Construction and functionalization of infinite metal complexes showing inclusion properties

显示包含物特性的无限金属配合物的构建和功能化

• 批准号: 07640737
• 负责人: FUJITA Makoto
• 金额: $ 1.54万
• 依托单位: Okazaki National Research Institutes (1997)Chiba University (1995-1996)
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07640737/
• 关键词: inclusion complexes; supramolecules; cadmium complexes; nanotechnology; coordination polymers; molecular recognition; coordination zeolites; 有機ゼオライト; 自己集合

Inorganic materials with inner cavities such as zeolites are known to bind many organic molecules in the cavity and often exhibit unique catalysis for organic reactions, in which high regio-stereo-, and shape-selectivities are observed. Construction of the inner cavities mainly surroundedby organic componentsis attractive since the shae, size, and function of the cavity become designable.Thus, a two-dimensional square network material {[Cd (4,4'-bpy)_2] (NO_3)_2} ・ (1) (bpy=bipyridine) was prepared from Cd (NO_3)_2 and 4,4'-bpy. Having inner cavities surroundedby 4,4'-bpy units as shown by crystallographicanalysis, this matcrial behaved like inorganicporous materials such as zeolites. Thus, the complex 1 easily formed the clathrate complex {[Cd (4,4'-bpy)_2] (NO_3)_2・2G}・(2, G=o-C_6H_4X_2 or C_6h_5X,X=Br, Cl) with some aromatic compounds and exhibited heterogeneous catalysis for cyanosilylation of aldegydes.X-ray diffractin study of 2 (G=o- C_6H_4Br_2) showed the layred array of the two-dimensional network.We also showed the enclathration of a relatively wide variety of aromatic guests by a "swellable" two-dimensional network assembling from cadmium (II) and flexible ligand PyCH_2C_6F_4CH_2Py (3). That is, this network is constructedif the guest is small, but is expandedif the guest becomes large.Furthermore, we unprecedentedly observed the appearance of quite different network patterns from almost the same crystallographic molecules : i.e., upon complexation with Cd (NO_3)_2, pyridine-based ligand PyCH_2C_6F_4CH_2Py (4) gave an indinite molecular ladder, while ligand 4 afforded an infinite molecular brick despite the very similar unit crystal structures of these complexes.

具有内部空腔的无机材料如沸石已知在空腔中结合许多有机分子，并且通常对有机反应表现出独特的催化作用，其中观察到高的区域立体选择性和形状选择性。以Cd（NO_3）_2和4，4 '-bpy为原料，制备了二维正方形网络材料{[Cd（4，4'-bpy）_2]（NO_3）_2}·（1）（bpy = bipyridine）。晶体学分析表明，该材料的内腔被4，4 ′-bpy单元包围，表现出类似沸石等无机多孔材料的性质。因此，配合物1容易形成笼形配合物{[Cd（4，4'-bpy）_2]（NO_3）_2·2G}·（2）G = o-C_6H_4X_2或C_6h_5X，X = Br，Cl）与芳香族化合物反应，对醛类化合物的硅腈化反应表现出多相催化作用（G = o-C_6H_4Br_2）所形成的二维层状网络，以及Cd（II）与PyCH_2C_6F_（10）所形成的"溶胀"二维网络，对各种芳香客体的包合作用4CH_2Py（3）.也就是说，如果客体很小，这个网络就会被构建，但是如果客体变大，这个网络就会被扩展。此外，我们前所未有地观察到几乎相同的晶体分子出现了完全不同的网络图案：吡啶基配体PyCH_2C_6F_4CH_2Py（4）与Cd（NO_3）_2络合后形成了茚满分子梯，而配体4则形成了无限大的分子砖，尽管这两种配合物的单元晶体结构非常相似。

项目成果

M.Fujita, et al.: "“Self-assembling[2]catenanes:molecular magic rings"" Supramolecular Science. 3. 37 (1996)

M. Fujita 等人：“自组装[2]链烷：分子魔环””《超分子科学》，3. 37 (1996)。

M.Fujita, H.Oka, K.Ogura: ""Palladium (0) /LiCI Promoted Cross-Coupling Reaction of (4-Pyridyl) stannanes and Aromatic Bromides : Easy Access to Poly (4-pyridyl) -Substituted Aromatics"" Tetrahedron Lett.636. 5247 (1995)

M.Fujita、H.Oka、K.Ogura：“钯 (0) /LiCI 促进 (4-吡啶基) 锡烷和芳香族溴化物的交叉偶联反应：轻松获得聚 (4-吡啶基) 取代芳香族化合物””

M.Fujita, K.Ogura: ""Transition-Metal-Directed Assembly of Well-Defined Organic Architectures Possessing Large Voids : From Macrocycles to [2] Catenanes"" Coord.Chem.Rev.148. 249 (1996)

M.Fujita、K.Ogura：“具有大空隙的明确有机结构的过渡金属定向组装：从大环化合物到 [2] 链烷烃””Coord.Chem.Rev.148。

M.Fujita,K.Ogura: "Transition-metal-directed assembly of well-defined organic architechtuers possessing large voids:" Coord.Chem.Rev.148. 249-264 (1996)

M.Fujita，K.Ogura：“具有大空隙的明确有机架构的过渡金属定向组装：”Coord.Chem.Rev.148。

M.Fujita, et al.: "“Interpenetrating Molecular Ladders and Bricks"" J.Am.Chem.Soc.117. 7287 (1995)

M.Fujita 等人：“互穿分子梯和砖””J.Am.Chem.Soc.117 (1995)。