Creation of an unexpected plane of enhanced covalency in cerium(III) and berkelium(III) terpyridyl complexes
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Fecha
2021-12
Profesor/a Guía
Facultad/escuela
Idioma
en
Título de la revista
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Título del volumen
Editor
Nature Research
Nombre de Curso
Licencia CC
Atribution 4.0 International (CC BY 4.0)
Licencia CC
https://creativecommons.org/licenses/by/4.0/deed.es
Resumen
Controlling 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.
Notas
Indexación: Scopus.
Palabras clave
Berkelium, Computational Chemistry, Nuclear Chemistry, Solid-state Chemistry, Electrochemical Data, Terpyridine, cerium(III), CeIII
Citación
Nature Communications Volume 12, Issue 1December 2021 Article number 7230
DOI
10.1038/s41467-021-27576-y