SUPPLEMENTARY INFORMATION

Transcription

1 SUPPLEMENTARY INFORMATION De Novo Synthesis of a Metal-Organic Framework Material Featuring Ultra-High Surface Area and Gas Storage Capacities Omar K. Farha, 1 A. Özgür Yazaydın, 2 Ibrahim Eryazici, 1 Christos D. Malliakas, 1 Brad G. Hauser, 1 Mercouri G. Kanatzidis, 1 SonBinh T. Nguyen, 1 Randall Q. Snurr, 2,* Joseph T. Hupp 1,* 1 Department of Chemistry and International Institute for Nanotechnology, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, USA. 2 Department of Chemical and Biological Engineering, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, USA. *To whom correspondence should be addressed. o-farha@northwestern.edu, snurr@northwestern.edu, and j-hupp@northwestern.edu Table of contents Section S1. General Procedures, Materials, and Instrumentation Section S2. Synthesis of Ligand Precursors, Ligand, and NU-100 Section S3. Single Crystal X-ray Diffraction Analysis Section S4. Molecular Simulations Section S5. BET Surface Area Analysis Section S6. Gas Adsorption Analyses References S2 S3-S7 S8-S10 S11-S16 S17-S20 S21-S234 S25 nature chemistry 1

2 supplementary information SECTION S1. General Procedures, Materials, and Instrumentation All air- or water-sensitive reactions were carried out under a dry nitrogen atmosphere using standard Schlenk techniques. Reagents and reagent-grade solvents were purchased from either Acros, Strem or Aldrich Chemical Company and used as received. Silica gel was purchased from VWR or Sorbent Technologies. Deuterated solvents were purchased from Cambridge Isotope Laboratories and used without further purification. Dry solvents were prepared by passing HPLC-grade solvents through a column packed with neutral alumina via a Dow-Grubbs solvent system. All dry solvents were collected under inert gases, degassed under vacuum, and stored under nitrogen in a Strauss flask prior to use. 1 H and 13 C NMR spectra were recorded on a Bruker 500 FT-NMR spectrometer ( MHz for 1 H, MHz for 13 C). 1 H NMR data are reported as follows: chemical shift (multiplicity (b = broad singlet, s = singlet, d = doublet, dd = doublet of doublets, ddd = doublet of doublets of doublets, t = triplet, q = quartet, and m = multiplet), integration, and peak assignments, coupling constants). In 1 H NMR spectra, the outside benzene ring in compounds 9 and 10 (LH 6 ) was assigned as Ben 1, middle benzene ring assigned as Ben 2 and the central benzene ring assigned as Ben 3 (Scheme S1). 1 H and 13 C chemical shifts are reported in ppm from TMS with residual solvent resonances as internal standards. A Bruker Autoflex III Smartbeam MALDI-ToF (Time of Flight) mass spectrometer was used. Mass-accurate match spectra were obtained by using an Agilent 6210 LC-MS ToF mass spectrometer with electro-spray ionization (ESI). Samples were dissolved in DMF and diluted in MeOH. Powder X-ray diffraction (PXRD) data were recorded on a Rigaku ATX-G diffractometer using nickel-filtered Cu Kα radiation. Data were collected over the range of 1 < 2(θ) < 35 in 0.05 steps at a scan rate of 2 /min. Crystal structure data were collected on a STOE IPDS II diffractometer equipped with a graphite monochromatized Mo radiation source (λ = Å) and an image plate detector. Thermogravimetric analyses (TGA) were performed on a Mettler-Toledo TGA/SDTA851e. Samples were places in alumina pans and heated from 25 o C to 700 o C at 10 o C/minute under N 2. Supercritical CO 2 processing was performed with a Tousimis Samdri PVT-30 critical point dryer as detailed below (p. S10). Low-pressure (< 1 bar) adsorption measurements were performed using an Autosorb 1-MP instrument from Quantachrome Instruments. Ultra-high purity grade CO 2, N 2, Ar, He and H 2 were used for adsorption measurements. Low-pressure CO 2 adsorption isotherms were measured at 273K; the temperature was held constant using an ice water bath. Isotherms measured at 77K (N 2 and H 2 ) were carried out in a liquid nitrogen bath; isotherms measured at 87K (Ar and H 2 ) were carried out in a liquid argon bath. High-pressure (1 to 70 bar) adsorption measurements were carried out on an HPVA- 100 from VTI Instruments. For the measurements a 1cc stainless steel sample holder. 300 mg of as synthesized NU-100 was activated and loaded to the sample holder in an argon atmosphere dry box. For excess hydrogen adsorption, the sample was held at 77K 2 nature chemistry

