Supplementary information for Nature Materials. Gas-induced transformation and expansion of a 'nonporous'

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1 Supplementary information for Nature Materials Gas-induced transformation and expansion of a 'nonporous' organic solid Praveen K. Thallapally, 1, * B. Peter McGrail, 1, Scott J. Dalgarno, 2 Herbert T. Schaef, 1 Jian Tian, 2 and Jerry L. Atwood*, Battelle Blvd., Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352, USA. Fax: (+1) , Tel: (+1) , Praveen.Thallapally@pnl.gov 2 Department of Chemistry, University of Missouri-Columbia, Columbia, Missouri 65211, USA. Fax: (+1) ; Tel: (+1) , AtwoodJ@missouri.edu Supporting Online Material contains 22 figures. Crystal packing diagrams of all the known forms of 1 and the effect of pressure and temperature. DSC plot of sublimed phase 1a Simulated and experimental powder diffraction plots of high density phase and low density phase at variable temperature and pressure conditions. Gas absorption and desorption plots Solid-State NMR Single crystal photographs of crystal 1b before and after exposing the crystal to CO 2 gas. Crystal Packing diagrams of self-included p-tert-butylthiacalix[4]arene, 2 Powder plots of 2 1

2 Single Crystal X-ray analysis: X-ray data were collected on a Bruker SMART diffractometer (Bruker AXS, Madison, WI). CCDC contains the crystallographic data for this paper. This can be obtained free of charge at Crystal data for 1b: C 44 H 54.5 O 4, M = , colorless square,.2 x.15 x.1 mm 3, monoclinic, space group P2 1 /c (No. 14), a = 9.675(19), b = 3.647(6), c = 13.68(3) Å, β = (3), V = (13) Å 3, Z = 4, D c = g/cm 3, F = 142, MoKα radiation, λ =.7173 Å, T = 273(2)K, max = 54.2º, 1732 reflections collected, 7426 unique (R int =.357). Final GooF = 1.16, R1 =.828, wr2 =.1936, R indices based on 3613 reflections with I >2sigma(I) (refinement on F 2 ), 537 parameters, restraints. Lp and absorption corrections applied, λ =.71 mm -1. Unit cell dimensions of 1a and 1c = Å, b = Å, c = Å, β = 9.27 V = 414 Å 3 ; a = 12.8 Å, b = 12.8 Å, c = Å, V = 216 Å 3. Fig. S1. All known forms of 1, guest free low and high density forms 1a and 1b, 1:1 and 2:1 host guest 5, 1 complexes. The transformation of 1:1, 2:1 and 1a to 1b was reported by Ripmeester. 2

3 Fig. S2. The bilayer packing mode of low density phase 1a. The cavities are shown in yellow spheres. Hydrogen atoms are removed for clarity. Fig. S3. The 4 Å 3 voids shown in yellow between the two layers are separated by the tert-butyl groups in different layers of 1b. Fig. S4. 1:1 host guest complex of 1. Guest molecules and hydrogen atoms are removed for clarity. 3

4 Fig. S5. 2:1 host guest complex of 1. Guest molecules are hydrogen atoms are removed Heat Flow, mw Temperature, C Fig. S6 Thermal profile of 1a shows a possible structural transformation around 19 C. Time, minutes a Temperatuare Ramp (Vacuum) 2 C 14 C 1 C 25 C Temperature, C

5 Fig. S7 Powder plots of phase 1a at various temperatures under vacuum. Presence of low and high density phases at 14 C. Complete phase transformation occurs at 2 C. Fig. S8 Simulated powder pattern of structure 1b obtained from tetradecane solution. Notice PXRD s of Fig. 8 and 9 are identical. Fig. S9 Calculated powder pattern of 1b (obtained after heating 1a at 2 C for 3 minutes). Compare with the simulated powder pattern in Fig. 7. Time, Minutes Temperature Decrease C 8 C Temperature, C C

6 Fig. S1 Irreversible nature of phase 1b as a function of temperature. Form 1b was cooled to room temperature over a period of 24 hrs. Time, Minutes T = 25 C 4.83 MPa MPa 2.97 MPa 1.45 MPa CO 2 Pressure, MPa Vacuum Fig. S11 Effect of CO 2 gas pressure on phase 1a confirms no structural change at high pressure and room temperature MPa of H 2 at room temperature After 24 hrs 5 Vaccum Fig. S12. Effect of hydrogen gas pressure on 1a indicates no phase transformation. 6

