(Supporting Information: 47 pages including this page) Pradip Pachfule, Chandan Dey, Kumar Vanka and Rahul Banerjee*

Transcription

1 Structural Diversity in Fluorinated Metal Organic Frameworks (F-MOFs) Composed of Divalent Transition Metals, 1,10-Phenanthroline and Fluorinated Carboxylic Acid (Supporting Information: 47 pages including this page) Pradip Pachfule, Chandan Dey, Kumar Vanka and Rahul Banerjee* Physical/Materials Chemistry Division, National Chemical Laboratory, Dr. Homi Bhaba Road Pune , India Fax: ; Tel: Section S1. Detailed synthesis procedures for F-MOFs S-2 Section S2. Single crystal X-ray diffraction data collection, structure solution and refinement procedures S-12 Section S3. Thermal stability of F-MOFs, TGA S-41 1

2 Section S1: Detailed synthesis procedures for F-MOFs including multi-gram scale products, experimental and simulated PXRD patterns and elemental microanalyses. 4, 4 -Hexafluoroisopropylidene-bis-benzoic acid (H 2 fbba), Mn(NO 3 ) 2 XH 2 O and 2, 9- Dimethyl-1, 10-Phenanthroline (Neo) were purchased from the Aldrich Chemicals. 1, 10- Phenanthroline (Phen), Zn(NO 3 ) 2 6H 2 O, Co(NO 3 ) 2 6H 2 O were purchased from the Loba chemicals. N, N-dimethylformamide (DMF) was purchased from Rankem chemicals. All starting materials were used without further purification. All experimental operations were performed in air and all the stock solutions were prepared in N, N-dimethylformamide (DMF). Synthesis of Co 3 (hfbba) 6 (phen) 2 (F-MOF-6): 0.5 ml 1,10-Phenanthroline stock solution (0.20 M) and 1.5 ml 4,4 -Hexafluoroisopropylidene-bis-benzoic acid stock solution (0.20 M) were mixed in a 5 ml vial. To this solution was added 0.5 ml Co(NO 3 ) 2 6H 2 O stock solution (0.20 M). The vial was capped and heated to 85 ºC for 72 h. The mother liquor was decanted and the products were washed with DMF (15 ml) three times. Pink colored crystals of F-MOF-6 were collected by filtration and dried in air (10 min) (yield: 70%). Crystals suitable for X-ray diffraction were grown by heating the reaction mixture for 96h. However heating the reaction mixture for a longer period decreases the yield. FT-IR : (KBr cm -1 ): 3467(br), 3077(w), 2932(w), 2857(w), 2188(w), 1950(w), 1673(s), 1612(m), 1562(w), 1403(s), 1255(m), 1212(w), 1175(s), 1090(w), 1021(m), 970(m), 860(m), 845(m), 781(s), 727(s), 659(w). 2

3 Figure S1. Comparison of the experimental PXRD pattern of as-synthesized F-MOF-6 (top) with the one simulated from its single crystal structure (bottom). Synthesis of Co(hfbba)(phen) 2 2(H 2 hfbba)(h 2 O)(HCO 2 ) (F-MOF-7) : Hydrothermal reaction of Co(NO 3 ) 2 6H 2 O (0.035 g, 0.12 mmol) with 1,10-Phenanthroline (0.023 g, 0.12 mmol) and excess 4,4 -Hexafluoroisopropylidene-bis-benzoic acid (0.196 g, 0.50 mmol) in a 25 ml aciddigestion bomb using de-ionized water (7 ml) at C for 72 h produced pink colored crystals of F-MOF-7 in quantitative yield. Crystals were collected by filtration, washed with Ethanol and dried in air (10 min). 3

4 FT-IR : (KBr cm -1 ): 3498(br), 3071(w), 2618(w), 1937(w), 1705(s), 1611(w), 1517(m), 1425(s), 1291(w), 1250(m), 1175(m), 959(w), 945(w), 848(s), 782(w), 724(m), 643(w), 513(w). Figure S2. Comparison of the experimental PXRD pattern of as-prepared F-MOF-7 (top) with the one simulated from its single crystal structure (bottom). Synthesis of Zn(hfbba) 0.5 (phen)(hco 2 ) (F-MOF-8): 0.5 ml 1,10-Phenanthroline stock solution (0.20 M) and 1.5 ml 4,4 -Hexafluoroisopropylidene-bis-benzoic acid stock solution (0.20 M) were mixed in a 5 ml vial. To this solution was added 0.5 ml Zn(NO 3 ) 2 6H 2 O stock solution (0.20 M). The vial was capped and heated to 85 ºC for 72 h. The mother liquor was decanted and the products were washed with DMF (15 ml) three times. Colorless crystals of F- MOF-8 were collected by filtration and dried in air (10 min) (yield: 55%). Crystals suitable for 4

