Isoreticular MOFs derived from arylphosphonate linkers

衍生自芳基膦酸酯连接体的等网状 MOF

• 批准号: 415076322
• 负责人: Professor Dr. Jens Beckmann
• 金额: --
• 依托单位: Institut für Anorganische Chemie und Kristallographie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2018
• 资助国家: 德国
• 起止时间: 2017-12-31 至 2022-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/415076322?language=en
• 关键词: Isoreticular; MOFs; derived; arylphosphonate; linkers

The synthesis of metal-organophosphonate compounds (MOPh) by design is the ultimate goal of scientists working in the field of metal organic frameworks (MOFs). Metal-organophosphonate MOFs exhibit excellent chemical stability and they are less air sensitive compared to the conventional carboxylate MOFs. However, the reticular chemistry of MOPhs has not been developed yet and no isoreticular expansions have been reported using the metal-arylophosphonate chemistry to produce materials with predictable pore sizes. The ability to introduce predictable pore sizes into MOPh chemistry will create tremendous potential in medicinal and material applications etc. The structure and geometry of the bridging ligand is the most important factor determining the final structure of the MOFs. To establish the basics of MOPh reticular chemistry, linker molecules with different tether lengths and three-dimensional geometries need to be explored. To date, systematic studies to establish the reticular chemistry of MOPhs have not been conducted. Therefore, we have designed three complimentary geometries (denoted V, Y, X) of organophosphonate linkers with increasing tether lengths to study their metal complexes, to create predictable pores with selected transition metals ions plus Zn, Al and Ca metal ions. The first group of linkers is composed of V-shaped arylphosphonates including 1,2-bis(p-phosphonatophenyl)benzene, 1,2-bis(p-phosphonatobisphenyl)benzene and 1,2-bis(p-phosphonatoterphenyl)benzene and also at 1,3- positions. The Y-shaped second linker geometry includes the ligands 1,3,5-tris-(4-phosphonophenyl)benzene, 1,3,5-tris-(4-phosphonobisphenyl)benzene and 1,3,5-tris-(4-phosphonoterphenyl)benzene. The third group includes planar X-shaped tetratopic phosphonate ligands based on the porphyrine core and tetrahedral X-shaped linkers based on methane and silane cores expanding into three dimensions. The X-shaped linkers based on planar porphyrine core expanding in two dimensions include meso-tetra(4-phosphorylphenyl) porphine, meso-tetra(4-phosphorylbisphenyl) porphine, and meso-tetra(4-phosphorylterphenyl) porphine, and the fourth group of linkers have tetrahedral methane and silane cores expanding into three-dimensions, which includes methane tetra-p-tetraterphenylphosphonic acid, methane tetra-p-tetrabiphenylphosphonic acid, methane tetra-p-phenylphosphonic acid and their silane derivatives. This study will be the first systematic approach to establish the reticular chemistry of MOPh compounds using the arylphosphonate linkers by gradually extending their tether lengths. The synthesis of proposed linkers and their systematic structural studies with transition metal ions, zinc and aluminum will be carried using hydrothermal and solvothermal synthesis. Single crystal and powder X-ray diffraction will be used to reveal the MOPh crystal structures and BET analysis for the promising ones will be conducted. Proton conducting properties will be investigated.

通过设计合成金属有机膦酸酯化合物（MOPh）是金属有机框架（MOFs）领域科学家的最终目标。金属有机膦酸酯MOF表现出优异的化学稳定性，并且与常规羧酸酯MOF相比，它们对空气的敏感性较低。然而，MOPhs的网状化学尚未开发，并且没有报道使用金属-芳基膦酸盐化学产生具有可预测孔径的材料的等网状扩张。将可预测的孔径引入MOPh化学的能力将在医药和材料应用等方面创造巨大的潜力。桥连配体的结构和几何形状是决定MOFs最终结构的最重要因素。为了建立MOPh网状化学的基础，需要探索具有不同系链长度和三维几何形状的连接分子。迄今为止，尚未进行系统的研究，以建立网状化学的MOPhs。因此，我们设计了三个互补的几何形状（表示为V，Y，X）的有机膦酸酯连接体与增加系绳长度，以研究其金属络合物，创造可预测的孔与选定的过渡金属离子加上锌，铝和钙金属离子。第一组接头由V形芳基膦酸酯组成，包括1，2-双（对膦酸基苯基）苯、1，2-双（对膦酸基二苯基）苯和1，2-双（对膦酸基三联苯）苯，并且也在1，3-位。Y形第二接头几何结构包括配体1，3，5-三-（4-膦酰基苯基）苯、1，3，5-三-（4-膦酰基二苯基）苯和1，3，5-三-（4-膦酰基三联苯）苯。第三组包括基于卟啉核的平面X形四配位膦酸酯配体和基于甲烷和硅烷核扩展到三维的四面体X形连接体。基于平面卟啉核的X形连接体在二维扩展，包括meso-tetra meso-四（4-磷酰基苯基）卟啉（4-磷酰基联苯）卟啉和meso-四（4-磷酰基三联苯）卟啉，第四组连接基具有扩展成三维的四面体甲烷和硅烷核，其包括甲烷四-对-四三联苯膦酸，甲烷四-对-四联苯膦酸，甲烷四对苯基膦酸及其硅烷衍生物。这项研究将是第一个系统的方法来建立网状化学的MOPh化合物使用的芳基膦酸酯连接逐渐延长其系绳长度。将使用水热和溶剂热合成进行所提出的连接体的合成及其与过渡金属离子、锌和铝的系统结构研究。单晶和粉末X射线衍射将用于揭示MOPh晶体结构，并对有希望的MOPh进行BET分析。质子导电性能将被调查。