Fabrication of inorganic-organic hybrid compounds possessing a specific hydrophobic space

在这项研究中，具有特定的疏水空间的无机-有机杂化化合物的制造进行了研究。从实验化学、物理化学和理论化学的角度研究表明，（1）支撑配体的空间体积、（2）桥连配体的长度和刚性、（3）溶剂的影响等因素，是控制由阳离子过渡金属组成的超分子结构的先决条件（钯）络合物和有机桥接配体。基于对超分子的这些认识，合成了具有120°角桥联配体的新型分子六边形。由于分子的六边形与分子的菱形平衡，这些分子的单独合成也通过调节支持配体和一种溶剂的空间体积来完成。特别是从X射线晶体学的分子六边形，它具有特征的疏水空腔的直径约为。1.35纳米的晶格中的分子六边形的阵列产生沿沿着c轴的管状通道。然后，将抗衡阴离子定位在阳离子钯中心附近和疏水腔的外部。因此，通过对空腔内结晶溶剂的去除，可以预期分子的客体包结能力。1 nm。核磁共振（NMR）谱和扩散有序谱（DOSY）显示聚氧乙烯酸酯包封在分子六边形的空腔内。这些结果为聚氧乙烯酸酯的超分子功能化提供了新的途径，也为制备具有超大疏水空间的无机-有机杂化化合物提供了新的途径。

In this study, the fabrication of inorganic-organic hybrid compounds possessing a specific hydrophobic space was investigated. The researches from the view points of the experimental chemistry, physical chemistry, and theoretical chemistry revealed that these factors, such as (1) the steric bulkiness of the supporting ligand, (2) the length and rigidity of the bridging ligand, and (3) the effect of solvent, are prerequisite for the control of the supramolecular structures consisting of the cationic transition metal (palladium) complexes and the organic bridging ligands. Based on these insights into supramolecules, the synthesis of the novel molecular hexagon with a 120° angular bridging ligand was attained. Since the molecular hexagon equilibrates with the molecular rhomboid, the separate syntheses of these molecules were also accomplished by tuning the steric bulkiness of the supporting ligand and a kind of solvent. Particularly from X-ray crystallography of the molecular hexagon, it possesses the characteristic hydrophobic cavity with the diameter of ca. 1.35 nm and that the array of the molecular hexagon in the crystal lattice creates the tubular channel along c-axis. Then, the counter anions were positioned near the cationic palladium center and outside of the hydrophobic cavity. Therefore, the guest inclusion ability might be expected by the removal of the solvents of crystallization inside the cavity.Successively, the guest inclusion ability of the molecular hexagon was investigated using Keggin-type polyoxometalate with the diameter of ca. 1 nm. The nuclear magnetic resonance (NMR) spectrum with the diffusion ordered spectroscopy (DOSY) revealed the encapsulation of polyoxometalate inside the cavity of molecular hexagon. These results pave the way for the novel method for the functionalization of polyoxometalate by the supramolecule and lead to the novel method for the fabrication of inorganic-organic hybrid compound with the extra large hydrophobic space.