Creation of an unexpected plane of enhanced covalency in cerium(III) and berkelium(III) terpyridyl complexes

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dc.contributor.authorGaiser, Alyssa N.
dc.contributor.authorCelis-Barros, Cristian
dc.contributor.authorWhite, Frankie D.
dc.contributor.authorBeltran-Leiva, Maria J.
dc.contributor.authorSperling, Joseph M.
dc.contributor.authorSalpage, Sahan R.
dc.contributor.authorPoe, Todd N.
dc.contributor.authorGomez Martinez, Daniela
dc.contributor.authorJian, Tian
dc.contributor.authorWolford, Nikki J.
dc.contributor.authorJones, Nathaniel J.
dc.contributor.authorRitz, Amanda J.
dc.contributor.authorLazenby, Robert A.
dc.contributor.authorGibson, John K.
dc.contributor.authorBaumbach, Ryan E.
dc.contributor.authorPáez-Hernández, Dayán
dc.contributor.authorNeidig, Michael L.
dc.contributor.authorAlbrecht-Schönzart, Thomas E.
dc.date.accessioned2023-04-19T21:42:27Z
dc.date.available2023-04-19T21:42:27Z
dc.date.issued2021-12
dc.descriptionIndexación: Scopus.es
dc.description.abstractControlling the properties of heavy element complexes, such as those containing berkelium, is challenging because relativistic effects, spin-orbit and ligand-field splitting, and complex metal-ligand bonding, all dictate the final electronic states of the molecules. While the first two of these are currently beyond experimental control, covalent M‒L interactions could theoretically be boosted through the employment of chelators with large polarizabilities that substantially shift the electron density in the molecules. This theory is tested by ligating BkIII with 4’-(4-nitrophenyl)-2,2’:6’,2”-terpyridine (terpy*), a ligand with a large dipole. The resultant complex, Bk(terpy*)(NO3)3(H2O)·THF, is benchmarked with its closest electro chemical analog, Ce(terpy*)(NO3)3(H2O)·THF. Here, we show that enhanced Bk‒N inter actions with terpy* are observed as predicted. Unexpectedly, induced polarization by terpy* also creates a plane in the molecules wherein the M‒L bonds trans to terpy* are shorter than anticipated. Moreover, these molecules are highly anisotropic and rhombic EPR spectra for the CeIII complex are reported.es
dc.description.urihttps://www-nature-com.recursosbiblioteca.unab.cl/articles/s41467-021-27576-y
dc.identifier.citationNature Communications Volume 12, Issue 1December 2021 Article number 7230es
dc.identifier.doi10.1038/s41467-021-27576-y
dc.identifier.issn2041-1723
dc.identifier.urihttps://repositorio.unab.cl/xmlui/handle/ria/48749
dc.language.isoenes
dc.publisherNature Researches
dc.rights.licenseAtribution 4.0 International (CC BY 4.0)
dc.rights.urihttps://creativecommons.org/licenses/by/4.0/deed.es
dc.subjectBerkeliumes
dc.subjectComputational Chemistryes
dc.subjectNuclear Chemistryes
dc.subjectSolid-state Chemistryes
dc.subjectElectrochemical Data
dc.subjectTerpyridine
dc.subjectcerium(III)
dc.subjectCeIII
dc.titleCreation of an unexpected plane of enhanced covalency in cerium(III) and berkelium(III) terpyridyl complexeses
dc.typeArtículoes
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