Research On Syntheses,Structures And Luminescent Properties Of Cu(Ⅰ) Complexes

Cu(Ⅰ)complexes have attracted widespread attention because of their flexible structures and rich photophysical and photochemical properties.The design and synthesis of novel luminescent Cu(Ⅰ)complexes is always one of research hot spots in coordination chemistry.In this paper,we synthesize a series of rich luminescent Cu(Ⅰ)complexes by regulating the nitrogen-containing heterocyclic ligands or phosphine ligands(there have several blue-emitting complexes),and systemic studied the structures,luminescence properties and stability.The details are summarized as follows:(1)Cu(Ⅰ)complexes based 1,3-bis(diphenyphosphino)propane(dppp)had synthesized as listing below:[Cu4I4(3-Acepy)2(dppp)2]·2CH2Cl2 Complex P-1[Cu4I4(5-Brpm)2(dppp)2]·2CH2Cl2 Complex P-2 Cu4I4(dppp)2(4-Acepy)2 Complex P-3 Cu4I4(dppp)2(4-Pic)2 Complex P-4[Cu2I2(4-Pic)2(dppp)]n Complex P-5[Cu2I2(3-Clpy)2(dppp)]n Complex P-6[Cu2I2(3-Brpy)2(dppp)]n Complex P-7[Cu2I2(3-Pic)2(dppp)]n Complex P-8[Cu2I2(2,6-Dmpz)2(dppp)]n Complex P-9[Cu2I2(4-CNpy)2(dppp)]n Complex P-10[Cu2I2(bpp)(dppp)]n Complex P-11(2)Cu(Ⅰ)complexes based 1,2-bis(diphenyphosphino)propane(dppe)had synthesized as listing below:Cu4I4(dppe)3(4-bzpy)2 Complex E-1[Cu2I2(dppe)(4-Pic)2]n Complex E-2[Cu2I2(dppe)(3-Brpy)2]n Complex E-3[Cu2I2(dppe)(3-Pic)2]n Complex E-4[Cu2I2(dppe)(3,5-Dmpy)2]n Complex E-5[Cu2I2(dppe)(3-Clpy)2]n Complex E-6[Cu2I2(dppe)(2,6-Dmpz)2 · 2CHCl3]n Complex E-7[Cu6I6(dppe)6(pz)]·4CH2Cl2 Complex E-8(3)Several blue-emitting Cu(I)complexes had synthesized as listing below:[CuI(POP)(4-NMe2py)]· 1/2C2H5OC2H5 Complex D-1 CuI(POP)(4-NH2py)Complex D-2 CuCl(PPh3)2(4-NMe2py)Complex D-3 CuI(PPh3)2(4-NH2py)Complex D-4In this paper,we used ether diffusion and volatilization methods to obtain twenty-three Cu(I)complexes.all of the complexes were determined by X-ray single crystal diffractive technology.And the structure of all complexes are described and summarized in details.Most complexes have been further characterized by X-ray power diffraction,IR,UV-vis absorption spectrum,UV-vis diffuse reflection.Through the single crystal structure analysis,all the complexes either 0-D complexes or 1-D chain complexes.complexes P-1-P-4,E-1,E-8,D-1-D-4 are 0-D complexes,which including tetranuclear complexes for P-1-P-4,E-1,hexanuclear complexes for E-8,mononuclear complexes for D-1～D-4.Besides,complexes P-5～P-11,E-2～E-7 are 1-D chain complexes.Among these complexes,1-D chain complex for P-11 is linked Cu2I2 cluster by nitrogen-containing heterocyclic ligand(bpp ligand),other 1-D chain complexes are linked Cu2I2 cluster by phosphine ligands(dppp or dppe).At room temperature,luminescence properties of all the complexes were studied,the highest value is obtained for complex E-6,~82.5%.And part of the complexes dopped into PMMA matrix were analysized.Simultaneously,some complexes with similar structure were performed cyclic voltammetry to identify electron-donating ability of the corresponding ligands.We investigated luminescence properties of some selected compounds at the low temperature,the results preliminary concluded that these compounds were TADF materials.