Class B Sodalites: Nonstoichiometric Silver,Sodium Halosodalites

Andreas Stein, Geoffrey A. Ozin, Galen D. Stucky

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Nonstoichiometric silver,sodium bromosodalites of the compositions M8-2nN2nX2-pOHp-SOD and M8-2nN2nX2-p[]p-SOD have been synthesized, where. N = Ag+, Na+, X = Cl-, Br-, I-, 2n = 0-8, p = 0-2, [] refers to anion-free cages ana SOD = (SiAlO4)66-. These materials allow one to control the filling of both Ag+ and X- ions in a sodalite host lattice in a systematic manner to fabricate Na4-nAgnX semiconductor-component clusters. Combined results from powder XRD, Rietveld refinement, 23Na MAS and DOR NMR, and far-IR and mid-IR spectroscopy indicate that these sodalites form a solid solution of Na3-mAgm clusters in anion-free β-cages interspersed with Na4-nAgnX clusters. The clusters are statistically distributed throughout the lattice. However, silver ions are associated preferentially with cavities containing halide anions. The data also demonstrate that these materials offer the opportunity to manipulate the extent of collective electronic and vibrational interactions between monodispersed Na4-nAgnBr clusters in a perfectly crystalline host. The anion strongly mediates the vibrational coupling. The electronic coupling between clusters increases with Ag+ and X- loading levels. Support for this idea comes from extended Hückel molecular orbital calculations. At low Ag+/X- loadings, intrasodalite AgX resembles the gas-phase molecule (bond length, optical spectra). Optical absorption bands broaden and the absorption edge moves toward that of the bulk semiconductor at higher Ag+/X- loadings.

Original languageEnglish (US)
Pages (from-to)8119-8129
Number of pages11
JournalJournal of the American Chemical Society
Issue number21
StatePublished - Oct 1 1992


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