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 and Thomas E. Albrecht-Schönzart ()
Additional contact information
Alyssa N. Gaiser: Florida State University
Cristian Celis-Barros: Florida State University
Frankie D. White: Florida State University
Maria J. Beltran-Leiva: Florida State University
Joseph M. Sperling: Florida State University
Sahan R. Salpage: Florida State University
Todd N. Poe: Florida State University
Daniela Gomez Martinez: Florida State University
Tian Jian: Lawrence Berkeley National Laboratory
Nikki J. Wolford: University of Rochester
Nathaniel J. Jones: Florida State University
Amanda J. Ritz: Florida State University
Robert A. Lazenby: Florida State University
John K. Gibson: Lawrence Berkeley National Laboratory
Ryan E. Baumbach: National High Magnetic Field Laboratory
Dayán Páez-Hernández: Universidad Andres Bello
Michael L. Neidig: University of Rochester
Thomas E. Albrecht-Schönzart: Florida State University

Nature Communications, 2021, vol. 12, issue 1, 1-9

Abstract: Abstract 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.

Date: 2021
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DOI: 10.1038/s41467-021-27576-y

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