3 supplementary information in a liquid nitrogen bath. Negligible loss of liquid nitrogen was noticed over the duration of the measurement. For carbon dioxide adsorption, samples were held at 298K with a circulating water bath. Section S2. Synthesis of Ligand Precursors, Ligand, and NU-100 Synthesis of Ligand (LH 6 ). Scheme S1. Synthesis of the hexacarboxylate ligand 10 (LH 6 ). Synthesis of 1,3-diethylcarboxylate-4-iodobenzene (1). To a stirring solution of 1,3-dimethylcarboxylate-4-iodobenzene (20 g, 62.5 mmol) in ethanol (400 ml), HCl gas, which was generated by slow addition of concentrated HCl (100 ml, 35%) into nature chemistry 3

4 supplementary information concentrated H 2 SO 4 (100 ml, 98%), was bubbled. The reaction mixture was then refluxed for 30 h. Acidic EtOH was then removed with a rotary evaporator and the remaining solid was dried under high vacuum to afford the product 1 as a white solid. Yield = 21.5 g (99%). 1 H NMR (CDCl 3 ): δ 1.4 (t, 6 H, CO 2 CH 2 CH 3, J = 7.2 Hz), 4.39 (q, 4 H, CO 2 CH 2 CH 3, J = 7.2 Hz), 8.51 (s, 2 H, 4,6-BenH), 8.6 (s, 1 H, 2-BenH). 13 C NMR (CDCl 3 ): δ 14.5, 61.9, 93.6, 129.9, 132.6, 142.4, Synthesis of 1,3-diethylcarboxylate-4-(trimethylsilylethynyl)benzene (2). To a stirring solution of 1 (20 g, 57.5 mmol) in THF (100 ml) and diisopropylamine (100 ml), (trimethylsilyl)acetylene (15.2 g, 155 mmol) was added. The mixture was degassed and back-filled with N 2 (3 ). Tetrakis(triphenylphosphine)palladium (2 g, 1.73 mmol, 3 mol%) and CuI (660 mg, 3.5 mmol) were then added to the flask. The resulting mixture was degassed and back-filled with N 2 (2 ), and then stirred for 15 h at 25 ºC. The mixture was filtered and washed with hexanes (200 ml). The filtrate was concentrated to dryness, redissolved in a minimum amount of CH 2 Cl 2, and column chromatographed over silica gel (400 mm length 70 mm diameter) using a mixture of hexanes:ch 2 Cl 2 (1:1 v/v) to give 2 as a white solid after isolation. Yield = 16.6 g (91%). 1 H NMR (CDCl 3 ): δ 0.25 (s, 9 H, Si(CH 3 ) 3 ), 1.45 (t, 6 H, CO 2 CH 2 CH 3, J = 7.2 Hz), 4.45 (q, 4 H, CO 2 CH 2 CH 3, J = 7.2 Hz), 8.32 (s, 2 H, 4,6-BenH), 8.65 (s, 1 H, 2-BenH). 13 C NMR (CDCl 3 ): δ 0.1, 14.5, 61.8, 96.7, 103, 124.2, 130.5, 131.3, 136.9, Synthesis of 1,3-diethylcarboxylate-4-ethynylbenzene (3): To a stirring solution of 2 (16.6 g, 47.7 mmol) in THF (200 ml) and EtOH (100 ml), cesium fluoride (8 g, 52.5 mmol) was added. The reaction mixture was stirred for 1 h at 25 ºC and then concentrated. The remaining solid was redissolved in a minimum amount of CH 2 Cl 2 and passed through a plug of silica gel (200 mm length 70 mm diameter) using CH 2 Cl 2 to give 3 as a white solid after isolation. Yield = 11.6 g (99%). 1 H NMR (CDCl 3 ): δ 1.42 (t, 6 H, CO 2 CH 2 CH 3, J = 7.2 Hz), 3.18 (s, 1 H, Ben-C CH), 4.42 (q, 4 H, CO 2 CH 2 CH 3, J = 7.2 Hz), 8.32 (s, 2 H, 4,6-BenH), 8.64 (s, 1 H, 2-BenH). 13 C NMR (CDCl 3 ): δ 14.5, 61.8, 79.2, 81.9, 123.2, 130.8, 131.4, 137.1, Synthesis of 1-iodo-4-(trimethylsilylethynyl)benzene (4). To a stirring solution of 1,4-diiodobenzene (20 g, 60.6 mmol) in THF (150 ml) and diisopropylamine (150 ml), (trimethylsilyl)acetylene (6 g, 60.6 mmol) was added. The mixture was degassed and back-filled with N 2 (3 ). Tetrakis(triphenylphosphine)palladium (2.1 g, 1.8 mmol, 3 mol%) and CuI (700 mg, 3.7 mmol) were added to the flask. The resulting mixture was degassed and back-filled with N 2 (2 ), and then stirred for 15 h at 25 ºC. The mixture was filtered and washed with hexanes (200 ml). The filtrate was concentrated to dryness, redissolved in a minimum amount of CH 2 Cl 2, and column chromatographed over silica gel (500 mm length 70 mm diameter) using hexanes to give 4 as a white solid after isolation. Yield = 8.8 g (48%). 1 H NMR (CDCl 3 ): δ 0.25 (s, 9 H, Si(CH 3 ) 3 ), 7.18 (d, 2 H, 2,6-BenH, J = 8.4 Hz), 7.65 (d, 2 H, 3,5-BenH, J = 8.4 Hz). 13 C NMR (CDCl 3 ): δ 0.1, 94.7, 96.1, 104.2, 122.8, 133.6, Synthesis of 1,3-diethylcarboxylate-5-[(4-(trimethylsilylethynyl)phenyl)ethynyl]- benzene (5). To a stirring solution of 4 (8.8 g, 29.3 mmol) in THF (100 ml) and diisopropylamine (100 ml), 3 (11.5 g, 46.9 mmol) was added. The mixture was degassed and back-filled with N 2 (3 ). Tetrakis(triphenylphosphine)palladium (1 g, nature chemistry

