Argentar Harold
Institute for Materials Research, National Bureau of Standards, Washington, D.C. 20234.
J Res Natl Bur Stand A Phys Chem. 1976 Mar-Apr;80A(2):173-187. doi: 10.6028/jres.080A.019. Epub 1976 Apr 1.
A chemical model is proposed for describing charge-transfer complexes between aromatic amines and electron-accepting benzene derivatives containing a group having a double- or triple-bond conjugated with the benzene ring. According to this model, an electron migrates from the nitrogen atom of the amine to one of the atoms of the multiple-bonded group during charge-transfer interaction. Structure-property relationships were derived for correlating: (1), the transition energies of the complexes; (2), the ionization, or oxidation, potentials of the amines, and (3), the electron affinities or reduction potentials of the electron acceptors, with the electron-donating abilities of the substituents of the various compounds. Transition energies calculated from reported spectroscopic data for these complexes were correlated using equations derived in this study. Similarly correlated were reported data for the above properties of the amine and electron acceptor. Equations were derived for correlating the effect of variation in solvent on the transition energies of the complexes. Correlation of reported spectroscopic data indicated that the greatest effect is caused by variation in the refractive index; of secondary importance was the change in dielectric constant.
提出了一种化学模型，用于描述芳香胺与含与苯环共轭的双键或三键基团的电子受体苯衍生物之间的电荷转移络合物。根据该模型，在电荷转移相互作用过程中，电子从胺的氮原子迁移到多键基团的一个原子上。推导了结构-性质关系，用于关联：（1）络合物的跃迁能；（2）胺的电离或氧化电位；（3）电子受体的电子亲和势或还原电位，与各种化合物取代基的给电子能力。利用本研究推导的方程，对根据这些络合物的报道光谱数据计算出的跃迁能进行了关联。同样被关联的还有胺和电子受体上述性质的报道数据。推导了用于关联溶剂变化对络合物跃迁能影响的方程。对报道光谱数据的关联表明，最大的影响是由折射率的变化引起的；次要的是介电常数的变化。
