基于混合桥联的3d-3d 杂自旋类多孔单链磁体的构筑与性能研究

In recent years, porous magnet materials have attracted more and more considerable interest. The study of porous single-chain magnets in the field of heterospins 3d-3d complexes is still a virgin soil. Therefore, in this project, a series of multifunctional complexes with the novel tetrazolate-carboxylate / tetrazolate-azide bridges were synthesized by heterospins metal ions (Fe(II)-Fe(III)、Co(II)-Cu(II)、Mn(III)-Ni(II)、Mn(III)-Fe(III)、Fe(III)-Co(II))and tetrazolate and derivatives and / or halogen-like (azide ions). We will study different spins and spin ratios and adsorption/ desorption guest molecules tune structures and magnetic behaviors and study influence magnetic properties by different spins and spin ratios and different guest molecules in the porous. We will explore the approaches and pathways toward tuning the properties of single-chain magnet and improving the blocking temperature. This research will provide studying foundation, academic value and application prospect from the single magnetic complexes to multifunctional molecular materials. Magnetic modulation under adsorption/ desorption guest molecules for their promising applications such as magnetic sensors, magnetic separation media. magnetic switchers and multifunctional magnetic devices.

近年来，具有多孔性质的分子磁性材料越来越受到人们的重视。在此领域3d-3d杂自旋多孔单链磁体尚未见报道。为此，本项目采用四唑类配体或/和类卤素与顺磁性金属离子（Fe(II)-Fe(III)、Co(II)-Cu(II)、Mn(III)-Ni(II)、Mn(III)-Fe(III)、Fe(III)-Co(II)等）合成具有新颖的化学桥来传递磁性的四唑-羧基/类卤素混桥多功能配合物。研究不同自旋离子及比例对磁性的调控作用，以及在客体吸脱附过程中骨架可能发生的变化，从而导致磁性的变化，并研究孔道中不同的客体分子对磁性质的影响。探索调控单链磁体性质、尤其是提高其工作温度的方法和途径。这为从单一磁性质的分子化合物向具有复合功能的分子材料的研究奠定基础，具有很高的学术价值和应用前景。这种不同自旋离子及比例和客体分子调控的磁性材料在磁性传感、磁性开关、磁性分离以及多功能磁性器件等方面有潜在的应用价值。

近年来，合理的设计和合成配合物磁性材料在配位化学和材料科学领域吸引广泛的兴趣。本课题以多功能有机配体（四唑类，羧酸类等）和/或无机小分子（叠氮离子）与过渡金属离子在常规或水热（溶剂热）或原位的条件下进行配位组装获得了系列金属配合物，研究了它们相关的性质，探索了结构与性能的关系，发现了些有趣的磁行为如慢弛豫自旋玻璃行为、铁磁有序行为、自旋倾斜磁行为等。同时本课题在多孔配合物，发光材料等研究方面也取得了一些创新性的成果。有关研究成果已在Dalton Trans.，CrystEngComm., RSC Adv., Inorg. Chim. Acta等国内外刊物上发表SCI论文10余篇，其中影响因子大于4.0的论文3篇。