5 supplementary information mmol, 3 mol%) and CuI (330 mg, 3.72 mmol) were added to the flask. The resulting mixture was degassed and back-filled with N 2 (2 ), and then stirred for 15 h at 25 ºC. The mixture was filtered and washed with hexanes (200 ml). The filtrate was concentrated to dryness, redissolved in a minimum amount of CH 2 Cl 2, and column chromatographed over silica gel (400 mm length 70 mm diameter) using with a mixture of hexanes:ch 2 Cl 2 (1:1 v/v) to give 5 as a white solid after isolation. Yield = 11.5 g (94%). 1 H NMR (CDCl 3 ): δ 0.26 (s, 9 H, Si(CH 3 ) 3 ), 1.43 (t, 6 H, CO 2 CH 2 CH 3, J = 7.2 Hz), 4.44 (q, 4 H, CO 2 CH 2 CH 3, J = 7.2 Hz), 7.47 (d, 2 H, 2,6-Ben 2 H, J = 8.6 Hz), 7.49 (d, 2 H, 3,5- Ben 2 H, J = 8.6 Hz), 8.35 (s, 2 H, 4,6-Ben 1 H), 8.64 (s, 1 H, 2-Ben 1 H). 13 C NMR (CDCl 3 ): δ 0.1, 14.5, 61.8, 89.5, 90.9, 96.9, 104.6, 122.7, 123.7, 124.1, 130.4, 131.5, 131.7, 132.2, 136.6, Synthesis of 1,3-diethylcarboxylate-5-[(4-(ethynyl)phenyl)ethynyl]benzene (6). To a stirring solution of 5 (10.2 g, 24.4 mmol) in THF (130 ml) and EtOH (70 ml), cesium fluoride (4.1 g, 27.1 mmol) was added. The reaction mixture was stirred for 1 h at 25 ºC and concentrated to dryness. The remaining solid was redissolved in a minimum amount of CH 2 Cl 2 and passed through a plug of silica gel (200 mm length 70 mm diameter) using CH 2 Cl 2 to give 6 as a white solid after isolation. Yield = 8.4 g (99%). 1 H NMR (CDCl 3 ): δ 1.44 (t, 6 H, CO 2 CH 2 CH 3, J = 7.2 Hz), 3.21 (s, 1 H, Ben-C CH), 4.44 (q, 4 H, CO 2 CH 2 CH 3, J = 7.2 Hz), 7.5 (d, 2 H, 2,6-Ben 2 H, J = 8.6 Hz), 7.51 (d, 2 H, 3,5-Ben 2 H, J = 8.6 Hz), 8.36 (s, 2 H, 4,6-Ben 1 H), 8.64 (s, 1 H, 2-Ben 1 H). 13 C NMR (CDCl 3 ): δ 14.5, 61.8, 79.5, 83.3, 89.5, 90.7, 122.7, 123.1, 124.1, 130.4, 131.5, 131.8, 132.4, 136.6, Synthesis of 1,3,5-tris(trimethylsilyl)benzene (7). To a stirring solution of 1,3,5- tribromobenzene (10 g, 31.8 mmol) in THF (60 ml), trimethylsilylchloride (25.7 g, 237 mmol) was added dropwise over 30 minutes. The mixture was cooled to -78 C (acetone/dry-ice bath) and n-buli (58 ml, 2.5 M in hexane, 145 mmol) was added dropwise over 1 h. Caution: n-buli should be handled under a dry nitrogen atmosphere. The resulting solution was kept at -78 C for 3 more hours and then allowed to warm to 25 ºC. The reaction mixture was subsequently quenched with saturated aqueous NH 4 Cl solution (100 ml) and extracted with CH 2 Cl 2 (3 150 ml). The organic layers were combined, dried over MgSO 4, and then concentrated to a minimum. The remaining residue was distilled (100 mm Hg, 80 C) to afford 1,3,5-tri(trimethylsilyl)benzene as a colorless oil. Yield = 8.1 g (86%). 1 H NMR (CDCl 3 ): δ 0.38 (s, 27 H, 1,3,5-Ben- Si(CH 3 ) 3 ), 7.79 (s, 3 H, 2,4,6-BenH). 13 C NMR (CDCl 3 ): δ 0.8, 138.5, Synthesis of 1,3,5-triiodobenzene (8). To a stirring solution of 7 (8.1 g, 27.5 mmol) in CCl 4 (150 ml), ICl (35 g, 200 mmol) in CCl 4 (50 ml) was added. The resulting mixture was stirred for 20 h at 25 ºC. The reaction was subsequently quenched with a saturated aqueous Na 2 SO 3 solution (100 ml) and extracted with CH 2 Cl 2 (3 150 ml). The organic layers were combined, dried over MgSO 4, and then concentrated until white precipitate appeared. The concentrated solution was then kept at 0 ºC for 1 h to induce more product precipitation. The precipitate was collected via filtration and further recrystallized in EtOH to give 8 as a white solid. Yield = 7.9 g (63%). 1 H NMR (CDCl 3 ): δ 8.01 (s, 3 H, 2,4,6-BenH). 13 C NMR (CDCl 3 ): δ 95.5, nature chemistry 5

