关键词: 联吡啶P, 菲咯啉, 菲绕啉, 钌络合物, 密度函数, 八面体配位

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.

Key words: BIPYRIDINE P, PHENANTHROLINE, PHENATHROLINE, RUTHENIUM COMPLEX, OCTAHEDRAL COORDINATION