纳米孔洞型d-f混金属配位聚合物作为重金属离子荧光探针的研究

According to Hard-Soft acids and bases theory (HSAB theory), the nitrogen- containing organic polycarboxylic acids with rational structures are designed and synthesized as the linker, as a result that carboxyl oxygen atoms of the ligands coordinate with strong fluorescence of rare earth ions and the nitrogen atoms coordinate with the transition metal ions with half full or full d orbital electrons. Using hydrothermal/solvothermal method, the d-f Heterometal metal coordination polymers with nanoporous structure can be achieved by self-assembling. Using mixed metal coordination polymer porous structures and its unsaturated coordination sites and highly sensitive characteristic fluorescence of rare earth ions on the coordination environment, they are studied as the heary metal ions fluorescent probes of organisms or environmental chemistry to ascertain chemical mechanisms why the polymers with different porous structures being some ion fluorescence probes. This investigation intends to realize the design ideas that ligands carry out effective chemical regulation in the self-assembling process, so that some d-f mixed metal coordination polymer fluorescent probes with novel structures are achieved. This study also elucidate the regulating law and influencing factors of the polymer nanoporous size and shape, in which discover the coordination environment in nanometer holes with regard to the detected heary metalions and the chemical mechanisms that the rare earth ions sensitize or quench fluorescence. It can provide designing ideas, synthetic technology and basic theoretical guidance through this research in order to investigate mixed metal coordination polymer fluorescent probes in the organism and environment.

根据软硬酸碱理论，设计并合成结构合理的含氮类有机多羧酸作为连接体，使配体的羧基氧原子和荧光较强的稀土离子配位、氮原子和d轨道电子半满或全满的过渡金属离子配位，自组装得到具有纳米孔洞结构的d-f混金属配位聚合物晶体；利用混金属配位聚合物的孔洞结构及未饱和的配位点、稀土离子荧光对配位环境高度敏感的特性，研究其作为生物体和环境化学中重离子荧光探针，探明聚合物不同孔洞结构作为一些重离子荧光探针的化学作用机理。本研究拟实现配体在自组装过程中进行有效化学调控的设计思想，得到一些具有新颖结构的d-f混金属配位聚合物金属离子荧光探针，阐明聚合物纳米孔洞大小和形状的调控规律，揭示被检测重金属离子对纳米孔洞中配位环境的影响因素和稀土离子荧光敏化或淬灭的化学机理。通过本研究，为设计和研制生物体与环境中混金属配位聚合物重金属荧光探针提供设计思想、合成制备技术和基础理论指导。

根据有关文献合成和购买了一些含氮有机多羧酸配体，如2,2'-联吡啶-3,3', 6,6'-四羧酸，5-氨基二乙酸基间苯二甲酸，N,N,N',N'-四乙酸基-1,4-苯二胺，4-(吡啶-3-氧基)-邻苯二甲酸，5-羟基-2-吡啶羧酸，苯甲酮-3,3',4,4'-四羧酸，1, 4-双二氧1, 2-苯二酸，4-(2,2';6',2'')四吡啶-4'-苯甲酸，4-(3,5-二苯甲酸)-2,2:6,2’-吡啶，4-(2,2';6',2'')四吡啶-4'-苯甲酸等有机多羧酸配体，选择4f金属如Sm、Eu、Tb、Dy等元素和一些过渡金属如Zn、Cd等元素作为模板，构筑了系列的d-f混金属、过渡金属、稀土金属配位聚合物。找到了最佳的水热/溶剂热合成反应工艺条件，得到一些d-f混金属、过渡金属、稀土金属高维金属配位聚合物晶体；测试了d-f混金属、过渡金属、稀土金属配位聚合物晶体的重金属离子荧光探针等工作，研究了稀土离子的配位环境及其配体能量匹配，为发光的d-f混金属配位聚合物、过渡金属、稀土金属配位聚合物作为金属离子的探针的做好了基础工作。. 总结和探索了水热/溶剂热反应规律，发现了聚合物结构构型和成键模式，探讨了物质结构和荧光探针之间的内在关系；研究了发光的d-f混金属、过渡金属、稀土金属配位聚合物的荧光强度与被检测金属离子浓度之间的物理关系；提出了被检测离子进入金属有机框架后稀土离子荧光敏化或者淬灭的化学机理以及对配位聚合物稀土荧光特性的影响规律，阐明了配位聚合物的结构和作为离子荧光探针之间的内在关系及化学键作用。本项目共发表了16篇论文，并准备申请专利。