光响应型多核稀土配位超分子笼的配位导向自组装合成与磁性能调控探索

随着信息技术的高速发展，高密度磁存储材料的研究日益受到人们的关注。单分子磁体因其可以在分子水平上实现信息的高密度存储并易于器件的小型化，在量子计算、自旋电子器件等领域有着潜在的应用价值，成为了磁性材料研究领域的一个研究热点。本项目旨在利用配位导向自组装的策略，设计合成系列光响应型稀土配位超分子笼，实现自由基桥连配体构筑的四核以上该类型笼零的突破。利用后合成修饰和刺激响应的研究方法，研究后修饰过渡金属离子、光照诱导框架自由基、空腔内包裹稳定自由基以及包裹自由基之后的光诱导电荷转移(主体自由基和客体自由基之间的主客体相互作用)对稀土配位超分子磁性能的调控，阐明稀土之间的磁相互作用以及稀土离子的磁各项异性的协同效应能否提升稀土配位超分子的磁性能。本课题的实施不仅会丰富稀土配位超分子笼的结构类型，而且会加深人们对离域电子调控稀土磁性能的理解，为寻找有实际应用价值的单分子磁体做出一定的贡献。

With the rapid development of information technology, the investigations focused on high-density magnetic storage material have attracted much attention of scientists. Single molecule magnets (SMMs) become a research hotspot in the field of magnetic materials, due to their potential applications in high-density data storage at the molecular level, smaller magnetic devices, quantum computations and spintronic devices. The aim of this project is to adopt the coordination-directed self-assembly strategy，design and synthesize a serious of rare-earth coordination supramolecular nano-cage with light-responsive behavior, and achieve higher nuclear (nuclear larger than 4) supramolecular cage fabricated by radical bridging ligands. With the post-synthetic modification and stimulus response methods, the effect of post-synthetic modification of transition metals, light-induced framework radical, stable free radical encapsulated in the cavity of cage and the light-induced charge transfer after the free radical encapsulation (interactions between host radicals and guest radicals) on tuning magnetic behavior of the rare-earth coordination supramolecular will be investigated. The synergistic effect of the magnetic interactions and anisotropy of rare-earth ions on enhancing the magnetic behavior of the rare-earth coordination supramolecular will also be investigated and elucidated. This work will not only enriches the structure type of rare-earth supramolecular cage, but also helpful for understanding the effect of delocalized electrons on modification the magnetic behavior of rare-earth ions, and make some contributions for seeking SMMs with potential application.