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dc.contributor.authorBassey, Euanen
dc.contributor.authorPaddison, Joseph AMen
dc.contributor.authorKeyzer, Evan Nen
dc.contributor.authorLee, Jeongjaeen
dc.contributor.authorManuel, Pascalen
dc.contributor.authorda Silva, Ivanen
dc.contributor.authorDutton, Sianen
dc.contributor.authorGrey, Clareen
dc.contributor.authorCliffe, Matthew Jen
dc.date.accessioned2020-07-17T14:17:35Z
dc.date.available2020-07-17T14:17:35Z
dc.date.issued2020-08en
dc.identifier.issn0020-1669
dc.identifier.urihttps://www.repository.cam.ac.uk/handle/1810/308075
dc.description.abstractUnderstanding the effect of chemical composition on the strength of magnetic interactions is key to the design of magnets with high operating temperatures. The magnetic divalent first-row transition metal (TM) thiocyanates are a class of chemically simple layered molecular frameworks. Here, we report two new members of the family, manganese (II) thiocyanate, Mn(NCS)₂, and iron (II) thiocyanate, Fe(NCS)₂. Using magnetic susceptibility measurements on these materials and on cobalt (II) thiocyanate and nickel (II) thiocyanate, Co(NCS)₂ and Ni(NCS)₂, respectively, we identify significantly stronger net antiferromagnetic interactions between the earlier TM ions—a decrease in the Weiss constant, θ, from 29 K for Ni(NCS)₂ to −115 K for Mn(NCS)₂—a consequence of more diffuse 3d orbitals, increased orbital overlap and increasing numbers of unpaired t2g electrons. We elucidate the magnetic structures of these materials: Mn(NCS)₂, Fe(NCS)₂ and Co(NCS)₂ order into the same antiferromagnetic commensurate ground state, whilst Ni(NCS)₂ adopts a ground state structure consisting of ferromagnetically ordered layers stacked antiferromagnetically. We show that significantly stronger exchange interactions can be realised in these thiocyanate frameworks by using earlier TMs.
dc.description.sponsorshipEPSRC NPIF 2018 fund Laboratory Directed Research and Development Program of Oak Ridge National Laboratory NSERC of Canada PGSD fund Trinity College, Cambridge School of Chemistry, University of Nottingham Hobday Fellowship EPSRC Strategic Equipment Grant EP/M000524/1
dc.format.mediumPrint-Electronicen
dc.languageengen
dc.publisherAmerican Chemical Society
dc.rightsAll rights reserved
dc.titleStrengthening the Magnetic Interactions in Pseudobinary First-Row Transition Metal Thiocyanates, M(NCS)2.en
dc.typeArticle
prism.endingPage11639
prism.issueIdentifier16en
prism.publicationDate2020en
prism.publicationNameInorganic chemistryen
prism.startingPage11627
prism.volume59en
dc.identifier.doi10.17863/CAM.55170
dcterms.dateAccepted2020-07-08en
rioxxterms.versionofrecord10.1021/acs.inorgchem.0c01478en
rioxxterms.versionAM
rioxxterms.licenseref.urihttp://www.rioxx.net/licenses/all-rights-reserveden
rioxxterms.licenseref.startdate2020-08en
dc.contributor.orcidBassey, Euan [0000-0001-8827-7175]
dc.contributor.orcidDutton, Sian [0000-0003-0984-5504]
dc.contributor.orcidGrey, Clare [0000-0001-5572-192X]
dc.contributor.orcidCliffe, Matthew J [0000-0002-0408-7647]
dc.identifier.eissn1520-510X
rioxxterms.typeJournal Article/Reviewen
pubs.funder-project-idEPSRC (EP/M000524/1)
cam.orpheus.successMon Aug 03 08:53:50 BST 2020 - Embargo updated*
cam.orpheus.counter2*
rioxxterms.freetoread.startdate2021-07-27


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