Journal
CHEMICAL SCIENCE
Volume 10, Issue 5, Pages 1472-1482Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c8sc01959b
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Funding
- EPSRC [EP/I011870]
- ERC [AdG 742041]
- University of Manchester
- International Postdoctoral Exchange Fellowship Program from China and the Sino-British Fellowship (Royal Society)
- Laboratory Directed Research and Development program at ORNL
- Boreskov Institute of Catalysis [AAAA-A17-117041710084-2]
- EPSRC [EP/I020942/1, EP/I011870/2, EP/P001386/1] Funding Source: UKRI
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Modulation of pore environment is an effective strategy to optimize guest binding in porous materials. We report the post-synthetic modification of the charge distribution in a charged metal-organic framework, MFM-305-CH3, [Al(OH)(L)]Cl, [(H2L) Cl = 3,5-dicarboxy-1-methylpyridinium chloride] and its effect on guest binding. MFM-305-CH3 shows a distribution of cationic (methylpyridinium) and anionic (chloride) centers and can be modified to release free pyridyl N-centres by thermal demethylation of the 1-methylpyridinium moiety to give the neutral isostructural MFM-305. This leads simultaneously to enhanced adsorption capacities and selectivities (two parameters that often change in opposite directions) for CO2 and SO2 in MFM-305. The host-guest binding has been comprehensively investigated by in situ synchrotron X-ray and neutron powder diffraction, inelastic neutron scattering, synchrotron infrared and H-2 NMR spectroscopy and theoretical modelling to reveal the binding domains of CO2 and SO2 in these materials. CO2 and SO2 binding in MFM-305-CH3 is shown to occur via hydrogen bonding to the methyl and aromatic-CH groups, with a long range interaction to chloride for CO2. In MFM-305 the hydroxyl, pyridyl and aromatic C-H groups bind CO2 and SO2 more effectively via hydrogen bonds and dipole interactions. Post-synthetic modification via dealkylation of the assynthesised metal-organic framework is a powerful route to the synthesis of materials incorporating active polar groups that cannot be prepared directly.
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