Highly Efficient Bifunctional Amide Functionalized Zn and Cd Metal Organic Frameworks for One-Pot Cascade Deacetalization-Knoevenagel Reactions

A pyridine-based amide functionalized tetracarboxylic acid, 5,5'-(pyridine-2, 6-dicarbonyl)bis(azanediyl)}diisophthalic acid (H₄L), was synthesized and its coordination chemistry toward zinc(II) and cadmium(II) ions was studied. The reactions of H₄L with Zn(NO₃)₂.6H₂O and Cd(NO₃)₂.4H₂O led to its full or partial deprotonation, respectively, and the formation of the 2D coordination polymers [Zn₂(L)(H₂O)₄]_n.4n(H₂O) (1) and [Cd₃(HL)₂(DMF)₄]_n.4n(DMF) (2) (DMF = N,N'-dimethylformamide), respectively. They were characterized by elemental analysis, FT-IR, photoluminescence, thermogravimetry, and single-crystal and powder X-ray diffraction. In 1, the L^4- ligand is planar with every carboxylate anion binding a Zn(II) cation and giving rise to a 2D grid with the metals with tetrahedral environments. In 2, the combination of bridging HL^3- and dimethylformamide to form trinuclear Cd(II) clusters engenders secondary building block units and generates a layer-type 2D network with the metals with octahedral and pentagonal bipyramid coordination geometries. The topological analyses of 1 and 2 reveal 2,4-connected and 3,6-connected binodal nets, respectively. On account of the presence of Lewis acid (Zn or Cd centers) as well as basic (uncoordinated pyridine and amide groups) sites, 1 and (to a much lower extent) 2 effectively catalyze the one-pot cascade deacetalization-Knoevenagel condensation reactions under quite mild conditions. They act as heterogeneous catalysts, being easy to recover and recycle without losing activity.