6 supplementary information Synthesis of 1,3,5-tris[(1,3-diethylcarboxylate-5-(4-(ethynyl)phenyl))ethynyl]- benzene (9) To a stirring solution of 8 (2 g, 4.4 mmol) in THF (200 ml) and diisopropylamine (200 ml), 6 (7.6 g, 22 mmol) was added. The mixture was degassed and back-filled with N 2 (3 ). Tetrakis(triphenylphosphine) palladium (460 mg, 0.4 mmol, 3 mol% per iodo functionality) and CuI (150 mg, 0.8 mmol) were added to the flask. The resulting mixture was degassed and back-filled with N 2 (2 ), and then stirred for 3 days at 25 ºC before being filtered. The collected precipitate was sonicated in H 2 O (50 ml) giving a suspension which was re-filtered to remove the dissolved diisopropylamine salt. The remaining solid was dissolved in THF (50 ml) and combined with hexanes (50 ml). The resulting mixture was kept at 0 ºC for 1 h to yield a precipitate which was collected via filtration and dried to give 9 as a white solid. Yield = 4.1 g (84%). 1 H NMR (CDCl 3 ): δ 1.45 (t, 18 H, CO 2 CH 2 CH 3, J = 7.2 Hz), 4.45 (q, 13 H, CO 2 CH 2 CH 3, J = 7.2 Hz), 7.56 (d, 6 H, 2,6-Ben 2 H, J = 8.4 Hz), 7.57 (d, 6 H, 3,5-Ben 2 H, J = 8.4 Hz), 7.7 (s, 3 H, 2,4,6-Ben 3 H), 8.37 (s, 6 H, 4,6-Ben 1 H), 8.65 (s, 3 H, 2-Ben 1 H). 13 C NMR (CDCl 3 ): δ 14.5, 61.9, 89.7, 89.9, 90.5, 90.7, 123, 123.3, 124.1, , 130.5, 131.5, 131.9, 132, 134.5, 136.6, HRMS (calc.) m/z = ( [M+H] + ). Synthesis of 1,3,5-tris[(1,3-carboxylic acid-5-(4-(ethynyl)phenyl))ethynyl]- benzene (10-LH 6 ). To a stirring solution of 9 (1 g, 0.9 mmol) in THF (50 ml), KOH (120 ml of a 1 M aqueous solution, 120 mmole) was added. The mixture was refluxed for 15 h until it became clear. THF was removed using rotary evaporator and the remaining aqueous solution was acidified to ph 2 using concentrated HCl (15 ml of a 37% aqueous solution). The resulting precipitate was collected via filtration, washed with H 2 O (200 ml), and dried under high vacuum to afford 10 as a white solid. Yield = 810 mg (95 %). 1 H NMR (DMSO-d 6 ): δ 7.67 (d, 6 H, 2,6-Ben 2 H, J = 8.1 Hz), 7.71 (d, 6 H, 3,5-Ben 2 H, J = 8.1 Hz), 7.83 (s, 3 H, 2,4,6-Ben 3 H), 8.27 (s, 6 H, 4,6-Ben 1 H), 8.45 (s, 3 H, 2-Ben 1 H), 13.6 (b, 6 H, CO 2 H). 13 C NMR (DMF-d 6 ): δ 90.0, 90.2, 90.9, 91.0, 123.3, 124.0, 124.5, 130.7, 132.5, 132.6, 133.0, 134.7, 136.3, HRMS (calc.) m/z = ( [M+H] + ). Synthesis of NU-100. A mixture of Cu(NO 3 ) H 2 O (600 mg, 2.6 mmol) and LH 6 (300 mg, 0.32 mmol) was dissolved in a mixture of DMF (36 ml) and HBF 4 (0.2 ml) in a beaker. This solution was divided between thirty 1-dram vials. The vials were capped and placed into an oven at 75 C for 20 h. The resulting teal crystals were washed with DMF. Yield calculated from evacuated sample = 32% based on LH 6. SCD activation of NU-100. Prior to drying, DMF-solvated MOF samples were soaked in absolute ethanol, replacing the soaking solution every 24 h for 3 days. After soaking, the ethanol-containing samples were placed inside the supercritical CO 2 dryer and the ethanol was exchanged with CO 2 (liq.) over a period of 10 h. During this time the liquid CO 2 was vented under positive pressure for five minutes every two hours. The rate of venting of CO 2 (liq.) was always kept below the rate of filling so as to maintain a full drying chamber. Following venting, the chamber was sealed and the temperature was raised to 40 ºC (i.e., above the critical temperature for carbon dioxide), at which time the chamber was slowly vented over the course of 15 h. The color of the MOF changed from teal to purple. The collected MOF sample was then stored inside an inert-atmosphere glovebox until further analysis. 6 nature chemistry

