title: Corner capping of silsesquioxane cages by chemical warfare agent simulants.
abstract: 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 bombardment-mass 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.
authors.affiliation: Department of Chemistry, Virginia Polytechnic Institute and State University, Blacksburg, Virginia 24061, USA.
authors.forename: Melinda K
authors.initials: MK
authors.lastname: Ferguson-McPherson
authors.forename: Emily R
authors.initials: ER
authors.lastname: Low
authors.forename: Alan R
authors.initials: AR
authors.lastname: Esker
authors.forename: John R
authors.initials: JR
authors.lastname: Morris