Novel Open Frameworks of Metals, Metal Complexes, or Metal Clusters Interconnected with Multifunctional Linkers

技术摘要具有新型开放式骨架结构的新材料将从分子构建块如单个金属原子、金属络合物和金属簇合成。金属中心将通过配位连接到多齿有机连接剂，如聚羧酸酯或聚膦酸酯。另一方面，阳离子金属络合物将通过广泛的电荷辅助氢键与有机二磺酸盐相互连接。最后，金属簇如最近开发的钼-聚氧乙烯酸盐具有易于共价互连的外部磷酸根或膦酸根基团。使用适当的有机二膦酸酯将这些簇桥接成具有超大开口的框架，这些开口由互连簇节点的大尺寸产生。这些开放式框架材料的交换性能以及它们的光学和磁性的变化，可能会发生在这样的交换溶剂分子或电荷平衡阳离子将得到解决。合成技术，结构表征和性能测量将为培养研究生和本科生提供机会，使他们掌握在固态化学和溶液化学方面进行研究的尖端工具和方法。该项目与圣母大学现有的基础设施和从代表性不足的群体中招收学生的计划相结合，将用于吸引少数民族和女性同事。该项目旨在影响经济的各个重要领域，如新催化剂的开发，用于分离和离子交换的新膜材料，石油裂化，纳米技术以及光学和传感器材料。这些应用中的许多又将导致更好的化学加工和更高的能源使用效率。一个例子是这些材料作为安全和环境友好的气体储存和运输容器的潜在用途。该项目的更广泛影响还将是提供受过高等教育和实际培训的博士学位。学生和博士后研究员在科学和工程的前沿推进高质量的研究。

Technical Abstract New materials with novel open-framework structures will be synthesized from molecular building blocks such as individual metal atoms, metal complexes, and metal clusters. The metal centers will be linked by coordination to multidentate organic linkers such as polycarboxylates or polyphosphonates. The cationic metal complexes, on the other hand, will be interconnected via extensive charge-assisted hydrogen bonding to organic disulfonates. Lastly, metal clusters such as the recently developed molbydenum-polyoxometalates have external phosphate or phosphonate groups that are readily available for covalent interlinking. The use of appropriate organic diphosphonates will bridge such clusters into frameworks with extra large openings resulting from the large size of the interconnected cluster nodes. The exchange properties of these open-framework materials as well as changes in their optical and magnetic properties that may occur upon such exchange of solvent molecules or charge-balancing cations will be addressed. The synthetic techniques, structure characterization, and properties measurements will provide opportunities for training graduate and undergraduate students in cutting-edge tools and methodologies for doing research in both solid-state chemistry and solution chemistry. The project, in combination with the existing University of Notre Dame infrastructure and programs for recruiting students from underrepresented groups, will be used to attract minority and female coworkers. Non-Technical Abstract This project aims to impact various important areas of the economy such as the development of new catalysts, new membrane materials for separation and ion exchange, petroleum cracking, nanotechnology, and optical and sensor materials. Many of these applications will, in turn, lead to better chemical processing and to higher energy-use efficiencies. An example is the potential use of these materials as safe and environmentally benign containers for gas storage and transportation. The broader impact of the project will be also on providing highly educated and practically trained Ph.D. students and postdoctoral fellows to advance high quality research at the forefront of science and engineering.