Acta Phys. -Chim. Sin. ›› 2011, Vol. 27 ›› Issue (02): 315-321.doi: 10.3866/PKU.WHXB20110236

• THEORETICAL AND COMPUTATIONAL CHEMISTRY • Previous Articles     Next Articles

Electronic Structures and Nonlinear Optical Properties of Pyridine- Based Ru(II) Complexes Containing Thiophene Rings

SUN Xiu-Xin, LIU Yan, ZHAO Hai-Bo, SUN Shi-Ling, LIU Chun-Guang, QIU Yong-Qing   

  1. Institute of Functional Material Chemisty, Faculty of Chemistry, Northeast Normal University, Changchun 130024, P. R. China
  • Received:2010-09-20 Revised:2010-12-02 Published:2011-01-25
  • Contact: QIU Yong-Qing E-mail:qiuyq466@nenu.edu.cn
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (20873017) and Natural Science Foundation of Jilin Province, China (20101154).

Abstract:

Density functional theory (DFT) with the B3LYP functional was used to investigate the electronic structures and nonlinear optical (NLO) properties of a series of pyridine-based Ru(II) complexes containing thiophene rings. The results indicate that stable chemical bonds do not form between the coordinated atoms and the metal ion for [RuII(NH3)5L]2+ (L: organic groups containing the thiophene ring) complexes. However, strong donor-acceptor (D-A) interactions do exist. The Ru(II) and carbon atoms form stable σ-π coordinated bonds after NH3 is substituted by CO, which decreases the unoccupied orbital energies of the acceptor groups. The degree of system conjugation increases because of an increase in the number of thiophene rings, which is favorable for intramolecule charge transfer. The polarizability α and the first-order hyperpolarizability β values of all the systems are enhanced significantly because of the abovementioned reasons. According to the frontier molecular orbitals, the contribution to the second-order NLO coefficient mainly comes from an intraligand charge transfer (ILCT) and an interligand charge transfer (LLCT). The introduction of CO increases the β value for the [RuII(CO)5L]2+ complex about seven times compared with the [RuII(NH3)5L]2+ analogue, which can be attributed to a ligand-to-metal charge transfer (LMCT).

Key words: Density functional theory, Pyridine-based Ru(II) complex, Electronic structure, Nonlinear optical property

MSC2000: 

  • O641