Effect of Solvent Molecule in Pore for Flexible Porous Coordination Polymer upon Gas Adsorption and Iodine Encapsulation

Abstract

Four new Zn(II)-coordination polymers, namely, [Zn-2(mu(6)-ao(2)btc)(mu-obix)(2)](n), (1), [Zn-2(mu(4)-ao(2)btc)(mu-obix)(2)](n) (2), [Zn-2(mu(4)-ao(2)btc)(mu-mbix)(2)](n) (3), and {[Zn-2(mu(4)-ao(2)btc)(mu-pbix)(2)]center dot 2DMF center dot 8H(2)O}(n) (4), where ao(2)btc = dioxygenated form of 3,3',5,5'-azobenzenetetracarboxylate and obix, mbix, and pbix = 1,2-, 1,3-, and 1,4-bis(imidazol-1-ylmethyl)benzene, have been synthesized with azobenzenetetracarboxylic acid and isomeric bis(imidazole) ligands and characterized by elemental analyses, IR spectra, single-crystal X-ray diffraction, powder X-ray diffraction, and thermal analyses. X-ray results showed that 1, 2, and 4 had two-dimensional structures with 3,4L13 topology, while 3 was a three-dimensional coordination polymer with bbf topology. For 4, two types of activation strategies, solvent exchange + heating (which produced 4a) and direct heating (which produced 4b), were used to investigate the effect of a guest molecule in a flexible framework. Gas adsorption and iodine encapsulation properties of activated complexes were studied. The CO, uptake capacities for 4a and 4b were 3.62% and 9.50%, respectively, and Langmuir surface areas calculated from CO2 isotherms were 167.4 and 350.7 m(2)/g, respectively. Moreover, 4b exhibited 19.65% and 15.27% iodine uptake in vapor phase and cyclohexane solution, respectively, which corresponded to 1.47 and 0.97 molecules of iodine/formula unit, respectively. Moreover, photoluminescence properties of the complexes were studied.