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

具有纳米级量子通道的一维多孔晶体中功能分子的固定

• 批准号: 13440201
• 负责人: TADOKORO Makoto
• 金额: $ 7.04万
• 依托单位: Osaka City University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-13440201/
• 关键词: Hydrogen Bond; Ziolite; Crystal Engineering; Supra-molecular Chemistry; Nanosience; Ruthenium Complex; Molecular Crystal; Electrochemistry; 水; 超分子; ポーラスクリスタル; プロトン伝導; 水分子クラスター; 氷多形; 多孔質結晶; 金属錯体; 水クラスター; 氷-水相転移; カルボン酸; ポーラス結晶; Crystal E

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

对微孔固体的研究主要集中在无机材料如沸石上。虽然已经实现了这些原型的片段的合成，但是通过常规合成向三维网络的扩展已经难以实现。一种合理设计具有这些片段的这种网络的方法已经通过使用过渡金属络合物的配位和分子间氢键性质、几何形状和组成来实现，所述过渡金属络合物天然地倾向于形成一定阵列的几个良好分类的固体网络。本研究的目标是设计新的功能材料，而不限制沸石的性质，如选择性吸附和催化活性。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。基于模块化方法的设计， ...更多信息 嵌段[M^<III>（Hbim）_3]（M = Co）和均苯三酸形成具有扩展的蜂窝状片的晶体结构（孔隙直径约为100 nm）。16岁）。具有1-D通道的整个结构由层沿着c轴的堆叠产生。在这项研究中，我们将纳米尺度的水分子团簇内的多孔晶体形成的分子块专门设计来研究封闭的水分子的分子动力学。充满水的晶体的X射线晶体学表明，在一维纳米通道中发现的水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过渡的连续动力学，其在Ca以下产生“三层冰”状态。-38℃。在冰态下，我们观察到了立方冰相I_c中结构相似的水团簇的新碎片。该碎片被认为是在冰I_c上异质成核的晶胚的一种独特的结构模型。此外，他们还证明了一种独特的水四聚体的存在，它含有三个最近的氢键，而没有正常的四面体氢键。少

项目成果

M.Tadokoro, H.Kanno, T.Kitajima, H.S-.Umemoto, N.Nakanishi, K.Isobe, K.Nakasuji: "Self-Organizing Super-Structures Fomed From Hydrogen-Bonded Biimidazolate Metal Complexes"Proc.Natl.Acad.Sci.USA. 99. 4950-4955 (2002)

M.Tadokoro、H.Kanno、T.Kitajima、H.S-.Umemoto、N.Nakanishi、K.Isobe、K.Nakasuji：“氢键联咪唑金属配合物形成的自组织超结构”Proc.Natl.Acad

M.Tadokoro, H.Kanno, et al.: "Self-Organizing Super-Structures Fomed From Hydrogen-Bonded Biimidazolate Metal Complexes"The Proceedings of the National Academy of Sciences. (in press).

M.Tadokoro、H.Kanno 等人：“氢键联咪唑金属配合物形成的自组织超级结构”美国国家科学院院刊。

田所 誠: "総説「水素結合型金属錯体を用いた結晶設計と配列制御」"有機合成化学会誌. 62(in press). (2004)

Makoto Tadokoro：“评论“使用氢键金属配合物进行晶体设计和排列控制”有机合成化学学会杂志。62（印刷中）。（2004）

Y.Morita, T.Murata, S.Yamada, M.Tadokoro, A.Ichimura, K.Nakasuji: "Novel building blocks for crystal engineering : the first synthesis of oligo(imidazole)s"J.Chem.Soc., Perkin Trans. 1. 2598-2600 (2004)

Y.Morita、T.Murata、S.Yamada、M.Tadokoro、A.Ichimura、K.Nakasuji：“晶体工程的新型构建模块：低聚（咪唑）的首次合成”J.Chem.Soc.，Perkin

M.Tadokoro H.Kanno, T.Kitajima, H.S-.Umemoto, N.Nakanishi, K.Isobe, K.Nakasuji: "Self-Organizing Super-Structures Fomed from Hydrogen-Bonded Biimidazolate Metal Complexes"Proc.Natl.Acad.Sci.USA. 99. 4950-4955 (2002)

M.Tadokoro H.Kanno、T.Kitajima、H.S-.Umemoto、N.Nakanishi、K.Isobe、K.Nakasuji：“由氢键联咪唑金属配合物形成的自组织超结构”Proc.Natl.Acad。