Enclathration and Confinement of Small Gases by the Intrinsically 0D Porous Molecular Solid, Me,H,SiMe<sub>2</sub> Christopher M. Kane Arash Banisafar Timothy P. Dougherty Leonard J. Barbour K. Travis Holman 10.1021/jacs.5b11395.s029 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 The stable, guest-free crystal form of the simple molecular cavitand, <b>Me</b>,<b>H</b>,<b>SiMe</b><sub><b>2</b></sub>, is shown to be intrinsically porous, possessing discrete, zero-dimensional (0D) pores/microcavities of about 28 Å<sup>3</sup>. The incollapsible 0D pores of <b>Me</b>,<b>H</b>,<b>SiMe</b><sub><b>2</b></sub> have been exploited for the enclathration and room temperature (and higher) confinement of a wide range of small gases. Over 20 isostructural <i>x</i>(gas/guest)@<b>Me,H,SiMe</b><sub><b>2</b></sub> (<i>x</i> ≤ 1) clathrates (guest = H<sub>2</sub>O, N<sub>2</sub>, Ar, CH<sub>4</sub>, Kr, Xe, C<sub>2</sub>H<sub>4</sub>, C<sub>2</sub>H<sub>6</sub>, CH<sub>3</sub>F, CO<sub>2</sub>, H<sub>2</sub>S, CH<sub>3</sub>Cl, CH<sub>3</sub>OCH<sub>3</sub>, CH<sub>3</sub>Br, CH<sub>3</sub>SH, CH<sub>3</sub>CH<sub>2</sub>Cl, CH<sub>2</sub>Cl<sub>2</sub>, CH<sub>3</sub>I, CH<sub>3</sub>OH, BrCH<sub>2</sub>Cl, CH<sub>3</sub>CH<sub>2</sub>OH, CH<sub>3</sub>CN, CH<sub>3</sub>NO<sub>2</sub>, I<sub>2</sub>), and a propyne clathrate (CH<sub>3</sub>CCH@<b>Me,H,SiMe</b><sub><b>2</b></sub>·2CHCl<sub>3</sub>), 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 = H<sub>2</sub>O, N<sub>2</sub>, CO<sub>2</sub>, Kr, CH<sub>3</sub>F) 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 CO<sub>2</sub> gas are shown to be taken up by single crystals of empty <b>Me</b>,<b>H</b>,<b>SiMe</b><sub><b>2</b></sub> at room temperature, but sorption rates are slow, occurring over weeks to months. Thus, <b>Me</b>,<b>H</b>,<b>SiMe</b><sub><b>2</b></sub> 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 CO<sub>2</sub>) sorption to be quantified by single crystal X-ray diffraction. The data are well fit to a simple three-dimensional diffusion model. 2016-03-08 00:00:00 3CH 3CN 2H 3OH 2S 3SH 2O 0 D pore Å3. Intrinsically 0 D Porous Molecular 3F SC 3OCH 3CCH CH water vapor 3I CO 2 gas room temperature incollapsible 0 D pores 3NO