Fluorine-functionalized metal–organic frameworks and porous coordination polymers
Source abstract
Abstract
Fluorine, the element with the highest electronegativity and low electric polarizability, can produce a variety of characteristics, including specific adsorption sites for molecules as well as flexibility to the host materials. In this review, we will introduce fluorine-functionalized metal–organic frameworks/porous coordination polymers that show unique and unprecedented structures, structural transformations, and gas and vapor adsorption/separation properties derived from the fluorine characteristics. Adding chemistry's most electronegative atom to porous polymer networks may lead to gas-specific filters capable of flexible ‘breathing’. The tunable activity of metal–organic frameworks towards specific guest molecules, such as drugs or pollutants, has led to a flurry of recent research reports. Shin–ichiro Noro and Takayoshi Nakamura from Hokkaido University in Japan review these findings to show the potential of fluorinated building blocks in porous polymers. The hydrophobic nature and strong bond polarity of organic–fluorine units induce preferential adsorption sites and hydrophobic character useful for oil spill clean-ups. Alternatively, combining inorganic fluorine anions with neutral molecules produces weaker network bonds that easily slip and deform in certain directions. Framework flexibilities and other properties including luminescent emission for sensors are adjustable through appropriate organic or inorganic fluorine units. Fluorine, the element with the highest electronegativity and low electric polarizability, can produce a variety of characteristics, including specific adsorption sites for molecules as well as flexibility to the host materials. In this review, we will introduce fluorine-functionalized metal–organic frameworks/porous coordination polymers that show unique and unprecedented structures, structural transformations, and gas and vapor adsorption/separation properties derived from the fluorine characteristics.
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Research context
OpenAlex topics: Metal-Organic Frameworks: Synthesis and Applications · Covalent Organic Framework Applications · Luminescence and Fluorescent Materials
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (66)
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1. Kitagawa, S., Kitaura, R. & Noro, S. Functional porous coordination polymers. Angew. Chem. Int. Ed. 43, 2334–2375 (2004).10.1002/anie.200300610 ↗
2. Yaghi, O. M., O’Keeffe, M., Ockwig, N. W., Chae, H. K., Eddaoudi, M. & Kim, J. Reticular synthesis and the design of new materials. Nature 423, 705–714 (2003).10.1038/nature01650 ↗
3. Férey, G. Hybrid porous solids: past, present, future. Chem. Soc. Rev. 37, 191–214 (2008).10.1039/B618320B ↗
4. Furukawa, H., Ko, N., Go, Y. B., Aratani, N., Choi, S. B., Choi, E., Yazaydin, A. Ö., Snurr, R. Q., O’Keeffe, M., Kim, J. & Yaghi, O. M. Ultrahigh porosity in metal-organic frameworks. Science 329, 424–428 (2010).10.1126/science.1192160 ↗