5 X-ray diffraction were grown by heating the reaction mixture for 96h. However heating the reaction mixture for a longer period decreases the yield. FT-IR : (KBr cm -1 ): 3697(w), 3064(s), 2927(w), 2873(m), 2751(w), 2519(w), 2238(w), 1951(w), 1928(m), 1820(w), 1605(m), 1571(m), 1519(w), 1392(m), 1291(w), 1142(m), 971(m), 856(s), 787(m), 728(m), 642(m), 559(m), 459(w). Figure S3. Comparison of the experimental PXRD pattern of as-prepared F-MOF-8 (top) with the one simulated from its single crystal structure (bottom). Synthesis of [Zn(hfbba)(phen) 2 ] 2(H 2 hfbba)(h 2 O)(HCO 2 ) (F-MOF-9) : Hydrothermal reaction of Zn(NO 3 ) 2 6H 2 O (0.036, 0.12 mmol) with 1,10-Phenanthroline (0.023 g, 0.12 mmol) 5

6 and excess 4,4 -Hexafluoroisopropylidene-bis-benzoic acid (0.196 g, 0.50 mmol) in a 25 ml aciddigestion bomb using de-ionized water (7 ml) at 120 C for 72 h produced colorless crystals of F-MOF-9 in quantitative yield. Crystals were collected by filtration, washed with Ethanol and dried in air (10 min). FT-IR : (KBr cm -1 ): 3491(br), 3071(s), 2625(w), 2518(w), 1938(w), 1814(w), 1708(s), 1609(m), 1556(w), 1519(m), 1416(m), 1291(w), 1211(w), 1175(m), 1136(w), 1020(w), 970(w), 945(w), 850(s), 783(m), 725(s), 691(w), 543(w), 515(m), 494(w). 6

7 Figure S4. Comparison of the experimental PXRD pattern of as-prepared F-MOF-9 (top) with the one simulated from its single crystal structure (bottom). Synthesis of Mn 3 (hfbba) 6 (phen) 2 (F-MOF-10): 0.5mL 1,10-Phenanthroline stock solution (0.20 M) and 1.5 ml 4,4 -Hexafluoroisopropylidene-bis-benzoic acid stock solution (0.20 M) were mixed in a 5 ml vial. To this solution was added 0.5 ml Mn(NO 3 ) 2 xh 2 O stock solution (0.20 M). The vial was capped and heated to 85 ºC for 72 h. The mother liquor was decanted and the products were washed with DMF (15 ml) three times. Colorless crystals of F-MOF-10 were collected by filtration and dried in air (10 min) (yield: 72%). Crystals suitable for X-ray diffraction were grown by heating the reaction mixture for 96h. However heating the reaction mixture for a longer period decreases the yield. FT-IR : (KBr cm -1 ): 3353(br), 3075(w), 2934(w), 2345(w), 1947(m), 1814(w), 1666(s), 1555(w), 1403(s), 1292(w), 1254(w), 1211(w), 1175(w), 1102(w), 1021(s), 971(w), 845(s), 845(s), 782(w), 727(m), 688(w), 639(w), 468(w). 7

8 Figure S5. Comparison of the experimental PXRD pattern of as-prepared F-MOF-10 (top) with the one simulated from its single crystal structure (bottom). Synthesis of Mn(Hhfbba) 2 (phen) (F-MOF-11) : Hydrothermal reaction of Mn(NO 3 ) 2 xh 2 O (0.035, 0.12 mmol) with 1,10-Phenanthroline (0.023 g, 0.12 mmol) and excess 4,4 - Hexafluoroisopropylidene-bis-benzoic acid (0.196 g, 0.50 mmol) in a 25 ml acid-digestion bomb using de-ionized water (7 ml) at C for 72 h produced colorless crystals of F-MOF-11 in 8

9 quantitative yield. Crystals were collected by filtration, washed with Ethanol and dried in air (10 min). FT-IR : (KBr cm -1 ): 3443(br), 3016(w), 2925(m), 2324(w), 1609(w), 1494(s), 1448(w), 1401(w), 1262(m), 1089(s), 1050(s), 869(w), 823(s), 685(w), 603(w), 516(w), 466(w). Figure S6. Comparison of the experimental PXRD pattern of as-prepared F-MOF-11 (top) with the one simulated from its single crystal structure (bottom). 9

10 Synthesis of [Mn(hfbba) 2 (neo)] (H 2 O) (F-MOF-11A) : Hydrothermal reaction of Mn(NO 3 ) 2 6H 2 O (0.035, 0.12 mmol) with 2, 9-Dimethyl-1, 10-Phenanthroline (0.025 g, 0.12 mmol) and excess 4,4 -Hexafluoroisopropylidene-bis-benzoic acid (0.196 g, 0.50 mmol) in a 25 ml acid-digestion bomb using de-ionized water (7 ml) at C for 72 h produced colorless crystals of F-MOF-11A in quantitative yield. Crystals were collected by filtration, washed with Ethanol and dried in air (10 min). FT-IR : (KBr cm -1 ): 3070(br), 2633(w), 1983(w), 1938(w), 1712(m), 1598(m), 1567(w), 1505(w), 1397(m), 1323(w), 1255(w), 1172(m), 1150(w), 1021(m), 971(m), 930(m), 855(m), 782(s), 725(m), 610(m), 780(s), 571(w), 527(w), 499(w), 472(w). 10

