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dc.contributor.authorRamsay, William Jen
dc.contributor.authorRizzuto, Felixen
dc.contributor.authorRonson, Tanyaen
dc.contributor.authorCaprice, Kenjien
dc.contributor.authorNitschke, Jonathanen
dc.date.accessioned2016-06-21T12:15:11Z
dc.date.available2016-06-21T12:15:11Z
dc.date.issued2016-05-23en
dc.identifier.issn0002-7863
dc.identifier.urihttps://www.repository.cam.ac.uk/handle/1810/256411
dc.description.abstractZinc(II), a dimolybdenum(II) paddlewheel tetramine A, and 2-formylpyridine self-assembled to generate a cubic Zn$^{II}$$_{8}$(L$^{A}$)$_{6}$ assembly. The paddlewheel faces of this assembly exhibited two distinct conformations, whereas the analogous Fe$^{II}$$_{8}$(L$^{A}$)$_{6}$ framework displayed no such perturbation to its structure. This variation in behavior is attributed to the subtle difference in ligand rotational freedom between the Zn$^{II}$- and Fe$^{II}$-cornered cubes. The incorporation of a fluorinated Mo$^{II}$$_{2}$ paddlewheel, B, into analogous Zn$^{II}$$_{8}$(L$^{B}$)$_{6}$ and Fe$^{II}$$_{8}$(L$^{B}$)$_{6}$ structures resulted in changes to the rotational dynamics of the ligands. These differing dynamics perturbed the energies of the frontier orbitals of these structures, as determined through spectroscopic and electrochemical methods. The result of these perturbations was an inversion of the halide binding preference of the Zn$^{II}$$_{8}$(L$^{B}$)$_{6}$ host as compared to its Zn$^{II}$$_{8}$(L$^{A}$)$_{6}$ congener, whereas the Fe$^{II}$$_{8}$(L$^{B}$)$_{6}$ host maintained a similar binding hierarchy to Fe$^{II}$$_{8}$(L$^{A}$)$_{6}$.
dc.description.sponsorshipSeventh Framework Programme
dc.languageEnglishen
dc.language.isoenen
dc.publisherAmerican Chemical Society
dc.rightsAttribution 4.0 International*
dc.rightsAttribution 4.0 Internationalen
dc.rightsAttribution 4.0 Internationalen
dc.rightsAttribution 4.0 Internationalen
dc.rightsAttribution 4.0 Internationalen
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/*
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/en
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/en
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/en
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/en
dc.titleSubtle Ligand Modification Inverts Guest Binding Hierarchy in M$^{II}$$_{8}$L$_{6}$ Supramolecular Cubesen
dc.typeArticle
dc.description.versionThis is the final version of the article. It first appeared from the American Chemical Society via http://dx.doi.org/10.1021/jacs.6b03858en
prism.endingPage7267
prism.publicationDate2016en
prism.publicationNameJournal of the American Chemical Societyen
prism.startingPage7264
prism.volume138en
dc.identifier.doi10.17863/CAM.353
dcterms.dateAccepted2016-05-23en
rioxxterms.versionofrecord10.1021/jacs.6b03858en
rioxxterms.versionVoRen
rioxxterms.licenseref.urihttp://creativecommons.org/licenses/by/4.0/en
rioxxterms.licenseref.startdate2016-05-23en
dc.contributor.orcidRizzuto, Felix [0000-0003-2799-903X]
dc.contributor.orcidRonson, Tanya [0000-0002-6917-3685]
dc.contributor.orcidNitschke, Jonathan [0000-0002-4060-5122]
dc.identifier.eissn1520-5126
rioxxterms.typeJournal Article/Reviewen
pubs.funder-project-idEPSRC (EP/K039520/1)
pubs.funder-project-idEPSRC (EP/M008258/1)
cam.orpheus.successThu Jan 30 10:20:22 GMT 2020 - The item has an open VoR version.*
rioxxterms.freetoread.startdate2100-01-01


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Attribution 4.0 International
Except where otherwise noted, this item's licence is described as Attribution 4.0 International