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Inorg Chem. 2013 Sep 3;52(17):9727-40. doi: 10.1021/ic4002829. Epub 2013 Aug 20.

Synthesis, characterization, and photophysical properties of heteroleptic copper(I) complexes with functionalized 3-(2'-pyridyl)-1,2,4-triazole chelating ligands.

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School of Metallurgy and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, People's Republic of China.


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.

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