11 Figure S7. Comparison of the experimental PXRD pattern of as-prepared F-MOF-11A (top) with the one simulated from its single crystal structure (bottom). 11

12 Section S2. Single crystal X-ray diffraction data collection, structure solution and refinement procedures. General Data Collection and Refinement Procedures: All single crystal data were collected on a Bruker SMART APEX three circle diffractometer equipped with a CCD area detector and operated at 1500 W power (50 kv, 30 ma) to generate Mo Kα radiation (λ= Å). The incident X-ray beam was focused and monochromated using Bruker Excalibur Gobel mirror optics. Crystals of the F-MOFs reported in the paper were mounted on nylon CryoLoops (Hampton Research) with Paraton-N (Hampton Research). Crystals were flash frozen to 100(2) K in a liquid nitrogen cooled stream of nitrogen. Initial scans of each specimen were performed to obtain preliminary unit cell parameters and to assess the mosaicity (breadth of spots between frames) of the crystal to select the required frame width for data collection. In every case frame widths of 0.5 were judged to be appropriate and full hemispheres of data were collected using the Bruker SMART 1 software suite. Following data collection, reflections were sampled from all regions of the Ewald sphere to redetermine unit cell parameters for data integration and to check for rotational twinning using CELL_NOW 2. In no data collection was evidence for crystal decay encountered. Following exhaustive review of the collected frames the resolution of the dataset was judged. Data were integrated using Bruker SAINT 3 software with a narrow frame algorithm and a fractional lower limit of average intensity. Data were subsequently corrected for absorption by the program SADABS 4. The absorption coefficient (μ) ranges between 1 and 2 for all of the F-MOFs reported in this paper. However, it is should be noted that μ is based on the atomic contents and these contents are uncertain for most of these structures. In some cases the precise guest molecule (solvent) 12

13 content is not known because the small solvent molecules neither fit tightly nor reproducibly into the voids of these framework structures. The space group determinations and tests for merohedral twinning were carried out using XPREP 3. In all cases, the highest possible space group was chosen. All structures were solved by direct methods and refined using the SHELXTL 97 5 software suite. Atoms were located from iterative examination of difference F-maps following least squares refinements of the earlier models. Final models were refined anisotropically (if the number of data permitted) until full convergence was achieved. Hydrogen atoms were placed in calculated positions (C-H = 0.93 Å) and included as riding atoms with isotropic displacement parameters times U eq of the attached C atoms. In some cases modeling of electron density within the voids of the frameworks did not lead to identification of recognizable solvent molecules in these structures, probably due to the highly disordered contents of the large pores in the frameworks. Highly porous crystals that contain solvent-filled pores often yield raw data where observed strong (high intensity) scattering becomes limited to ~1.0 Å at best, with higher resolution data present at low intensity. A common strategy for improving X-ray data, increasing the exposure time of the crystal to X-rays, did not improve the quality of the high angle data in these cases, as the intensity from low angle data saturated the detector and minimal improvement in the high angle data was achieved. Additionally, diffuse scattering from the highly disordered solvent within the void spaces of the framework and from the capillary to mount the crystal contributes to the background and the washing out of the weaker data. The only optimal crystals suitable for analysis were generally small and weakly diffracting. Unfortunately, larger crystals, which would usually improve the quality of the data, presented a lowered degree of crystallinity and attempts to optimize the crystal growing conditions for large high-quality 13

14 specimens have not yet been fruitful. Data was collected at 298(2) K for F-ACID, F-MOF-7, -8, -11 and -11A. All other F-MOFs reported in this paper data were collected at 100(2)K. This lower temperature was considered to be optimal for obtaining the best data. Electron density within void spaces has not been assigned to any guest entity but has been modeled as isolated oxygen and/or carbon atoms. The foremost errors in all the models are thought to lie in the assignment of guest electron density. All structures were examined using the Adsym subroutine of PLATON 7 to assure that no additional symmetry could be applied to the models. All ellipsoids in ORTEP diagrams are displayed at the 30% probability level unless noted otherwise. For all structures we note that elevated R-values are commonly encountered in MOF crystallography for the reasons expressed above by us and by other research groups Table S1 contains crystallographic data for the seven F-MOFs and 4, 4 -Hexafluoroisopropylidene-bis-benzoic acid. 1. Bruker (2005). APEX2. Version Bruker AXS Inc., Madison, Wisconsin, USA. 2. Sheldrick, G. M. (2004). CELL_NOW. University of Göttingen, Germany. Steiner, Th. (1998). Acta Cryst. B54, Bruker (2004). SAINT-Plus (Version 7.03). Bruker AXS Inc., Madison, Wisconsin, USA. 4. Sheldrick, G. M. (2002). SADABS (Version 2.03) and TWINABS (Version 1.02).University of Göttingen, Germany. 5. Sheldrick, G. M. (1997). SHELXS 97 and SHELXL 97. University of Göttingen, Germany. 6. WINGX 7. A. L. Spek (2005) PLATON, A Multipurpose Crystallographic Tool, Utrecht University, Utrecht, The Netherlands. 14

