Synthesis And Luminescent Properties Of Copper(?) Complexes Containing Aminophenyl,Biphenyldiphosphine And Phenyldinitrogen Monophosphine

Organic light emitting diode(OLED)is illuminated,wide angle,high contrast,low energy consumption,fast response and bright colors,etc.Transition metals such as osmium,iridium,platinum,ruthenium with spin-orbit coupling effect,as high-efficiency phosphorescent materials,are often used to assemble OLED.But the metal abundance is low,the price is expensive,to a certain extent hindered the application of OLED Copper has replace the potential of these precious metals,the quantum yield(QY)of the copper complexes with thermal activation delay fluorescence(TADF)can reach 100%in theory,can rival phosphorescent materials,thus attracted much attention.In this thesis,on the basis of consulting the neutral copper(I)complexes on the OLED application background,three ligands of amino phenyl phosphine,biphenyl diphosphine and phenyl dinitrogen phosphine have been designed and synthesized.Then they react with CuX to obtain three three-coordinate dinuclear,three four-coordinate dinuclear and one four-coordinate hexanuclear neutral halide Cu(I)complexes.Their structures and photophysical properties are characterized by NMR,IR,MS,X-ray diffraction,UV-vis and PL spectra.Density functional theory(DFT)calculation is used to reveal the luminescent mechanism.In order to further obtain highly efficient neutral copper(I)complexes with thermal activation delay fluorescence,it provides a meaningful exploration.Chapter I IntroductionThis chapter introduces the development,device structure and working principle of OLED,as well as the mechanism of electroluminescence.It focuses on the copper(I)complexes of mono,di and multinuclear which exhibiting TADF,including the structures,coordination ways,luminescent properties and applications in OLEDs.The design idea of this thesis is put forward.Chapter II Synthesis,characterization and luminescent properties of three-coordinate copper(I)halide complexes containing diphenylamino monodentate phosphine ligandA series of three-coordinate dinuclear copper(I)halide complexes containing a diphenylamino monodentate phosphine ligand,[CuX(dpnp)]2(dpnp =N-[2-(diphenylphosphino)-4,5-dimethylphenyl]-N-phenylaniline,X = I(1),Br(2)and Cl(3)),were synthesized.Two copper(I)centers are bridged by two halogen ligands to form a dinuclear structure with a four-membered Cu2X2 ring.These complexes exhibit blue emission in the solid state at room temperature and have peak emission wavelengths at 483-487 nm with microsecond lifetimes(? = 13.9-38.1 ?s)and low emission quantum yields(<0.01%).The emission of complex 1 mainly originates from intraligand(IL)transition,whereas the emissions of complexes 2 and 3 are from a combination of metal-to-ligand charge transfer(MLCT),halide-to-ligand charge transfer(XLCT)and IL(intraligand)transitions.The three complexes displayed good thermal stability.Chapter III Synthesis,characterization and luminescent properties of copper(I)halide complexes containing biphenyl bidentate phosphine ligandA series of four-coordinate dinuclear copper(I)halide complexes,[CuX(bpbp)]2(bpbp =2,2'-bis(diphenylphosphino)biphenyl,X = I(4),Br(5)and Cl(6)),were synthesized.Two copper(I)centers are bridged by two halogen ligands to form a dinuclear structure with a four-membered Cu2X2 ring.These complexes exhibit yellow to blue emission in the solid state at room temperature and have peak emission wavelengths at 575-487 nm with microsecond lifetimes(?= 6.2-19.8 ?s)and low emission quantum yields(<0.01%).The emissions of 4-6 originate from MLCT,XLCT,and IL transitions.Three complexes displayed good thermal stability.Chapter IV Synthesis,characterization and photophysical properties of phenyldinitrogen monophosphine copper(I)iodide complexA four-coordinate hexanuclear copper(I)iodide complex containing phenyldinitrogen monophosphine ligand,[Cu6I6(ppda)2]{ppda =2-[2-(dimthylamino)phenyl(phenyl)phosphino]-N,N-dimethylaniline),7},was synthesized.All six copper atoms are four-coordinate,including four CuPNI2 and two CuI4 units.This complex exhibits white emission in the solid state at room temperature and has peak emission wavelength at 476 nm with microsecond lifetime(?= 2.7 ?s),with CIE coordinate at(0.2297,0.2737).At room temperature,the quantum yield of complex 7 is 14.8%,The emission of complex 7 originates from a combination of MLCT and XLCT transitions.