Hydrothermal Assembly, Structural Multiplicity, and Catalytic Knoevenagel Condensation Reaction of a Series of Coordination Polymers Based on a Pyridine-Tricarboxylic Acid

基于吡啶三羧酸的一系列配位聚合物的水热组装、结构多样性和催化Knoevenagel缩合反应

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Abstract

A pyridine-tricarboxylic acid, 5-(3',5'-dicarboxylphenyl)nicotinic acid (H(3)dpna), was employed as a adjustable block to assemble a series of coordination polymers under hydrothermal conditions. The seven new coordination polymers were formulated as [Co(μ(3)-Hdpna)(μ-dpey)](n)·nH(2)O (1), [Zn(4.5)(μ(6)-dpna)(3)(phen)(3)](n) (2), [Co(1.5)(μ(6)-dpna)(2,2'-bipy)](n) (3), [Zn(1.5)(μ(6)-dpna)(2,2'-bipy)](n) (4), [Co(3)(μ(3)-dpna)(2)(4,4'-bipy)(2)(H(2)O)(8)](n)·2nH(2)O (5),[Co(bpb)(2)(H(2)O)(4)](n)[Co(2)(μ(3)-dpna)(2)(H(2)O)(4)](n)·3nH(2)O (6), and [Mn(1.5)(μ(6)-dpna)(μ-dpea)](n) (7), wherein 1,2-di(4-pyridyl)ethylene (dpey), 1,10-phenanthroline (phen), 2,2'-bipyridine(2,2'-bipy),4,4'-bipyridine(4,4'-bipy),1,4-bis(pyrid-4-yl)benzene (bpb), and 1,2-di(4-pyridyl)ethane (dpea) were employed as auxiliary ligands. The structural variation of polymers 1-7 spans the range from a 2D sheet (1-4, 6, and 7) to a 3D metal-organic framework (MOF, 5). Polymers 1-7 were investigated as heterogeneous catalysts in the Knoevenagel condensation reaction, leading to high condensation product yields (up to 100%) under optimized conditions. Various reaction conditions, substrate scope, and catalyst recycling were also researched. This work broadens the application of H(3)dpna as a versatile tricarboxylate block for the fabrication of functional coordination polymers.

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