Selective gas and vapor sorption and magnetic sensing by an. isoreticular mixed-metal-organic framework

Transcription

1 Supporting Information (SI) for the manuscript: Selective gas and vapor sorption and magnetic sensing by an isoreticular mixed-metal-organic framework Jesús Ferrando-Soria, Pablo Serra-Crespo, Martijn de Lange, Jorge Gascon,* Freek Kapteijn, Miguel Julve, Joan Cano, Francesc Lloret,* Jorge Pasan, Catalina Ruiz-Pérez, Yves Journaux, and Emilio Pardo* S1

2 Experimental Section Materials. Na 4 [Cu 2 (Me 3 mpba) 2 ] 4H 2 O was synthesized according to literature methods. 1 All chemicals were of reagent grade quality, and they were purchased from commercial sources and used as received. [Na(H 2 O) 3.25 ] 4 {Mn 4 [Cu 2 (Me 3 mpba) 2 (H 2 O) 3.33 ] 3 } 37 H 2 O (H 2 O@iso1): X-ray quality bright green tiny prisms of H 2 O@iso1 were grown by slow diffusion of aqueous solutions containing stoichiometric amounts of Na 4 [Cu 2 (Me 3 mpba) 2 ]. 4H 2 O (0.011 g, mmol) and Mn(NO 3 ). 2 4H 2 O (0.005 g, mmol) in a H-shaped tube on standing at room temperature after four weeks. Yield: g, 58%; elemental analysis calcd (%) for C 78 H 180 N 12 O 96 Na 4 Cu 6 Mn 4 (3515.3): C 26.65, H 5.16, N 4.78; found: C 26.59, H 5.11, N IR (KBr) 1602 cm -1 (CO). Physical Techniques. Elemental analyses (C, H, N) were performed at the Microanalytical Service of the Universitat de València. The thermogravimetric analysis was performed on crystalline samples of H 2 O@iso1 under a dry N 2 atmosphere with a Mettler Toledo TGA/STDA 851 e thermobalance operating at a heating rate of 10 ºC min 1. High-pressure adsorption isotherms of CO 2, CH 4, N 2 and H 2 (purity of %) were determined using the volumetric technique with an apparatus from BEL Japan (Belsorp HP). Around 0.5 gram of H 2 O@iso1 were placed in the sample container. Before the measurement, the adsorbent was pre-treated by increasing the temperature to 373 K at a rate of 10 K/min under vacuum and maintaining the temperature for two hours in order to have the dehydrated derivative iso1. Methanol and water adsorption isotherms were measured at 298 K in an apparatus from Quantachrome, model autosorb I. The samples were degassed in the same device by applying vacuum and a temperature of 373 K for 16 h. Around 100 mg were used for the measurements. 1 Ferrando-Soria, J.; Pasán, J.; Ruiz-Pérez, C.; Journaux, Y.; Julve, M.; Lloret, F.; Cano, J.; Pardo, E.; Inorg. Chem. 2011, 50, S2

3 Crystal Structure Data Collection and Refinement. Crystal data for H 2 O@iso1: C 78 H 180 Cu 6 Mn 4 N 12 Na 4 O 96, tetragonal, space group P4/mmm, a = (5) Å, c = (3) Å, V = 20075(6) Å 3, T = 100(2) K, λ = Å, Z = 4, ρ calc = g.cm -3, µ = mm -1, of the reflections collected, 9434 are unique and 9389 observed with I > 2σ(I). Refinement of 551 parameters gave R = and R w = for reflections with I > 2σ(I) and R = and R w = for all reflections, with S = The final Fourier-difference map showed maximum and minimum height peaks of and e.å -3. The data collection was carried out at the BM16 beamline in the ESRF (Grenoble, France); a special care was taken to prevent the degradation upon dehydration, and the crystal was mounted in a grease drop and immediately frozen. The data was indexed, integrated and scaled using the HKL2000 program by Otwinowski and Minor. 2 The structure was solved by direct methods and refined with full-matrix least-squares technique on F 2 using the SHELXS-97 and SHELXL-97 programs by Sheldrick. 3 All non-hydrogen atoms were refined anisotropically. The hydrogen atoms of the organic ligands were set on geometrical positions and refined with a riding model, those of the water molecules were neither found nor set. The sodium(i) counterions have been found in different positions, therefore all the sodium ions shared occupancies. The water molecules are disordered within the pores of the structure; partial occupation was applied when needed. Residual electron density peaks of significant magnitude were found around the metal ions (maximum of 3.54 e Å -3 ), and also high values of R 1, wr2 and S result in the best refinement achieved; these problems were not solved by the absorption correction, and probably, they are caused by the contribution of the disordered solvent to the diffraction intensitities, which cannot be modelled satisfactorily, and the poor diffraction power of the sample (see Figure S9). Crystallographic data (excluding structure factors) for the structure reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB21EZ, UK (fax: (+44) ; deposit@ccdc.cam.ac.uk). 2 Z. Otwinowski, W. Minor, Processing of X-ray diffraction data collected in oscillation mode, in Methods in Enzymology: Macromolecular Crystallography, Part A, Vol. 276 (eds C. W. Jr. Carter, R. M. Sweet) 307, G. M. Sheldrick, Acta Cryst. 2008, A64, S3

