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

Simple item page
dc.contributor.authorCadman, Laura K.
dc.contributor.authorBristow, Jessica K.
dc.contributor.authorStubbs, Naomi E.
dc.contributor.authorTiana, Davide
dc.contributor.authorMahon, Mary F.
dc.contributor.authorWalsh, Aron
dc.contributor.authorBurrows, Andrew D.
dc.contributor.funderEngineering and Physical Sciences Research Councilen
dc.contributor.funderRoyal Societyen
dc.date.accessioned2018-07-06T11:12:30Z
dc.date.available2018-07-06T11:12:30Z
dc.date.issued2016-01
dc.date.updated2018-07-03T11:06:53Z
dc.description.abstractA 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.sponsorshipEngineering and Physical Sciences Research Council (EPSRC studentship)en
dc.description.statusPeer revieweden
dc.description.versionPublished Versionen
dc.format.mimetypeapplication/pdfen
dc.identifier.citationCadman, 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/c5dt04045ken
dc.identifier.doi10.1039/c5dt04045k
dc.identifier.endpage4326en
dc.identifier.issn1477-9226
dc.identifier.journaltitleDalton Transactionsen
dc.identifier.startpage4316en
dc.identifier.urihttps://hdl.handle.net/10468/6426
dc.identifier.volume45en
dc.language.isoenen
dc.publisherRoyal Society of Chemistry (RSC)en
dc.relation.projectinfo:eu-repo/grantAgreement/RCUK/EPSRC/EP/G03768X/1/GB/Doctoral Training Centre in Sustainable Chemical Technologies/en
dc.relation.projectinfo:eu-repo/grantAgreement/EC/FP7::SP2::ERC/277757/EU/Hybrid Semiconductors: Design Principles and Material Applications/HYBRIDSen
dc.relation.projectinfo: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.projectinfo:eu-repo/grantAgreement/RCUK/EPSRC/EP/L000202/1/GB/MATERIALS CHEMISTRY HIGH END COMPUTING CONSORTIUM/en
dc.relation.urihttp://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 Licenceen
dc.rights.urihttps://creativecommons.org/licenses/by/3.0/en
dc.subjectPorous coordination polymersen
dc.subjectMinimum energy pathsen
dc.subjectElastic band methoden
dc.subjectCrystal-structuresen
dc.subjectHydrogen storageen
dc.subjectSaddle-pointsen
dc.subjectProgramen
dc.subjectAdsorptionen
dc.subjectStabilityen
dc.titleCompositional control of pore geometry in multivariate metal-organic frameworks: an experimental and computational studyen
dc.typeArticle (peer-reviewed)en
Files
Original bundle
Now showing 1 - 2 of 2
Thumbnail Image
Name:
c5dt04045k.pdf
Size:
2.44 MB
Format:
Adobe Portable Document Format
Description:
Published version
Download
Thumbnail Image
Name:
c5dt04045k1.pdf
Size:
2.13 MB
Format:
Adobe Portable Document Format
Description:
Supplementary file
Download
License bundle
Now showing 1 - 1 of 1
Thumbnail Image
Name:
license.txt
Size:
2.71 KB
Format:
Item-specific license agreed upon to submission
Description:
Download
Collections
Chemistry - Journal Articles