The reactions of porous two-dimensional copper dicarboxylates (copper fumarate, copper terephthalate, copper styrene dicarboxylate, and copper 4,4‘-biphenyl dicarboxylate) with triethylenediamine as a pillar ligand yielded porous three-dimensional coordination polymers. The characterization by gas adsorption indicated that these coordination polymers have uniform micropores, high porosities, and gas adsorption capacities. These properties depend on the kind of dicarboxylate, and by changing it, the porosity and the pore size of the polymer can be controlled. The measurements of methane adsorption isotherms revealed that all coordination polymers have methane adsorption capacities, and especially, polymers synthesized from copper styrene dicarboxylate and copper 4,4‘-biphenyl dicarboxylate, which have ideal pore sizes and distributions for methane adsorption, have higher methane adsorption capacities than that of the theoretical maximum for activated carbon.

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Copper(II) terephthalate absorbs a large amount of gases such as N2, Ar, O2, and Xe. The maximum amounts of absorption of gases were 1.8, 1.9, 2.2, and 0.9 mole per one mole of the copper(II) salt for N2, Ar, O2, and Xe, respectively, indicating that the gases were not adsorbed on the surface but occluded within the solid. The porous structure of copper(II) terephthalate, in which the gas is occluded, is deduced from the temperature dependence of magnetic susceptibilities and the linear structure of terephthalate.

A three-dimensional coordination polymer was synthesized from porous copper(II) terephathlate and triethylenediamine (TED) as a pillar ligand, which has a higher porosity and higher capacity for methane adsorption than zeolites and porous coordination polymers reported previously.

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Some microporous coordination polymers have been synthesized from copper salts and dicarboxylic acids. These stuctures were characterized by gas adsorption methods. The methane adsorption capacities of these coordination polymers were measured under high pressure. The measurement disclosed that these coordination polymers had uniform micropores and methane adsorption capacities almost the same as that of zeolite 5A.

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