7 supplementary information Preparation of NU-100 for adsorption measurements (after SCD activation and prior to sorption measurements). The SCD-activated MOF material was evacuated under dynamic vacuum (10-5 torr) at room temperature for 4 h, at 50 ºC for 30 min, at 70 ºC for 30 min, at 90 ºC for 30 min, and then at 110 ºC for 15 h. a) DMSO CH 2 Cl 2 H 2 O b) * * = DMF * * CH 2 Cl 2 Fig. S1 NMR spectra of LH6 a) 1 H and b) 13 C. nature chemistry 7

8 supplementary information Section 3. Single Crystal X-ray Diffraction Analyses Intensity data were collected on a STOE IPDS II diffractometer equipped with a graphite monochromatized Mo radiation (λ = Å) and an Image Plate (IP) detector. The data were collected with an ω-scan technique and an arbitrary φ-angle. Data reduction was performed with the X-Area package 1. An analytical absorption correction was performed (X-Shape2 within X-Area) and the crystal structure was refined with SHELXTL software 2. Table S1. Crystal data and structure refinement for NU-100 at 100(3) K. Empirical formula C 480 H 192 Cu 24 O 120 Formula weight Temperature Wavelength Crystal system 100(3) K Å Cubic Space group Fm 3 m a = (2) Å, α = Unit cell dimensions b = (2) Å, β = c = (2) Å, γ = Volume (13) Å 3 Z 4 Density (calculated) g/cm 3 Absorption coefficient mm -1 F(000) Crystal size mm 3 θ range for data collection 1.36 to Index ranges Reflections collected <=h<=71, -71<=k<=71, -71<=l<=71 Independent reflections 8864 [R int = ] Completeness to θ = % Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 8864 / 132 / 140 Goodness-of-fit Final R indices [>2σ(I)] R obs = , wr obs = R indices [all data] R all = , wr all = Largest diff. peak and hole and e Å -3 R = Σ F o - F c /Σ F o, wr = {Σ[w( F o 2 - F c 2 ) 2 ]/Σ[w( F o 4 )]} 1/2 and w = 1/[σ 2 (Fo 2 ) + (0.0673P) 2 ] where P = (Fo 2 +2Fc 2 )/3 8 nature chemistry

9 supplementary information Fig. S2. An ORTEP representation of NU-100, Atoms are drawn at 60% probability. H atoms were removed for clarity. In the CheckCIF: RINTA01-ALERT-3-A and PLAT020-ALERT-3-A alerts are related to the high R~int~value because of the large number of weak high angle reflections due to the very large cubic cell (around 60 %A). Most of the strong reflections are located in the low resolution region [sin(q)/\l < 0.3 ]and for these strong reflections the R~int~ is around 0.10 indicating that the space-group is most probably correct. PLAT220-ALERT-2-A alert is related to the partial disorder due to the large empty space (voids) around several carbon atoms that belong to the phenyl-rings. nature chemistry 9

10 supplementary information Fig. S3. A schematic illustration using a Space-filled representation of NU nature chemistry

