基于稀土配位聚合物的新型高效荧光材料的构筑、可调的发光性质及白光发射

Construction and fabrication of highly effective luminescent materials is still a big challenge in the research field of material science. We will focus our research on the construction and fabrication of rare earth (RE(III)) coordination polymers with RE(III) metal as main luminescence center and F-rich and N-rich ligands as auxiliary luminescence groups to screening novel highly effective luminescent materials. The F-rich and N-rich ligands will be firstly design and synthesized or selected. After solvothermal reaction with rare earth (RE(III)) metal, a group of rare earth (RE(III)) coordination polymer will be synthesized, and then the crystal structures, thermal stabilities will be studied. Luminescence property as the most important property of the complexes will be investigated in detail, such as surveying the photoluminescence of the complexes, exploring the influence of the ligands on the luminescence of the complexes and trying to obtain the relation between the ligands and synthesized rare earth (RE(III)) luminescence coordination polymers. Based on these preliminary research, the means of the RE(III)-doped approach will be tried to modulate the luminescence properties of the obtained complexes, and ultimately to achieve the goal of white-light emission. The luminescence properties, the quality of the white light and the energy transfer mechanism between different RE(III) ions will be investigated. The influence of different dopants and the doping concentration of RE(III) ions on the luminescence of the doped complexes will be also explored. Thus, based on the rational design of F-rich and N-rich ligands and carful selection of metal ion, high-efficiency white-light emitting materials of the rare earth single-metal complexes or f-d heterometallic complexes will be prospectively obtained. The CIE(Commission Internationale de l'Eclairage) chromaticity coordinates, color rendering index(CRI) and correlated color temperature(CCT) of these high-efficiency white-light emitting materials can meet the requirement of the color properties for solid-state lighting (SSL). Moreover, the work will provide experimental results and theoretical basis for white-light emitting materials based on rare earth coordination polymers in promising practical applications.

构建高发光效率的荧光发光材料仍然是新型材料研究领域的难点和热点。本研究主要是以稀土离子作为发光中心，选择富含F和富含N有机配体作为辅助发光基团，合成结构新颖的稀土配位聚合物以期筛选新型高发光效率的荧光发光材料。分析配合物的晶体结构并表征其热稳性等相关性质。以探讨稀土离子的荧光发光为中心，研究配体和配合物的结构与发光性质的关系，获得高发光效率的发光配合物。在此基础上，我们将进一步通过稀土离子掺杂的手段实现掺杂稀土配合物的发光性质的调控和白光发射。研究掺杂配合物的发光性质、色纯度以及稀土离子之间的能量转移机制，分析研究不同掺杂稀土离子及不同掺杂摩尔浓度的配合物发光。基于配体的设计和合理选择金属离子，实现高效单组份稀土配合物或异金属(f-d)配合物的直接白光发射，并使颜色的色坐标、显色指数，色温达到固体发光材料颜色的需求。本研究将为稀土配合物作为白光发射材料的潜在应用提供实验和理论基础。

构建高发光效率的荧光发光材料是新型材料研究领域的难点和热点。稀土Eu（III）和 Tb(III)离子，在紫外光激发下，分别发射强的红光和绿光。稀土配位聚合物的白光发射仅有少量的文献报道，主要是使用“红、绿、蓝”光（“GRB”）三基色组份掺杂获得的,而且发光效率较低。选择合适的有机多功能羧酸做桥联配体，引入邻菲啰啉衍生物等含N大共轭螯合辅助配体，可构筑结构新颖的高效发光稀土配位聚合物，可实现配位聚合物发光性质的调控及白光发射。. 选用刚性/半刚性多酸如四氟邻苯二甲酸(H2TFpht)、4,4’-二苯醚二甲酸(4.4’-oba)、萘二磺酸(nds)、间苯二甲酸(1,3’-BDC)、2,3’-二苯醚二甲酸（2,3’- H2oba）和5-(2-羧基-苯氧基)间苯二甲酸（O-cpiaH3）等为桥联配体，邻菲罗啉(phen)或1H-咪唑-[4,5-f][1,10]-邻菲罗啉(IP)等为辅助配体，水热法合成了60余个稀土/过渡-有机配位聚合物。用元素分析、ICP、IR和X-射线衍射分析等表征配合物，测定晶体结构，用TG-DTA和变温X-射线粉末衍射进行配合物的热稳定性分析，在荧光分光光度计上记录样品的发光光谱、测定发光量子产率和寿命。重点研究稀土配合物的发光性能、白光发射及荧光传感。.获得了高发光效率稀土配合物。配合物Eu(O-cpia) (phen)(H2O) 荧光量子产率高达83.36 %；[Ln2(2,3’-oba)3(phen)2]n Eu(III)/Tb(III) 荧光量子产率高达75.57%/41.86%；[Eu2(1,3-BDC)2(phen)2ox]荧光量子产率为63.21%。基于配合物[Ln(4,4’-oba)(phen)(ox)0.5， Gd-Eu-Tb三掺杂配合物实现高发光效率的白光发射，量子产率高达38.74%；实现了基于[Ln2(1,5-NDS)(IP)(H2O)0.5]·9H2O的 Sm(III)配合物单组份以及 Gd-Eu、Dy-Eu、Pr-Eu双组份掺杂配合物的白光发射。探讨了配体、配合物的结构、掺杂稀土离子与发光性质的关系。实现了发光配合物作为化学传感器检测硝基苯、Fe3+离子、PO43-和F-等。发表SCI论文18篇。. 为设计高效发光稀土-有机配位聚合物和为在理论研究和开发稀土配位聚合物的白光发射材料和荧光化学传感器提供实例和基础。