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Tailoring porosity and rotational dynamics in a series of octacarboxylate metal-organic frameworks

Moreau, Florian; Kolokolov, Daniil L.; Stepanov, Alexander G.; Easun, Timothy L.; Dailly, Anne; Lewis, William; Blake, Alexander J.; Nowell, Harriett; Lennox, Matthew J.; Besley, Elena; Yang, Sihai; Schröder, Martin

Authors

Florian Moreau

Daniil L. Kolokolov

Alexander G. Stepanov

Timothy L. Easun

Anne Dailly

William Lewis

Alexander J. Blake

Harriett Nowell

Matthew J. Lennox

ELENA BESLEY Elena.Besley@nottingham.ac.uk
Professor of Theoretical Computational Chemistry

Sihai Yang

Martin Schröder M.Schroder@man.ac.uk



Abstract

Modulation and precise control of porosity of metal-organic frameworks (MOFs) are of critical importance to their materials function. Here we report the first 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 show absence of network interpenetration, robust structures and permanent porosity. Interestingly, activated MFM-185a shows a record high BET surface area of 4734 m2 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 v/v (298 K, 5-65 bar) recorded for MFM-185a due to selective elongation of tubular cages. Dynamics of molecular rotors in deuterated MFM-180a-d16 and MFM-181a-d16 were investigated by variable-temperature 2H solid state NMR spectroscopy to reveal the reorientation mechanisms within these materials. Analysis of the flipping modes of the mobile phenyl groups on the linkers, their rotational rates and transition temperatures, paves the way to controlling and understanding the role of molecular rotors through organic linker design within porous MOF materials.

Citation

Moreau, F., Kolokolov, D. L., Stepanov, A. G., Easun, T. L., Dailly, A., Lewis, W., …Schröder, M. (2017). Tailoring porosity and rotational dynamics in a series of octacarboxylate metal-organic frameworks. Proceedings of the National Academy of Sciences, 114(12), 3056-3061. https://doi.org/10.1073/pnas.1615172114

Journal Article Type Article
Acceptance Date Jan 26, 2017
Online Publication Date Mar 9, 2017
Publication Date Mar 21, 2017
Deposit Date Feb 28, 2017
Publicly Available Date Mar 9, 2017
Journal Proceedings of the National Academy of Sciences
Print ISSN 0027-8424
Electronic ISSN 1091-6490
Publisher National Academy of Sciences
Peer Reviewed Peer Reviewed
Volume 114
Issue 12
Pages 3056-3061
DOI https://doi.org/10.1073/pnas.1615172114
Keywords metal organic framework, crystal engineering, methane, 2H NMR, molecular dynamics
Public URL http://eprints.nottingham.ac.uk/id/eprint/40880
Publisher URL http://www.pnas.org/cgi/doi/10.1073/pnas.1615172114
Copyright Statement Copyright information regarding this work can be found at the following address: http://eprints.nottingham.ac.uk/end_user_agreement.pdf

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Copyright Statement
Copyright information regarding this work can be found at the following address: http://eprints.nottingham.ac.uk/end_user_agreement.pdf





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