Highly Interlocked Anion-Bridged Supramolecular Networks from Interrupted Imidazole-Urea Gels. Supplementary Information

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1 Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 204 Highly Interlocked Anion-Bridged Supramolecular etworks from Interrupted Imidazole-Urea Gels Supplementary Information Samuel J. James, Andrea Perrin, Christopher D. Jones, Dmitry S. Yufit and Jonathan W. Steed * Instrumental and Analytical Measurements CH elemental microanalysis was performed using an Exeter CE-440 Elemental Analyser. All materials submitted were dried for at least three hours under vacuum in an Abderhalden drying pistol. FT-IR spectra of all solids were recorded over 24 scans on a Perkin-Elmer Spectrum 00 Series spectrometer fitted with the universal ATR sampling accessory, at a resolution of cm -. MR experiments were all run in DMSO-d 6 on a Bruker Avance 400. Liquid chromatography electrospray ionisation mass spectrometry was conducted on mg ml - methanol solutions using a Waters Ltd. TQD mass spectrometer. SEM samples were imaged using an FEI Helios anolab DualBeam microscope in immersion mode, with beam settings of.5 kv and 43 pa. Prior to imaging, samples were air dried for 2 days before coating with 3 nm of chromium using a Cressington 328 Ultra High Resolution EM Coating System. Oscillatory stress sweep experiments were performed between Pa at a constant frequency of Hz on a TA instruments AR 2000 rheometer equipped with a rough plate geometry. When preparing the sample, 2 ml of hot gelator solution was transferred to a glass cylinder sealed with vacuum grease to the lower plate. The gels were allowed 30 minutes to equilibrate before the geometry was lowered onto the sample at a pre-determined gap of 2.5 mm, and the glass cylinder gently removed before running the experiment. Crystallography The single crystal diffraction data for all compounds were collected at 20 K on an Agilent XCalibur diffractometer (Sapphire-3 CCD detector, graphite monochromator, λmokα radiation λ = Å) equipped with Cryostream (Oxford Cryosystems) open flow nitrogen cryostat. Structures were solved and refined using the SHELX programs operating within the Olex2 interface, 2 or using Superflip. 3 Syntheses [2 (H imidazol 4 yl)ethyl] 3 (4 methylphenyl)urea (a) Histamine (.0 g, 9.9 mmol) was dissolved in anhydrous chloroform (20 ml) under gentle heating in a three necked round bottomed flask fitted with a stirrer bar, condenser, dropping funnel and flowing 2. The mixture was heated to reflux and a solution of p-tolyl isocyanate (.32 g, 9.9 mmol) in anhydrous chloroform (0 ml) was slowly added via the dropping funnel over the course of 2 hours, before refluxing for a further 8 hours. The resulting white precipitate was H H O 7 H 8 9 0

2 filtered under reduced pressure, washed with chloroform (3 x 50 ml) and dried under vacuum in a drying pistol for three hours to yield the pure product as a white powder (2.22 g, 9. mmol, 92%); Anal. found: C, 63.50; H, 6.54;, %. Calc. for C 3 H 6 4 O: C, 63.9; H, 6.60;, 22.93%; ν max /cm w and 325w (H), 546s (CO), 598 (Ph C-C), 562 and 55 (imid. ring); δ H (400 MHz; DMSO-d 6 ; Me 4 Si).86 ( H, br s, H2), 8.40 ( H, s, H7), 7.56 ( H, d, J.2, H), (2 H, m, H8), (2 H, m, H9), 6.82 ( H, d, J., H3), 6.09 ( H, t, J 5.7, H6), 3.32 (2 H, q, J 6.9 H5), 2.65 (2 H, t, J 6.9, H4), 2.2 (3 H, s, H0); δ C { H} (0 MHz; DMSO) 55.69, 38.50, 35.4, 30.05, 29.47, 8.3, 7.30, 39.57, 28.04, 20.76; m/z (LC ESI-MS) 245 [M+H] [M] +, 489 [2M+H] +, 289, 39. Recrystallisation from MeC yielded single crystals of a. Crystal Data. C 3 H 6 4 O, M = , orthorhombic, a = (3), b = 0.28(3), c = (3) Å, V = 22.37(6) Å 3, T = 20 K, space group Pn2 a, Z = 4, 477 reflections measured, 3557 unique (R int = ). The final wr(f 2 ) was (all data). [2 (H imidazol 4 yl)ethyl] 3 phenylurea (b) Compound b has been reported previously. 4 Histamine (0.4 g,.2 mmol) was dissolved in anhydrous acetonitrile (40 ml) under gentle heating in a round bottomed flask fitted with a stirrer bar, condenser, dropping funnel and flowing 2. The mixture was heated to reflux and a solution of phenyl isocyanate (0.5 g,.2 mmol) in anhydrous acetonitrile (5 ml) was slowly added via the dropping funnel over the course of 2 hours, before refluxing for a further 8 hours. The solvent was then removed on a rotary evaporator, and the white residue was recrystallized from acetonitrile before drying under vacuum for three hours to yield the off-white product (0.8 g, 0.8 mmol, 64 %); δ H (400 MHz; DMSO-d 6 ; Me 4 Si).85 ( H, br s, H2), 8.52 ( H, s, H7), 7.56 ( H, s, H), 7.38 (2 H, d, J 7.9, H8), 7.2 (2 H, t, J 7.9, H9), 6.88 (2 H, t, J 7.3, H0), 6.84 ( H, s, H3), 6.4 ( H, t, J 5.6, H6), (2 H, m, H5), 2.66 (2 H, t, J 6.9, H4); δ C { H} (0 MHz; DMSO) 55.60, 4.04, 35.20, 29.08, 2.37, 8.0, 39.56, [Cu(a) 4 Cl]Cl (2) Compound a (0.0 mg, 0.04 mmol) was dissolved in a few drops of methanol in a 2 ml vial. A solution of copper(ii) chloride dihydrate (0.25 eq.,.75 mg, 0.00 mmol) in methanol (0.2 ml) was added, to yield a deep blue solution. The open vial was placed inside a larger 5 ml vial containing diethyl ether (2 ml), and the outer vial was sealed. Within 2 days, dark blue feather-like crystals of 22b formed as ether diffused into the inner vial. Anal. found: C, 56.7; H, 5.9;, 9.96 %. Calc. for C 52 H 64 Cl 2 Cu 6 O 4 : C, 56.8; H, 5.8;, 20.6 %; IR. ν max /cm w, 324w and 3000w (H), 66s (CO) 595s (Ph C-C), 540s and 497s (imid. ring). Crystal structure determination of 2 Crystal data for C 52 H 64 6 O 4 CuCl 2 : M =.64 g mol -, blue block, 0.2 x x 0.04 mm 3, tetragonal, space group P4/n (no. 85), a = 9.982(6) Å, b = 9.982(6) Å, c = (4) Å, α = 90.0 o, β = 90.0 o, γ = 90.0 o, V = 2775.(2) Å 3, Z = 2, D c =.330 g cm -, F 000 = 66, Mo Kα radiation, λ = Å, T = 20 K, 2θ max = 52.0 o, 3969 reflections collected, 2730 unique (R int = 0.003). Final GooF =.042, R = , wr2 = , R indices based on 2202 reflections with I >2σ(I) (refinement on F 2 ), 84 parameters, 0 restraints. Lp and absorption corrections applied, µ = mm -. 2 H H O 7 H 8 9 0

