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dc.contributor.authorSorensen, Mikkel A.en_US
dc.contributor.authorVinum, Morten G.en_US
dc.contributor.authorMortensen, Jesper S.en_US
dc.contributor.authorDoerrer, Linda H.en_US
dc.contributor.authorWeihe, Hognien_US
dc.contributor.authorBendix, Jesperen_US
dc.date.accessioned2017-11-08T19:43:06Z
dc.date.available2017-11-08T19:43:06Z
dc.date.issued2017-05-01
dc.identifierhttp://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000400553000031&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=6e74115fe3da270499c3d65c9b17d654
dc.identifier.citationMikkel A. Sorensen, Hogni Weihe, Morten G. Vinum, Jesper S. Mortensen, Linda H. Doerrer, Jesper Bendix. 2017. "Imposing high-symmetry and tuneable geometry on lanthanide centres with chelating Pt and Pd metalloligands." Chemical Science, v. 8, Issue 5, pp. 3566 - 3575 (10).
dc.identifier.issn2041-6520
dc.identifier.issn2041-6539
dc.identifier.urihttps://hdl.handle.net/2144/24828
dc.description.abstractExploitation of HSAB preferences allows for high-yield, one-pot syntheses of lanthanide complexes chelated by two Pd or Pt metalloligands, [MII(SAc)4]2− (SAc− = thioacetate, M = Pd, Pt). The resulting complexes with 8 oxygen donors surrounding the lanthanides can be isolated in crystallographically tetragonal environments as either [NEt4]+ (space group: P4/mcc) or [PPh4]+ (space group: P4/n) salts. In the case of M = Pt, the complete series of lanthanide complexes has been structurally characterized as the [NEt4]+ salts (except for Ln = Pm), while the [PPh4]+ salts have been structurally characterized for Ln = Gd–Er, Y. For M = Pd, selected lanthanide complexes have been structurally characterized as both salts. The only significant structural difference between salts of the two counter ions is the resulting twist angle connecting tetragonal prismatic and tetragonal anti-prismatic configurations, with the [PPh4]+ salts approaching ideal D4d symmetry very closely (φ = 44.52–44.61°) while the [NEt4]+ salts exhibit intermediate twist angles in the interval φ = 17.28–27.41°, the twist increasing as the complete 4f series is traversed. Static magnetic properties for the latter half of the lanthanide series are found to agree well in the high temperature limit with the expected Curie behavior. Perpendicular and parallel mode EPR spectroscopy on randomly oriented powder samples and single crystals of the Gd complexes with respectively Pd- and Pt-based metalloligands demonstrate the nature of the platinum metal to strongly affect the spectra. Consistent parametrization of all of the EPR spectra reveals the main difference to stem from a large difference in the magnitude of the leading axial term, B02, this being almost four times larger for the Pt-based complexes as compared to the Pd analogues, indicating a direct Pt(5dz2)–Ln interaction and an arguable coordination number of 10 rather than 8. The parametrization of the EPR spectra also confirms that off-diagonal operators are associated with non-zero parameters for the [NEt4]+ salts, while only contributing minimally for the [PPh4]+ salts in which lanthanide coordination approximates D4d point group symmetry closely.en_US
dc.description.sponsorshipLHD acknowledges support from NSF-CCT EMT 08-517. (08-517 - NSF-CCT EMT)en_US
dc.format.extentp. 3566 - 3575 (10)en_US
dc.languageEnglish
dc.language.isoen_US
dc.publisherRoyal Society of Chemistryen_US
dc.relation.ispartofChemical Science
dc.rightsAttribution-NonCommercial 4.0 Internationalen_US
dc.rights.urihttp://creativecommons.org/licenses/by-nc/3.0/
dc.subjectScience & technologyen_US
dc.subjectPhysical sciencesen_US
dc.subjectChemistry, multidisciplinaryen_US
dc.subjectSingle-molecule magnetsen_US
dc.subjectHeterobimetallic lantern complexesen_US
dc.subjectIon magneticsen_US
dc.subjectMetal-complexesen_US
dc.subjectSpin qubitsen_US
dc.subjectRelaxationen_US
dc.subjectLiganden_US
dc.subjectCoordinationen_US
dc.subjectTemperatureen_US
dc.titleImposing high-symmetry and tuneable geometry on lanthanide centres with chelating Pt and Pd metalloligandsen_US
dc.typeArticleen_US
dc.identifier.doi10.1039/c7sc00135e
pubs.elements-sourceweb-of-scienceen_US
pubs.notesEmbargo: No embargoen_US
pubs.organisational-groupBoston Universityen_US
pubs.organisational-groupBoston University, College of Arts & Sciencesen_US
pubs.organisational-groupBoston University, College of Arts & Sciences, Department of Chemistryen_US
pubs.publication-statusPublisheden_US
dc.identifier.orcid0000-0002-2437-6374 (Doerrer, Linda H)


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