Compositional control of pore geometry in multivariate metal-organic frameworks: an experimental and computational study

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dc.contributor.author Cadman, Laura K.
dc.contributor.author Bristow, Jessica K.
dc.contributor.author Stubbs, Naomi E.
dc.contributor.author Tiana, Davide
dc.contributor.author Mahon, Mary F.
dc.contributor.author Walsh, Aron
dc.contributor.author Burrows, Andrew D.
dc.date.accessioned 2018-07-06T11:12:30Z
dc.date.available 2018-07-06T11:12:30Z
dc.date.issued 2016-01
dc.identifier.citation Cadman, L. K., Bristow, J. K., Stubbs, N. E., Tiana, D., Mahon, M. F., Walsh, A. and Burrows, A. D. (2016) 'Compositional control of pore geometry in multivariate metal-organic frameworks: an experimental and computational study', Dalton Transactions, 45(10), pp. 4316-4326. doi: 10.1039/c5dt04045k en
dc.identifier.volume 45 en
dc.identifier.startpage 4316 en
dc.identifier.endpage 4326 en
dc.identifier.issn 1477-9226
dc.identifier.uri http://hdl.handle.net/10468/6426
dc.identifier.doi 10.1039/c5dt04045k
dc.description.abstract A new approach is reported for tailoring the pore geometry in five series of multivariate metal-organic frameworks (MOFs) based on the structure [Zn-2(bdc)(2)(dabco)] (bdc = 1,4-benzenedicarboxylate, dabco = 1,8-diazabicyclooctane), DMOF-1. A doping procedure has been adopted to form series of MOFs containing varying linker ratios. The series under investigation are [Zn-2(bdc)(2-x)(bdc-Br)(x)(dabco)]center dot nDMF 1 (bdc-Br = 2-bromo-1,4-benzenedicarboxylate), [Zn-2(bdc)(2-x)(bdc-I)(x)(dabco)]center dot nDMF 2 (bdc-I = 2-iodo-1,4-benzenedicarboxylate), [Zn-2(bdc)(2-x)(bdc-NO2)(x)(dabco)]center dot nDMF 3 (bdc-NO2 = 2-nitro-1,4-benzenedicarboxylate), [Zn-2(bdc)(2-x)(bdc-NH2)(x)(dabco)]center dot nDMF 4 (bdc-NH2 = 2-amino-1,4-benzenedicarboxylate) and [Zn-2(bdc-Br)(2-x)(bdc-I)(x)(dabco)] nDMF 5. Series 1-3 demonstrate a functionality-dependent pore geometry transition from the square, open pores of DMOF-1 to rhomboidal, narrow pores with increasing proportion of the 2-substituted bdc linker, with the rhomboidal-pore MOFs also showing a temperature-dependent phase change. In contrast, all members of series 4 and 5 have uniform pore geometries. In series 4 this is a square pore topology, whilst series 5 exhibits the rhomboidal pore form. Computational analyses reveal that the pore size and shape in systems 1 and 2 is altered through non-covalent interactions between the organic linkers within the framework, and that this can be controlled by the ligand functionality and ratio. This approach affords the potential to tailor pore geometry and shape within MOFs through judicious choice of ligand ratios. en
dc.description.sponsorship Engineering and Physical Sciences Research Council (EPSRC studentship) en
dc.format.mimetype application/pdf en
dc.language.iso en en
dc.publisher Royal Society of Chemistry (RSC) en
dc.relation.uri http://dx.doi.org/10.1039/C5DT04045K
dc.rights © The Royal Society of Chemistry 2016. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence en
dc.rights.uri https://creativecommons.org/licenses/by/3.0/ en
dc.subject Porous coordination polymers en
dc.subject Minimum energy paths en
dc.subject Elastic band method en
dc.subject Crystal-structures en
dc.subject Hydrogen storage en
dc.subject Saddle-points en
dc.subject Program en
dc.subject Adsorption en
dc.subject Stability en
dc.title Compositional control of pore geometry in multivariate metal-organic frameworks: an experimental and computational study en
dc.type Article (peer-reviewed) en
dc.internal.authorcontactother Davide Tiana, Chemistry, University College Cork, Cork, Ireland. +353-21-490-3000 Email: davide.tiana@ucc.ie en
dc.internal.availability Full text available en
dc.date.updated 2018-07-03T11:06:53Z
dc.description.version Published Version en
dc.internal.rssid 391816990
dc.internal.wokid WOS:000371710500031
dc.contributor.funder Engineering and Physical Sciences Research Council en
dc.contributor.funder Royal Society en
dc.description.status Peer reviewed en
dc.identifier.journaltitle Dalton Transactions en
dc.internal.copyrightchecked Yes en
dc.internal.licenseacceptance Yes en
dc.internal.IRISemailaddress davide.tiana@ucc.ie en
dc.relation.project info:eu-repo/grantAgreement/RCUK/EPSRC/EP/G03768X/1/GB/Doctoral Training Centre in Sustainable Chemical Technologies/ en
dc.relation.project info:eu-repo/grantAgreement/EC/FP7::SP2::ERC/277757/EU/Hybrid Semiconductors: Design Principles and Material Applications/HYBRIDS en
dc.relation.project info:eu-repo/grantAgreement/RCUK/EPSRC/EP/K004956/1/GB/Applying Long-lived Metastable States with Switchable Functionality via Kinetic Control of Molecular Assembly - a Programme in Functional Materials/ en
dc.relation.project info:eu-repo/grantAgreement/RCUK/EPSRC/EP/L000202/1/GB/MATERIALS CHEMISTRY HIGH END COMPUTING CONSORTIUM/ en


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© The Royal Society of Chemistry 2016. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence Except where otherwise noted, this item's license is described as © The Royal Society of Chemistry 2016. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence
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