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

基本信息

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

项目摘要

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.

已知具有内部空腔（例如沸石）的无机材料在腔中结合许多有机分子，并经常暴露于有机反应中的独特催化剂，其中观察到高的区域性和形状选择性。自从腔的shae，大小和功能变得可吸引人的有机成分所包围的内部空腔的构造。因此，一种二维平方网络材料{[CD（4,4'-BPY）_2]（no_3）_2} _2} _2} ・（1）（bpy = bpy = bipyridine）（bpy = bpy = bpy = bipyridine）。如晶体分析所示，内部空腔围绕4,4'BPY单位，其表现像无机材料，例如沸石。 That, 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 exposed heterogeneous catalysis for cyanosilylation of aldegydes.X-ray diffractin study of 2（g = o- c_6h_4br_2）显示了二维网络的铺设阵列。我们还显示了来自cadmium（ii）和灵活的PYCH_2C_2C_6F_6F_4CH_4CH_2PY（3）的“可膨胀”二维网络组装的相对广泛芳族客人的围场。也就是说，如果客人很小，则建立该网络，但是如果客人变大，则可以扩展。曲折，我们前所未有地观察到与几乎相同的晶体学分子的网络模式的出现：即，在与CD（NO_3）_2络合时，基于吡啶的ligand pych_2c_6f_6f_4ch_4ch_2py（4）syrect（no_3）_2，同时给予了ligch_2c_4ch_2py（4）提供了无限的分子砖目的地，这些复合物的非常相似的单位晶体结构。