Isoreticular MOFs derived from arylphosphonate linkers

设计合成金属-有机膦酸盐化合物（MOPh）是金属有机骨架（MOFs）领域研究人员的终极目标。与传统的羧酸盐mof相比，金属-有机膦酸盐mof具有优异的化学稳定性和较低的空气敏感性。然而，mofs的网状化学尚未得到发展，也没有报道使用金属-芳基膦酸盐化学来制备具有可预测孔径的材料的等网状膨胀。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。桥接配体的结构和几何形状是决定mof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来建立mofs的网状化学。因此，我们设计了三种互补的几何形状（表示为V， Y， X）的有机膦酸盐连接体，它们的系链长度不断增加，以研究它们的金属配合物，通过选择过渡金属离子加上Zn， Al和Ca金属离子形成可预测的孔。第一组连接剂由v形芳基膦酸盐组成，包括1,2-二（对膦基联苯）苯、1,2-二（对膦基联苯）苯和1,2-二（对膦基联苯）苯，也在1,3-位置。y形的第二连接体几何结构包括配体1,3,5-三-（4-膦苯）苯、1,3,5-三-（4-膦苯）苯和1,3,5-三-（4-膦苯）苯。第三类包括基于卟啉核心的平面x形四异位膦酸盐配体和基于甲烷和硅烷核心扩展到三维的四面体x形连接体。基于平面卟啉核的二维扩展的x型连接体包括中-四（4-磷基苯基）卟啉、中-四（4-磷基双苯基）卟啉和中-四（4-磷基二苯基）卟啉，第四类连接体具有四面体甲烷和硅烷核，扩展为三维，包括甲烷四-对四苯基膦酸、甲烷四-对四苯基膦酸、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化合物使用芳基膦酸盐连接剂逐渐延长其系链长度。将采用水热法和溶剂热法合成过渡金属离子、锌和铝的连接剂及其系统结构研究。单晶和粉末x射线衍射将揭示MOPh的晶体结构，并对有希望的晶体进行BET分析。将研究质子的导电特性。

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.