A Designed 3D Porous Hydrogen-Bonding Network Based on a Metal-Organic Polyhedron

Transcription

1 Supporting Information A Designed 3D Porous Hydrogen-Bonding Network Based on a Metal-Organic Polyhedron Wei Wei,*, Wanlong Li, Xingzhu Wang, Jieya He Department of Chemistry, Capital Normal University, Beijing, , P. R. China. wwei@cnu.edu.cn Contents 1. Experimental procedures 2. X-Ray crystallographic analysis 3. Power X-Ray diffraction (PXRD) Fig S1. Experimental and simulated PXRD patterns for Thermogravimetric analysis (TGA) Fig S2. TGA curve for crystal UV-Vis Absorption spectra analysis Fig S3. UV-Vis absorption spectra of crystal violet solution absorbed by 1. Fig S4. UV-Vis Absorption spectra of crystal violet (standard solution). Fig S5. Calibration curve for UV-Vis absorption of crystal violet. 6. Fluorescence emission spectra analysis Fig S6. Fluorescence emission spectra of rhodamine 6G solution absorbed by 1. Fig S7. Fluorescence emission spectra of rhodamine 6G (standard solution). Fig S8. Calibration curve for fluorescence emission of rhodamine 6G. 7. Gas sorption isotherms of N 2 Fig S9. Gas sorption isotherms of N 2 at 77 K.

2 1. Experimental procedures General: All chemicals were of reagent grade from commercial sources and used without further purification. Powder X-ray diffraction (PXRD) patterns were collected in a sealed glass capillary on a Rigaku DMAX 2500 power diffractometer with ultra 18 KW Cu radiation. Thermogravimetric analysis (TGA) was performed using a Shimadzu TGA-60 equipped with a platinum pan and heated at a rate of 10 C/min under nitrogen atmosphere. The fluorescence spectra were recorded on an FL4500 fluorescence spectrophotometer (Japan Hitachi company) at room temperature. UV-Vis absorption spectra were obtained using a Shimadzu UV-2550 PC UV-Vis recording Spectrophotometer. The contents of Na, Cu and Ru were determined by a Varian 710-ES Inductively Coupled Plasma-Atomic Emission Spectrometer (ICP-AES). Synthesis of crystal 1 : A CH 3 OH solution (8 ml) of NaH 2 (5-SO3-1,3-BDC) (NaL) (269 mg) was mixed with a 15 ml CH 3 OH/DMA solution (v/v = 1:1) of Cu 2 (OAc) 4 H 2 O (200 mg), and the mixture was stirred for 30 min at room temperature. After that, a CH 3 OH (6 ml) solution of guanidinium (G) chloride (95 mg) was diffused into the mixture. After several days large amounts of bulk blue crystals 1 {Na 12 G 4 [Cu 24 L 24 G 8 (H 2 O) 24 ] 74DMF} were obtained after immersed in DMF for 48h. Yield: ca. 95%. ICP-AES determinations for sodium and copper deduced a 1:2 molar ratio of Na:Cu. The solvent was removed under vacuum at 120 C, yielding materials for elemental analyses. Anal. Calcd. for C 204 H 144 Cu 24 N 36 Na 12 O 168 S 24 : C, 29.32; H, 1.74; N, 6.03%. Found: C, 30.29; H, 2.21; N, 6.68%. Dye inclusion experiments (a) Crystal violet uptake by crystal 1. Fresh crystal 1 (90 mg) was soaked in a DMF solution of Crystal violet (10 mm) overnight. The resulting crystals were washed with DMF thoroughly until the washings become colorless. The washed samples were dissolved in H 2 O solution (50 ml). Absorption experiments were performed on Shimadzu UV-2550 PC UV-Vis recording Spectrophotometer. The material was treated under vacuum at 120 C to remove the solvent for elemental analyses. Anal.

3 Calcd. Found: C, 29.14; H, 2.14; N, 6.41%. (b) Tris(2,2'-bipyridyl)ruthenium chloride uptake by crystal 1. Similar procedures as above were carried out for Tris(2,2'-bipyridyl)ruthenium chloride uptake studies. ICP-AES experiments were performed on Varian 710-ES, deducing a 21:1 molar ratio of Cu : Ru. The material was treated under vacuum at 120 C to remove the solvent for elemental analyses. Anal. Calcd. Found: C, 29.93; H, 2.19; N, 6.61%. (c) Rhodamine 6G uptake by crystal 1. Fresh crystal 1 (13 mg) was soaked in a DMF solution of rhodamine 6G (50 μm) overnight. The resulting solution was filtered. Fluorescence emission experiments of the resulting solution were performed on FL4500 fluorescence spectrophotometer (Japan Hitachi company) at room temperature. The material was treated under vacuum at 120 C to remove the solvent for elemental analyses. Anal. Calcd. Found: C, 29.80; H, 2.18; N, 6.57%. 2. X-Ray crystallographic analysis Data collections for crystal 1 were collected on a Bruker-AXS CCD-based diffractometer equipped with a graphite monochromated Cu-Kα radiation (λ = Å) by using the ω-scan mode at 293 K with an exposure time of 30 s/frame. An absorption correction was applied using the SADABS program.[1] The structures were solved by direct methods and refined on F 2 by full-matrix least-squares using the SHELXTL-97 program package.[2] All non-hydrogen atoms were refined anisotropically in crystal 1, where hydrogen atoms were placed in idealized positions and allowed to ride on the relevant non-hydrogen atoms. The hydrogen atoms attached to the water molecules are not included in the least-squares refinement. The solvent molecules were highly disordered and could not be modeled properly, thus the SQUEEZE routine of PLATON was applied to remove the contributions to the scattering from the solvent molecules.[3] The reported refinements are of the guest-free structures using the *.hkp files produced using the SQUEEZE routine. Thus, there are large differences between the calculated and the reported data such as chemical formula, molecular weight, density and so on.

4 3. Power X-Ray diffraction (PXRD) Fig S1. Experimental and simulated powder X-Ray diffraction patterns for crystal 1. Synthesized (blue), in air for 2 days (red) and the simulate pattern using the CIF file of crystal 1 (black). 4. Thermogravimetric analysis (TGA) Fig S2. TGA curve for crystal 1. The sample was heated to 600 o C at the heating rate 10 C/min under nitrogen atmosphere.

5 5. UV-Vis Absorption spectra analysis Fig S3. UV-Vis Absorption spectra of crystal 1 loaded with Crystal violet. Fig S4. UV-Vis Absorption spectra of Crystal violet (standard solution).

6 Fig S5. Calibration curve for UV-Vis absorption of Crystal violet. 6. Fluorescence emission spectra analysis Fig S6. Fluorescence emission spectra of Rhodamine 6G solution absorbed by crystal 1.

7 Fig S7. Fluorescence emission spectra of Rhodamine 6G (standard solution). Fig S8. Calibration curve for Fluorescence emission of Rhodamine 6G.

8 7. Gas sorption isotherms of N 2. Fig S9. Gas sorption isotherms of N 2 at 77 K. References: [1] G. M. Sheldrick, SADABS, Program for area detector adsorption correction, Institute for Inorganic Chemistry, University of Göttingen, Germany, [2] (a) G. M. Sheldrick, SHELXS-97, Program for solution of crystal structures, University of Göttingen, Germany, 1997; (b) G. M. Sheldrick, SHELXL-97, Program for refinement of crystal structures, University of Göttingen, Germany, [3] Platon program: A. L. Spek, Acta Crystallogr. Sect. A, 1990, 46, 194.