Construction and functionalization of infinite metal complexes showing inclusion properties

有机材料与内腔体如沸石是已知的，可将许多有机分子结合在一起，并在洞穴和经常展出，用于有机反应，在高区域立体声-中，形状选择是可见的。内部洞穴的构造主要由有机成分吸引，因为洞穴成为可设计的形状、大小和功能。因此，两个尺寸正方形网络材料{[Cd （4，4'-bpy）_2] （NO_3）_2} · （1） （bpy=双吡啶）是由Cd （NO_3）_2和4，4'-bpy制成的。拥有内部洞穴周围的4，4'-Bpy单元由晶体分析显示，这个矩阵行为像非有机材料这样的沸石。Thus， The Complex 1很容易形成clathrate complex [CD]（4，4'-bpy）_2] （NO_3）_2·2 G}·（2， G= o-C_6 H_4 X_2 or C_6 h_5 X，X=Br，Cl）与某些芳香化合物和展示的异源性催化，用于代谢的氰化物化。X射线干扰素研究2（G= o-C_6H_4Br_2） showed the layred array of the two-dimensional network。我们还展示了aromatic guest by a "swellable" two-dimensional network assembling from cadmium （II） and flexible ligand PyCH_2C_6F_4CH_2Py （3）。这就是说，这个网络是构造性的，客人是小的，但它扩展了客人成为大的。更多，我们无法预测地从几乎相同的晶体学分子中观察到了明显不同的网络模式的外观：是的，upon complexation with Cd （NO_3）_2， pyridine-based ligand PyCH_2C_6F_4CH_2Py （4） gave an indinite molecular ladder， while ligand4 afforded an infinite molecular brick despite the very similar unit crystal structures of these complexes。

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.