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

Alyssa N. Gaiser, Cristian Celis-Barros, Frankie D. White, Maria J. Beltran-Leiva, Joseph M. Sperling, Sahan R. Salpage, Todd N. Poe, Daniela Gomez Martinez, Tian Jian, Nikki J. Wolford, Nathaniel J. Jones, Amanda J. Ritz, Robert A. Lazenby, John K. Gibson, Ryan E. Baumbach, Dayán Páez-Hernández, Michael L. Neidig, Thomas E. Albrecht-Schönzart

Resultado de la investigación: Contribución a una revistaArtículorevisión exhaustiva

1 Cita (Scopus)

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 electrochemical analog, Ce(terpy*)(NO3)3(H2O)·THF. Here, we show that enhanced Bk‒N interactions 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.

Idioma originalInglés
Número de artículo7230
PublicaciónNature Communications
Volumen12
N.º1
DOI
EstadoPublicada - dic. 2021

Áreas temáticas de ASJC Scopus

  • Química (todo)
  • Bioquímica, genética y biología molecular (todo)
  • Física y astronomía (todo)

Huella

Profundice en los temas de investigación de 'Creation of an unexpected plane of enhanced covalency in cerium(III) and berkelium(III) terpyridyl complexes'. En conjunto forman una huella única.

Citar esto