5. Serre, C., Millange, F., Thouvenot, C., Noguès, M., Marsolier, G., Louër, D. & Férey, G. Very large breathing effect in the first nanporous chromium(III)-based solids: MIL-53 or CrIII(OH){O2C-C6H4-CO2}{HO2C-C6H4-CO2H}x•H2Oy . J. Am. Chem. Soc. 124, 13519–13526 (2002).10.1021/ja0276974 ↗
6. Sato, H., Kosaka, W., Matsuda, R., Hori, A., Hijikata, Y., Belosludov, R. V., Sakaki, S., Takata, M. & Kitagawa, S. Self-accelerating CO sorption in a soft nanoporous crystal. Science 343, 167–170 (2014).10.1126/science.1246423 ↗
7. Pachfule, P. & Banerjee, R. in Encyclopedia of Inorganic and Bioinorganic Chemistry, 1–124. (John Wiley & Sons, Ltd., 2014).10.1002/9781119951438.eibc2199 ↗
8. Kasai, K. & Fujita, M. Guest-dependent flexible coordination networks with fluorinated ligands. Chem. Eur. J. 13, 3089–3105 (2007).10.1002/chem.200501067 ↗
9. Hulvey, Z., Falcao, E. H. L., Eckert, J. & Cheetham, A. K. Enhanced H2 adsorption enthalpy in the low-surface area, partially fluorinated coordination polymer Zn5(triazole)6(tetrafluoroterephthalate)2(H2O)2•4H2O. J. Mater. Chem. 19, 4307–4309 (2009).10.1039/b900879a ↗
10. Forrest, K. A., Pham, T., Georgies, P. A., Pinzan, F., Cioce, C. R., Unruh, T., Eckert, J. & Space, B. Investigating H2 sorption in a fluorinated metal–organic framework with small pores through molecular simulation and inelastic neutron scattering. Langmuir 31, 7328–7336 (2015).10.1021/acs.langmuir.5b01664 ↗
11. Zhang, D.-S., Chang, Z., Li, Y.-F., Jiang, Z.-Y., Xuan, Z.-H., Zhang, Y.-H., Li, J.-R., Chen, Q., Hu, T.-L. & Bu, X.-H. Fluorous metal-organic frameworks with enhanced stability and high H2/CO2 storage capacities. Sci. Rep. 3, 3312 (2013).10.1038/srep03312 ↗
12. Bae, Y.-S., Farha, O. K., Hupp, J. T. & Snurr, R. Q. Enhancement of CO2/N2 selectivity in a metal-organic framework by cavity modification. J. Mater. Chem. 19, 2131–2134 (2009).10.1039/b900390h ↗
13. Monge, A., Snejko, N., Gutiérrez-Puebla, E., Medina, M., Cascales, C., Ruiz-Valero, C., Iglesias, M. & Gómez-Lor, B. One teflon®-like channelled nanoporous polymer with a chiral and new uninodal 4-connected net: sorption and catalytic properties. Chem. Commun. 1291–1293 (2005).10.1039/B415960H ↗
14. Mukherjee, S., Kansara, A. M., Saha, D., Gonnade, R., Mullangi, D., Manna, B., Desai, A. V., Thorat, S. H., Singh, P. S., Mukherjee, A. & Ghosh, S. K. An ultrahydrophobic fluorous metal–organic framework derived recyclable composite as a promising platform to tackle marine oil spills. Chem. Eur. J. 22, 10937–10943 (2016).10.1002/chem.201601724 ↗
15. Yang, C., Kaipa, U., Mather, Q. Z., Wang, X., Nesterov, V., Venero, A. F. & Omary, M. A. Fluorous metal–organic frameworks with superior adsorptioin and hydrophobic properties toward oil spill cleanup and hydrocarbon storage. J. Am. Chem. Soc. 133, 18094–18097 (2011).10.1021/ja208408n ↗
16. Nijem, N., Canepa, P., Kaipa, U., Tan, K., Roodenko, K., Tekarli, S., Halbert, J., Oswald, I. W. H., Arvapally, R. K., Yang, C., Thonhauser, T., Omary, M. A. & Chabal, Y. J. Water cluster confinement and methane adsorption in the hydrophobic cavities of a fluorinated metal-organic framework. J. Am. Chem. Soc. 135, 12615–12626 (2013).10.1021/ja400754p ↗
