S. Galli, N. Masciocchi, V. Colombo
Feb 9, 2010
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Journal
Chemistry of Materials
Abstract
Highly porous homoleptic Ni(bpb) and Zn(bpb) materials have been obtained by reaction of nickel(II) and zinc(II) salts with the deprotonated form of the 1,4-(4-bispyrazolyl)benzene ligand (H2bpb). Ab-initio structure solution methods and thermodiffractometry have allowed the determination of their crystal structures, framework flexibility, and thermal stability. The different stereochemical requirements of the Ni(II) and Zn(II) ions induce, in Ni(bpb) and Zn(bpb), rhombic and square channels, respectively, accounting for 57 and 65% of the total cell volume. The two materials feature high adsorption capacities toward small gaseous molecules (N2 and Ar at 77 K, CO2 and CH4 at 273 K), peaking at 22 mmol g−1 of N2 in the case of the zinc(II) derivative, which is reflected by a very large surface area (above 2000 m2 g−1). The flexibility, size, and hydrophobic nature of their channels are adequate also for the incorporation of organic vapors. In this regard, the adsorption of benzene and cyclohexane has been s...