Fixation of functional Molecules Confined to One-dimentional Porous Crystal with Nanometer-scale Quantum Channels

对微孔固体的研究主要集中在沸石等无机材料上。虽然已经实现了这些原型片段的合成，但通过常规合成将三维网络扩展到三维网络一直很难实现。通过利用过渡金属络合物的配位和分子间氢键性质、几何构型和组成，可以合理地设计具有这些碎片的此类网络，这些金属络合物自然地倾向于形成一系列分类良好的固体网络。本研究的一个目标是设计一种新型的功能材料，而不限制沸石的选择性吸附和催化活性等性能。氢键配位化合物的分子合成工具将有助于设计由过渡金属离子和氢键构成的新型微孔固体。一种基于BU…的模块化设计更多的烧结块[M^&lt；III&gt；(HBIM)_3](M=Co)和偏三甲酸形成了延伸的蜂窝片(孔洞直径约16Å)的晶体结构。具有一维通道的整个结构是沿着c轴的层的堆叠的结果。在这项研究中，我们将纳米尺度的水团簇放置在由专门设计用于研究承压水分子的分子动力学的分子块形成的多孔晶体中。充水晶体的X射线结晶学研究表明，在一维纳米通道中发现的水团簇由具有氢键网络的多层水结构组成。水管表现出类似于水-冰转变的连续动力学，在Ca以下产生“三层冰”状态。-38℃。在冰态下，我们在结构相似的立方冰相Ic中观察到了新的水团簇碎片。该碎片被认为是冰上异相成核中晶体胚胎的独特结构模型。此外，它们还证明了独特的水四聚体的存在，该水四聚体含有具有三个最接近的氢键的水分子，而不是正四面体的氢键。较少

Research on microporous solids has focused largely on inorganic materials such as zeolites. Although syntheses of fragments of these prototypes have been achieved, extensions to three-dimensional networks by conventional synthesis have been difficult to realize. One approach to rational design of such networks with these fragments has been achieved by using the coordinating and intermolecular hydrogen-bonding properties, the geometly, and the composition of transition metal complexes which are naturally predisposed to form a certain array of several well categorized solid networks. A goal of this research has been the design of new functional materials without restraint at the properties of zeolite such as selective adsorption and catalytic activity. The tools of molecular synthesis of hydrogen-bonded coordination compounds would be useful to engineer new types of microporous solids constructed by transition metal ions and hydrogen bonding. A design based on a modular approach using bu … More ilding blocks [M^<III>(Hbim)_3] (M = Co) and trimesic acids forms a crystal structure with extended honeycomb sheets (diameter of porosity ca. 16Å). The whole structure with 1-D channels results from stacking of the layers along the c axis. In this study we have placed nanometer-scale water clusters within the porous crystal formed from molecular blocks specifically designed to investigate the molecular dynamics of confined water molecules. X-ray crystallography of a crystal filled with water has demonstrated that water clusters found in a one-dimensional nanochannel consist of multi-layered water structure with hydrogen bonding networks. The water-tubes exhibit continuous dynamics resembling a water-ice transition, which produces a "three-layered ice" state below Ca. -38℃. In the ice state, we have observed novel fragments of water clusters in a cubic ice phase I_c of similar structure. The fragment was recognized as a distinct structural model of the crystal embryo in heterogeneous nucleation on an ice I_c. Furthermore, they demonstrated the existence of a unique water tetramer containing water molecules with three nearest neighbouring hydrogen bonds without normal tetrahedral ones. Less