Supporting Information

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1 Supporting Information Systematic and Dramatic Tuning on Gas Sorption Performance in Heterometallic Metal Organic Frameworks Quan-Guo Zhai, Xianhui Bu,* Chengyu Mao, Xiang Zhao, Pingyun Feng* Department of Chemistry, University of California, Riverside, CA 92521, USA. Department of Chemistry and Biochemistry, California State University, Long Beach, CA 90840, USA. S1

2 Experimental details: Materials: In(NO 3 ) 3 xh 2 O, Ga(NO 3 ) 3 xh 2 O, VCl 3, MnCl 2 4H 2 O, FeCl 3 6H 2 O, NiCl 2 6H 2 O, InCl 3, Mg(OAc) 2 4H 2 O, Sc(OAc) 3 xh 2 O, Co(OAc) 2 4H 2 O, N,N-dimethylacetamide (DMA), N,N-Diethylformamide (DEF), CH 3 CN, HNO 3 (65%, GR grade), and HCl (37%, AR grade) were purchased from Aldrich Chemical Co. and used as received without further purification. 3,3,5,5 -azobenzenetetracarboxylic acid (H 4 ABTC) was prepared according to the methods previously reported. [S1] Synthesis of [In 3 O(ABTC) 1.5 (H 2 O) 3 ] (NO 3 ) (CPM-200-In): The indium form of CPM-200 was first reported by M. Eddaoudi. [S2] However, the quality of the sample obtained by following the reported recipe was not satisfactory for unknown reasons. The better quality sample was obtained through the following procedure. In a 20 ml glass vial, 22.0 mg of In(NO 3 ) 3 xh 2 O and 16.0 mg of H 4 ABTC were dissolved in a mixture of 2.0 g of DMA and 1.0 g of CH 3 CN. After addition of mg HNO 3, the vial was sealed and placed in a 90 o C oven for 3 days. Pure yellow cubic crystals were obtained after cooling to room temperature. Pure sample was obtained by filtering and washing the raw product with DMA. The yield was about 56% based on In. Synthesis of [InMg 2 (OH)(ABTC) 1.5 (H 2 O) 3 ] (CPM-200-In/Mg): In a 20 ml glass vial, 22.1 mg of InCl 3, 86.0 mg of Mg(OAc) 2 4H 2 O, and 35.6 mg of H 4 ABTC were dissolved in a mixture of 4.0 g of DMA and 0.8 g of H 2 O. After addition of 120 mg HCl, the vial was sealed and placed in a 90 o C oven for 2 days. Pure yellow cubic crystals (Figure S2a) were obtained after cooling to room temperature. Pure sample was obtained by filtering and washing the raw product with DMA. The yield was about 85% based on In. It should be noted that to obtain the above optimized synthesis conditions of heterometallic CPM-200 MOFs, a large amount of experimental factors have been investigated. The detailed experimental results showed that the utilization of In(NO 3 ) 3 xh 2 O or Mg(NO 3 ) 2 6H 2 O invariably lead to yellow powder. InCl 3 is S2

