Three-Dimensional Porous Coordination Polymer Functionalized with Amide Groups Based on Tridentate Ligand: Selective Sorption and Catalysis

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)2·4H2O 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]·6H2O·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 × 7.3 Å2. 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.