11 supplementary information Section 4. Molecular Simulations Prediction of the structure of NU-100SP. The design of NU-100SP started with manual replacement of the ligand Yan and co-workers used for NOTT with L 6- in the same cubic space group (Fm 3 m) using the Materials Studio Visualizer. The copper paddlewheel clusters were not modified and the unit cell dimensions were adjusted according to the length of L 6- to give a starting geometry with 3168 atoms in a unit cell. This unit cell did not include any coordinated solvent molecules. From this point, the unit cell was subject to symmetry-constrained geometry optimization runs based on molecular mechanics simulations. These simulations were performed with the Forcite module of Materials Studio 4, using an algorithm which is a cascade of the steepest descent, adjusted basis set Newton-Raphson, and quasi-newton methods. The bonded and the short range (van der Waals) non-bonded interactions between the atoms were modeled using the Universal Force Field (UFF) 5, as implemented in Forcite. In this force field, bond stretching is described by a harmonic term, angle bending by a three-term Fourier cosine expansion, torsions and inversions by cosine-fourier expansion terms, and the van der Waals interactions by the Lennard-Jones potential. The long range (electrostatic) non-bonded interactions, which arise due to the presence of partial atomic charges, were modeled using a Coulombic term. An LJ cutoff distance of 18.5 Å was used for all geometry optimization simulations. The Ewald sum method was used to compute the electrostatic interactions. When the first version of NU-100SP was built, its internal degrees of freedom such as bond lengths, angles etc., were obviously far from their equilibrium values since the unit cell was constructed manually. To bring them to reasonable values and accelerate the overall structure refinement process, the geometry of the first structure was quickly optimized by using the partial atomic charges derived from the charge equilibration method (QEq) as implemented in Forcite. The QEq method was originally developed by Rappe and Goddard 6, and calculating partial atomic charges using this method only takes a few seconds. This quick first-optimization run provided us an improved structure. The geometry of NU-100SP was then refined via a self-consistent iterative procedure in which successive geometry optimization calculations were performed until the difference between the two successive unit cell dimensions was smaller than 0.001Å. This criterion was satisfied after the fourth optimization run. Before the start of each geometry optimization run, new partial atomic charges were derived from single point density functional theory (DFT) calculations. This is a much longer, but more precise, way of deriving atomic charges. More information about how partial atomic charges were derived using DFT calculation is given in the next section. The final predicted structure of NU-100SP had cubic unit cell dimensions of a = b = c = Å. The overall structure prediction process is summarized in Scheme S2. nature chemistry 11

12 supplementary information Scheme S2. A flowchart showing the structure prediction process for NU-100SP. DFT calculations. DFT calculations were performed to derive the charges to be used in the geometry optimization simulations to predict the final structure of NU-100SP and in the grand canonical Monte Carlo (GCMC) simulations to estimate the adsorption isotherms of N 2, CO 2, and H 2 in NU-100SP and NU-100. They were performed on clusters isolated from the unit cells of NU-100SP and NU-100, with the atomic coordinates of the latter taken from the experimental crystallographic data. These clusters included building units (e.g., metal ion nodes and the organic linker) representative of their respective unit cells. Details of structure and atom types of the NU-100SP and NU-100 clusters are shown in Figs. S4 and S5, respectively. All DFT calculations were performed with the Gaussian 09 7 software using the B3LYP level of theory and the 6-31G* basis set. Partial atomic charges were extracted using the ChelpG 8 method by fitting them to reproduce the electrostatic potential generated by the DFT calculations. Resulting partial charges for NU-100SP and NU-100 are given in Tables S2 and S3, respectively. Grand canonical Monte Carlo (GCMC) simulations. Atomistic GCMC simulations were performed to estimate the adsorption isotherms of CO 2, H 2, and N 2 in NU-100SP and NU-100. Interaction potential. Interaction energies between non-bonded atoms were computed through the Lennard-Jones (LJ) and Coulomb potentials: V ij ij 4 ij r ij 12 ij r ij 6 qiq j 4 r 0 ij 12 nature chemistry

13 supplementary information where i and j are interacting atoms, and r ij is the distance between atoms i and j. ε ij and σ ij are the LJ well depth and diameter, respectively. q i and q j are the partial charges of the interacting atoms, and ε 0 is the dielectric constant. LJ parameters between different types of sites were calculated using the Lorentz-Berthelot mixing rules. Fig. S4. Cluster used for deriving partial charges on atoms in NU-100SP. Table S2. Partial atomic charges for atoms in NU-100SP. Atom No Charge (e) (Cu) (O) (C) (C) (C) (C) Atom No Charge (e) (C) (C) (C) (C) (C) (C) Atom No Charge (e) (C) (C) (C) (C) (C) (H) Atom No Charge (e) (H) (H) (H) (H) nature chemistry 13

14 supplementary information Fig. S5. Cluster used for deriving partial charges on atoms in NU-100. Table S3. Partial atomic charges for atoms in NU-100. Atom No Charge (e) (Cu) (O) (C) (C) (C) (C) Atom No Charge (e) (C) (C) (C) (C) (C) (C) Atom No Charge (e) (C) (C) (C) (C) (C) (H) Atom No Charge (e) (H) (H) (H) (H) 14 nature chemistry