4 Powder X-Ray Diffraction Measurements. Powder X-ray diffraction patterns of as synthetized iso1, H 2 O@iso1 and CH 3 OH@iso1 were collected at 100 K using synchrotron radiation (λ = Å) on the BM16-CRG beamline in the ESRF (Grenoble, France). A bunch of crystals were mounted on a cryoloop and immediately freezed to 100 K to prevent any solvent loss and the measurements were carried out with a sample to detector distance of 200 mm, φ rotation of 20º, and 60 s of exposure time. A LaB6 standard was used for detector distance and tilting corrections and center positioning. The collected data were converted with the Fit2D program 4 and analyzed with the Fullprof suite 5. Magnetic Measurements. Variable-temperature direct current (dc) and alternating current (ac) magnetic susceptibility measurements as well as variable-field magnetization measurements were carried out on crystalline samples of iso1, H 2 O@iso1, CH 3 OH@iso1, CO and CH with a Quantum Design SQUID magnetometer. Crystals of H 2 O@iso1 were picked from the mother liquor and then they were immediately introduced at 110 K without vacuum under a continuous He flow to prevent any partial water loss, while those of iso1 were kept at 373 K for 30 min under vacuum to ensure complete water removal prior to carry out the magnetic measurements. CH 3 OH@iso1 was obtained after immersing iso1 for 30 minutes in methanol, and it was measured immediately after filtration. Finally, the magnetic properties of CO and CH were measured after inserting iso1 in a capillary tube filled with CO 2 or CH 4 and closed with a pressure of 1 bar. The susceptibility data were corrected for the diamagnetism of both the constituent atoms and the sample holder. 4 Hammersley, A. P. ESRF Internal Report, ESRF97HA02T, in FIT2D: An Introduction and Overview (1997). 5 Rodríguez-Carvajal, J. FULLPROF program (ILL, 2009). S4

5 Figure S1. Projection views of the crystal packing of (a) and (b) along the crystallographic c (top) and b (bottom) axes emphasizing the different pore size distribution of the octagonal pores of the open-framework structures (the void spaces are represented by pale yellow spheres). Metal and ligand atoms are represented by balls and sticks, respectively (Cu, green; Mn, purple). S5

6 Figure S2. (a) Perspective view of the unit cell of with the labeling of the metal atoms [symmetry codes: (a) = x, y, z + 1; (b) = x, y, z + 1; (c) = x, y + 1, z + 1]. Metal and ligand atoms are represented by balls and sticks, respectively (Cu, green; Mn, purple; Na, yellow; C, grey; N, blue; and O, red). Weak coordinative interactions with the sodium countercations are represented by solid lines. Free water molecules and hydrogen atoms are omitted for clarity. (b) Projection view of the crystal packing of H2O@iso1 along the crystallographic c axis showing the filling of the small square and large octagonal pores of the open-framework structure by crystallization water molecules (red spheres) and sodium atoms (yellow spheres). S6

7 Figure S3. TGA of under dry N2 atmosphere. S7

8 Figure S4. Water (a) and methanol (b) vapor adsorption ( ) and desorption ( ) isotherms of iso1 at 298 K. S8

9 Figure S5. CO2 ( ), CH4 ( ), N2 ( ) and H2 ( ) adsorption isotherms on compound iso1 at 298 K. S9

10 Figure S6. N2 adsorption ( ) and desorption ( ) isotherms of iso1 at 77 K. S10

11 Figure S7. XRD patterns of at 300 K (red line), after heating at 368 K for 30 min. to give iso1 (purple line) and at 300 K after immersion of iso1 in aqueous or methanol solutions to give H2O@iso1 (blue line) and MeOH@iso1 (green line) respectively. S11

12 Figure S8. (a) Temperature dependence of the product of the direct current (dc) molar magnetic susceptibility by the temperature (χmt) of iso1 (green), (red), and (blue). (b) Field dependence of the magnetization (M) of iso1 (green), (red), and (blue) at T = 2.0 K. The solid lines are eye-guides. S12

13 Figure S9. A frame of the X-ray diffraction experiment data collection carried out at the BM16 beamline in the ESRF (Grenoble, France). Edge of the frame represents a 0.85 Å resolution with λ = Å. S13