Three-dimensional porous coordination polymer functionalized with amide groups based on tridentate ligand: Selective sorption and catalysis
Three-dimensional porous coordination polymer functionalized with amide groups based on tridentate ligand: Selective sorption and catalysis
复制标题
DOI：
10.1021/ja067374y
复制
发表时间：
2007-03-07
影响因子：
15
通讯作者：
Kitagawa, Susumu
中科院分区：
文献类型：
--
作者：
Hasegawa, Shinpei;Horike, Satoshi;Kitagawa, Susumu
为了产生官能化的多孔化合物，在多孔框架中使用酰胺基团以与客体分子产生吸引相互作用。为了避免这些酰胺基团之间形成氢键，我们的策略是使用三齿酰胺配体作为三连接器部分来构建三维（3D）配位网络。由Cd（NO3）（2）中心点4 H（2）O和一个带有酰胺基的三连接体配体合成了一种基于八面体Cd（II）中心的三维多孔配位聚合物{[Cd（4-btapa）（2）（NO3）（2）]中心点6 H（2）O中心点2DMF}（n）（1a）（4-btapa = 1，3，5-苯三甲酸三[N-（4-吡啶基）酰胺]）.作为客体相互作用位点的酰胺基团出现在尺寸为4.7 x 7.3 A（2）的通道表面。X射线粉末衍射测量表明，去溶剂化的化合物（1b）选择性地包括客人与并发的灵活的结构（无定形到结晶）的转变。通道中高度有序的酰胺基团在与客体分子的相互作用中起着重要作用，这一点通过热重分析、吸附/脱附测量和X射线晶体学得到证实。我们还进行了Knoevenagel缩合反应催化1a，以证明其选择性多相碱催化性能，这取决于反应物的大小。固体催化剂1a在反应后保持其结晶骨架并易于再循环。
To create a functionalized porous compound, amide group is used in porous framework to produce attractive interactions with guest molecules. To avoid hydrogen-bond formation between these amide groups our strategy was to build a three-dimensional (3D) coordination network using a tridentate amide ligand as the three-connector part. From Cd(NO3)(2)center dot 4H(2)O and a three-connector ligand with amide groups a 3D porous coordination polymer (PCP) based on octahedral Cd(II) centers, {[Cd(4-btapa)(2)(NO3)(2)]center dot 6H(2)O center dot 2DMF}(n) (1a), was obtained (4-btapa = 1,3,5-benzene tricarboxylic acid tris[N-(4-pyridyl)amide]). The amide groups, which act as guest interaction sites, occur on the surfaces of channels with dimensions of 4.7 x 7.3 A(2). X-ray powder diffraction measurements showed that the desolvated compound (1b) selectively includes guests with a concurrent flexible structural (amorphous-to-crystalline) transformation. The highly ordered amide groups in the channels play an important role in the interaction with the guest molecules, which was confirmed by thermogravimetric analysis, adsorption/desorption measurements, and X-ray crystallography. We also performed a Knoevenagel condensation reaction catalyzed by 1a to demonstrate its selective heterogeneous base catalytic properties, which depend on the sizes of the reactants. The solid catalyst 1a maintains its crystalline framework after the reaction and is easily recycled.