3 [Cu(a) 6 ](O 3 ) 2 2MeOH (3) Compound a (0.0 mg, 0.04 mmol) was dissolved in a few drops of methanol in a 2 ml vial. A solution of copper(ii) nitrate hemi(pentahydrate) (0.5 eq.,.305 mg, mmol) in methanol (0.2 ml) was added, to yield a bright blue solution. The vial was sealed and set aside. Pale blue single crystals of the product formed within 24 hours. Anal. found: C, 56.4; H, 5.93;, 2.7 %. Calc. for C 80 H 04 Cu 26 O 4 : C, 55.95; H, 6.;, 2.2 %; ν max /cm w and 342w (H), 662vs (CO), 598s (Ph C-C), 545s and 509s (imid. ring), 37s (O 3- ). Crystal structure determination of 3 Crystal data for C 80 H O 4 Cu: M = g mol -, blue block, x x mm 3, triclinic, space group P- (no. 2), a = 3.000(7) Å, b = (7) Å, c = 3.440(6) Å, α = 75.23(4) o, β = 77.75(4) o, γ = 74.72(4) o, V = 27.59(9) Å 3, Z =, D c =.33 gcm -, F 000 = 907, Mo Kα radiation, λ = Å, T = 20 K, 2θ max = 52.0 o, reflections collected, 8537 unique (R int = ). Final GooF =.062, R = , wr2 = 0.452, R indices based on 6765 reflections with I >2σ(I) (refinement on F 2 ), 608 parameters, 0 restraints. Lp and absorption corrections applied, µ = mm -. 3

4 Analysis Figure S. wt. % compound a gels in H2O/MeOH mixtures. Left to right: H2O, H2O/MeOH 2:, H2O/MeOH 4:, H2O/MeOH 9: Re-dissolve and briefly sonicate A B Figure S2. Optical microscope images of A) a wt. % compound a hydrogel that has cooled normally at room temperature and B) a wt. % compound a hydrogel that has been sonicated for 3 seconds upon cooling. ote the loss of crystallinity. Both images were taken at the same magnification. B A Figure S3. SEM images of two different regions in a dried sonication-induced compound a hydrogel sample. 4

5 a wt. % oscillatory stress sweep a gels: G dependence on concentration a gels: Change in yield point with gelator concentration Figure S4. A) oscillatory stress sweep rheomety of a hydrogel of compound a, B) G as a function of gelator concentration in weight percent, C) concentration dependence of the yield stress. The decreased final value may reflect incomplete dissolution. 5

6 Figure S5. SEM micrograph of the xerogel of a weak compound a hydrogel in the presence of 0. molar equivalents of Cu(O 3 ) eq eq. 0. eq G / Pa Oscillatory 2 stress 3 / Pa Figure S6. Stress sweep rheometry of compound a hydrogel in the presence of increasing equivalents of Cu(O 3 ) 2. 6

7 00 0 eq eq eq eq G / Pa Oscillatory 7 stress 8 / Pa 9 0 Figure S7. Stress sweep rheometry of compound a hydrogel in the presence of increasing equivalents of ZnCl G / Pa 600 CuCl2 ZnCl2 Cu(O3)2 o salt Oscillatory 2 stress 3 / Pa Figure S8. Stress sweep rheometry of compound a hydrogel in the presence of 0.05 of CuCl 2, ZnCl 2 and Cu(O 3 ) 2. 7

8 Figure S9 SEM images showing the heterogeneous structure of gels of a with added metal salts (left to right 0. equivalents of Cu(O 3 ) 2, CuCl 2 and ZnCl 2 ).. G. M. Sheldrick, Acta Crystallogr. Sect. A, 2008, 64, O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann, J. Appl. Cryst., 2009, 42, L. Palatinus and G. Chapuis, J. Appl. Crystallogr., 2007, 40, Y. M. Legrand, M. Michau, A. van der Lee and M. Barboiu, CrystEngComm, 2008, 0,