二茂铁基咪唑二羧酸金属-有机骨架的制备与性能

We hope to introduce the ferrocenyl group into the imidazole-4,5-dicarboxylate system getting a new type of imidazole dicarboxylate multifunctional ligand. Several novel metal-organic frameworks (MOFs) can be afforded by the reactions of these ferrocene-based imidazole dicarboxylate compounds with the metal salts under mild conditions. The MOFs are characterized by EA, NMR, IR and single-crystal X-ray crystallography. The coordination features of the ferrocenyl imidazole dicarboxylate ligands are studied. Furthermore, the electrochemical and thermal properties of the MOFs are investigated. We believe that coordination modes and abilities of the ferrocenyl imidazole dicarboxylate ligands must change significantly due to the stereo and electrical effect of the ferrocenyl group. Interesting points: (1) To design promising organic ligands, the coordination features of the ferrocene-based imidazole dicaroxylates will be explored from both theoretical and experimental aspects. (2) The structure-effect relationship of the MOFs containing the ferrocenyl imidazole dicarboxylates will be researched.

引入具有夹心构型、性能特殊的二茂铁基团到咪唑-4,5-二羧酸体系，制备出独特的二茂铁基咪唑二羧酸多功能配体。采用溶剂挥发法或者低温溶剂热法，使此类配体与金属盐自组装，得到多个二茂铁基金属-有机骨架材料。通过对其分子结构的表征，研究二茂铁基咪唑二羧酸配体的配位特点，随后考察二茂铁基对金属-有机骨架的电化学、热稳定性等的影响，为构筑新型的二茂铁基金属-有机骨架功能材料提供了新思路。 突出意义：（1）对二茂铁基咪唑二羧酸的配位特性进行理论预测和实验验证, 指导此类配体的设计；（2）研究二茂铁咪唑二羧酸基金属-有机骨架的构效关系，开辟应用研究新渠道。

采用三种2-位二茂铁基咪唑二羧酸衍生物，单独或者在中性含氮配体的存在下，与金属盐通过溶液反应，制得了12个相关配合物，需要指出的是，由于此类配合物单晶的培养比较困难，因此它们的分子结构的表征主要以波谱分析为主。主要通过元素分析、红外、核磁图谱对它们的分子结构进行了测试。研究了二茂铁咪唑二羧酸衍生物的配位特性，并进一步研究了这些配合物的热稳定性以及电化学性能。.在此基础上，重点研究了4个2-位芳香基取代的咪唑二羧酸构筑的Eu和Tb发光金属有机框架的合成和小分子识别性能，提出了识别机理。