本项目拟合成一系列含不同中心杂原子，特别是含功能性稀土杂原子的Anderson型多酸，然后利用不同类型的含三羟甲基基团的tris类有机配体，通过两步酯化反应，对其进行分步修饰，可控高效地合成Anderson型多酸的不对称双边修饰有机衍生物。本项目将结合理论计算研究Anderson型多酸不对称修饰的反应机理，优化反应条件，发展可控制备不对称双边有机修饰Anderson型多酸衍生物的新方法，构建新颖的手性多酸。并通过亚胺化、酯化、偶联等有机反应或无机配位反应，将其与合适的功能有机分子、过渡金属或有机金属离子、多酸簇或金属簇进行组装，合成一系列新颖的多酸基有机无机杂化分子，对它们的结构进行表征，考察其超分子组装、催化、铁电和非线性光学等性能，研究其结构与性能之间的构效关系，为开发新型多酸基分子材料奠定基础。

In this project, Anderson-type polyoxometalate cluters containing different metal ions, especially rare earth ions, as the central heteratom will be synthesized. They will be modified stepwise by two different triol ligands to prepare asymmetrically-substituted organic derivatives of Anderson-type POMs. Combined with theoretical computation, the reaction mechanism of asymmetric modification of Anderson-type POMs will be studied and the reaction conditions will be optimized. The controllable synthetical route to asymmetrically-substituted organic hybrids of Anderson-type POMs clusters will be developed, and novel chiral POM clusters will be fabricated. These asymmetric POM-organic hybrids will be assembled with proper functional organic molecules, transitional metal or organometallic ions, POM cluters and metal cluters by imidoylation, esterification, coupling reaction and coordination reaction to obtain a series of POMs-based organic-inorganic hybrids. The sturctures and the supramolecular assembly, catalysis, ferroelectricity and nonlinear optics properties of these hybrids will be explored,and the relationship of crystal structures and properties will also be investigated. This project will lay down the foundation for developing POMs-based molecular materials.