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Title: Luminescent three- and four-coordinate dinuclear copper(I) complexes triply bridged by bis(diphenylphosphino)methane and functionalized 3-(2 '-pyridyl)-1,2,4-triazole ligands
Authors: He, LH
Luo, YS
Di, BS
Chen, JL 
Ho, CL
Wen, HR
Liu, SJ
Wang, JY
Wong, WY 
Issue Date: 2017
Publisher: American Chemical Society
Source: Inorganic chemistry, 2017, v. 56, no. 17, p. 10311-10324 How to cite?
Journal: Inorganic chemistry 
Abstract: A new series of bimetallic Cu(I) complexes 1-5 triply bridged by a monoanionic or charge-neutral functionalized 3-(2'-pyridyl)-1,2,4-triazole in a mu-eta(1)(N),eta(2)(N,N) tridentate binding mode and two bis(diphenylphosphino)methane (dppm) ligands have been synthesized. Complexes 1-5 are singly or doubly charged dinuclear Cu(I) species with an eight-membered Cu2C2P4 ring of {Cu(mu-dppm)(2)Cu} unit, in which 3 and 4 adopt the boat boat-conformation, while 1, 2, and 5 display the chair-boat form. In these dimeric copper(I) complex cations, one of the two Cu(I) ions is four-coordinated, in a highly distorted N2P2 tetrahedral environment and the other is three-coordinated, in a distorted NP2 trigonal planar arrangement. All these Cu(I) complexes exhibit a comparatively weak low-energy absorption in CH2Cl2 solution, ascribed to the charge-transfer transitions with appreciable (MLCT)-M-1 contribution, as suggested by time-dependent density functional theory (TDDFT) analyses. Complexes 1-5 display good emission properties in both solution and solid states at ambient temperature, which are well-modulated via structural modification of 3-(2'-pyridyl)-1,2,4-triazole, including the alteration of the substituent type (-CF3, -H, -CH3, and C(CH3)(3)) and position (ortho-, meta-, and para-position). Furthermore, the variation of the substituent (-CF3 and -C(CH3)(3)) on the 5-site of the 1,2,4-triazolyl ring markedly influences the proton activity of the 1,2,4-triazolyl-NH, thus leading to the formation of both singly and doubly charged bimetallic Cu(I) species regulated by the NH <-> N- conversion, resulting from NH deprotonation of the 1,2,4-triazolyl ring.
ISSN: 0020-1669
EISSN: 1520-510X
DOI: 10.1021/acs.inorgchem.7b01159
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