Synthesis And Photophysical Properties Of PVK-supported Metallopolymer-type Hybrid Materials

In consideration of the shortcomings of low thermal stability,bad mechanical property and difficulty to film-forming for small-molecule lanthanide complexes,this thesis focused on the development of PVK-supported(polyvinyl-carbazole)Ln3+-containing metallopolymer-type hybrid materials.The main content is as follows:Firstly,based on the copolymerization of the obtained Ln3+-complex [Ln(Qf)34vbzdpa](Ln = La,1;Nd,2;Yb,3;Er,4;Gd,5){Qf =(Z)-3-methyl-1-phenyl-4-(2,2,2-trifluoro-1-hydroxyethylidene)-1H-pyrazol-5(4H)-one);4vbzdpa=N-(4-vinylbenzyl)-N-(pyridin-2-yl)pyridin-2-amine} with NVK(vinylcarbazole)in the presence of AIBN(2,2-azobisisobutyronitrile),seires of PVK-supported grafting-type metallopolymer-type hybrid materials Poly{NVK-co-[Ln(Qf)34vbzdpa]} were obtained,respectively.Especially for Poly{NVK-co-[Ln(Qf)34vbzdpa]}(Ln = Nd,2;Yb,3;Er,4),all the Ln3+-centered nearinfrared luminescent properties were confirmed.Secodly,based on the copolymerization of NVK with the synthesized AMA(AMA = anthracen-10-ylmethyl methacrylate)in the presence of AIBN,the polymer Poly(NVK-coAMA)was obtained.Moreover,through the grafting of complex monomer [Ln(Qf)3MP](Ln = La,6;Nd,7;Yb,8;Er,9;Gd,10){MP = 1-(1,10-phenanthrolin-5-yl)-1H-pyrrole-2,5-dione} with Diels-Alder reaction,series of Poly{(NVK-co-AMA)-[Ln(Qf)3MP]}(Ln = La,6;Nd,7;Yb,8;Er,9;Gd,10)were obtained,respectively.Similarly,as to Poly{(NVK-co-AMA)-[Ln(Qf)3MP]}(Ln = Nd,7;Yb,8;Er,9),photo-excitation gave the Ln3+-centered nearinfrared luminescent properties,respectively.Finally,series of complex monomers [Ln(BA)3MP](Ln = La,11;Eu,12;Tb,13;Gd,14)(BA=(Z)-4-hydroxy-4-phenylbut-3-en-2-one)were synthesized,respectively.Moreover,through the grating-content control of complexes 12 and 13 with Diels-Alder reaction,the new Eu3+-Tb3+-containing metallopolymer-type hybrid materials Poly{(NVK-coAMA)(100:1)-(12-13)}were obtained,in which,at the molar ratio {1:(1:29)},photoexcitation(360 nm)rendered the hybrid material direct white-light(CIE = 0.323,0.311,CRI = 89 and CCT = 5963 K).