Journal
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
Volume 114, Issue 12, Pages 3056-3061Publisher
NATL ACAD SCIENCES
DOI: 10.1073/pnas.1615172114
Keywords
metal-organic framework; copper; CO2; CH4; molecular rotors
Categories
Funding
- Engineering and Physical Sciences Research Council UK [EP/I011870]
- University of Nottingham
- University of Manchester
- European Research Council [AdG 226593, 307755 FIN]
- Russian Ministry of Science and Education [14.Z50.31.0006]
- Royal Society [IE150114]
- European Research Council (ERC) [307755] Funding Source: European Research Council (ERC)
- EPSRC [EP/P001386/1, EP/I011870/2, EP/K038869/1, EP/I011870/1] Funding Source: UKRI
- Engineering and Physical Sciences Research Council [EP/I011870/1, EP/P001386/1, EP/I011870/2, EP/K038869/1] Funding Source: researchfish
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Modulation and precise control of porosity of metal-organic frameworks (MOFs) is of critical importance to their materials function. Here we report modulation of porosity for a series of isoreticular octacarboxylate MOFs, denoted MFM-180 to MFM-185, via a strategy of selective elongation of metal-organic cages. Owing to the high ligand connectivity, these MOFs do not show interpenetration, and are robust structures that have permanent porosity. Interestingly, activated MFM-185a shows a high Brunauer-Emmett-Teller (BET) surface area of 4,734 m(2) g(-1) for an octacarboxylate MOF. These MOFs show remarkable CH4 and CO2 adsorption properties, notably with simultaneously high gravimetric and volumetric deliverable CH4 capacities of 0.24 g g(-1) and 163 vol/ vol (298 K, 5-65 bar) recorded for MFM-185a due to selective elongation of tubular cages. The dynamics of molecular rotors in deuterated MFM-180a-d(16) and MFM181a-d(16) were investigated by variable-temperature H-2 solid-state NMR spectroscopy to reveal the reorientation mechanisms within these materials. Analysis of the flipping modes of the mobile phenyl groups, their rotational rates, and transition temperatures paves the way to controlling and understanding the role of molecular rotors through design of organic linkers within porous MOF materials.
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