含多金属氧簇超分子体系的设计与构筑：从分子组装到材料制备

Supramolecular materials generated by self-assembly have diverse applications in nano-materials, supramolecular devices, molecular regulation, and so on. This project intends to graft Hamilton wedge- and barbiturate-functionalized groups on the two sides of an Anderson-type polyoxometalate cluster, resulting in polyoxometalate-containing hybrids with two binding sites. Furthermore, we will also prepare barbiturate-containing compound with three, four or six binding sites. Mixing the resultant polyoxometalate-containing hybrid and barbiturate-containing compound will afford the formation of linear and cross-linked supramolecular materials by means of sextuple hydrogen bonding interactions. With the aim to summarizing the possible applications, the influences of assembly behavior in solution, and various properties will be carefully studied through the research of concentration, molar ratio, solvent polarity and temperature. By design and construction of polyoxometalate-containing two-dimensional or three-dimensional ordered supramolecular structures, and study of the properties of supramolecular materials, this project aims to study the corresponding relations between complex structures and special functions, and combine the chemical structures, assembly behaviors and material properties. Our goal is to realize the unification of molecular assembly and material preparation.

通过自组装来设计开发新型超分子材料在纳米材料、超分子器件、分子调控等方面显示出广泛的应用前景。本项目拟将汉密尔顿楔形受体和巴比妥酸通过共价键改性到Anderson型多金属氧簇两端，形成含多金属氧簇的双头基杂化物。进一步地，制备巴比妥酸为端基的三头、四头和六头基化合物，利用位于多金属氧簇两端的汉密尔顿楔形受体和巴比妥酸之间的六重氢键作用，自组装形成直链型与交联型超分子材料。深入研究杂化物与多头基化合物在不同摩尔比、浓度、溶剂极性及温度条件下的组装行为，并对形成的超分子材料的各种性能进行有益探索，总结材料的可能应用方向。本项目通过设计和构筑含多金属氧簇的二维或三维有序的自组装结构体系，并检测相应材料的各种性能，旨在研究材料的复杂结构与其特殊性能之间的对应关系或内在规律，期望将结构构筑与功能组装相结合，实现分子组装与材料制备的统一。

通过自组装来设计开发新型超分子材料在纳米材料、超分子器件、分子调控等方面显示出广泛的应用前景。其中，通过超分子自组装设计并构建具有特定形貌的含POM的超分子杂化材料，引起了科研者们的广泛关注。这是由于其组装行为带来的独特超分子结构形貌，致使其作为功能材料展现出显著的特殊优异性能。然而，影响因素究竟如何影响含POM杂化物的超分子结构依然是很难确定的。在本项目中，我们将巴比妥酸与汉密尔顿楔形受体通过共价键改性到Anderson型多金属氧簇上，分别制备了巴比妥酸–POM–Tris杂化物、巴比妥酸–POM杂化物与汉密尔顿楔形受体–POM杂化物，并使用核磁、质谱、红外光谱及元素分析对杂化物分子结构进行了详细表征。通过研究单独的杂化物及混合物在不同溶剂极性条件下的组装行为，构筑了不同含POM的三维有序超分子结构形貌。进一步地，研究了相应超分子材料的催化活性，发现具有特定超分子结构形貌的超分子材料对有机染料具有良好的催化活性。此外，研究了含POM超分子凝胶对有机染料与抗癌药物的包封与释放能力，结果表明由巴比妥酸–POM杂化物与双汉密尔顿楔形受体化合物通过六重氢键作用构筑的超分子杂化材料在有机小分子染料与药物载体领域具有潜在的应用前景。