17. Drache, F., Bon, V., Senkovska, I., Marschelke, C., Synytska, A. & Kaskel, S. Postsynthetic inner-surface functionalization of the highly stable zirconium-based metal–organic framework DUT-67. Inorg. Chem. 55, 7206–7213 (2016).10.1021/acs.inorgchem.6b00829 ↗
18. Subramanian, S. & Zaworotko, M. J. Porous solids by design: [Zn(4,4′-bpy)2(SiF6]n•xDMF, a single framework octahedral coordination polymer with large square channels. Angew. Chem. Int. Ed. 34, 2127–2129 (1995).10.1002/anie.199521271 ↗
19. Noro, S., Kitagawa, S., Kondo, M. & Seki, K. A new, methane adsorbent, porous coordination polymer [{CuSiF6(4,4′-bipyridine)2}n]. Angew. Chem. Int. Ed. 39, 2082–2084 (2000).10.1002/1521-3773(20000616)39:12<2081::AID-ANIE2081>3.0.CO;2-A ↗
20. Burd, S. D., Ma, S., Perman, J. A., Sikora, B. J., Snurr, R. Q., Thallapally, P. K., Tian, J., Wojtas, L. & Zaworotko, M. J. Highly selective carbon dioxide uptake by [Cu(bpy-n2(SiF6] (bpy-1=4,4′-Bipyridine; bpy-2=1,2-Bis(4-pyridyl)ethene. J. Am. Chem. Soc. 134, 3663–3666 (2012).10.1021/ja211340t ↗
21. Cui, X., Chen, K., Xing, H., Yang, Q., Krishna, R., Bao, Z., Wu, H., Zhou, W., Dong, X., Han, Y., Li, B., Ren, Q., Zaworotko, M. J. & Chen, B. Pore chemistry and size control in hybrid porous materials for acetylene capture from ethylene. Science 353, 141–144 (2016).10.1126/science.aaf2458 ↗
22. Nugent, P., Rhodus, V., Pham, T., Tudor, B., Forrest, K., Wojtas, L., Space, B. & Zaworotko, M. Enhancement of CO2 selectivity in a pillared pcu MOM platform through pillar substitution. Chem. Commun. 49, 1606–1608 (2013).10.1039/c3cc37695h ↗
23. Nugent, P., Belmabkhout, Y., Burd, S. D., Cairns, A. J., Luebke, R., Forrest, K., Pham, T., Ma, S., Space, B., Wojtas, L., Eddaoudi, M. & Zaworotko, M. J. Porous materials with optimal adsorption thermodynamics and kinetics for CO2 separation. Nature 495, 80–84 (2013).10.1038/nature11893 ↗
24. Chen, K.-J., Scott, H. S., Madden, D. G., Pham, T., Kumar, A., Bajpai, A., Lusi, M., Forrest, K. A., Space, B., Perry, J. J. IV & Zaworotko, M. J. Benchmark C2H2/CO2 and CO2/C2H2 separation by two closely related hybrid ultramicroporous materials. Chem. 1, 753–765 (2016).10.1016/j.chempr.2016.10.009 ↗
25. Noro, S., Kitaura, R., Kondo, M., Kitagawa, S., Ishii, T., Matsuzaka, H. & Yamashita, M. Framework engineering by anions and porous functionalities of Cu(II)/4,4′-bpy coordination polymers. J. Am. Chem. Soc. 124, 2568–2583 (2002).10.1021/ja0113192 ↗
26. Elsaidi, S. K., Mohamed, M. H., Schaef, H. T., Kumar, A., Lusi, M., Pham, T., Forrest, K. A., Space, B., Xu, W., Halder, G. J., Liu, J., Zaworotko, M. J. & Thallapally, P. K. Hydrophobic pillared square grids for selective removal of CO2 from simulated flue gas. Chem. Commun. 51, 15530–15533 (2015).10.1039/C5CC06577A ↗
27. Elsaidi, S. K., Mohamed, M. H., Simon, C. M., Braun, E., Pham, T., Forrest, K. A., Xu, W., Banerjee, D., Space, B., Zaworotko, M. J. & Thallapally, P. K. Effect of ring rotation upon gas adsorption in SIFSIX-3-M (M=Fe, Ni) pillared square grid networks. Chem. Sci. 8, 2373–2380 (2017).10.1039/C6SC05012C ↗
