Mixed dysprosium-lanthanide nitride clusterfullerenes DyM2N@C80-: I h and Dy2MN@C80- i h (M = Gd, Er, Tm, and Lu): Synthesis, molecular structure, and quantum motion of the endohedral nitrogen atom

dc.bibliographicCitation.firstPage13139
dc.bibliographicCitation.issue27
dc.bibliographicCitation.lastPage13153
dc.bibliographicCitation.volume11
dc.contributor.authorSchlesier, C.
dc.contributor.authorLiu, F.
dc.contributor.authorDubrovin, V.
dc.contributor.authorSpree, L.
dc.contributor.authorBüchner, B.
dc.contributor.authorAvdoshenko, S.M.
dc.contributor.authorPopov, A.A.
dc.date.accessioned2022-12-05T09:41:57Z
dc.date.available2022-12-05T09:41:57Z
dc.date.issued2019
dc.description.abstractSystematic exploration of the synthesis of mixed-metal Dy-M nitride clusterfullerenes (NCFs, M = Gd, Er, Tm, Lu) is performed, and the impact of the second metal on the relative yield is evaluated. We demonstrate that the ionic radius of the metal appears to be the main factor allowing explanation of the relative yields in Dy-M mixed-metal systems with M = Sc, Lu, Er, and Gd. At the same time, Dy-Tm NCFs show anomalously low yields, which is not consistent with the relatively small ionic radius of Tm3+ but can be explained by the high third ionization potential of Tm. Complete separation of Dy-Gd and Dy-Er, as well as partial separation of Dy-Lu M3N@C80 nitride clusterfullerenes, is accomplished by recycling HPLC. The molecular structures of DyGd2N@C80 and DyEr2N@C80 are analyzed by means of single-crystal X-ray diffraction. A remarkable ordering of mixed-metal nitride clusters is found despite similar size and electronic properties of the metals. Possible pyramidalization of the nitride clusters in these and other nitride clusterfullerenes is critically analyzed with the help of DFT calculations and reconstruction of the nitrogen inversion barrier in M3N@C80 molecules is performed. Although a double-well potential with a pyramidal cluster structure is found to be common for most of them, the small size of the inversion barrier often leads to an apparent planar structure of the cluster. This situation is found for those M3N@C80 molecules in which the energy of the lowest vibrational level exceeds that of the inversion barrier, including Dy3N@C80 and DyEr2N@C80. The genuine pyramidal structure can be observed by X-ray diffraction only when the lowest vibrational level is below the inversion barrier, such as those found in Gd3N@C80 and DyGd2N@C80. The quantum nature of molecular vibrations becomes especially apparent when the size of the inversion barrier is comparable to the energy of the lowest vibrational levels.eng
dc.description.versionpublishedVersion
dc.identifier.urihttps://oa.tib.eu/renate/handle/123456789/10495
dc.identifier.urihttp://dx.doi.org/10.34657/9531
dc.language.isoeng
dc.publisherCambridge : RSC Publ.
dc.relation.doihttps://doi.org/10.1039/c9nr03593a
dc.relation.essn2040-3372
dc.relation.ispartofseriesNanoscale 11 (2019), Nr. 27eng
dc.rights.licenseCC BY 3.0 Unported
dc.rights.urihttps://creativecommons.org/licenses/by/3.0/
dc.subjectBinary alloyseng
dc.subjectCrystal atomic structureeng
dc.subjectDysprosium compoundseng
dc.subjectElectronic propertieseng
dc.subjectErbium alloyseng
dc.subjectGadolinium alloyseng
dc.subjectIonic conduction in solidseng
dc.subjectIonization potentialeng
dc.subjectLutetium alloyseng
dc.subjectLutetium compoundseng
dc.subjectMetalseng
dc.subjectMolecular structureeng
dc.subjectMoleculeseng
dc.subjectNitrideseng
dc.subjectNitrogeneng
dc.subjectRefractory metal compoundseng
dc.subjectSingle crystalseng
dc.subjectThulium alloyseng
dc.subjectX ray diffractioneng
dc.subject.ddc600
dc.titleMixed dysprosium-lanthanide nitride clusterfullerenes DyM2N@C80-: I h and Dy2MN@C80- i h (M = Gd, Er, Tm, and Lu): Synthesis, molecular structure, and quantum motion of the endohedral nitrogen atomeng
dc.typearticle
dc.typeText
dcterms.bibliographicCitation.journalTitleNanoscale
tib.accessRightsopenAccess
wgl.contributorIFWD
wgl.subjectPhysikger
wgl.subjectChemieger
wgl.typeZeitschriftenartikelger
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