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    Corner Capping of Silsesquioxane Cages by Chemical Warfare Agent Simulants

    Year: 2005

    Journal: Langmuir 2005, 21, 11226-11231, 20111221

    Authors: Melinda K. Ferguson-McPherson, Emily R. Low, Alan R. Esker, and John R. Morris

    Organizations: Department of Chemistry, Virginia Polytechnic Institute and State University, Blacksburg, Virginia 24061

    The room-temperature uptake and reactivity of gas-phase methyl dichlorophosphate (MDCP) and trichlorophosphate (TCP) within trisilanolphenyl-polyhedral oligomeric silsesquioxane (POSS) Langmuir- Blodgett films are investigated. The halogenated phosphate molecules are found to readily diffuse into and react with the hybrid inorganic-organic silicon-oxide films under ambient conditions. Reflection absorption infrared spectroscopy (RAIRS), X-ray photoelectron spectroscopy (XPS), and fast atom bombardmentmass spectrometry (FAB-MS) measurements suggest that the chlorophosphates undergo hydrolysis with the silanol groups of the POSS LB-film. Substitution and elimination reactions appear to cap the corner of the POSS molecules, leaving a surface-bound phosphoryl group and a resulting structure that is highly stable at elevated temperatures.