28. Elsaidi, S. K., Mohamed, M. H., Pham, T., Hussein, T., Wojtas, L., Zaworotko, M. J. & Space, B. Crystal engineering of a 4,6-c fsc platform that can serve as a carbon dioxide single-molecule trap. Cryst. Growth Des. 16, 1071–1080 (2016).10.1021/acs.cgd.5b01632 ↗
29. Cadiau, A., Adil, K., Bhatt, P. M., Belmabkhout, Y. & Eddaoudi, M. A metal-organic framework-based splitter for separating propylene from propane. Science 353, 137–140 (2016).10.1126/science.aaf6323 ↗
30. Bhatt, P. M., Belmabkhout, Y., Cadiau, A., Adil, K., Shekhah, O., Shkurenko, A., Barbour, L. J. & Eddaoudi, M. A fine-tuned fluorinated MOF addresses the needs for trace co2 removal and air capture using physisorption. J. Am. Chem. Soc. 138, 9301–9307 (2016).10.1021/jacs.6b05345 ↗
31. Kondo, A., Noguchi, H., Ohnishi, S., Kajiro, H., Tohdoh, A., Hattori, Y., Xu, W.-C., Tanaka, H., Konoh, H. & Kaneko, K. Novel expansion/shrinkage modulation of 2D layered MOF triggered by clathrate formation with CO2 molecules. Nano Lett. 6, 2581–2584 (2006).10.1021/nl062032b ↗
32. Kondo, A., Noguchi, H., Carlucci, L., Proserpio, D. M., Ciani, G., Kajiro, H., Ohba, T., Kanoh, H. & Kaneko, K. Double–step gas sorption of a two–dimensional metal–organic framework. J. Am. Chem. Soc. 129, 12362–12363 (2007).10.1021/ja073568h ↗
33. Noro, S., Hijikata, Y., Inukai, M., Fukushima, T., Horike, S., Higuchi, M., Kitagawa, S., Akutagawa, T. & Nakamura, T. Highly selective CO2 adsorption accompanied with low-energy regeneration in a two-dimensional Cu(II) porous coordination polymer with inorganic fluorinated PF6− anions. Inorg. Chem. 52, 280–285 (2013).10.1021/ic301823j ↗
34. Kondo, A., Chinen, A., Kajiro, H., Nakagawa, T., Kato, K., Takata, M., Hattori, Y., Okino, F., Ohba, T., Kaneko, K. & Kanoh, H. Metal-ion-dependent gas sorptivity of elastic layer-structured MOFs. Chem. Eur. J. 15, 7549–7553 (2009).10.1002/chem.200901208 ↗
35. Noro, S., Tanaka, D., Sakamoto, H., Shimomura, S., Kitagawa, S., Takeda, S., Uemura, K., Kita, H., Akutagawa, T. & Nakamura, T. Selective gas adsorption in one-dimensional, flexible CuII coordination polymers with polar units. Chem. Mater. 21, 3346–3355 (2009).10.1021/cm9012969 ↗
36. Noro, S., Akutagawa, T. & Nakamura, T. Selective separation of larger molecules from a Lewis-base mixture by flexible one-dimensional Cu(II) coordination polymer with shape-recognizing space. Chem. Commun. 46, 3134–3136 (2010).10.1039/b924181g ↗
37. Noro, S., Ochi, R., Inubushi, Y., Kubo, K. & Nakamura, T. CH4/CO2 and CH4/C2H6 gas separation using a flexible one-dimensional Copper(II) porous coordination polymer. Microporous Mesoporous Mater 216, 92–96 (2015).10.1016/j.micromeso.2015.03.021 ↗
38. Kotani, R., Kondo, A. & Maeda, K. Gate adsorption of CO2 on a flexible one-dimensional copper-based coordination polymer crystal. Chem. Commun. 48, 11316–11318 (2012).10.1039/c2cc35739a ↗
39. Noro, S., Matsuda, R., Hijikata, Y., Inubushi, Y., Takeda, S., Kitagawa, S., Takahashi, Y., Yoshitake, M., Kubo, K. & Nakamura, T. High CO2/CH4 selectivity of a flexible copper(II) porous coordination polymer under humid conditions. ChemPlusChem. 80, 1517–1524 (2015).10.1002/cplu.201500278 ↗