15 supplementary information MOF models. LJ parameters for NU-100SP and NU-100 atoms were taken from the DREIDING 9 force field except for the copper atom; its parameters were taken from UFF. For the adsorption of light gases in MOFs, adsorption isotherms obtained with GCMC simulations which used parameters from these force fields have agreed well with experiments in previous work Partial charges for the atoms in MOF were derived from DFT calculations as explained above. Table S4 shows the LJ parameters for all atom types found in NU-100SP and NU-100. Table S4. LJ parameters for atoms in NU-100SP and NU-100. Atom type σ (Å) ε/k B (K) C O H Cu Nitrogen Model: Nitrogen molecules were modeled using the TraPPE 14 force field, which was originally fit to reproduce the vapor-liquid coexistence curve of nitrogen. In this force field the nitrogen molecule is a rigid structure where the N-N bond length is fixed at its experimental value of 1.10 Å. This model reproduces the experimental gasphase quadrupole moment of nitrogen by placing partial charges on N atoms and on a point located at the center of mass (COM) of the molecule. Table S5 shows the LJ parameters and partial charges for nitrogen. Table S5. LJ parameters and partial charges for the sites in the nitrogen molecule. σ (Å) ε/k B (K) q (e) N N 2 COM Carbon Dioxide Model: Carbon dioxide molecules were modeled using the TraPPE force field 14, which was originally fit to reproduce the vapor-liquid coexistence curve of carbon dioxide. In this force field the carbon dioxide molecule is a rigid, linear structure where the C-O bond length is fixed at 1.16 Å. This model reproduces the experimental gas-phase quadrupole moment of carbon dioxide by placing partial charges on C and O atoms. Table S6 shows the LJ parameters and partial charges for the atoms. nature chemistry 15

16 supplementary information Table S6. LJ parameters and partial charges for the sites in the carbon dioxide molecule. σ (Å) ε/k B (K) q (e) C O Hydrogen Model. For the hydrogen molecules, we used the model used by Darkrim et al. 15 for Monte Carlo simulations of the adsorption of hydrogen in carbon nanotubes. In this model, the hydrogen molecule is a rigid structure where the H-H bond length is fixed at 0.74 Å. This model reproduces the experimental gas-phase quadrupole moment of hydrogen by placing partial charges on H atoms and on a point located at the center of mass (COM) of the hydrogen molecule. Table S7 shows the LJ parameters and partial charges for hydrogen. Table S7. LJ parameters and partial charges for the sites in the hydrogen molecule. σ (Å) ε/k B (K) q (e) H H 2 COM General GCMC simulation settings. All GCMC simulations included a cycle equilibration period followed by a cycle production run. A cycle consists of n Monte Carlo steps; where n is equal to the number of molecules (which fluctuates during a GCMC simulation). All simulations included random insertion/deletion, translation and rotation moves of molecules with equal probabilities. Atoms in MOF were held fixed at their crystallographic positions. An LJ cutoff distance of 15.0 Å was used for all simulations. The Ewald sum technique was used to compute the electrostatic interactions. One unit cell of NU-100SP or NU-100 was used for the simulations. N 2 isotherms were simulated at 77 K up to 0.9 bar, CO 2 isotherms were simulated at 298 K up to 40 bars, and H 2 isotherms were simulated at 77 K up to 70 bars. Fugacities needed to run the GCMC simulations were calculated using the Peng-Robinson equation of state. GCMC simulations report the absolute adsorption data which are then used to compute the excess adsorption data for comparison with experimental data using the relation N total N excess gas V p where ρ gas is the bulk density of the gas 16 at simulation conditions, and V p is the pore volume calculated by the helium insertion method as detailed elsewhere nature chemistry

17 supplementary information SECTION 5. BET Surface Area Analyses BET surface areas (SA) were obtained by using the data points on the simulated N 2 adsorption isotherms of NU-100SP and NU-100, and experimental N 2 adsorption isotherm of NU100 (Fig. S6). When applying the BET theory, we made sure that our analysis satisfied the two consistency criteria as detailed by Walton et al N2 uptake (cc/g) NU-100 expt. NU-100SP sim. NU-100 sim Pressure (P/P.) Fig. S6. Simulated N 2 isotherms of NU-100SP and NU-100, and measured N 2 isotherm of NU-100 used for calculating the BET surface areas. The isotherms show changes of slope in the low-pressure region due to successive filling of the different sized cavities. nature chemistry 17

18 supplementary information Fig. S7. Top: v(p 0 - P) vs. P/P 0 for simulated N 2 isotherm in NU-100SP. Only the range below P/P 0 = 0.17 satisfies the first consistency criterion for application of the BET theory. Bottom: Plot of the linear region for the BET equation, which satisfies the second criterion for application of the BET theory. 18 nature chemistry

19 supplementary information Fig. S8. Top: V(P 0 - P) vs. P/P 0 for simulated N 2 isotherm in NU-100. Only the range below P/P 0 = 0.18 satisfies the first consistency criterion for application of the BET theory. Bottom: Plot of the linear region for the BET equation, which satisfies the second criterion for application of the BET theory. nature chemistry 19

20 supplementary information Fig. S9. Top: V(P 0 - P) vs. P/P 0 for experimental N 2 isotherm in NU-100. Only the range below P/P 0 = 0.26 satisfies the first consistency criterion for application of the BET theory. Bottom: Plot of the linear region for the BET equation, which satisfies the second criterion for application of the BET theory. 20 nature chemistry

