Coordination Polymers from an Amino-Functionalized Terphenyl-Tetracarboxylate Linker: Structural Multiplicity and Catalytic Properties.

Abstract

An amino-functionalized terphenyl-tetracarboxylic acid, 2'-amino-[1,1':4',1″-terphenyl]-3,3″,5,5″-tetracarboxylic acid (H4tpta), was used as an adaptable linker to synthesize, under hydrothermal conditions, eight coordination polymers (CPs). The obtained products were formulated as [Co(μ6-H2tpta)]n (1), [Co(μ3-H2tpta)(2,2'-bipy)]n (2), [M3(μ6-Htpta)2(2,2'-bipy)2]n (M = Mn (3), Cd (4)), [Ni2(μ4-tpta)(phen)2(H2O)4]n (5), [Zn2(μ6-tpta)(phen)2]n (6), {[Zn2(μ6-tpta)(μ-4,4'-bipy)]·H2O}n (7), and [Zn2(μ6-tpta)(μ-H2biim)(H2O)2]n (8), wherein 2,2'-bipyridine (2,2'-bipy), 4,4'-bipyridine (4,4'-bipy), 1,10-phenanthroline (phen), or 2,2'-biimidazole (H2biim) are present as additional stabilizing ligands. The structural types of 1-8 vary from one-dimensional (1D) (2, 5) and two-dimensional (2D) (3, 4, 6) CPs to three-dimensional (3D) metal-organic frameworks (MOFs) (1, 7, and 8) with a diversity of topologies. The products 1-8 were investigated as catalysts in the Knoevenagel condensation involving aldehydes and active methylene derivatives (malononitrile, ethyl cyanoacetate, or tert-butyl cyanoacetate), leading to high condensation product yields (up to 99%) under optimized conditions. Various reaction conditions, substrate scope, and catalyst recycling were investigated. This work broadens the application of H4tpta as a versatile tetracarboxylate linker for the generation of diverse CPs/MOFs.