3 irreplaceable for the formation of heterometallic CPM-200 MOFs, however, pure InCl 3 cannot lead to the formation of CPM-200-In. On the other hand, the mass ratio of DMA and water must be near to 5:1, otherwise, yellow powder will be produced along with cubic crystals. Moreover, under the above optimized reaction conditions, our results showed that the In/Mg ratio of the ultimate crystalline materials changed with the starting molar ratios of InCl 3 to Mg(OAc) 2 4H 2 O. The detailed results are summarized as following: No. InCl 3 Mg(OAc) 2 4H 2 O Product In/Mg ratio of MOFs Code mg mg pure yellow cubic (1.0 mmol) (8.0 mmol) crystals 1:2 CPM-200-In/Mg mg 86.0 mg pure yellow cubic (1.0 mmol) (4.0 mmol) crystals 1:2 CPM-200-In/Mg mg 64.5 mg pure yellow cubic (1.0 mmol) (3.0 mmol) crystals 1:1.5 CPM-200-In/Mg-A mg 43.0 mg pure yellow cubic (1.0 mmol) (2.0 mmol) crystals 1:1 CPM-200-In/Mg-B mg 21.5 mg (1.0 mmol) (1.0 mmol) yellow powder unidentified unidentified mg 21.5 mg (2.0 mmol) (1.0 mmol) yellow powder unidentified unidentified Synthesis of [InNi 2 (OH)(ABTC) 1.5 (H 2 O) 3 ] (CPM-200-In/Ni): In a 20 ml glass vial, 22.1 mg of InCl 3, 95.2 mg of NiCl 2 6H 2 O, and 35.6 mg of H 4 ABTC were dissolved in a mixture of 4.0 g of DMA and 0.8 g of H 2 O. After addition of 120 mg HCl, the vial was sealed and placed in a 90 o C oven for 2 days. Pure yellow cubic crystals (Figure S2b) were obtained after cooling to room temperature. Pure sample was obtained by filtering and washing the raw product with DMA. The yield was about 85% based on In. Synthesis of [InCo 2 (OH)(ABTC) 1.5 (H 2 O) 3 ] (CPM-200-In/Co): In a 20 ml glass vial, 22.1 mg of InCl 3, 99.6 mg of Co(OAc) 2 4H 2 O, and 35.6 mg of H 4 ABTC were dissolved in a mixture of 4.0 g of DMA and 0.8 g of H 2 O. After addition of 120 mg HCl, the vial was sealed and placed in a 90 o C oven for 3 days. Pure reddish-brown cubic crystals S3

4 (Figure S2c) were obtained after cooling to room temperature. Pure sample was obtained by filtering and washing the raw product with DMA. The yield was about 88% based on In. Synthesis of [InMn 2 (OH)(ABTC) 1.5 (H 2 O) 3 ] (CPM-200-In/Mn): In a 20 ml glass vial, 22.1 mg of InCl 3, 79.2 mg of MnCl 2 4H 2 O, and 35.6 mg of H 4 ABTC were dissolved in a mixture of 4.0 g of DMA and 0.8 g of H 2 O. After addition of 120 mg HCl, the vial was sealed and placed in a 90 o C oven for 1 days. Pure yellow cubic crystals (Figure S2d) were obtained after cooling to room temperature. Pure sample was obtained by filtering and washing the raw product with DMA. The yield was about 78% based on In. Synthesis of [GaMg 2 (OH)(ABTC) 1.5 (H 2 O) 3 ] (CPM-200-Ga/Mg): In a 20 ml glass vial, 25.6 mg of Ga(NO 3 ) 3 xh 2 O, 86.0 mg of Mg(OAc) 2 4H 2 O, and 35.6 mg of H 4 ABTC were dissolved in a mixture of 4.0 g of DMA and 0.8 g of H 2 O. After addition of 120 mg HCl, the vial was sealed and placed in a 90 o C oven for 3 days. Pure yellow irregular polyhedral crystals (Figure S2e) were obtained after cooling to room temperature. Pure sample was obtained by filtering and washing the raw product with DMA. The yield was about 52% based on Ga. Synthesis of [FeMg 2 (OH)(ABTC) 1.5 (H 2 O) 3 ] (CPM-200-Fe/Mg): In a 20 ml glass vial, 27.0 mg of FeCl 3 6H 2 O, 86.0 mg of Mg(OAc) 2 4H 2 O, and 35.6 mg of H 4 ABTC were dissolved in a mixture of 4.0 g of DEF and 0.8 g of H 2 O. After addition of 120 mg HCl, the vial was sealed and placed in a 90 o C oven for 5 days. Pure yellow cubic crystals (Figure S2f) were obtained after cooling to room temperature. Pure sample was obtained by filtering and washing the raw product with DEF. The yield was about 65% based on Fe. Synthesis of [VMg 2 (OH)(ABTC) 1.5 (H 2 O) 3 ] (CPM-200-V/Mg): In a 20 ml glass vial, 15.7 mg of VCl 3, 86.0 mg of Mg(OAc) 2 4H 2 O, and 35.6 mg of H 4 ABTC were dissolved S4