21 supplementary information Section 6. Gas Adsorption Analyses 2000 N2 uptake (cc/g) ads des Pressure (P/P.) Fig. S10. Experimental N 2 isotherm for NU-100 at 77 K, including both adsorption and desorption cumulative area (cc/å/g) pore width (Å) Fig. S11. Pore-size distribution plot for NU-100 as calculated from experimental Ar adsorption isotherm using the nonlocal density functional theory (NLDFT). nature chemistry 21

22 supplementary information 200 Volume of H 2 (cc/g) K ads 77K des 50 87K ads 87K des Pressure (atm) Fig. S12. Experimental low-pressure H 2 isotherms for NU-100 at 77K and 87K Volume H2 (cc/g) Ads Des Pressure (bar) Fig. S13. Experimental high-pressure H 2 isotherm for NU-100 at 77 K. Volume H2 (cc/g) Pressure (bar) Run #1 Run #3 Fig. S14. Plots of the first and third cycles of high-pressure H 2 uptake by NU-100 at 77 K, showing excellent reproducibility and thus high stability of this material. 22 nature chemistry

23 supplementary information Hydrogen Heats of Adsorption. Both hydrogen isotherms (77K and 87K) were fitted to the virial type equation given in Equation Fitting parameters from Equation 1 were used to calculate the heat of adsorption from Equation 2. Isotherms and fitting parameters are given in Figure S14. Red lines are virial fits. 7 6 ln P (torr) Chi 2 /DoF = R 2 = a ± a ± a ± a ± a ± b ± b ± N (mg/g) 77K 87K Fig. S15. Details of the fitting of the hydrogen isotherms (77K and 87K) of NU-100 and the corresponding calculations of the isosteric hydrogen heats of adsorption. 6 5 q st (kj/mol) N (mg/g) Fig. S16. Plots of the isosteric H 2 heat of adsorption of NU-100. nature chemistry 23

24 supplementary information Volume of CO2 (cc/g) Ads Des Pressure (atm) Fig. S17. Experimental low-pressure CO 2 isotherm of NU-100 at 298K Volume of CO2 (cc/g) Ads Des Pressure (bar) Fig. S18. Experimental high-pressure CO 2 isotherm of NU-100 at 298K N2 uptake (cc/g) Run 1 Run 2 Run 3 Run 4 Run Pressure (P/P.) Fig. S19. Plots of five cycles of N 2 uptake by NU-100 at 77K, showing excellent reproducibility and thus high stability of this material. 24 nature chemistry

25 supplementary information References: 1. I. S. X-AREA, STOE & Cie GmbH, Darmstadt, Sheldrick, G. M. SHELXL-97: Program for crystal structure refinement; University of Göttingen, Göttingen, Germany, Yan, Y. et al. Exceptionally high H 2 storage by a metal-organic polyhedral framework. Chem. Commun., (2009). 4. Materials Studio 5.0., Accelrys Software Inc., San Diego, CA 92121, USA. 5. Rappe, A. K., Colwell, K. S., Goddard III, W. A. & Skiff, W. M. UFF, A full periodic table force field for molecular mechanics and molecular dynamics simulations. J. Am. Chem. Soc. 114, (1992). 6. Rappe, A. K. & Goddard III, W. A. Charge equilibration for molecular dynamics simulations. J. Phys. Chem. 95, (1991). 7. Frisch, M. J. et al. Gaussian09, Gaussian, Inc., Wallingford, CT 06492, USA. 8. Breneman, C. M. & Wiberg, K. B. Determining atom-centered monopoles from molecular electrostatic potentials. The need for high sampling density in formamide conformational analysis. J. Comput. Chem. 11, (1990). 9. Mayo, S. L., Olafson, B. D. & Goddard, W. A., DREIDING: A Generic Force Field for Molecular Simulations. J. Phys. Chem. 94, (1990). 10. Düren, T., Sarkisov, L., Yaghi, O. M. & Snurr, R. Q. Design of new materials for methane storage. Langmuir 20, (2004). 11. Frost, H., Düren, T. & Snurr, R.Q. Effects of surface area, free volume, and heat of adsorption on hydrogen uptake in metal organic frameworks J. Phys. Chem. B 110, (2006). 12. Walton, K. S. & Snurr, R. Q. Applicability of the BET method for determining surface areas of microporous metal-organic frameworks. J. Am. Chem. Soc. 129, (2007). 13. Yazaydın, A. Ö. et al. Screening of metal-organic frameworks for carbon dioxide capture from flue gas using a combined experimental and modeling approach. J. Am. Chem. Soc. 131, (2009). 14. Potoff, J. J. & Siepmann, J. I. Vapor-liquid equilibria of mixtures containing alkanes, carbon dioxide and nitrogen. AIChE J. 47, (2001). 15. Darkrim, F. & Levesque, D. Monte carlo simulations of hydrogen adsorption in single-walled carbon nanotubes. J. Chem. Phys. 109, (1998) Czepirski, L. & Jagiello, J. Virial-type thermal equation of gas-solid adsorption. Chem. Eng. Sci. 44, (1989). nature chemistry 25