15 8. Dakin, L. A., Ong P. C., Panek, J. S., Staples, R. J. & Stavropoulos, P. Organometallics 19, (2000). 9. Noro, S., Kitaura, R., Kondo, M., Kitagawa, S., Ishii, T., Matsuzaka, H. & Yamashita, M. J. Am. Chem. Soc. 124, (2002). 10. Eddaoudi, M., Kim, J., Vodak, D., Sudik, A., Wachter, J., O Keeffe, M. & Yaghi, O. M. Proc. Natl. Acad. Sci. U.S.A. 99, (2002). 11. Heintz, R. A., Zhao, H., Ouyang, X., Grandinetti, G., Cowen, J. & Dunbar, K. R. Inorg. Chem. 38, (1999). 12. Biradha, K., Hongo, Y. & Fujita, M. Angew. Chem. Int. Ed. 39, (2000). 13. Grosshans, P., Jouaiti, A., Hosseini, M. W. & Kyritsakas, N. New J. Chem, (Nouv. J. Chim,) 27, (2003). 14. Takeda, N., Umemoto, K., Yamaguchi, K. & Fujita, M. Nature (London) 398, (1999). 15. Eddaoudi, M., Kim, J., Rosi, N., Vodak, D., Wachter, J., O Keeffe, M. & Yaghi, O. M. Science 295, (2002). 16. Kesanli, B., Cui, Y., Smith, M. R., Bittner, E. W., Bockrath, B. C. & Lin, W. Angew. Chem. Int. Ed. 44, (2005). 17. Cotton, F. A., Lin, C. & Murillo, C. A. Inorg. Chem. 40, (2001). 15

16 F-ACID (MONOCLINIC) Experimental and Refinement Details for F-ACID A colorless prismatic crystal ( mm 3 ) of F-ACID was placed in a 0.7 mm diameter nylon CryoLoops (Hampton Research) with Paraton-N (Hampton Research). The loop was mounted on a SMART APEX three circle diffractometer equipped with a CCD area detector and operated at 1500 W power (50 kv, 30 ma) to generate Mo Kα radiation (λ = Å). A total of reflections were collected of which 7837 were unique and 3221 of these were greater than 2σ(I). The range of θ was from 2.76 to 19.69º. All non-hydrogen atoms were refined anisotropically. F-MOF-1 contains two 4,4 -hexafluoroisopropylidene-bis-benzoic acid in the asymmetric unit. F-ACID has a slightly higher R int (0.07) which could possibly be due to a deformed or irregular shaped crystal. Final full matrix least-squares refinement on F 2 converged to R 1 = (F >2σF)) and wr 2 = (all data) with GOF =

17 Figure S8. ORTEP drawing of F-ACID. Oxygen, red; Carbon, grey; Fluorine, green. 17

18 Table S1. Crystal data and structure refinement for F-ACID (H 2 hfbba) Empirical formula C17 H10 F6 O4 Formula weight Temperature Wavelength Crystal system Space group 298(2) K Å Monoclinic P2/c Unit cell dimensions a = (3) Å α = 90 b = (6) Å β = (2) c = (13) γ = 90 Volume (5) Z 8 Density (calculated) Absorption coefficient F(000) 1584 Crystal size mm 3 Theta range for data collection Index ranges -39 <= h <= 38, -9 <= k <= 9, -19 <= l <= 20 Reflections collected Independent reflections 3221 [Rint= 0.07] Completeness to theta = % Absorption correction Semi-empirical from equivalents Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 7837 / 0 / 491 Goodness-of-fit on F Final R indices [I>2sigma(I)] R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = Largest diff. peak and hole and e.Å -3 18

19 F-MOF-6 (MONOCLINIC) Experimental and Refinement Details for F-MOF-6 A colorless needle shaped crystal ( mm 3 ) of F-MOF-6 was placed in a 0.7 mm diameter nylon CryoLoops (Hampton Research) with Paraton-N (Hampton Research). The loop was mounted on a SMART APEX three circle diffractometer equipped with a CCD area detector and operated at 1500 W power (50 kv, 30 ma) to generate Mo Kα radiation (λ = Å) while being flash frozen to 100(2) K in a liquid N 2 cooled stream of nitrogen. A total of reflections were collected of which 9111 were unique and 6347 of these were greater than 2σ(I). The range of θ was from 1.41 to 25.00º. Analysis of the data showed negligible decay during collection. The structure was solved in the monoclinic C2/c space group, with Z = 4, using direct methods. Atoms Co1, C1, C4, C8, C17, C21 and C24, were refined isotropically. All other non-hydrogen atoms were refined isotropically with hydrogen atoms generated as spheres riding the coordinates of their parent atoms. F-MOF-6 is composed of one half 4,4 - hexafluoroisopropylidene-bis-benzoic acid, and one phenanthroline per 1.5 Co. An asymmetric unit contains one half 4,4 -hexafluoroisopropylidene-bis-benzoic acid, and one phenanthroline molecule. The attempts made to model the guests (solvent molecules) did not lead to identification of guest entities in this structure due to the limited periodicity of the solvent molecules in the crystals. Since the solvent is neither bonded to the framework nor tightly packed into the voids, solvent disorder can be expected for these structures. Thus, electron density within void spaces which could not be assigned to any definite guest entity was modeled as isolated carbon or oxygen atoms, and the foremost errors in all the models lies in the assignment of guest electron density. It should be noted that the precision of this model is low; however, the 19

