| In consideration of the potential applications of Ln3+-centered(Nd3+,Yb3+,Er3+,etc.)near-infrared luminescence in optical communication,night vision,biological imaging and medical treatment,there has an urgent requirement of organo-Ln3+hybrid materials with excellent photo-physical property.In this thesis,two series of PVK-supported hybrid materials grafted from bis-benzimidazole-Ln3+and Schiff-base-Ln3+complexes were obtained,respectively,where besides excellent near-infrared luminescent performance,their high thermal stability,good mechanical strength and film-forming were also realized.Moreover,using the selected PVK-supported hybrid material as the light-emitting layer,polymer light-emitting diode?NIR-PLED?with Ln3+-centered(Nd3+,Yb3+,Er3+,etc.)near-infrared luminescence was developed.Firstly,through the self-assembly of the?-diketone organic ligand HL1?HL1=?Z?-3-methyl-1-phenyl-4-?2,2,2-trifluoro-1-hydroxyethylidene?-1H-pyrazol-5?4H?-one?,the bis-benzimidazole ligand 4v-bpbim?4v-bpbim=1-?4-vinylbenzyl?-5-?1-?4-vinylbenzyl?-2-?pyridin-2-yl?-1H-benzo[d]imidazol-5-yl?-2-?pyridin-2-yl?-1H-benzo[d]imidazole?and LnCl3·6H2O?Ln=La,Nd,Yb,Er,Gd?,series of dinuclear while vinyl-modified complex monomers[?4v-bpbim?Ln2?L1?6]?Ln=La,1;Nd,2;Yb,3;Er,4;Gd,5?were obtained,respectively.Moreover,further based on their copolymerization with NVK?N-vinylcarbazole?in the presence of AIBN?2,2-azobisisobutyronitrile?,series of PVK-supported metallopolymer-type hybrid materials Poly?NVK-co-[?4v-bpbim?Ln2?L1?6]?were afforded,respectively.Furthermore,besides the characterization of elemental analysis?EA?,1H NMR,FT-IR and GPC,the photo-physical properties of complex monomers 1-5 and their metallopolymer-type hybrid materials were also explored.The results showedtNd=4.12ms and?NdL=0.47%for complex 2,tYb=22.86ms and?LYb=0.98%for complex 3 andtEr=7.33ms and?ErL=0.008%for complex 4,respectively.In contrast,for the metallopolymer-type hybrid materials Poly?NVK-co-[?4v-bpbim?Ln2?L1?6]??200:1?,the significantly improved NIR luminescence oftNd=6.69ms and?LNd=0.52%for Poly?NVK-co-2?,tYb=38.35ms and?LYb=1.11%for Poly?NVK-co-3?andtEr=19.83ms and?ErL=0.19%for Poly?NVK-co-4?,respectively,was realized.Secondly,based on the self-assembly of the complex precursor of[Zn?L2??4vp?]?H2L2=N,N'-bis?salicylidene?-1,2-diamine,4vp=1-?chloromethyl?-4-vinylbenzene?,the?-diketone HL1 and LnCl3·6H2O?Ln=La,Nd,Yb,Er,Gd?,the series of hetero-dinuclear complex monomers[Zn?L2??4vp?Ln?L1?3]?Ln=La,6;Nd,7;Yb,8;Er,9;Gd,10?were obtained,respectively.Especially,based on the X-ray single crystal diffraction?XRD?analysis of the representative complex monomer[Zn?L2??4vp?Gd?L1?3]?10?,the bridging of the five-coordinate Zn2+ion and the eight-coordinate Gd3+ion leads to the formation of a stable Zn2+-Gd3+-heterobinuclear structural framework.Meanwhile,the photophysical properties of[Zn?L2??4vp?Ln?L1?3]?7-9?are as follows:7:tNd=2.98ms and?LNd=0.58%;8:tYb=26.82ms and?LYb=1.04%;9:tEr=16.36ms and?LEr=0.01%.Finally,through the copolymerization of one of the complex monomers[Zn?L2??4vp?Ln?L1?3]?Ln=La,6;Nd,7;Yb,8;Er,9;Gd,10?with NVK,the series of PVK-supported metallopolymer-type hybrid materials Poly?NVK-co-[Zn?L2??4vp?Ln?L1?3]??Ln=La,6;Nd,7;Yb,8;Er,9;Gd,10?were obtained,respectively.In dependence of their characterization and photo-physical property,at a feeding molar ratio of 75:1,Poly?NVK-co-7?givestNd=7.14ms and?NdNd=0.71%,Poly?NVK-co-8?givestYb=31.86ms and?YbL=1.34%and Poly?NVK-co-9?givestEr=20.12ms and?LEr=0.20%,respectively.Especially,using Poly?NVK-co-[Zn?L2??4vp?Yb?L1?3]??75:1?as the light-emitting layer,NIR-PLED was designed,and the performances of the turn-on voltage at 9 V,the maximum eternal quantum yields?EQE?of 0.049%and the maximum irradiance is 78.68mW/cm2 at 16 V,were realized,respectively. |
PDF Full Text Request