ChemInform Abstract: Expanded Prussian Blue Analogues Incorporating [Re6Se8(CN)6]3-/4- Clusters: Adjusting Porosity via Charge Balance

Autor: Jeffrey R. Long, Matthew P. Shores, Laurance G. Beauvais, Miriam V. Bennett
Rok vydání: 2010
Předmět:
Zdroj: ChemInform. 32
ISSN: 1522-2667
0931-7597
Popis: Face-capped octahedral [Re6Se8(CN)6]3-/4- clusters are used in place of octahedral [M(CN)6]3-/4- complexes for the synthesis of microporous Prussian blue type solids with adjustable porosity. The reaction between [Fe(H2O)6]3+ and [Re6Se8(CN)6]4- in aqueous solution yields, upon heating, Fe4[Re6Se8(CN)6]3·36H2O (4). A single-crystal X-ray analysis confirms the structure of 4 to be a direct expansion of Prussian blue (Fe4[Fe(CN)6]3·14H2O), with [Re6Se8(CN)6]4- clusters connected through octahedral Fe3+ ions in a cubic three-dimensional framework. As in Prussian blue, one out of every four hexacyanide units is missing from the structure, creating sizable, water-filled cavities within the neutral framework. Oxidation of (Bu4N)4[Re6Se8(CN)6] (1) with iodine in methanol produces (Bu4N)3[Re6Se8(CN)6] (2), which is then metathesized to give the water-soluble salt Na3[Re6Se8(CN)6] (3). Reaction of [Co(H2O)6]2+ or [Ni(H2O)6]2+ with 3 in aqueous solution affords Co3[Re6Se8(CN)6]2·25H2O (5) or Ni3[Re6Se8(CN)6]2·33H2O...
Databáze: OpenAIRE
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