20 structure is reported to display the framework for F-MOF-6 as isolated in the crystalline form. Other supporting characterization data (vide infra Materials and Methods) are consistent with the crystal structure. Final full matrix least-squares refinement on F 2 converged to R 1 = (F >2σF)) and wr 2 = (all data) with GOF = When only framework atoms are included in the latter structure factor calculation, the residual electron density in the F-map is located within the pores of F-MOF-6. 20

21 Figure S8. ORTEP drawing of F-MOf-6. Oxygen, red; Carbon, grey; Fluorine, green; Nitrogen, blue. 21

22 Table S2. Crystal data and structure refinement for F-MOF-6 Empirical formula C75 H40 Co3 F18 N4 O12 Formula weight Temperature Wavelength Crystal system Space group 100(2)K Å Monoclinic C2/c Unit cell dimensions a = (6)Å α = 90 b = (2)Å β = (2) c = (4) γ = 90 Volume 10340(3) Z 4 Density (calculated) Absorption coefficient F(000) 3428 Crystal size mm 3 Theta range for data collection Index ranges -43 <= h <= 43, -16 <= k <= 16, -31 <= l <= 31 Reflections collected Independent reflections 6347 [Rint= 0.12] Completeness to theta = % Absorption correction Semi-empirical from equivalents Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 9111 / 0 / 473 Goodness-of-fit on F Final R indices [I>2sigma(I)] R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = Largest diff. peak and hole and e.Å -3 22

23 F-MOF-7 (MONOCLINIC) Experimental and Refinement Details for F-MOF-7 A colorless prismic crystal ( mm 3 ) of F-MOF-7 was placed in a 0.7 mm diameter nylon CryoLoops (Hampton Research) with Paraton-N (Hampton Research). The loop was mounted on a SMART APEX three circle diffractometer equipped with a CCD area detector and operated at 1500 W power (50 kv, 30 ma) to generate Mo Kα radiation (λ = Å). A total of reflections were collected of which were unique and of these were greater than 2σ(I). The range of θ was from 1.44 to 26.01º. Analysis of the data showed negligible decay during collection. The structure was solved in the monoclinic P2 1 /c space group, with Z = 4, using direct methods. All other non-hydrogen atoms were refined anisotropically with hydrogen atoms generated as spheres riding the coordinates of their parent atoms. F-MOF-7 is composed of three 4,4 -hexafluoroisopropylidene-bis-benzoic acid, one phenanthroline, one formic acid and one water molecule per Co. An asymmetric unit contains three 4,4 -hexafluoroisopropylidene-bis-benzoic acid, one phenanthroline, one formic acid and one water molecule. Since the solvent is neither bonded to the framework nor tightly packed into the voids, solvent disorder can be expected for these structures. It should be noted that the precision of this model is low; however, the structure is reported to display the framework for F- MOF-7 as isolated in the crystalline form. Other supporting characterization data (vide infra Materials and Methods) are consistent with the crystal structure. Final full matrix least-squares refinement on F 2 converged to R 1 = (F >2σF)) and wr 2 = (all data) with GOF = When only framework atoms are included in the latter structure factor calculation, the residual electron density in the F-map is located within the pores of F-MOF-7. 23

24 Table S3. Crystal data and structure refinement for F-MOF-7 Empirical formula C76 H45 Co F18 N4 O15 Formula weight Temperature Wavelength Crystal system Space group 293(2) K Å Monoclinic P2(1)/c Unit cell dimensions a = (5)Å α = 90 b = (4)Å β = (13) c = (6)Å γ = 90 Volume 6839(3) Z 4 Density (calculated) Absorption coefficient F(000) 3352 Crystal size mm 3 Theta range for data collection Index ranges -24 <= h <= 24, -16 <= k <= 16, -36 <= l <= 36 Reflections collected Independent reflections [Rint= 0.12] Completeness to theta = % Absorption correction Semi-empirical from equivalents Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters / 0 / 1031 Goodness-of-fit on F Final R indices [I>2sigma(I)] R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = Largest diff. peak and hole and e.Å -3 24

