴定提供了一个合理的定量基础.文中根据这些特征,对于一些前人未曾分类的吸收峰进行了分类,并对一些以前的显然不合理的分类,进行了改正.

In this paper the rule of homologous linearity for electronic spectra, namely,v=a+b (1/α)2/N has been extended to the homologous series of P-polyphenyls and cats-and pori-condensed aromatic hydrocarbons.For genuine homologous of the latter type, namely, condensed aromatic compounds of the same general structural formula and also with the same number of aromatic sextets, all the absorption peaks in each band of their electronic spectra conform alike to the linearity rule.The correlations are very satisfactory in almost all the cases studied.Furthermore, the linearity of the homologous lines obtained in this work is shown to be superior in precision to that based on the transition energies (mm+1-mm)calculated by the Hueckel molecular orbital method.