| Lanthanide polynuclear complexes with novel structure and excellent luminescent properties has become a hot research. It was widely used in optical communications, defense, biomedical, organic light emitting displays, and many other fields. However, Lanthanide polynuclear complexes themselves still have shortcomings, such as poor stability of light and magnetism, difficult in processing. Therefore, It is important to design and synthesize new rare earth metalpolymer and dopants hybrid materials,which both have unique light, magnetic, electrical and other characteristics of ions, but also have good properties like strong impact, easy processing film and good stability, It is extremely valuable functional materials applied in many fields showing attractive application prospects.Based on the above point, in this paper, novel rare earth polynuclear complexes1-20, novel rare earth allyl polynuclear complexes21-32and two kinds of rare earth hybrid materials were designed and synthesized. And their molecular structures were characterized by FT-IR, EA, GPC,1H-NMR and X-ray crystal diffraction respectively. Besides, their photophysical properties were analyzed by UV-Vis absorption spectra and Fluorescence spectroscopy.Firstly, the Salen-type Schiff base ligand H2L has been synthesized and was used to prepare three series of lanthanide tetranuclear complexes,[Ln4(L)2(HL)2(NO3)2(O H)2]-2(NO3)(Ln=La,1; Ln=Nd,2; Ln=Yb,3; Ln=Er,4; Ln=Gd,5; Ln=Eu,6; Ln=Tb,7; Ln=Sm,8);[Ln4(L)2(HL)2(μ3-OH)2Cl2]-2Cl (Ln=La,9; Ln=Nd,10; Ln=Yb,11; Ln=Er,12; Ln=Gd,13; Ln=Eu,14; Ln=Tb,15; Ln=Sm,16);[Ln4(L)2(μ3-OH)2(OAc)6](Ln=Nd,17; Ln=Yb,18; Ln=Er,19; Ln=Gd,20). And their structures were characterized by chemical analysis methods like FI-IR, EA,1H-NMR, GPC and X-ray single crystal diffraction, and their photophysical properties were also discussed by optical means. Secondly, the functionalized Schiff base allyl ligand H2L1was used to prepare two series of lanthanide tetranuclear complexes,[Ln4(L1)2(HL1)2(NO3)2(OH)2]·2(NO3)(Ln=La,21; Ln=Nd,22; Ln=Yb,23; Ln=Er,24; Ln=Gd,25; Ln=Eu,26; Ln=Tb,27):[Ln4(L1)2(HL1)2(μ3-OH)2Cl2]-2Cl (Ln=La,28; Ln=Nd,29; Ln=Yb,30; Ln=Er,31; Ln=Gd,32), And their molecular structures and photophysical properties were also studied.Thirdly, a series of rare earth copolymer PNBE-co-[Ln4(L1)2(HL1)2Cl2(μ3-OH)2]·2Cl (Ln=La,33; Nd.34; Yb,35; Er,36; Gd,37)successfully synthesized by the copolymerization of norbornene and polynuclear complexes28-32using the Grubbs Ⅱ catalyst. The structures, molecular weight and luminescence properties of copolymer hybrid materials were characterized by FT-IR,1H-NMR, GPC, UV-Vis absorption spectra and excitation and emission spectra, respectively.Finally, the complexe28and the polymer PMMA, PS and PVC were doped respectively under the same ratio to obtain three kinds of blends, which were analysized by FI-IR and1H NMR. PMMA and complex30were Physically doped at different ratios1:50,1:100and1:200. using Fluorescence spectroscopy analysized the effects of luminescence intensity on the different content of rare earth in the hybrid materials. |
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