5 in a mixture of 4.0 g of DEF and 0.8 g of H 2 O. After addition of 120 mg HCl, the vial was sealed and placed in a 90 o C oven for 5 days. Pure yellow cubic crystals (Figure S2g) were obtained after cooling to room temperature. Pure sample was obtained by filtering and washing the raw product with DMA. The yield was about 45% based on V. Synthesis of [ScMg 2 (OH)(ABTC) 1.5 (H 2 O) 3 ] (CPM-200-Sc/Mg): In a 20 ml glass vial, 22.2 mg of Sc(OAc) 3 xh 2 O, 86.0 mg of Mg(OAc) 2 4H 2 O, and 35.6 mg of H 4 ABTC were dissolved in a mixture of 4.0 g of DEF and 0.8 g of H 2 O. After addition of 120 mg HCl, the vial was sealed and placed in a 90 o C oven for 5 days. Pure yellow cubic crystals (Figure S2h) were obtained after cooling to room temperature. Pure sample was obtained by filtering and washing the raw product with DEF. The yield was about 40% based on Sc. Single crystal X-ray diffraction: The single crystal samples of CPM-200-In/Mg, CPM-200-In/Ni, CPM-200-In/Mn, CPM-200-In/Co, CPM-200-Ga/Mg, and CPM-200-V/Mg were selected for single-crystal X-ray analysis, which was performed on a Bruker Smart APEX II CCD area diffractometer with nitrogen-flow temperature controller using graphite-monochromated MoKα radiation (λ = Å), operating in the ω and φ scan mode. The SADABS program was used for absorption correction. The structures were solved by direct methods and refined using SHELXTL. [S3] All non-hydrogen atoms in the framework were refined with anisotropic displacement parameters. The M 2+ /M 3+ metal ratios were estimated from the occupancy refinement with single crystal X-ray diffraction data and further supported by the EDS analysis. The large volume fractions of solvents in the lattice pores could not be modelled in terms of atomic sites and were treated using the SQUEEZE routine in the PLATON software package. [S4] Crystal data as well as details of data collection and refinements were summarized in Tables S1-S3. Powder X-ray diffraction: Powder X-ray diffraction (XRD) data were collected on a Bruker D8 Advance powder diffractionmeter with CuKα radiation (40 kv, 40 ma, λ = S5

6 Å). The simulated powder pattern was calculated using single-crystal X-ray diffraction data and processed by the Mercury 2.3 program provided by the Cambridge Crystallographic Data Centre. Energy dispersive spectroscopy (EDS): The semi-quantitative elemental analyses of different samples were performed by using a Philips FEI XL30 field emission scanning electron microscope (FESEM) equipped with PGT-IMIX PTS energy dispersive spectroscopy (EDS) detector. Data acquisition was performed with an accelerating voltage of 20 kv and 60 s accumulation time. Gas adsorption: Gas sorption isotherms of all CPM-200 MOFs were measured on a Micromeritics ASAP 2020M surface-area and pore-size analyzer up to 1 atm of gas pressure by the static volumetric method. All the as-synthesized crystalline samples were immersed in CH 3 OH for 3 days; during the exchange, the CH 3 OH was refreshed three times. The resulting CH 3 OH-exchanged samples were then evacuated (10-3 torr) at 80 o C for 12 h. All gases used were of 99.99% purity, and the impurity trace water was removed by passing the gases through the molecular sieve column equipped in the gas line. The gas sorption isotherms for N 2 and H 2 were measured at 77 K. The gas sorption isotherms for CO 2, CH 4 and C 2 H 2 were measured at 273 K or 298 K. Isosteric heat of CO 2 adsorption. The isosteric heat of CO 2 adsorption was estimated for all the CPM-200 MOFs from the CO 2 sorption data measured at 273 K and 298 K. A virial-type expression was used (eq 1). [S5, S6] In eq 1, P is pressure (atm), N is the amount adsorbed CO 2 gas (mmol/g), T is temperature (K), and m and n represent the number of coefficients required to adequately describe the isotherms. To estimate the values of the isosteric heat of CO 2 adsorption, eq 2 was applied, where R is the universal gas constant. The isotherms and fitted virial parameters are presented in Figures S18, S19 and S20. S6

