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.
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.
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