40. Fukuhara, K., Noro, S., Sugimoto, K., Akutagawa, T., Kubo, K. & Nakamura, T. Porous coordination polymer polymorphs with different flexible pores using structurally flexible and bent 1,3-Bis(4-pyridyl)propane ligand. Inorg. Chem. 52, 4229–4237 (2013).10.1021/ic301949n ↗
41. Noro, S., Fukuhara, K., Hijikata, Y., Kubo, K. & Nakamura, T. Rational synthesis of a porous copper(II) coordination polymer bridged by weak Lewis-base inorganic monoanions using an anion-mixing method. Inorg. Chem. 52, 5630–5632 (2013).10.1021/ic400276c ↗
42. Fujie, K., Otsubo, K., Ikeda, R., Yamada, T. & Kitagawa, H. Low temperature ionic conductor: ionic liquid incorporated within a metal–organic framework. Chem. Sci. 6, 4306–4310 (2015).10.1039/C5SC01398D ↗
43. Jang, M., Yamaguchi, T., Ohara, K., Kawano, M. & Fujita, M. Fluorous pores in coordination networks. Chem. Asian J. 4, 1524–1526 (2009).10.1002/asia.200900293 ↗
44. Jeon, H. J., Matsuda, R., Kanoo, P., Kajiro, H., Li, L., Sato, H., Zheng, Y. & Kitagawa, S. The densely fluorinated nanospace of a porous coordination polymer composed of perfluorobutyl-functionalized ligands. Chem. Commun. 50, 10861–10863 (2014).10.1039/C4CC04505J ↗
45. Deria, P., Mondloch, J. E., Tylianakis, E., Ghosh, P., Bury, W., Snurr, R. Q., Hupp, J. T. & Farha, O. K. Perfluoroalkane functionalization of NU-1000 via solvent-assisted ligand incorporation: synthesis and CO2 adsorption studies. J. Am. Chem. Soc. 135, 16801–16804 (2013).10.1021/ja408959g ↗
46. Williams, J. H. The molecular electric quadrupole moment and solid-state architecture. Acc. Chem. Res. 26, 593–598 (1993).10.1021/ar00035a005 ↗
47. Kasai, K., Aoyagi, M. & Fujita, M. Flexible coordination networks with fluorinated backbones. Remarkable ability for induced-fit enclathration of organic molecules. J. Am. Chem. Soc. 122, 2140–2141 (2000).10.1021/ja992553j ↗
48. Desiraju, G. R. & Steiner, T. The Weak Hydrogen Bond, Oxford University Press Inc.: New York, USA, (2001).10.1093/acprof:oso/9780198509707.001.0001 ↗
49. Yang, C., Wang, X. & Omary, M. A. Fluorous metal–organic frameworks for high-density gas adsorption. J. Am. Chem. Soc. 129, 15454–15455 (2007).10.1021/ja0775265 ↗
50. Shekhah, O., Belmabkhout, Y., Adil, K., Bhatt, P. M., Cairns, A. J. & Eddaoudi, M. A facile solvent-free synthesis route for the assembly of a highly CO2 selective and H2S tolerant NiSIFSIX metal–organic framework. Chem. Commun. 51, 13595–13598 (2015).10.1039/C5CC04487A ↗
51. Wilkes, J. S. A short history of ionic liquids–from molten salts to neoteric solvents. Green Chem. 4, 73–80 (2002).10.1039/b110838g ↗
52. Blake, A. J., Hill, S. J., Hubberstey, P. & Li, W.-S. Rectangular grid two-dimensional sheets of copper(II) bridged by both co-ordinated and hydrogen bonded 4,4′-bipyridine (4,4′-bipy) in [Cu(μ-4,4′-bipy)(H2O)2(FBF3 2]•4,4′-bipy. J. Chem. Soc. Dalton Trans. 913–914 (1997).10.1039/a700036g ↗
53. Hiraide, S., Tanaka, H. & Miyahara, M. T. Understanding gate adsorption behaviour of CO2 on elastic layer-structured metal–organic framework-11. Dalton Trans. 45, 4193–4202 (2016).10.1039/C5DT03476K ↗
54. Noro, S., Horike, S., Tanaka, D., Kitagawa, S., Akutagawa, T. & Nakamura, T. Flexible and shape-selective guest binding at CuII axial sites in 1-dimensional CuII–1,2-bis(4-pyridyl)ethane coordination polymers. Inorg. Chem. 45, 9290–9300 (2006).10.1021/ic0609249 ↗