7 Selectivity Prediction for Binary Mixture Adsorption. Ideal adsorbed solution theory (IAST) [S7, S8] was used to predict binary mixture adsorption from the experimental pure-gas isotherms. To perform the integrations required by IAST, the single-component isotherms should be fitted by a proper model. Several isotherm models were tested to fit the experimental pure isotherms for N 2 and CO 2, and the dual-site Langmuir Freundlich equation was found to be the best fit to the experimental data: q = q m1 [b 1 P 1/n1 / (1 + b 1 P 1/n1 )] + q m2 [b 2 P 1/n2 / (1 + b 2 P 1/n2 )] Here, P is the pressure of the bulk gas at equilibrium with the adsorbed phase (kpa), q is the adsorbed amount per mass of adsorbent (mol/kg), q m1 and q m2 are the saturation capacities of sites 1 and 2 (mol/kg), b 1 and b 2 are the affinity coefficients of the sites (1/kPa), and n 1 and n 2 are measures of the deviations from an ideal homogeneous surface. The R 2 values for all of the fitted isotherms were over Hence, the fitted isotherm parameters were applied to perform the necessary integrations in IAST. S7

8 Table S1. Crystal data and structure refinements for CPM-200-In/Ni and CPM-200-In/Co. CPM-200-In/Ni CPM-200-In/Co Empirical formula Ni 2 InC 24 H 16 N 3 O 16 Co 2 InC 24 H 16 N 3 O 16 Formula weight Temperature (K) 200(2) 200(2) Crystal system, Space group Cubic, P-43n Cubic, P-43n Unit cell dimensions a = b = c = (10) Å V = (8) Å 3 a = b = c = (4) Å V = (3) Å 3 Z, Density(cal.) 8, g/cm 3 8, g/cm 3 Absorption coefficient mm mm -1 F(000) Reflections collected / unique / 3383 [R(int) = ] / 3272 [R(int) = ] Data Completeness measured % 100.0% Parameter/Restraints/Data(obs.) 3383 / 0 / / 0 / 139 Goodness-of-fit Final R indices (I >2σ(I)) R1 = , wr2 = R1 = , wr2 = R indices (all) R1 = , wr2 = R1 = , wr2 = Largest difference peaks and e A and e A -3 a R1 = ( F o - F c ) / F o, wr2 = [ w(f o 2 F c 2 ) 2 / w(f o 2 ) 2 ] 0.5. S8

9 Table S2. Crystal data and structure refinements for CPM-200-In/Mn and CPM-200-In/Mg. CPM-200-In/Mn CPM-200-In/Mg Empirical formula Mn 2 InC 24 H 16 N 3 O 16 Mg 2 InC 24 H 16 N 3 O 16 Formula weight Temperature (K) 200(2) 200(2) Crystal system, Space group Cubic, P-43n Cubic, P-43n Unit cell dimensions a = b = c = (2) Å V = (17) Å 3 a = b = c = (5) Å V = (4) Å 3 Z, Density(cal.) 8, g/cm 3 8, g/cm 3 Absorption coefficient mm mm -1 F(000) Reflections collected / unique / 3363 [R(int) = ] / 2624 [R(int) = ] Data Completeness measured % % Parameter/Restraints/Data(obs.) 3363 / 0 / / 0 / 139 Goodness-of-fit Final R indices (I >2σ(I)) R1 = , wr2 = R1 = , wr2 = R indices (all) R1 = , wr2 = R1 = , wr2 = Largest difference peaks and e A and e A -3 a R1 = ( F o - F c ) / F o, wr2 = [ w(f o 2 F c 2 ) 2 / w(f o 2 ) 2 ] 0.5. S9

