[Ru(bpy)2(phen)]^2+主配体上双取代效应DFT法研究

对钌联吡啶菲咯啉配合物Ru(bpy)2(phen)]^2+及其主配体(phen)上5,6-双取代衍生物，用密度泛函(DFT)法在B3LYP/LanL2DZ水平上进行理论计算研究。探讨供电子基团(OH)和拉电子基团(F)在主配体上的取代对配合物的电子结构及相关性质，如配合物前沿分子轨道的能量、组成、光谱性质、原子的净电荷布居及配位键长键角等的影响规律。计算结果表明，取代基对该系列取代衍生物的电子结构，特别是第一激发态的电子云分布影响较大，拉电子基团(F)能活化主配体，钝化辅助配体；而代电子基团(OH)则相反。无认是供电子基团(OH),还是拉电子基团(F)都导致取代衍生物的电子基谱带红移。此外，用基于极性交替规律及极性叠加概念的多系列箭头的图示方法对主配体上的原子净电荷布居的特征作了讨论。计算结果能较好地解释有关的实验现象与规律。

Studies on the Di-substitution effects on the main ligand of [Ru(bpy) 2(phen)]^2+ with DFT method

Studies on complex Ru(bpy)2(phen)]^2+ and its derivatives of di- substitutions on the main ligands(phen) are carried out by using DFT method at B3LYP/LanL2DZ level. The regularities of the substitution effects of the electron-pushing group (OH) and the electron- withdrawing group (F) on the electronic structures and the related properties of the complexes, e.g. the energies and the compositions of some frontier molecular orbitals, the spectroscopy properties, the atomic net charge populations on main ligands, the coordination-bond lengths and the coordination-bond angles of the complexes, etc. have been investigated. The computational results show that the substituents have some interesting effects on the electronic structures, in particular, on the electron populations of the first electronic excited states of the complexes. The electron-withdrawing group(F) can activate the main ligand and passivate the co-ligands of the first excited state in the substitution derivative, whereas the effect of the electron-pushing group(OH) is contrary. Both of electron-pushing group(OH) and electron-withdrawing group(F) can cause a little red shift in the electronic ground bainds of complexes. In addition, the characteristics of the atomic net charge populations on main ligands are also simply and satisfactorily interpreted according to the schematic representation expressed by several series of arrow heads based on the law of polarity alternation and the idea of polarity interfernce. The calculation results can be better used to explain some experimental phenomena and regularities.