高比表面积和高稳定性的氢键基有机框架晶态功能材料的设计合成及性质研究

Hydrogen-bonded organic frameworks (HOFs) have emerged as a family of porous crystalline molecular functional materials, which are assembled from the discrete nonporous organic building blocks via hydrogen-bonding interactions. HOFs have important theoretical research significance and bright application prospective. Since 2010, design and synthesis of functional hydrogen-bonding organic framework materials with high specific surface area and high stability always is a hot topic in research community, and is very challenging. In order to catch the development opportunity and to lead the trend of this new kind of crystalline materials, a research project has been proposed to introduce the H-bond moieties including purine, pyrimidine and amido groups together with those modified species, which are widely existing in vivo, to enhance the hydrogen bonding interactions, to increase the diversity of organic skeletons as well as to explore the strategy in rationally constructing microporous and mesoporous HOFs; Introduction of photo-, electro-, and catalytic-active molecules, ions, nanoparticles or clusters into frameworks or pores to expand the realms of applications; HOFs-based membranes and devices will be fabricated by optimizing HOFs building units; With the help of theoretical simulation and various advanced spectroscopies, the assembly principle and structure-activity relationship of functional HOFs will be rationalized, HOFs chemistry will be gradually improved and completed for the purpose of providing supports and theory for the application of HOFs.

氢键基有机框架材料(HOFs)是一类新兴的多孔晶态分子功能材料，它由氢键连接不连续的无孔的构筑单元构筑而成，具有重要的理论研究价值和广阔的应用前景。自2010年以来，设计合成具有高比表面积和高稳定性的功能型氢键基有机框架材料一直是一个前沿的研究课题并非常具有挑战性。为了能够抓住这一新材料的发展机遇，引领这一材料领域发展潮流，申请人提出如下研究课题：拟开发生物体内广泛存在的嘌呤、嘧啶和酰胺类基团以及相关修饰基团作为氢键构筑子加强氢键连接作用，拓展有机分子骨架，探索微孔和介孔氢键基有机框架材料构筑策略；通过引入光、电和催化活性的分子，离子，纳米粒子或团簇到HOFs骨架或孔道内，拓展其应用领域；除立足于基础研究外，通过优化构筑单元制备HOFs薄膜和器件，满足实际应用要求；通过理论模拟和先进的谱学测试，探讨构筑原理和构效关系，逐渐完善HOFs化学，为HOFs材料的应用提供支撑条件和理论基础。

氢键基有机框架材料(HOFs)是一类新兴的多孔晶态分子功能材料，它由氢键连接不连续的无孔的构筑单元构筑而成，具有重要的理论研究价值和广阔的应用前景。自2010年以来，设计合成具有高比表面积和高稳定性的功能型氢键基有机框架材料一直是一个前沿的研究课题并非常具有挑战性。申请人基于科研课题“高比表面积和高稳定性的氢键基有机框架晶态功能材料的设计合成及性质研究”的研究目标开展了如下的研究内容：开发生物体内广泛存在的嘌呤基团以及容易合成的羧基作为氢键构筑子，拓展有机笼分子作为有机分子骨架，获得了一例比表面积高达1900 m2 g‒1的HOF、两例具有较好溶剂耐受性的HOF和一例具有光相应气体吸附行为的多孔有机分子晶体，还通过后合成策略构筑了具有分离丙炔丙烯性能的微孔HOF；通过后合成引入光催化和有机催化活性的分子和离子以及直接引入氧化还原活性基团到HOFs骨架上，拓展其应用光催化、有机催化和锂离子电池等领域；通过理论模拟和先进的谱学测试，探讨构效关系，完善HOFs化学，为HOFs材料的应用提供支撑条件和理论基础。此外，还进行了功能有机晶体、有机笼、多孔有机聚合物和共价有机框架方面的研究工作，交叉融合了多个领域的研究内容。相应的进展和成果为多孔有机材料领域的研究积累了一定的知识和研究素材。