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<inf>2</inf>(μ<inf>6</inf>-ao<inf>2</inf>btc)(μ-obix)<inf>2</inf>]<inf>n</inf> (1), [Zn<inf>2</inf>(μ<inf>4</inf>-ao<inf>2</inf>btc)(μ-obix)<inf>2</inf>]<inf>n</inf> (2), [Zn<inf>2</inf>(μ<inf>4</inf>-ao<inf>2</inf>btc)(μ-mbix)<inf>2</inf>]<inf>n</inf> (3), and {[Zn<inf>2</inf>(μ<inf>4</inf>-ao<inf>2</inf>btc)(μ-pbix)<inf>2</inf>]·2DMF·8H<inf>2</inf>O}<inf>n</inf> (4), where ao<inf>2</inf>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<inf>2</inf> uptake capacities for 4a and 4b were 3.62% and 9.50%, respectively, and Langmuir surface areas calculated from CO<inf>2</inf> isotherms were 167.4 and 350.7 m2/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. © 2015 American Chemical Society.