Synthesis And Characterization Of Copper(?)Complexes Containing Quinoline,Phenylnaphthyl And Terphenyl Phosphine

Organic light emitting diodes(OLEDs)are attracting a lot of attention in the field of optical display due to their unique self-luminescent properties.Currently luminescent materials used in OLEDs are mainly Ir3+,Pt2+,Ru2+ and Os2+ and other metal complexes.However,the high cost and resource scarcity of these noble metals restrict the application and promotion of OLEDs.Therefore,it is particularly important to find new cheap and efficient photoelectric materials.In this thesis,8-bromoquinoline,1-bromonaphthalene and o-xylene as the substrates,via dilithium reagent to get 8-diphenylphosphinoquinoline,1-diphenylphosphino naphthalene,4,5-dimethyl-1,2-bis(diphenylphosphino)benzene and terphenyl diphosphine ligands.Then react with CuX(X= I,Br,Cl)to obtain a series of neutral copper(?)halide complexes.The structures,luminescent and thermal properties of the complexes are characterized by NMR,IR,MS,X-ray diffraction,UV-vis,PL and TGA technology.The luminescent mechanism is studied by density functional theory calculation.Chapter ? IntroductionIn this chapter,it describes the generation,structures,mechanism of OLED and developing direction,as well as the principle of phosphorescence and fluorescent materials,the methods of improving luminescent efficiency,and the mechanism of thermally activated delayed fluorescence(TADF).The research status of mononuclear and dinuclear copper(?)halide complexes used in OLED devices is highlighted.Finally,the research aim and content are put forward.Chapter ? Synthesis and characterization of copper(?)halide complexes containing 8-(diphenylphosphino)quinoline and 1-(diphenylphosphino)naphthalene8-Bromoquinoline,1-bromonaphthalene as substrates,react with n-BuLi,diphenylphosphine chloride to get 8-diphenylphosphino quinoline and 1-diphenylphosphino naphthalene,then reacted with CuX(X = Cl,Br,I)at a ratio of 1:1:1 in dichloromethane.A series of four-coordinate mononuclear Gu(?)complexes were synthesized.Their molecular structures and photophysical properties are investigated.These complexes exhibit near-saturated red emission at room temperature and have peak emission wavelengths at 669-691 nm with microsecond lifetimes at 0.46-1.80 ?s.Small S1-T1 energy gaps in the solid state indicate that the emission occurs from TADF at ambient temperature.The emissions of the complexes mainly originate from MLCT(metal-to-ligand charge transfer),XLCT(halogen-to-ligand charge transfer)and LLCT(ligand-to-ligand charge transfer).They display good thermal stability.Chapter ? Synthesis,characterization and luminescent properties of copper(I)halide complexes containing 1,2-bis(diphenylphosphino)-4,5-dimethylbenzene and 1-(diphenylphosphino)naphthaleneO-xylene as the substrate,via halogenating reaction to get 1,2-dibromo-4,5-dimethylbenzene,then react with n-BuLi and chlorodiphenylphosphine to get 1,2-bis(diphenylphosphino)-4,5-dimethylbenzene,then react with 1-(diphenylphosphino)naphthalene and CuX at a ratio of 1:1:1 in dichloromethane.A series of four-coordinate mononuclear Cu(I)complexes are synthesized.Their molecular structures and photophysical properties are investigated.The complexes in solid state exhibit yellow green and greenish yellow emission at room temperature(?max= 546-576 nm)with lifetimes at 2.3-13.1 ?s.They display TADF.The emissions mainly originate from MLCT,XLCT and LLCT.Three complexes display good thermal stability.Chapter IV Synthesis and characterization of copper(I)halide complexes chelated with terphenyl bidentate phosphineO-xylene is used as starting material,via halogenation,intermolecular coupling reaction with n-butyllithium,terphenyl dilithium reagent is obtained and further react with chlorodiphenylphosphine,4,4',4",5,5',5"-hexamethyl-(1,1':2',1"-terphenyl)-2,2"-bis(diphenyl phosphine)is synthesized.The ligand is reacted with CuX(X= I,Br,Cl)in dichloromethane to produce three mononuclear neutral three-coordinate Cu(I)halide complexes.The structures and photophysical properties of the complexes are characterized.At room temperature,three complexes exhibit green,yellow green and yellowish green emission(?max= 493-547 nm).Small S1-T1 energy level results in TADF luminescent mechanism.The emissions of the complexes mainly originate from MLCT,XLCT and IL transitions.They show good thermal stability.