Highly porous architectures through designed rational self-assembly

配位聚合物和金属有机框架（MOFs）的范围从微孔材料到介孔材料，在过去的15年中获得了惊人的研究兴趣。这些配位基元是由各种各样的金属支点和有机连接体组合产生的，并且存在着合成合理设计的mof的潜力，具有广泛的应用范围（例如，与绿色化学和燃料电池技术相关的mof内气相反应催化，氢和甲烷燃料电池的简便气体储存和回收，石油和天然气工业中的二氧化碳封存以及独特的光学开关）。本课题主要研究顺磁性金属的大环和金属-有机骨架的结构-功能性质。新的有机连接物将被合成，以使框架在尺度的两端都表现出多孔性。为了研究客体分子的选择性吸收作为金属氧化态的函数，将以大孔径为目标，应用于小分子分离和存储领域；而小孔径将以具有高金属密度的功能材料为目标，应用于磁记忆存储领域的位模式介质材料。这两个领域的成功将产生广泛的影响，包括运输清洁燃烧燃料的船只，以及比现有技术更强的计算能力。实现这些目标所需的目标可以分为三大类：(a)新的金属有机框架和配位聚合物的设计、合成和表征，(b)金属配合物的气体吸附研究，作为小分子存储、分离或存储设备领域器件功能化的一步，以及(c)金属配合物的表面研究，作为比特模式介质领域器件功能化的一步。关于第三个目标，框架的顺磁性可以允许外部刺激来控制门控特性，而引入富电子取代基作为有机配体的外部锚点可以为多金属组件的可能表面附着提供位点。磁性MOF器件的应用尚未实现，部分原因是由于这些材料的薄膜制备困难，以及使用物理刺激来诱导开关。本研究计划的目标将在该领域贡献重要的新基础知识和应用知识。

Coordination polymers and metal-organic frameworks (MOFs) range from micro to mesoporous materials and have garnered a staggering amount of research interest in the past 15 years. These coordination motifs result from a large variety of metal pivots and organic linker combinations and the potential exists to synthesize rationally designed MOFs with an enormous range of applications (ex. intra-MOF catalysis of gas phase reactions related to green chemistry and fuel cell technology, facile gas storage and recovery for hydrogen- and methane-based fuel cells, CO2 sequestration in the oil-and-gas industry and unique optical based switches.) In this proposed research program, the structure-function properties of macrocycles and metal-organic frameworks with paramagnetic metals will be studied. New organic linkers will be synthesized in order to make framework that exhibit porosity at both ends of the scale: large pore size will be targeted in order to study the selective uptake of guest molecules as a function of metal oxidation state, with applications in the area of small molecule separation and storage, while small pore size will be targeted for functional materials that exhibit high metal density, with applications as materials for bit pattern media in the area of magnetic memory storage. Success in these two areas would have broad ranging implications, including vessels for the transport of cleaner burning fuels, and increased computing capabilities over current technology. The objectives required to meet these goals can be broken into three broad categories: (a) the design, synthesis and characterization of new metal-organic frameworks and coordination polymers, (b) gas adsorption studies of metal complexes as a step towards device functionalization in the area of small molecule storage, separation or memory devices, and (c) surface studies of metal complexes as a step towards device functionalization in the area of bit pattern media. In regards to the third objective, paramagnetic properties of the frameworks could allow for external stimulus to control gating properties, while introducing electron rich substituents as external anchors to the organic ligands could provide sites for possible surface attachment of the polymetallic assemblies. Magnetic MOF device application has not yet been achieved, in part due to the difficulties in the preparation of thin films of these materials, and the use of physical-stimulus to induce switching. The objectives of this research program will contribute significant new fundamental and applied knowledge in this area.