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

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

doi:10.1038/s41467-021-27576-y

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

Journal Article · 10 December 2021 · Nature Communications

DOI: https://doi.org/10.1038/s41467-021-27576-y · OSTI ID:1835151

;

; White, Frankie D.; Beltran-Leiva, Maria J.; Sperling, Joseph M.; Salpage, Sahan R.;

; Gomez Martinez, Daniela; Jian, Tian; Wolford, Nikki J.;

; Ritz, Amanda J.;

; Gibson, John K.;

; Páez-Hernández, Dayán;

;

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 Bk ^III with 4’-(4-nitrophenyl)-2,2’:6’,2”-terpyridine (terpy*), a ligand with a large dipole. The resultant complex, Bk(terpy*)(NO ₃ ) ₃ (H ₂ O)·THF, is benchmarked with its closest electrochemical analog, Ce(terpy*)(NO ₃ ) ₃ (H ₂ O)·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 Ce ^III complex are reported.

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Research Organization:: Florida State Univ., Tallahassee, FL (United States); Florida State University, Tallahassee, FL (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231; SC0010677; SC0016002; SC0021917

OSTI ID:: 1835151

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 12; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United Kingdom

Language:: English

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

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