Electronic supplementary information (ESI) Temperature dependent selective gas sorption of unprecedented

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1 Electronic supplementary information (ESI) Temperature dependent selective gas sorption of unprecedented stable microporous metal-imidazolate framework Shui-Sheng Chen, a,c Min Chen, a Satoshi Takamizawa, b Man-Sheng Chen, a Zhi Su a and Wei-Yin Sun* a a Coordination Chemistry Institute, State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing National Laboratory of Microstructures, Nanjing University, Nanjing 9, China sunwy@nju.edu.cn; Fax: b Graduate School of Nanobioscience, Yokohama City University, Kanazawa-ku, Yokohama, Kanagawa 6-7, Japan c School of Chemistry and Chemical Engineering, Fuyang Teachers College, Fuyang 6, China Experimental Materials and methods All commercially available chemicals are of reagent grade and were used as received without further purification. The ligand H L was prepared according to the literature. S Elemental analyses of C, H, and N were taken on a Perkin-Elmer C elemental analyzer at the analysis center of Nanjing University. Infrared spectra (IR) were recorded on a Bruker Vector FT-IR spectrophotometer by using KBr pellets. Thermogravimetric analyses (TGA) were performed on a simultaneous SDT 96 thermal analyzer under nitrogen with a heating rate of ºC min -. Powder X-ray diffraction (PXRD) patterns were measured on a Shimadzu XRD-6 X-ray diffractometer with Cu Kα (λ =.8 Å) radiation at room temperature. Carbon dioxide (CO ) and nitrogen (N ) sorption experiments were carried out on a Belsorp-max volumetric gas sorption instrument and methane (CH ) and hydrogen (H )

2 on Autosorb-MP, Quantachrome. The sample was activated by using the outgas function of the surface area analyzer for hours at 6 ºC. X-ray crystallography The crystallographic data collections for was carried out on a Bruker Smart Apex CCD area-detector diffractometer with graphite-monochromated Mo Kα radiation (λ =.77 Å) at 9() K using ω-scan technique. The diffraction data were integrated by using the SAINT program, S which was also used for the intensity corrections for the Lorentz and polarization effects. Semi-empirical absorption correction was applied using the SADABS program. S The structures were solved by direct methods and all the non-hydrogen atoms were refined anisotropically on F by the full-matrix least-squares technique using the SHELXL-97 crystallographic software package. S Figure S. The coordination environments of Cu atoms in. Atoms with A, B, C or D in labels are symmetry-generated. Symmetry code: A +x-y, -y,.-z; B -y, -x,.+z; C +x-y, +x, -z; D -x, -y, -z.

3 Figure S. (a) View of the -connected L - ligand. (b) -connected node of Cu(II). (c) Schematic representations of the (, )-connected framework of with (6 ) topology. (b) Δ H ads (KJ/mol) CO adsorbed (wt %) Figure S. CO adsorption enthalpy for calculated from the CO adsorption isotherms at 7 and 98 K. 9 (b) 8 Δ H ads (KJ/mol) H adsorbed (wt %) Figure S. H adsorption enthalpy for calculated from the H adsorption isotherms at 77 and 87 K. Analysis of Gas Sorption Isotherms: The methods are applied to deal with the sorption data according to the literature (J. Am. Chem. Soc., 7, 967). The Langmuir-Freundlich equation is used to fit CO and H adsorption isotherms and predict the adsorption capacity of the framework at saturation, and Clausius-Clapeyron equation is employed to calculation the enthalpies of CO and H

4 adsorption. P In H T =Δ T P ads RTT ( I ) Where P i = pressure for isotherm i T i = temperature for isotherm i R = 8. J / (K mol) The equation (I) can be applied to calculate the enthalpy of adsorption of a gas as a function of the quantity of gas adsorbed. Pressure as a function of the amount of gas adsorbed was determined using the Langmuir-Freundlich fit for the isotherms. (/ t) Q BP = ( II ) (/ t ) Qm + BP where Q = moles adsorbed Q m = moles adsorbed at saturation P = pressure B and t are constants Rearrange (II) to get: Q/ Q m P = B BQ/ Qm t (III) Replace P in equation (I) to obtain: H Q/ Q m RTT B BQ / Qm In T T Q/ Q m B BQ/ Qm Δ ads = t t ( IV ). Dealing with the carbon dioxide adsorption data in details: () Fitting CO adsorption isotherms using the Langmuir-Freundlich equation.

5 7K CO adsorption (ml/g) B langfr (User) Fit of B Equation: y = b*x^(/t)/(+b*x^(/t))*q Adj. R-Squar.9999 Value Standard Erro B t.6.69 B b.8. B q P(KPa) CO adsorption (ml/g) 98K B langfr (User) Fit of B Equation: y = b*x^(/t)/(+b*x^(/t))*q Adj. R-Squar Value Standard Erro B t.8. B b.9. B q P(KPa) () Building the relationship between lnp and the quantity of CO adsorbed for the two isotherms by calculating.

6 98K 7K lnp Adsorbed Volume (ml) () Calculating the H ads using the equation IV. Δ H ads (KJ/mol) CO adsorbed (wt %). Calculation of CO /N selectivity The methods are applied to estimate the CO /N selectivity according to the literature 8a (J. Am. Chem. Soc.,,, 8). The ratios of these initial slopes of the CO and N adsorption isotherms were applied to estimate the adsorption selectivity for CO over N. 6

7 . Gas Uptake (mmol/g)..... y =.6x -.6 R =.9988 y =.87x -. R = Pressure (KPa) Figure S6. The fitting initial slope for CO and N isotherms collected at 7K (CO : red squares; N : green triangles).. Gas Uptake (mmol/g) y =.97x+. R =.999 y =.9x -.98 R = Pressure (KPa) Figure S7. The fitting initial slope for CO and N isotherms collected at 98K (CO : red squares; N : green triangles).. Dealing with the hydrogen adsorption data in details: () Fitting H adsorption isotherms using the Langmuir-Freundlich equation. 7

8 7 6 77K H adsorption (ml/g) H adsorption (ml/g) 7 6 B langfr (User) Fit of B Equation: y = b*x^(/t)/(+b*x^(/t))*q Adj. R-Squar.9998 Value Standard Erro B t..89 B b..8 B q P(KPa) 87K B langfr (User) Fit of B Equation: y = b*x^(/t)/(+b*x^(/t))*q Adj. R-Squar.9998 Value Standard Erro B t.88. B b B q P(KPa) () Building the relationship between lnp and the quantity of hydrogen adsorbed for the two isotherms by calculating. 8

9 87K 77K lnp Adsorbed Volume (ml) () Calculating the H ads using the equation IV. 9 8 Δ H ads (KJ/mol) H adsorbed (wt %) Reference: S (a) R. ten Have, M. Huisman, A. Meetsma and A. M. van Leusen, Tetrahedron, 997,,. (b) S. S. Chen, J. Fan, T.-a. Okamura, M. S. Chen, Z. Su, W. Y. Sun and N. Ueyama, Cryst. Growth Des.,, 8. S SAINT, version 6.; Bruker AXS, Inc., Madison, WI,. S Sheldrick, G. M. SADABS, University of Göttingen, Göttingen, Germany. S Sheldrick, G. M. SHELXTL, version 6.; Bruker Analytical X-ray Systems, Madison, WI,. 9