25 Figure S8. ORTEP drawing of F-MOf-7. Oxygen, red; Carbon, grey; Fluorine, green; Nitrogen, blue. 25

26 F-MOF-8 (MONOCLINIC) Experimental and Refinement Details for F-MOF-8 A colorless needle shaped crystal ( mm 3 ) of F-MOF-8 was placed in a 0.7 mm diameter nylon CryoLoops (Hampton Research) with Paraton-N (Hampton Research). The loop was mounted on a SMART APEX three circle diffractometer equipped with a CCD area detector and operated at 1500 W power (50 kv, 30 ma) to generate Mo Kα radiation (λ = Å). A total of reflections were collected of which 4724 were unique and 3896 of these were greater than 2σ(I). The range of θ was from 0.97 to 28.20º. Analysis of the data showed negligible decay during collection. The structure was solved in the monoclinic C2/c space group, with Z = 4, using direct methods. All other non-hydrogen atoms were refined anisotropically with hydrogen atoms generated as spheres riding the coordinates of their parent atoms. F-MOF-8 is composed of half 4,4 -hexafluoroisopropylidene-bis-benzoic acid, one phenanthroline and one formic acid per Zn. An asymmetric unit contains half 4,4 - hexafluoroisopropylidene-bis-benzoic acid, one phenanthroline and one formic acid molecules. Other supporting characterization data (vide infra Materials and Methods) are consistent with the crystal structure. Final full matrix least-squares refinement on F 2 converged to R 1 = (F >2σF)) and wr 2 = (all data) with GOF = When only framework atoms are included in the latter structure factor calculation, the residual electron density in the F-map is located within the pores of F-MOF-8. 26

27 Figure S9. ORTEP drawing of F-MOF-8. Oxygen, red; Carbon, grey; Fluorine, green; Nitrogen, blue. 27

28 Table S4. Crystal data and structure refinement for F-MOF-8 Empirical formula C43 H26 F6 N4 O8 Zn2 Formula weight Temperature Wavelength Crystal system Space group 293(2) K Å Monoclinic C2/c Unit cell dimensions a = (8)Å α = 90 b = (15)Å β = (3) c = (8)Å γ = 90 Volume (12) Z 4 Density (calculated) Absorption coefficient F(000) 1960 Crystal size mm 3 Theta range for data collection Index ranges -54 <= h <= 53, -12 <= k <= 12, -56 <= l <= 54 Reflections collected Independent reflections 3896 [Rint= 0.12] Completeness to theta = % Absorption correction Semi-empirical from equivalents Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 4724 / 0 / 285 Goodness-of-fit on F Final R indices [I>2sigma(I)] R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = Largest diff. peak and hole and e.Å -3 28

29 F-MOF-9 (MONOCLINIC) Experimental and Refinement Details for F-MOF-9 A colorless prismic crystal ( mm 3 ) of F-MOF-9 was placed in a 0.7 mm diameter nylon CryoLoops (Hampton Research) with Paraton-N (Hampton Research). The loop was mounted on a SMART APEX three circle diffractometer equipped with a CCD area detector and operated at 1500 W power (50 kv, 30 ma) to generate Mo Kα radiation (λ = Å). A total of reflections were collected of which were unique and of these were greater than 2σ(I). The range of θ was from 1.44 to 26.01º. Analysis of the data showed negligible decay during collection. The structure was solved in the monoclinic P2 1 /c space group, with Z = 4, using direct methods. All non-hydrogen atoms were refined anisotropically with hydrogen atoms generated as spheres riding the coordinates of their parent atoms. F-MOF-9 is composed of three 4,4 -hexafluoroisopropylidene-bis-benzoic acid, one phenanthroline, one formic acid and one water molecule per Co. An asymmetric unit contains three 4,4 -hexafluoroisopropylidene-bis-benzoic acid, one phenanthroline, one formic acid and one water molecule. Since the solvent is neither bonded to the framework nor tightly packed into the voids, solvent disorder can be expected for these structures. It should be noted that the precision of this model is low; however, the structure is reported to display the framework for F- MOF-9 as isolated in the crystalline form. Other supporting characterization data (vide infra Materials and Methods) are consistent with the crystal structure. Final full matrix least-squares refinement on F 2 converged to R 1 = (F >2σF)) and wr 2 = (all data) with GOF = When only framework atoms are included in the latter structure factor calculation, the residual electron density in the F-map is located within the pores of F-MOF-9. 29

30 Figure S10. ORTEP drawing of F-MOF-9. Oxygen, red; Carbon, grey; Fluorine, green; Nitrogen, blue. 30

31 Table S5. Crystal data and structure refinement for F-MOF-9 Empirical formula C76 H47 F18 N4 O15 Zn Formula weight Temperature Wavelength Crystal system Space group 100(2)K Å Monoclinic P2(1)/c Unit cell dimensions a = (8)Å α = 90 b = (6)Å β = (2) c = (10)Å γ = 90 Volume 6814(5) Z 4 Density (calculated) Absorption coefficient F(000) 3372 Crystal size mm 3 Theta range for data collection Index ranges -23 <= h <= 23, -16 <= k <= 16, -36 <= l <= 36 Reflections collected Independent reflections [Rint= 0.12] Completeness to theta = % Absorption correction Semi-empirical from equivalents Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters / 6 / 1042 Goodness-of-fit on F Final R indices [I>2sigma(I)] R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = Largest diff. peak and hole and e.å -3 31