55. Tanaka, H., Hiraide, S., Kondo, A. & Miyahara, M. T. Modeling and visualization of CO2 adsorption on elastic layer-structured metal–organic framework-11: toward a better understanding of gate adsorption behavior. J. Phys. Chem. C 119, 11533–11543 (2015).10.1021/jp512870p ↗
56. Suzuki, T., Kotani, R., Kondo, A. & Maeda, K. Structural investigation of a flexible MOF [Cu(BF4 2(1,3-bis(4-pyridyl)propane)2] showing selective gate adsorption with dynamic pore-opening/pore-closing processes. J. Phys. Chem. C 120, 21571–21579 (2016).10.1021/acs.jpcc.6b07280 ↗
57. Decoste, J. B., Peterson, G. W., Smith, M. W., Stone, C. A. & Willis, C. R. Enhanced stability of Cu-BTC MOF via perfluorohexane plasma-enhanced chemical vapor deposition. J. Am. Chem. Soc. 134, 1486–1489 (2012).10.1021/ja211182m ↗
58. Chui, S. S.-Y., Lo, S. M.-F., Charmant, J. P. H., Orpen, A. G. & Williams, I. D. A chemically functionalizable nanoporous material [Cu3(TMA)2(H2O)3]n . Science 50, 1148–1150 (1999).10.1126/science.283.5405.1148 ↗
59. Chen, B., Yang, Y., Zapata, F., Qian, G., Luo, Y., Zhang, J. & Lobkovsky, E. B. Enhanced near-infrared–luminescence in an erbium tetrafluoroterephthalate framework. Inorg. Chem. 45, 8882–8886 (2006).10.1021/ic060568u ↗
60. Miyata, K., Ohba, T., Kobayashi, A., Kato, M., Nakanishi, T., Fushimi, K. & Hasegawa, Y. Thermostable organo-phosphor: low-vibrational coordination polymers that exhibit different intermoleculer interactions. ChemPlusChem 77, 277–280 (2012).10.1002/cplu.201200002 ↗
61. Fukushima, T., Horike, S., Inubushi, Y., Nakagawa, K., Kubota, Y., Takata, M. & Kitagawa, S. Solid solutions of soft porous coordination polymers: fine-tuning of gas adsorption properties. Angew. Chem. Int. Ed. 49, 4820–4824 (2010).10.1002/anie.201000989 ↗
62. Schwedler, I., Henke, S., Wharmby, M. T., Bajpe, S. R., Cheetham, A. K. & Fischer, R. A. Mixed-linker solid solutions of functionalized pillared-layer MOFs–adjusting structural flexibility, gas sorption, and thermal responsiveness. Dalton Trans. 45, 4230–4241 (2016).10.1039/C5DT03825A ↗
63. Noro, S., Fukuhara, K., Sugimoto, K., Hijikata, Y., Kubo, K. & Nakamura, T. Anion-dependent host-guest properties of porous assemblies of coordination complexes (PACs), [Cu(A)2(py)4] (A=PF6, BF4, CF3SO3, and CH3SO3; py=pyridine), based on Werner-type copper(II) complexes in the solid state. Dalton Trans. 42, 11100–11110 (2013).10.1039/c3dt51104a ↗
64. Miyasaka, H. Control of charge transfer in donor/acceptor metal–organic frameworks. Acc. Chem. Res. 46, 248–257 (2013).10.1021/ar300102t ↗
65. Yanai, N., Uemura, T., Kosaka, W., Matsuda, R., Kodani, T., Koh, Meiten, Kanemura, T. & Kitagawa, S. Inclusion and dielectric properties of a vinylidene fluoride oligomer in coordination nanochannels. Dalton Trans. 41, 4195–4198 (2012).10.1039/c2dt11891b ↗
66. Devic, T., Serre, C., Audebrand, N., Marrot, J. & Férey, G. MIL-103, a 3-D lanthanide-based metal organic framework with large one-dimensional tunnels and a high surface area. J. Am. Chem. Soc. 127, 12788–12789 (2005).10.1021/ja053992n ↗