Synthesis, Characterization And Luminescent Properties Of Copper (I) Complexes Of Pyridine Triazole

Cu(?)complexes have became one of the best luminescent materials,because of their high relative abundance,low cost,environmentally friendly,various intersting architectures,excellent luminescence properties as well as their wide application potential in many fields,such as organic light-emitting devices(OLEDs),photosensitive devices,biological labeling,communication devices etc.In this paper,we have designed and synthesized a new family of Cu(?)complexes by functionalized 3-(2-pyridyl)-1,2,4-triazole and phosphine ligands The structures and photophysical properties of these Cu(?)complexes have been investigated by X-ray single-crystal diffraction,NMR spectroscopy,elemental analysis,infrared spectroscopy,UV-vis absorption spectroscopy,fluorescence spectroscopy and TD-DFT calculation.1.Five bimetallic Cu(?)complexes [Cu2(?-dppm)2(?-?1(N),?2(N,N)-o-fmptz)](ClO4)(1),[Cu2(?-dppm)2(?-?1(N),?2(N,N)-m-fmptz)](ClO4)(2),[Cu2(?-dppm)2(?-?1(N),?2(N,N)-p-fmptz)]-(ClO4)(3),[Cu2(?-dppm)2(?-?1(N),?2(N,N)-fptz)](Cl O4)(4),and [Cu2(?-dppm)2(?-?1(N),?2(N,N)-o-bmptzH)](Cl O4)2(5)have been synthesized by using two bis(diphenylphosphino)-methane ligands and functionalized 3-(2-pyridyl)-1,2,4-triazole.The structures and photophysical properties of these Cu(?)complexes 1-5 have been studied.It is shown that complexes 1-5 are dinuclear Cu(?)species with an eight-membered Cu2C2P4 ring of {Cu(?-dppm)2Cu} unit,displaying the boat conformation for 3 and 4 and the chair form for 1,2 and 5.All Cu(?)atoms adopted ?-?1(N),?2(N,N)coordination mode: Cu1 is four-coordinated,in a highly distorted N2P2 tetrahedral environment,and Cu2 is three-coordinated,in a distorted N2 P trigonal planar arrangement.And it is also showed that by structural modification of 3-(2-pyridyl)-1,2,4-triazole can markedly influence the structures and luminescence properties of Cu(?)complexes: including the variation of the substituent type(-CF3,-H,-CH3 and-C(CH3)3)and position(ortho-,metaand para-position).2.Four mononuclear and dinuclear Cu(?)complexes,[Cu(bmptzH)(dppp)](ClO4)(6),[Cu2(bmptzH)2(?-dppb)2](ClO4)2(7),[Cu2(bmptz)2(?-dppb)2](8),[Cu2(bmptz)2(?-dppe)2](9),have been synthesized by using 5-tert-butyl-3-(-2-pyridyl)-1H-1,2,4-triazole and diphosphine mixed ligands.Moreover,the [Cu(bmptzH)(dppe)](ClO4)(10)has been documented in previous reports and referenced to this paper.The structures and luminescence properties of 6-9 have been investigated.X-ray single-crystal diffraction indicated that 6 is a four-coordinated,in a highly distorted N2P2 tetrahedral environment,but 7-9 are doubly bridged dinuclear by a pair of diphosphine ligands.Besides,9 and 10 can mutual conversion via the H-?NH.And it is also showed that the choice of diphosphine ligands and the deprotonation of the 1,2,4-triazolyl-NH have a significant influence on the structures and luminescence properties of Cu(?)complexes.