Study Of White-Light-Emitting Hybrid Materials Based On Doping Or Grafting Of Lanthanide Complexes Into Polymer

Lanthanide ions are receiving widespread attention due to the characteristics of the large Stokes shift and long fluorescence lifetime.In addition to the pure red or green luminescent materials,Ln3+-based white-light materials have also been concerned because of potential applications in white light organic light-emitting diodes.Nonetheless,there are several problems in the exploration of small molecule white light materials of lanthanide complexes,mainly as follows:i)Thermal stability is poor;ii)Film-forming is bad;iii)Lack of mechanical strength;iv)The cost of thermal-deposition procedure is high or the process of spin-coating while complicated multi-layer structure restricts their application in white light devices.In this thesis,we combine the photoluminescence uniqueness of lanthanide ions and the outstanding thermal stability and good film forming performance of organic polymer,and through the doping and covalently-bonding of small molecule lanthanide complexes into PMMA,two series of PMMA-supported doping and metallopolymer-type hybrid materials are obtained,respectively.The main contents are as follows:1.Based on different Ln3+-complexes,such as:[Zn(L1)(Py)Ln(L2)2(NO3)](Ln = La,1;Eu,2;Tb,3;Gd,4),we obtained series of PMMA-supported doping materials,and characterized their luminescent properties.White-light emission could be realized from the integration of Eu3+-centered red-light,and Tb3+-centered green-light with compensatory color from the ligand-centered by a typical trichromatic strategy.2.Based on different Ln3+-complexes,and through terpolymerization of vinyl-functionalized complex monomers 2-3([Zn(L)(4-vinyl-Py)Ln(BA)2(NO3)]Ln = Eu,2 or Ln = Tb,3;H2L=N,N’-bis(salicylidene)cyclohexane-1,2-diamine;4-vinyl-Py = 4-vinyl-pyridine;HBA=1-phenyl-1,3-butanedione)with dual emissions,and/or blue-light-compensatory[Zn(L)(4-vinyl-Py)Gd(BA)2(NO3)(4)with MMA(methyl methacrylate),we offer a robust pathway to single-component while heterometallic-containing metallopolymer-type hybrid materials with color-tunable white-light as featured like Zn2+-Eu3+-Tb3+-containing and Zn2+-Eu3+-Tb3+-Gd3+-containing metallopolymers3.Based on Ln3+-complexes[Zn(L1)(4-vinyl-Py)Ln(L2)2(NO3)],MMA and DVB(Divinylbenzene),we obtained series of grafting-type hybrid materials in the presence of AIBN(2,2-azobisisobutyronitrile).Moreover,their color-tunable for whit-light was also realized.Furthermore,besides their better thermal stability than that of complex monomers,the white-light hybrid materials also exhibited improved film-forming property.