Fluorous Metal−Organic Frameworks for High-Density Gas Adsorption

Yang, Chi; Wang, Xiaoping; Omary, Mohammad A.

doi:10.1021/ja0775265

Cited by 331 publications

(300 citation statements)

References 42 publications

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“…Hydrophobic behaviour was also confirmed by contact angle measurements with H 2 O, which revealed a contact angle of 132±1°. While this hydrophobicity has little precedent among the porous molecular crystals, fluorinated organic ligands were employed by Omary et al [36][37][38] in the construction of very hydrophobic fluorinated MOFs, which were in turn used for hydrocarbon capture. We have subsequently expanded on this work by developing routes to larger perfluorinated ligands 39 , while Nguyen and Cohen 40 used postsynthetic functionalization of amine-bearing MOFs with long-chain acyl chlorides to create superhydrophobic MOFs.…”

Section: Resultsmentioning

confidence: 99%

Thermally robust and porous noncovalent organic framework with high affinity for fluorocarbons and CFCs

et al. 2014

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Section: Resultsmentioning

confidence: 99%

Thermally robust and porous noncovalent organic framework with high affinity for fluorocarbons and CFCs

et al. 2014

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“…Although many interesting compounds were obtained, [8] to the best of our knowledge no synthesis of a perfluorinated counterpart of MOF-5, MIL-53, or MIL-101 has been achieved up to now. But it seems to be indispensable to compare isostructural MOFs with linkers 5 ]·2H 2 O was found and again confirmed by X-ray single crystal structure analysis (P1, Z = 2; CN = 8). Subtle changes of the cationic radii lead to different coordination spheres and thus to different compositions.…”

Section: Introductionmentioning

confidence: 89%

“…[5] FMOF-1 shows an enhanced thermal, light, and air stability as well as high H 2 gas uptake. [5,6] These results motivated extensive research efforts to find fluorous analogues of polycarboxylate based MOFs. [7] Probably most work was published on coordination polymers and MOFs based on perfluorinated terephthalate.…”

Section: Introductionmentioning

confidence: 99%

Reproducible Synthesis of a Monofluorinated Trimesate: A Versatile Linking Ligand for the Construction of Lanthanide Coordination Polymers

Krautwurst

Lamann

Ruschewitz

2017

Zeitschrift anorg allge chemie

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Abstract. The synthesis of monofluorinated trimesic acid (H 3 mfBTC = 2-fluoro-1,3,5-benzene-tricarboxylic acid) described in the literature leads in fact to its monopotassium salt K(H 2 mfBTC) (1), which was identified by a single crystal structure analysis (Pc, Z = 2). It is obtained as a single-phase product and shows good solubility in water so that from aqueous solutions fourteen new coordination polymers with Ln III cations were synthesized and structurally characterized.

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“…The fluorinated MOF, [Ag 6 (tz) 6 ] (tz = 3,5-bis(trifluoromethyl)-1,2,4-triazolate, Figure 3h), reported by Omary and colleagues, 49 showed the three-dimensional porous framework consisting of tetranuclear [Ag 4 (tz) 6 ] clusters connected by threecoordinate Ag(I) centers and had both large semi-rectangular channels (~12.2 and 7.3 Å) and small diamond-shaped cavities (~6.6 and 4.9 Å) coated with CF 3 groups of the fluorinated tz ligands (Figure 5a). Because of its CF 3 -coated channels and cavities, this MOF adsorbed a negligible amount of water even under almost 100% relative humidity condition and retained its original porous structure after soaking in water for several days.…”

Section: (Dmf) 4 ]mentioning

confidence: 99%

Fluorine-functionalized metal–organic frameworks and porous coordination polymers

2017

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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. NPG Asia Materials (2017) 9, e433; doi:10.1038/am.2017.165; published online 29 September 2017 INTRODUCTIONDuring the last two decades, metal-organic frameworks (MOFs)/ porous coordination polymers (PCPs) composed of metal ions and organic bridging ligands as main building units and, in some cases, inorganic ligands, have been investigated extensively because of their versatile structural diversity, high structural controllability (pore size, shape, dimension, flexibility and surface environment), high crystallinity, and their potential porous properties/functionalities in a variety of research fields such as storage and separation, catalysis, drug delivery and sensing ability. 1-3 The porous properties of MOFs/PCPs can be finely tailored by not only chemical modification of organic ligands and judicious choice of components but also a variety of techniques such as solid solution formation, defect engineering, core-shell structure, crystal morphology and size control, and so on. For example, the appropriate combination of organic bridging ligands provided the Zn(II) MOF, [Zn 4 O(bte) 4/3 (bpdc)] (bte = 4,4′,4′′-[benzene-1,3,5-triyl-tris (ethyne-2,1-diyl)]tribenzoate, bpdc = biphenyl-4,4′-dicarboxylate), with ultra-high Brunauer-Emmett-Teller and Langmuir specific surface areas close to 6000 and 10 000 m 2 g − 1 , respectively. 4 Unlike porous inorganic zeolites and porous carbon materials, MOFs often give flexible structures. As coordination bonds, hydrogen bonds and van der Waals interactions that are used to assemble each component are weaker (bonding energies are 10~200 kJ mol − 1 ) than covalent and ionic bonds (200~1000 kJ mol − 1 ), reversible rotation, bending and breaking of these weaker bonds easily occurs, resulting in structural changes. One representative of flexible MOFs is [Cr(OH)(1,4-bdc)] (MIL-53(Cr), 1,4-bdc = 1,4-benzenedicarboxylate), in which local reorientation of the coordination bond triggered by guest adsorption/ desorption induced the structural transformation between narrow pore and large pore forms. 5 In addition, many MOFs show high crystallinity as with porous inorganic zeolites, which is advantageous for understanding deeply the structure-property relationship using single-crystal and powder X-ray diffraction techniques. For example, the unprecedented highly selective CO sorption from a CO/N 2 mixture, which is

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Fluorous Metal−Organic Frameworks for High-Density Gas Adsorption

Cited by 331 publications

References 42 publications

Thermally robust and porous noncovalent organic framework with high affinity for fluorocarbons and CFCs

Thermally robust and porous noncovalent organic framework with high affinity for fluorocarbons and CFCs

Reproducible Synthesis of a Monofluorinated Trimesate: A Versatile Linking Ligand for the Construction of Lanthanide Coordination Polymers

Fluorine-functionalized metal–organic frameworks and porous coordination polymers

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