32 F-MOF-10 (MONOCLINIC) Experimental and Refinement Details for F-MOF-10 A colorless needle shaped crystal ( mm 3 ) of F-MOF-10 was placed in a 0.7 mm diameter nylon CryoLoops (Hampton Research) with Paraton-N (Hampton Research). The loop was mounted on a SMART APEX three circle diffractometer equipped with a CCD area detector and operated at 1500 W power (50 kv, 30 ma) to generate Mo Kα radiation (λ = Å) while being flash frozen to 100(2) K in a liquid N 2 cooled stream of nitrogen. A total of reflections were collected of which 9225 were unique and 6185 of these were greater than 2σ(I). The range of θ was from 2.20 to 25.00º. Analysis of the data showed negligible decay during collection. The structure was solved in the monoclinic C2/c space group, with Z = 4, using direct methods. All other non-hydrogen atoms were refined isotropically with hydrogen atoms generated as spheres riding the coordinates of their parent atoms. F-MOF-10 is composed of one half 4,4 -hexafluoroisopropylidene-bis-benzoic acid, and one phenanthroline per 1.5 Mn. An asymmetric unit contains one half 4,4 -hexafluoroisopropylidene-bis-benzoic acid, and one phenanthroline molecule. The attempts made to model the guests (solvent molecules) did not lead to identification of guest entities in this structure due to the limited periodicity of the solvent molecules in the crystals. Since the solvent is neither bonded to the framework nor tightly packed into the voids, solvent disorder can be expected for these structures. Thus, electron density within void spaces which could not be assigned to any definite guest entity was modeled as isolated carbon or oxygen atoms, and the foremost errors in all the models lies in the assignment of guest electron density. It should be noted that the precision of this model is low; however, the structure is reported to display the framework for F-MOF-10 as isolated in the crystalline form. 32

33 Other supporting characterization data (vide infra Materials and Methods) are consistent with the crystal structure. Final full matrix least-squares refinement on F 2 converged to R 1 = (F >2σF)) and wr 2 = (all data) with GOF = When only framework atoms are included in the latter structure factor calculation, the residual electron density in the F-map is located within the pores of F-MOF-6. Figure S11. ORTEP drawing of F-MOF-10. Oxygen, red; Carbon, grey; Fluorine, green; Nitrogen, blue. 33

34 Table S6. Crystal data and structure refinement for F-MOF-10 Empirical formula C153 H84 F36 Mn6 N8 O24 Formula weight Temperature Wavelength Crystal system Space group 100(2)K Å Monoclinic C2/c Unit cell dimensions a = 37.09(2)Å α = 90 b = (7)Å β = (2) c = (12)Å γ = 90 Volume 10609(9) Z 2 Density (calculated) Absorption coefficient F(000) 3448 Crystal size mm 3 Theta range for data collection Index ranges -48 <= h <= 48, -17 <= k <= 18, -39 <= l <= 38 Reflections collected Independent reflections 6778 [Rint= 0.12] Completeness to theta = % Absorption correction Semi-empirical from equivalents Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters / 0 / 523 Goodness-of-fit on F Final R indices [I>2sigma(I)] R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = Largest diff. peak and hole and e.å -3 34

35 F-MOF-11 (MONOCLINIC) Experimental and Refinement Details for F-MOF-11 A colorless prismic crystal ( mm 3 ) of F-MOF-11 was placed in a 0.7 mm diameter nylon CryoLoops (Hampton Research) with Paraton-N (Hampton Research). The loop was mounted on a SMART APEX three circle diffractometer equipped with a CCD area detector and operated at 1500 W power (50 kv, 30 ma) to generate Mo Kα radiation (λ = Å). A total of reflections were collected of which 5019 were unique and 3838 of these were greater than 2σ(I). The range of θ was from 0.89 to 28.01º. Analysis of the data showed negligible decay during collection. The structure was solved in the monoclinic C2/c space group, with Z = 4, using direct methods. All non-hydrogen atoms were refined anisotropically with hydrogen atoms generated as spheres riding the coordinates of their parent atoms. F-MOF-11 is composed of one 4,4 -hexafluoroisopropylidene-bis-benzoic acid, one phenanthroline, and one water molecule per Mn. An asymmetric unit contains one 4,4 - hexafluoroisopropylidene-bis-benzoic acid, one phenanthroline, and one water molecule. Since the solvent is neither bonded to the framework nor tightly packed into the voids, solvent disorder can be expected for these structures. It should be noted that the precision of this model is low; however, the structure is reported to display the framework for F-MOF-11 as isolated in the crystalline form. Other supporting characterization data (vide infra Materials and Methods) are consistent with the crystal structure. Final full matrix least-squares refinement on F 2 converged to R 1 = (F >2σF)) and wr 2 = (all data) with GOF = When only framework atoms are included in the latter structure factor calculation, the residual electron density in the F- map is located within the pores of F-MOF

