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Hydrothermal Synthesis of Two Cationic Bismuthate Clusters: An Alkylenedisulfonate Bridged Hexamer, [Bi6O4(OH)4(H2O)2][(CH2)2(SO3)2]3 and a Rare Nonamer Templated by Triflate, [Bi9O8(OH)6][CF3SO3]5

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posted on 2010-06-21, 00:00 authored by David L. Rogow, Honghan Fei, Daniel P. Brennan, Mariko Ikehata, Peter Y. Zavalij, Allen G. Oliver, Scott R. J. Oliver
This paper reports the synthesis, characterization, and application of two cationic bismuthate clusters by anion templating. The compounds were synthesized under mild hydrothermal treatment and characterized by powder and single-crystal X-ray diffraction, infrared spectroscopy, and thermogravimetric analysis. The first material consists of a cationic hexanuclear bismuthate cluster octahedral in geometry and linked by 1,2-ethanedisulfonate molecules. This structure is thermally stable to about 235 °C. In the second compound, discrete cationic nonanuclear bismuthate clusters interact electrostatically with trifluoromethanesulfonate anions to pack into a nearly layered assembly. The material undergoes a transformation to Bi2O3 upon loss of the triflate groups at about 385 °C. Both materials demonstrate the use of sulfonate groups for the anion-directed assembly of these rare cationic inorganic structures. The application of the 3D octahedral bismuth cluster material toward acidic heterogeneous catalysis is also reported.

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