Synthesis and Characterization of Self-Supported Coordination Polymer Catalysts.

自支撑的层状配位聚合物表现出优异的催化性能，大大超过了其固定化配位聚合物的催化性能。在本方案中，我们想要利用这一结果，并研究这种更好的性能是否是这些配位聚合物催化剂的普遍性质。因此，我们的目标是开发新型的镝配位聚合物，评价它们在卡宾转移反应中的催化性能，并用固体核磁共振(如有必要结合DNP增强)、扫描电子显微镜、透射电子显微镜和原子力显微镜对其进行表征，以及催化剂的催化效率和对映体选择性以及催化剂的结构和动态性质之间的关系。特别是，我们将使用13C CP MAS和19F MAS核磁共振来表征主体材料的结构，DNP增强的19F固体核磁共振谱来研究缺陷位的数量和结构，以及变温2H固体核磁共振(静态和MAS线形分析)来研究桥联分子在配位聚合物中的动态行为。对于块体配位聚合物的合成，将使用不同大小和官能度的重位配体。通过配体大小调节配位层间距，通过配位交换的方法制备了不同的块体配位聚合物。以苯乙烯和重氮乙酸乙酯之间的环丙烷化反应为模型反应，建立催化剂结构和催化效率之间的关系，对所得配位聚合物的催化效率和选择性进行评价。下一步，我们将合成含手性二羧酸配体的配位聚合物，并对其在C-H插入反应中的催化效率和对映体选择性进行评价。最后，对层状本体配位聚合物剥离法制备的纳米薄片的催化性能进行了研究。

Self-supported layered dirhodium coordination polymers exhibit an excellent catalytic performance, which strongly exceeds the performance of its immobilized counterparts. In the present proposal, we want to exploit this result and study, whether such a better performance is a general property of these coordination polymer catalysts. Accordingly, our objectives are the development of novel dirhodium coordination polymers, the evaluation of their catalytic performance in carbene transfer reactions, and their characterization by solid-state NMR (if necessary combined with DNP enhancement), SEM, TEM and AFM, and a correlation between catalytic efficiency and enantioselectivity of the catalyst, and structural and dynamic properties of the catalyst. In particular we will employ 13C CP MAS and 19F MAS NMR to characterize the structure of the bulk materials, DNP enhanced 19F-solid state NMR spectroscopy to study the number and structure of defect sites and variable temperature 2H solid state NMR (static and MAS line-shape analysis) to investigate the dynamic behavior of bridging linkers in the coordination polymers. For the synthesis of bulk dirhodium coordination polymers, ditopic ligands with different sizes and functionality will be employed. By adjusting the layer distance via ligand size, various bulk dirhodium coordination polymers are prepared via ligand exchange. The resulting coordination polymers will be evaluated with respect to their catalytic efficacy and selectivity, employing the cyclopropanation between styrene and ethyl diazoacetate as model reaction to establish the relationship between the structure of the catalyst and its catalytic efficiency. In the next step, dirhodium coordination polymers containing chiral dicarboxylic ligands will be synthesized and their catalytic efficiency and enantioselectivity in C-H insertion reactions will be evaluated. Finally, the catalytic properties of nano-flakes prepared by exfoliation from the layered bulk-coordination polymers will be investigated.