Multifunctional Microporous Hydrogen-Bonded Organic Framework Materials

非技术摘要材料在提高我们生活质量的先进技术中起着至关重要的作用。在固态与材料化学计划的支持下，本项目将通过氢键相互作用从有机化合物中设计和合成新型微孔材料。与传统的微孔材料如沸石和活性炭相比，它们可以直接合成、表征、再生和加工，并且成本低。它们可用于分离和生产对能源、环境和制药应用至关重要的许多化学品。拟议中的圣安东尼奥得克萨斯大学项目为代表性不足的少数民族和女性本科生和研究生提供了特殊的教育机会，并促进了广泛的国家/国际研究合作，帮助他们为未来在学术界和工业界的职业生涯做好准备。技术摘要本项目旨在从多种具有强氢键基序的有机建筑连接体中构建自组装多功能微孔氢键有机框架（霍夫）材料。两个独特的氢键基序DAT（DAT = 2，4-二氨基-1，3，5-三嗪-6-基）和CA（CA = -COOH）被引入到许多有机连接体中，用于构建多孔HOF，其孔可以系统地调节和官能化。这些新型的多孔材料将被检查用于小分子的分离，手性醇和胺的对映选择性分离，以及醇的非均相催化氧化成其相应的羰基化合物，酮酯的不对称氢化，以及不对称二乙基锌和炔基锌加成合成手性醇。该研究对可持续能源和对映体纯化合物的分离具有重要意义。一些小分子如C2-6烃、二甲苯和噻吩异构体的分离和纯化在工业上非常重要;然而，非常具有挑战性和耗能。新型微孔霍夫材料用于小分子分离纯化的实现提高了一些现有分离技术的分离纯化效率和能力，从而节省了能源成本。在再生方面，微孔霍夫材料上级其他已建立的多孔材料，因为它们可以通过简单的重结晶容易地回收。对映体纯微孔霍夫材料的出现不仅可以降低这些重要有机中间体的生产成本，而且可以为合成新的生物活性化合物以及医药、农业和精细化学品提供新的对映体纯有机中间体。

Non-technical AbstractMaterials play a crucial role in advanced technologies that can improve our life quality. With the support of the Solid State and Materials Chemistry program, this project will design and synthesize novel microporous materials from organic compounds through hydrogen bonding interactions. Compared with traditional microporous materials such as zeolites and activated carbons, they can be straightforwardly synthesized, characterized, regenerated and processed, and are of low cost. They can be applied to the separation and production of a number of chemicals important for energy, environmental and pharmaceutical applications. The proposed project at the University of Texas at San Antonio provides exceptional educational opportunities and facilitate extensive national/international research collaboration for underrepresented minority and women undergraduate and graduate students, helping them to prepare their future careers in academia and industry. Technical AbstractThis project aims to construct self-assembled multifunctional microporous hydrogen-bonded organic framework (HOF) materials from a variety of organic building linkers with strong hydrogen bonding motifs. Two unique hydrogen bonding motifs DAT (DAT = 2,4-diamino-1,3,5-triazin-6-yl) and CA (CA = -COOH) are incorporated into a number of organic linkers for their construction of porous HOFs whose pores can be systematically tuned and functionalized. These novel porous materials will be examined for separations of small molecules, enantioselective separations of chiral alcohols and amines, and heterogeneous catalytic oxidation of alcohols to their corresponding carbonyl compounds, asymmetric hydrogenation of keto esters, and asymmetric diethylzinc and alkynylzinc additions to synthesize chiral alcohols. The proposed research has significant impacts on the sustainable energy and separations of enantiopure compounds. Separation and purification of some small molecules such as C2-6 hydrocarbons, xylene and thiophene isomers are industrially very important; however, very challenging and energy-consuming. The realization of novel microporous HOF materials for the separation and purification of small molecules enhance the separation and purification efficiency and capacities of some existing separation technologies, and thus save energy costs. In terms of regeneration, microporous HOF materials are superior to other established porous materials because they can be easily recovered through simple recrystallization. The emerging of enantiopure microporous HOF materials for separations of enantiopure compounds can not only reduce the cost for the production of these important organic intermediates, but also initiate the new discoveries of these enantiopure organic intermediates for the synthesis of novel biologically active compounds, and pharmaceutical, agricultural, and fine chemicals.