title: Crystal structures and magnetic and luminescent properties of a series of homodinuclear lanthanide complexes with 4-cyanobenzoic ligand.
abstract: A series of homodinuclear lanthanide(III) complexes with the 4-cba ligand, [La2(4-cba)6(phen)2(H2O)6] (1) and [Ln2(4-cba)6(phen)2(H2O)2] (Ln = Pr (2), Nd (3), Sm (4), Eu (5), Gd (6), and Dy (7); 4-Hcba = 4-cyanobenzoic acid; phen = 1,10-phenanthroline), have been synthesized and structurally characterized by single-crystal X-ray diffraction. In 1, two water molecules bridge two nine-coordinated La ions, and six 4-cba ligands coordinate to the two La ions in terminal mode. In the isostructural complexes 2-7, two eight-coordinated Ln ions are connected by four bidentate 4-cba ligands, and another two 4-cba ligands terminate the two Ln ions. The variable-temperature magnetic properties of 2-7 have been investigated. Complex 7 shows a significant ferromagnetic interaction between Dy(III), while no magnetic interaction exists between Gd(III) ions in 6. In 2-5, the value of chi(M)T decreases with decreasing temperature, but the magnetic interactions between the Ln(III) ions cannot definitely be concluded. Notably, the spin-orbit coupling parameters, lambda, for Sm(III) (216(2) cm(-1)) and Eu(III) (404(2) cm(-1)) have been obtained in 4 and 5, respectively. The strong fluorescent emissions of 4, 5, and 7 demonstrate that ligand-to-Ln(III) energy transfer is efficient and that the coordinated water molecules do not quench their luminescence by the nonradiative dissipation of energy.
authors.affiliation: State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, P. R. China.
authors.forename: Yan
authors.initials: Y
authors.lastname: Li
authors.forename: Fa-Kun
authors.initials: FK
authors.lastname: Zheng
authors.forename: Xi
authors.initials: X
authors.lastname: Liu
authors.forename: Wen-Qiang
authors.initials: WQ
authors.lastname: Zou
authors.forename: Guo-Cong
authors.initials: GC
authors.lastname: Guo
authors.forename: Can-Zhong
authors.initials: CZ
authors.lastname: Lu
authors.forename: Jin-Shun
authors.initials: JS
authors.lastname: Huang