TY - DATA T1 - Enclathration and Confinement of Small Gases by the Intrinsically 0D Porous Molecular Solid, Me,H,SiMe2 PY - 2016/03/08 AU - Christopher M. Kane AU - Arash Banisafar AU - Timothy P. Dougherty AU - Leonard J. Barbour AU - K. Travis Holman UR - https://acs.figshare.com/articles/dataset/Enclathration_and_Confinement_of_Small_Gases_by_the_Intrinsically_0D_Porous_Molecular_Solid_Me_H_SiMe_sub_2_sub_/3120787 DO - 10.1021/jacs.5b11395.s029 L4 - https://ndownloader.figshare.com/files/4855204 KW - 3CH KW - 3CN KW - 2H KW - 3OH KW - 2S KW - 3SH KW - 2O KW - 0 D pore KW - Å3. KW - Intrinsically 0 D Porous Molecular KW - 3F KW - SC KW - 3OCH KW - 3CCH KW - CH KW - water vapor KW - 3I KW - CO 2 gas KW - room temperature KW - incollapsible 0 D pores KW - 3NO N2 - The stable, guest-free crystal form of the simple molecular cavitand, Me,H,SiMe2, is shown to be intrinsically porous, possessing discrete, zero-dimensional (0D) pores/microcavities of about 28 Å3. The incollapsible 0D pores of Me,H,SiMe2 have been exploited for the enclathration and room temperature (and higher) confinement of a wide range of small gases. Over 20 isostructural x(gas/guest)@Me,H,SiMe2 (x ≤ 1) clathrates (guest = H2O, N2, Ar, CH4, Kr, Xe, C2H4, C2H6, CH3F, CO2, H2S, CH3Cl, CH3OCH3, CH3Br, CH3SH, CH3CH2Cl, CH2Cl2, CH3I, CH3OH, BrCH2Cl, CH3CH2OH, CH3CN, CH3NO2, I2), and a propyne clathrate (CH3CCH@Me,H,SiMe2·2CHCl3), have been prepared and characterized, and their single crystal structures determined. Gas enclathration is found to be highly selective for gases that can be accommodated by the predefined, though slightly flexible 0D pore. The structure determinations provide valuable insight, at subangstrom resolution, into the factors that govern inclusion selectivity, gas accommodation, and the kinetic stability of the clathrates, which has been probed by thermal gravimetric analysis. The activation (emptying) of several clathrates (guest = H2O, N2, CO2, Kr, CH3F) is shown to occur in a single-crystal-to-single-crystal (SC → SC) fashion, often requiring elevated temperatures. Akin to open pore materials, water vapor and CO2 gas are shown to be taken up by single crystals of empty Me,H,SiMe2 at room temperature, but sorption rates are slow, occurring over weeks to months. Thus, Me,H,SiMe2 exhibits very low, but measurable, gas permeability, despite there being no obvious dynamic mechanism to facilitate gas uptake. The unusually slow exchange kinetics has allowed the rates of gas (water vapor and CO2) sorption to be quantified by single crystal X-ray diffraction. The data are well fit to a simple three-dimensional diffusion model. ER -