醇类溶剂溶剂化显色极性的理论分析

对一系列醇类溶剂分子进行了理论计算,运用多元线性回归分析方法从分子间相互作用的角度对四种溶剂化显色极性参数(E~T^N,π^*,Py和SPP)进行了理论分析。结果表明,对醇类溶剂而言,参数E~T^N和SPP实质上主要反映的是溶剂的氢键酸性性质;参数π^*中虽然包含了溶剂的极性因素,但同时与溶质-溶剂分子间的电荷转移相互作用有着密切的关系;而参数Py则较好地反映了溶剂的极性性质。

Theoretical analysis of solvatochromic polarity scales on alcoholic solvents

In present paper, ab intio calculations for a group of 55 alcoholic solvent molecules have been made at HF/6-31G^* level. Linear correlation of four solvatochromic parameters E~T^N, π^*, Py and SPP of these solvents to theoretical descriptors has been established by using multiple regression, and the signification of these correlations has been analyzed from the viewpoint of intermolecular interactions between the "probe solute" and the solvent. It appears that the polarity parameters E~T^N and SPP, for alcoholic solvents, mainly reflect in fact their hydrogen-bonding donor acidities, π^* contains the component of solvent polarity, but it is also related to the electron transfer intermolecular interaction, whereas Py parameter is an appropriate alcoholic solvent polarity scale.