10 Table S3. Crystal data and structure refinements for CPM-200-Ga/Mg and CPM-200-V/Mg. CPM-200-Ga/Mg CPM-200-V/Mg Empirical formula Mg 2 GaC 24 H 16 N 3 O 16 Mg 2 VC 24 H 16 N 3 O 16 Formula weight Temperature (K) 200(2) 200(2) Crystal system, Space group Cubic, P-43n Cubic, P-43n Unit cell dimensions a = b = c = (3) Å V = (3) Å 3 a = b = c = (7) Å V = (6) Å 3 Z, Density(cal.) 8, g/cm 3 8, g/cm 3 Absorption coefficient mm mm -1 F(000) Reflections collected / unique 7498 / 1360 [R(int) = ] / 1181 [R(int) = ] Data Completeness measured 96.7 % % Parameter/Restraints/Data(obs.) 1360 / 0 / / 0 / 139 Goodness-of-fit Final R indices (I >2σ(I)) R1 = , wr2 = R1 = , wr2 = R indices (all) R1 = , wr2 = R1 = , wr2 = Largest difference peaks and e A and e A -3 a R1 = ( F o - F c ) / F o, wr2 = [ w(f o 2 F c 2 ) 2 / w(f o 2 ) 2 ] 0.5. S10

11 (a) (b) (c) (d) (e) (f) Figure S1. (a) The distribution of six ABTC around each trimeric SBU in CPM-200 (soc-mofs). (b) The distribution of four trimeric SBUs around each ABTC. (c) The cubic cage formed by six trimer SBUs acting as vertex and six ABTC ligands acting as face. (d) The linkage between the cubic cages. (e) 3D porous framework. (f) The schematic polyhedral drawing of CPM-200. S11

12 (a) (b) (c) (d) (e) (f) (g) (h) Figure S2. Images for crystals of heterometallic CPM-200 MOFs: a In/Mg, b In/Ni, c In/Co, d In/Mn, e Ga/Mg, f Fe/Mg, g V/Mg, h Sc/Mg. S12

13 Figure S3 Experimental and simulated PXRD patterns for CPM-200 MOFs. S13

14 Figure S4 TGA curves for CH 3 OH-exchanged CPM-200 MOFs. (a) (b) (c) Figure S5. EDS results for CPM-200-In/Mg (a), CPM-200-In/Mg-A (b) and CPM-200-In/Mg-B (c). S14

15 Figure S6 EDS results for CPM-200 heterometallic MOFs (In/Ni, In/Co, In/Mn, Ga/Mg, Fe/Mg, V/Mg, Sc/Mg). S15

16 Figure S7 N 2, H 2, CO 2, CH 4 and C 2 H 2 adsorption isotherms for CPM-200-In. Figure S8 N 2, H 2, CO 2, CH 4 and C 2 H 2 adsorption isotherms for CPM-200-In/Ni. S16

17 Figure S9 N 2, H 2, CO 2, CH 4 and C 2 H 2 adsorption isotherms for CPM-200-In/Co. Figure S10 N 2, H 2, CO 2, CH 4 and C 2 H 2 adsorption isotherms for CPM-200-In/Mn. S17

18 Figure S11 N 2, H 2, CO 2, CH 4 and C 2 H 2 adsorption isotherms for CPM-200-In/Mg. Figure S12 CO 2 adsorption isotherms for CPM-200 MOFs with different In/Mg ratios. S18

19 Figure S13 N 2, H 2, CO 2, CH 4 and C 2 H 2 adsorption isotherms for CPM-200-Ga/Mg. Figure S14 N 2, H 2, CO 2, CH 4 and C 2 H 2 adsorption isotherms for CPM-200-Fe/Mg. S19

