基于氰基桥联金属簇合物的磁性功能材料设计合成与性能研究

Magnetic molecular functional materials have attracted much attention due to the structural diversity, characteristics of easy to processing molding, and so on. In this proposal, the research target is to construct various functional cluster polymers with different dimension and specific magnetic features from the assembly of designed cyano-bridged metal cluster with high spin states and strong magnetic anisotropy and organic bridging ligands, metal organic functional units and stereo restrain groups with super exchange interactions. The influence of the structural and electronic factors on magnetic properties of these functional cluster polymers will be explored. Those various structural and electronic factors comprise the molecular structure, steric configuration, organic bridging ligands, cyano-bridged metal clusters and their electronic structures, as well as the ground state spins of the clusters. The influencing mechanism for the sub-structure units of functional cluster polymers on the macroscopical magnetic properties will be studied and elucidated. It also aims at synthesis and preparation of molecule-based magnets with both three-dimensional ordered structures and high Tc temperatures, with the important goal to practically application of molecule-based magnet based on cyano-bridged metal cluster as functional magnetic materials.

磁性分子功能材料因其结构多样性、易于加工成型等特点而备受关注。本研究拟通过设计具有高基态自旋及强磁各向异性的氰基桥联金属簇合物，与具有超交换作用的多种有机桥连基团、金属有机功能单元、立体抑制基团等组装，建构多种具有不同维数和特定磁性能的功能簇聚物。研究与探讨功能簇聚物的分子结构、空间构型、有机桥连基团和氰基桥联金属簇合物及其基态自旋、电子结构等因素是如何影响功能簇聚物的磁性能。尝试阐明功能簇聚物的各种亚结构单元对其宏观磁性能的影响规律。合成与制备三维有序的高Ｔc温度的分子基磁体，探索这类基于氰基桥联金属簇合物的分子基磁体在磁性功能材料研究领域的实际应用。

本项目致力于氰基桥联金属配合物的设计、合成及其磁性能研究。申请人系统地研究了基于吡啶类有机桥联配体的氰基桥联金属配合物设计合成，探讨了有机桥联配体对氰基桥联金属配合物结构与性能关系的影响，为合成具有非典型氰基金属前驱体的氰基桥联金属配合物提供了新的途径。此外，申请人还研究了基于羧酸类金属前驱体[M(2,4-pydca)2]2– (M = Cu, Co)的金属配合物设计合成，通过引入镧系金属和碱土金属制备了系列杂双金属配合物，研究了这类配合物的磁性能；同时，申请人还探讨了辅助配体和合成方法对金属配合物结构和性能的影响。上述相关研究成果分别发表在国际学术期刊Dalton Transactions, CrystEngComm, Journal of Molecular Structure, Journal of Cluster Science, Journal of Chemical Science和Molecular Crystals and Liquid Crystals等杂志上。