Synthesis And Characterization Of Copper (Ⅰ) Halide Complexes Chelated With Phenyl And Naphthyl Diphosphine

OLED has high contrast,ultra-thin,wide viewing angle,fast response,colorful,flexible features,it is considered the latest generation of "green energy" display technology.Currently used in OLED luminescent materials are mainly Ir3+,Pt2_,Ru2+ and Os2+ and other metal complexes,however,these metals are expensive,less reserves,to a certain extent,restricted the promotion and application of OLED technology.Therefore,the development of new cheap and efficient photovoltaic materials is particularly important.In this paper,ortho-xylene and 1,8-diaminonaphthalene as the substrate,the use of bis-lithium reagent"prepared phenyl and naphthyl diphosphine ligand,with the reaction of cuprous halide three new binuclear quaternary neutral copper (Ⅰ)complexes,continue to react with triphenylphosphine to give six new mononuclear tetracoordinated neutral copper(Ⅰ) complexes.The structure and photophysical properties of the complexes were characterized by 1HNMR,single crystal X-ray diffraction,mass spectrometry(MS),infrared(IR),UV-vis and fluorescence spectroscopy.Chapter I IntroductionThis thesis describes the generation,classification,structure,luminescence principle and development of OLED,focuses on the kinds of organic materials used in OLED devices,ionic and neutral Cu(Ⅰ)complexes of the structure,properties and current research status.The design thought is proposed.Chapter II Synthesis and characterization of copper (Ⅰ) halide complexes containing 1,2-bis(diphenylphosphino)-4,5-dimethylbenzene and triphenylphosphine1,2-Bis(diphenylphosphino)-4,5-dimethylbenzene(dpmb),triphenylphosphine and CuX were prepared at room temperature in CH2Cl2 at a molar ratio of 1:1:1 to obtain three kinds of neutral mononuclear four-coordinate Cu(Ⅰ)complexes[Cu(dpmb)PPh3](X = I(1),Br(2),Cl(3)).At 293 K,three complexes exhibit intense blue emission and have peak emission wavelengths at 464-479 nm,with lifetimes at 3.52-4.87 μs,and quantum efficiencies of 0.23-0.53.Three complexes display thermally active delayed fluorescence(TADF).The emission of complex 1-3 mainly originates from MLCT(metal to ligand charge transition),XLCT(halogen to ligand charge transition)and intraligand transitions.Three complexes display moderate thermal stability.Chapter Ⅲ Synthesis and characterization of copper (Ⅰ) halide complexes chelated with 1,8-bis(diphenylphosphino)naphthaleneSynthesis of 1,8-dibromonaphthalene using diazotization reaction from 1,8-diaminonaphthalene as substrate.Further synthesis of diphosphine ligand 1,8-bis(diphenylphosphino)naphthalene(dppn)by n-butyllithium-halogen exchange method.Then reacted with CuX in a molar ratio of 1:1 to get three neutral copper complexes[CuX(dppn)]2(X = I(4),Br(5),Cl(6)).The crystal structures of complex 6 show that two copper atoms are bridged by two halogen atoms to form a dinuclear structure of four-membered ring Cu2X2.At 293 K,three complexes exhibit yellowish orange and orange emission and have peak emission wavelengths at 604-629 nm,with lifetimes at 13.8-21.4 ps,and the quantum yields of 0.0031-0.0041.Three complexes display TADF and the emission originates from MLCT,XLCT and IL(ligand)transitions.Chapter IV Synthesis and characterization of copper (Ⅰ) halide complexes containing 1,8-bis(diphenylphosphino)naphthalene and triphenylphosphine1,8-Bis(diphenylphosphino)naphthalene(dppn)and triphenylphosphine and cuprous halide,with the molar ratio of 1:1:1 in CH2Cl2,three new mononuclear four-coordinate neutral copper complexes[CuX(dppn)PPh3](X = I(7),Br(8),Cl(9))were obtained.Three complexes display TADF.At 293 K,three complexes exhibit orange and yellow emission with peak wavelengths at 568-624 nm,the lifetimes at 43.7-104.8 μs,and the quantum efficiencies of 0.012-0.047.The emission originates from MLCT,XLCT and IL(ligand)transitions.