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-substit utions on the main ligands(phen) are carried out by using DET method at B3L YP/LanL2DZ level. The regularities of the substitution effects of the elect ron-pushing group (OH) and the electron-withdrawing group (F) on the electr onic structures and the related properties of the complexes, e.g. the energ ies and the compositions of some frontier molecular orbitals, the spectrosc opy properties, the atomic net charge populations on main ligands, the coor dination-bond lengths and the coordination-bond angles of the complexes, et c. have been investigated. The computational results show that the substitu ents have some interesting effects on the electronic structures, in particu lar, on the electron populations of the first electronic excited states of the complexes. The electron-withdrawing group(F) can activate the main liga nd and passivate the co-ligands of the first excited state in the substitut ion derivative, whereas the effect of the electron-pushing group ( OH) is c ontrary. Both of electron-pushing group(OH) and electron-withdrawing group( F) can cause a little red shift in the electronic ground bands of complexes . In addition, the characteristics of the atomic net charge populations on main ligands are also simply and satisfactorily interpreted according to th e schematic representation expressed by several series of arrow heads based on the law of polarity alternation and the idea of polarity interference. The calculation results can be better used to explain some experimental phe nomena and regularities.