7 4 3.5 MPa of H 2 T = 25 C.1 hour 16.8 hour Fig. S13 Effect of Hydrogen and Helium gas on 1b at 3.5 MPa at room temperature over 16 hrs shows the irreversible transformation of 1b. Fig. S14. 2 g of 1b was obtained from tetradecane solution and pressurized with CO 2 and N 2 O at room temperature a).53 g of 1b was pressurized with 3.5 Mpa of CO 2 at room temperature and monitor the pressure drop as a function of time. The calculated CO 2 mass weight at this pressure was found to be 7. %, Sample volume V = 4.89 cm 3-. b) 1.1 g of 1b was subjected to N 2 O at 3.5 Mpa V = 3.5 cm 3. In both the cases, the material was transformed from 1b to 1a and to 1c as gas diffuses through the lattice in just 2 hrs as shown. The resulting material was evacuated for 24 hrs and repressurized and absorbs the same amount of gas, which indicate the irreversible nature of the transformation. Solid-State 13 C NMR Parameters The solid state 13 C NMR data were recorded using a CMX Infinity Varian 3 MHz wide bore spectrometer. Two different probes were used, a 5 mm HXY MAS probe build by Chemagnetics/Varian and a home built 5 mm HX MAS probe. The operating frequencies were MHz for 1H and MHz for 13C. Chemical shift data is externally referenced to TMS ( ppm). The spectra were taken using a 1 pulse with proton decoupling pulse sequence. A 3 degree flip angle was used for the carbon 7

8 pulse and the repetition delay was 2s. The spinning speed used was 1 khz (HXY probe) or 4 khz (HX probe) and the acquired fid s clearly extended past the 3 ms or 5 ms acquisition time used for the experiment. Longer acquisition times were not used in order to avoid extending the power capability for each probe. Explanation for the use of two probes: Two probes were used because the HXY MAS probe (which is capable of spinning 12 khz) broke and the HX MAS which is optimized to run 13C and DRAWS was used as a quick substitute. Accept for the fact that the DRAWS probe doesn t spin fast, the data should only affected by the fact that spinning side bands are visible for the up-field carbons in that spectrum. Both probes use 5 mm zirconia pencil design rotors. Fig. S15. The solid state NMR of form 1b was shown at the bottom, which was obtained from crystallizing 1 from tetradecane solution. 16 Sample 1b was pressurized at 3.5 MPa of CO 2 for over two days and degassed under vacuum for several hours to remove the trapped gas and the 13C NMR of resulting material was shown at the top, which indicates stability of kinetic phase upon gas removal. Fig. S16 Simulated powder pattern of tetragonal 1:1 host guest complex, 1c. Compare with experimental powder pattern Fig. 2c 8

9 Single Crystal X-ray Analysis: Single crystal X-ray analysis of 1b after exposing the crystal to CO 2 at 3.5 MPa (5 psig).. After 3 min exposure the single crystal retained its monoclinic high density guest free form 1b, and a further 3 min exposure resulted in a diffuse powder pattern indicating the crystal is not surviving the transformation as CO 2 diffuses into the solid (Supplementary Fig. 18-2). However, powder diffraction shows the presence of low and high density phases after 6 min exposure of CO 2 at room temperature and takes 2 hrs to complete the transformation (Fig. 3). The expansion and shrinkage of the host lattice by inclusion of gas molecules in a close packed organic solid has never before been observed. Fig. S17 Single crystal of 1b grown from a tetradecane solution before exposure to CO 2. a b c Fig. S18 Single crystal of 1b after exposure to 3.5 MPa (5 psig) of CO 2 at room temperature after a) 3 min. b) 6 min., and c) 12 hrs. 9

10 Fig. S19 Single crystal pattern of 1b before CO 2 exposure (left, characteristic of single crystallanity). Exposure of CO 2 to the same crystal for 6 min results in diffused pattern (right, 3.5 MPa) 6 5 1b 1b at 5 o C and 3.5 MPa of CO Fig. S2. Effect of higher temperature and pressure on form 1b. Transition to form 1a at 3.5 MPa CO 2 pressure does not occur even after two weeks. 1

11 Fig. S21. Self included form 2, which is isostructural to 1b (compare to Fig. 2). The voids (25 Å 3 ) are much smaller than 1b and guarded by tert-butyl groups. Orange and yellow shows the void space in MPa CO 2, 25 C (Total Duration hours) Relative, (CPS) T = T = 1.52 T = 1.72 T = Fig. S22. Experimental powder diffraction of 2 at high pressures of CO2 indicates no change powder pattern. 11