A Porous Framework Polymer Based on a Zinc(II) 4,4‘-Bipyridine-2,6,2‘,6‘-tetracarboxylate:  Synthesis, Structure, and “Zeolite-Like” Behaviors

• Published in: Journal of the American Chemical Society Vol. 128; no. 33; pp. 10745 - 10753
• Main Authors: Lin, Xiang, Blake, Alexander J, Wilson, Claire, Sun, Xue Zhong, Champness, Neil R, George, Michael W, Hubberstey, Peter, Mokaya, Robert, Schröder, Martin
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 23.08.2006
• Subjects: Chemistry; Coordination compounds; Exact sciences and technology; General and physical chemistry; Heterocyclic compounds; Heterocyclic compounds with only one n hetero atom and condensed derivatives; Inorganic chemistry and origins of life; Kinetics and mechanisms; Organic chemistry; Preparations and properties; Reactivity and mechanisms; Water; Methane; Molecular structure; Nitrogen heterocycle; Molecular interaction; Chiral compound; Metal; Porous material; Thermal stability; Pyridine derivatives; Carboxylic acid; Chirality; Helical structure; Chemical synthesis; Space group; Organic compounds; Complexation; Zinc II Chlorides; Pore structure; Zinc II; Polymer; Bipyridines; Desorption; Zeolite; Zinc II Compounds; Organic solvent; Adsorption; Kinetics; Porosity; Surface area; Inclusion compound; Hydrogen bond; Crystalline structure
• DOI: 10.1021/ja060946u
• ISSN: 0002-7863

The robust metal−organic framework compound {[Zn2(L)]·4H2O}∞ I has been synthesized by hydrothermal reaction of ZnCl2 and 4,4‘-bipyridine-2,6,2‘,6‘-tetracarboxylic acid (H4L). Compound I crystallizes in a chiral space group, P42212, with the chirality generated by the helical chains of hydrogen-bonded guest water molecules rather than by the coordination framework. Removal of guest water molecules from the crystal affords the porous material, [Zn2(L)]∞ (II), which has very high thermal stability and is chemically inert. The N2 isotherm of II at 77 K suggests a uniform porous structure with a BET surface area of 312.7 m2/g and a remarkably strong interaction with N2 molecules (βE 0 = 29.6 kJ mol-1). II also exhibits significant gas storage capacities of 1.08 wt % for H2 at 4 bar and 77 K and 3.14 wt % (44.0 cm3/g, 67 v/v) for methane at 9 Bar at 298 K. The adsorption behavior of II toward organic solvent vapors has also been studied, and isotherms reveal that for different solvent vapors adsorption is dominated by two types of processes, absorbate−absorbate or absorbate−absorbent interactions. The adsorption and desorption kinetic processes in II are determined mainly by the molecular size of the guest species and their interaction with the host.