Synthesis of Nanoporous Cubic In(CN)(3) and In(1)(-)(x)()Ga(x)()(CN)(3) and Corresponding Inclusion Compounds.

Abstract

Anhydrous In(CN)(3) and In(1)(-)(x)()Ga(x)()(CN)(3) phases with empty Prussian-blue-type structures have been prepared via low-temperature solution methods utilizing molecular templating agents. Quantitative X-ray powder diffraction was used to refine the In(CN)(3) cubic structure in which In is octahedrally surrounded by an average of three C and three N atoms. The symmetry is Pm&thremacr;m, a = 5.627(1) Å, and the In-(C,N) and C-N bond lengths are 2.251(1) and 1.125(1) Å, respectively. The compound reversibly incorporates krypton atoms into the empty cavities to form In(CN)(3).Kr, which is readily identified by powder diffraction. Similar inclusion systems with n-hexane in the porous framework are also synthesized. In(1)(-)(x)()Ga(x)()(CN)(3) solid solutions are formed by suitable combinations of the binary systems and have lattice constants adjustable between 5.293 Å for Ga(CN)(3) and 5.627(1) Å for In(CN)(3). The variation of the lattice parameters with composition obeys Vegard's Law.