Studies on 4,7‐di‐substitution effects of one ligand in [Ru(Phen) 3 ] 2 with DFT method

Abstract Studies on the complex [Ru(phen) 3 ] 2+ (phen = 1,10‐phenanthroline) and its derivatives with 4,7‐di‐substitution on one ligand(phen) were carried out using the DFT method at the B3LYP/LanL2DZ level of theory. The trends in the substituent effects caused by the electron‐pushing group (OH) and the electron‐withdrawing group (F), on the electronic structures and the related properties, for example, the energies and the components of some frontier molecular orbitals, the spectroscopy properties, and the net charge populations of some main atoms of the complexes, etc., have been investigated. The computational results show that the substituents have some interesting effects on the electronic structures and the related properties of the complexes. First, according to the analysis of components of LUMO of the complexes, the electron‐withdrawing group (F) can activate the main ligand (the substituted ligand, i.e., 2R‐phen) and passivate the coligands, on the contrary, the electron‐pushing group (OH) can activate the coligands and passivate the main ligand in the first electronic excited states of complexes. Second, both the electron‐pushing group (OH) and the electron‐withdrawing group (F) can cause a red shift in the electronic ground bands. Third, the characteristics of the atomic net charge populations on the main ligand can also be analyzed in detail by means of a schematic map expressed by several series of arrowheads based on the law of polarity alternation and the idea of polarity interference. The most negative charges are populated on N1, the next most net negative charges are populated on C3 among the skeleton atoms for the three complexes, etc. The computational results can be better used to explain some experimental phenomena and trends. © 2002 Wiley Periodicals, Inc. J Comput Chem 4: 436–443, 2002; DOI 10.1002/jcc.10038