36 Figure S12. ORTEP drawing of F-MOF-11. Oxygen, red; Carbon, grey; Fluorine, green; Nitrogen, blue. 36

37 Table S7. Crystal data and structure refinement for F-MOF-11 Empirical formula C46 H23 F12 Mn N2 O8 Formula weight Temperature Wavelength Crystal system Space group 293(2)K Å Monoclinic C2/c Unit cell dimensions a = 45.75(4)Å α = 90 b = (9)Å β = (15) c = 8.848(7)Å γ = 90 Volume 4332(6) Z 4 Density (calculated) Absorption coefficient F(000) 2040 Crystal size mm 3 Theta range for data collection Index ranges -60 <= h <= 59, -14 <= k <= 13, -11 <= l <= 11 Reflections collected Independent reflections 3838 [Rint= 0.12] Completeness to theta = % Absorption correction Semi-empirical from equivalents Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 5019/0/ 393 Goodness-of-fit on F Final R indices [I>2sigma(I)] R 1 = , wr 2 = R indices (all data) R , wr 2 = Largest diff. peak and hole 0.521and e.Å -3 37

38 F-MOF-11A (MONOCLINIC) Experimental and Refinement Details for F-MOF-11A A colorless prismic crystal ( mm 3 ) of F-MOF-11A was placed in a 0.7 mm diameter nylon CryoLoops (Hampton Research) with Paraton-N (Hampton Research). The loop was mounted on a SMART APEX three circle diffractometer equipped with a CCD area detector and operated at 1500 W power (50 kv, 30 ma) to generate Mo Kα radiation (λ = Å). A total of reflections were collected of which 5019 were unique and 3838 of these were greater than 2σ(I). The range of θ was from 1.49 to 28.32º. Analysis of the data showed negligible decay during collection. The structure was solved in the monoclinic P2/n space group, with Z = 4, using direct methods. All non-hydrogen atoms were refined anisotropically with hydrogen atoms generated as spheres riding the coordinates of their parent atoms. F-MOF-11A is composed of one 4,4 -hexafluoroisopropylidene-bis-benzoic acid, one substituted phenanthroline, and one water molecule per Mn. An asymmetric unit contains one one 4,4 -hexafluoroisopropylidene-bis-benzoic acid, one substituted phenanthroline, and one water molecule. Since the solvent is neither bonded to the framework nor tightly packed into the voids, solvent disorder can be expected for these structures. Other supporting characterization data (vide infra Materials and Methods) are consistent with the crystal structure. Final full matrix least-squares refinement on F 2 converged to R 1 = (F >2σF)) and wr 2 = (all data) with GOF = When only framework atoms are included in the latter structure factor calculation, the residual electron density in the F-map is located within the pores of F-MOF-11A. 38

39 Figure S12. ORTEP drawing of F-MOF-11A. Oxygen, red; Carbon, grey; Fluorine, green; Nitrogen, blue. 39

40 Table S8. Crystal data and structure refinement for F-MOF-11A Empirical formula C62 H40 F12 Mn2 N4 O9 Formula weight Temperature Wavelength Crystal system Space group 293(2)K Å Monoclinic P2/n Unit cell dimensions a = (19)Å α = 90 b = (13)Å β = (2) c = (3)Å γ = 90 Volume (7) Z 2 Density (calculated) Absorption coefficient F(000) 1340 Crystal size mm 3 Theta range for data collection Index ranges -19 <= h <= 19, -12 <= k <= 12, -27 <= l <= 27 Reflections collected Independent reflections 4771 [Rint= 0.12] Completeness to theta = % Absorption correction Semi-empirical from equivalents Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 6925/0/403 Goodness-of-fit on F Final R indices [I>2sigma(I)] R 1 = , wr 2 = R indices (all data) R 1 = , wr 2 = Largest diff. peak and hole and e.Å -3 40

41 Section S3. Thermal stability of FMOFs and the thermal gravimetric analysis (TGA) data: 100 TGA : F-MOF-6 (F-MOF-6) 80 Weight % Temperature ( O C ) Figure S16. Thermal stability and the thermal gravimetric analysis (TGA) data of F-MOF-6. 41

42 TGA : F-MOF F-MOF Weight % Temperature ( O C ) Figure S17. Thermal stability and the thermal gravimetric analysis (TGA) data of F-MOF-7. 42

43 TGA : F-MOF F-MOF-8 80 Weight % Temperature ( O C ) Figure S18. Thermal stability and the thermal gravimetric analysis (TGA) data of F-MOF-8. 43

44 TGA : F-MOF F-MOF-9 80 Weight % Temperature ( O C ) Figure S19. Thermal stability and the thermal gravimetric analysis (TGA) data of F-MOF-9. 44

45 TGA : F-MOF F-MOF Weight % Temperature ( O C ) Figure S20. Thermal stability and the thermal gravimetric analysis (TGA) data of F-MOF

46 TGA : F-MOF F-MOF Weight % Temperature ( O C ) Figure S21. Thermal stability and the thermal gravimetric analysis (TGA) data of F-MOF

47 TGA : F-MOF-11A 100 F-MOF-11A 80 Weight % Temperature ( O C ) Figure S22. Thermal stability and the thermal gravimetric analysis (TGA) data of F-MOF-11A. 47

48 Table S9: Free Energy (kcal/mol) for the optimized structures. Optimized Structures Free Energy in kcal/mol Case I Gas phase Case I DMF Case I Water Case II Gas phase Case II DMF Case II Water