title: Synthesis, characterization, and photophysical properties of heteroleptic copper(I) complexes with functionalized 3-(2'-pyridyl)-1,2,4-triazole chelating ligands.
abstract: A new series of mononuclear copper(I) complexes (1-9) with functionalized 3-(2'-pyridyl)-1,2,4-triazole chelating ligands, as well as the halide and/or phosphine ancillary ligands, have been synthesized. Complexes 1-9 were fully characterized by elemental analysis, NMR spectroscopy, mass spectroscopy, electronic absorption spectroscopy, fluorescence spectroscopy, cyclic voltammetry, and X-ray crystallography (1-8). They adopt a distorted tetrahedral configuration, and are considerably air-stable in solid state and in solution. All these Cu(I) complexes display a comparatively weak low-energy absorption in CH2Cl2 solution, assigned to charge-transfer transitions with appreciable MLCT character, as supported by TD-DFT studies. Cu(I) halide complexes 1-4 each shows bright solid-state emission at room temperature, although they are nonemissive in fluid solutions, in which the emission markedly depends on the halide and the substituent on the 2-pyridyl ring. Complexes 5-9 bearing 2-pyridyl functionalized 1,2,4-triazole and phosphine exhibit good photoluminescence properties in solution and solid states at ambient temperature, which are well-modulated via the alteration of the auxiliary phosphine ligand and the structural modification of 3-(2'-pyridyl)-1,2,4-triazole. Interestingly, cationic complex 6 and neutral derivative 7 can readily be interconverted through the ring inversion of the 1,2,4-triazolyl regulated by the NH ↔ N(-) transformation.
authors: School of Metallurgy and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, People's Republic of China. gzchenjinglin@126.com
authors: Jing-Lin
authors: JL
authors: Chen
authors: Xing-Fu
authors: XF
authors: Cao
authors: Jin-Yun
authors: JY
authors: Wang
authors: Li-Hua
authors: LH
authors: He
authors: Zong-Yong
authors: ZY
authors: Liu
authors: He-Rui
authors: HR
authors: Wen
authors: Zhong-Ning
authors: ZN
authors: Chen
mesh_terms: D002614:Chelating Agents / Q000737:chemistry*; D056831:Coordination Complexes / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D055664:Electrochemical Techniques; D008024:Ligands; D049449:Luminescence; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D011725:Pyridines / Q000737:chemistry; D014230:Triazoles / Q000737:chemistry*
chemical_list: D002614:Chelating Agents; D056831:Coordination Complexes; D008024:Ligands; D011725:Pyridines; D014230:Triazoles; C045575:1,2,4-triazole; D003300:Copper