20 Figure S15 N 2, H 2, CO 2, CH 4 and C 2 H 2 adsorption isotherms for CPM-200-V/Mg. Figure S16 N 2, H 2, CO 2, CH 4 and C 2 H 2 adsorption isotherms for CPM-200-Sc/Mg. S20

21 S21

22 S22

23 Figure S17 The comparison of N 2, CO 2, H 2, C 2 H 2 and CH 4 adsorption isotherms for CPM-200 MOFs. S23

24 Figure S18 Fitting parameters of the virial equation to the uptake values of CO 2 at 273 K and 298 K in case of CPM-200-In, CPM-200-In/Ni, and CPM-200-In/Co. S24

25 Figure S19 Fitting parameters of the virial equation to the uptake values of CO 2 at 273 K and 298 K in case of CPM-200-In/Mn, CPM-200-In/Mg, and CPM-200-Ga/Mg. S25

26 Figure S20 Fitting parameters of the virial equation to the uptake values of CO 2 at 273 K and 298 K in case of CPM-200-Fe/Mg, CPM-200-V/Mg, and CPM-200-Sc/Mg. S26

27 Figure S21 Isosteric heat for CO 2 for CPM-200 MOFs (top) and the CO 2 adsorption isotherms under 20 torr pressure (middle and bottom). S27

28 S28

29 Figure S22 The comparison of CO 2 and N 2 uptake isotherms and selectivity predicted by IAST for CPM-200-Fe/Mg, In/Mg, V/Mg, Ga/Mg and In/Co MOFs at 273 K. S29

30 Table S4 Summary of gas sorption properties for CPM-200 MOFs. Compound code In In/Ni In/Co In/Mn In/Mg Ga/Mg Fe/Mg V/Mg Sc/Mg S A Langmuir (m 2 /g) S A BET (m 2 /g) Pore volume (cm 3 /g) CO K, 1 bar (cm 3 /g) CO K, 1 bar (cm 3 /g) Q st 0 (kj/mol) C 2 H K, 1 bar (cm 3 /g) C 2 H K, 1 bar (cm 3 /g) CH K, 1 bar (cm 3 /g) CH K, 1 bar (cm 3 /g) H 2 77 K, 1 bar (cm 3 /g) S30

31 Table S5. Summary of gas adsorption for MOFs with [M 3 (O/OH)(COO) 6 ] trimer SBUs. Compound CO 2, 273 K, 1 atm CO 2, 298 K, 1 atm BET (m 2 /g) H 2, 77 K, 1 atm Reference (mmol/g) (mmol/g) (wt %) CPM-200-Fe/Mg this work CPM-200-In/Mg this work CPM-33b [S9] PEI-MIL [S10] CPM-200-V/Mg this work CPM-200-In/Co this work CPM-33a [S9] CPM-200-Ga/Mg this work tp-pmbb-1-asc [S11] CPM-33c [S9] CPM-200-In/Mn this work CPM-200-Sc/Mg this work CPM-200-In 4.89*/4.07** 2.75* 1244* 1.8* * this work **[S12] (In 3 O)(OH)(ADC) 2 (NH 2 IN) [S13] (In 3 O)(OH)(ADC) 2 (IN) [S13] CPM [S14] Fe2Ni-MIL-88B By [S15] CPM-200-In/Ni this work CPM [S16] CPM [S14} Tp-PMBB-5-acs [S17] [Ni II 2Ni III (μ 3 -OH)(IN) 3 (BDC) 1.5 ] [S18] tp-pmbb-1-lon-e-t-bu [S19] CPM-15-Mg [S20] Fe2Ni-MIL-88B Pz [S21] CPM [S21] CPF [S22] {[Ni 3 (OH)(L) 3 ] n(solv)} [S23] {[Fe 3 (O)(L) 3 ] n(solv)} [S23] MCF [S24] S31

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