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

doi:10.1038/s41467-021-27576-y

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

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12 Scopus citations

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*)(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 Ce^III complex are reported.

Original language	English
Article number	7230
Journal	Nature Communications
Volume	12
Issue number	1
DOIs	https://doi.org/10.1038/s41467-021-27576-y
State	Published - Dec 2021
Externally published	Yes

Funding

We thank the Radiation Safety and Control personnel, Jason Johnson and Ashley Gray at Florida State University for their oversight during these challenging experiments. We also thank Xingsong Lin for assistance in powder X-ray diffraction experiments. This work has been supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Heavy Elements Chemistry Program under Award Numbers DE-FG02-13ER16414 (to T.E.A.-S. for synthetic, crystallographic, spectroscopic, and electrochemical studies) and DE-AC02-05CH11231 (to J.K.G. for gas phase experiments), and U.S. Department of Energy, Office of Science, Early Career Research Program under Awards DE-SC0016002 and DE-SC0021917 (to M.L.N. for MCD and EPR spectroscopy). R.A.L. gratefully acknowledges Florida State University startup funds. D.P.-H. acknowledges the Chilean government through the grant Fondecyt 1180017.

Funders	Funder number
Heavy Elements Chemistry Program	DE-FG02-13ER16414
U.S. Department of Energy
Office of Science
Basic Energy Sciences	DE-AC02-05CH11231, DE-SC0021917, DE-SC0016002
Fondo Nacional de Desarrollo Científico y Tecnológico	1180017

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Gaiser, A. N., Celis-Barros, C., White, F. D., Beltran-Leiva, M. J., Sperling, J. M., Salpage, S. R., Poe, T. N., Gomez Martinez, D., Jian, T., Wolford, N. J., Jones, N. J., Ritz, A. J., Lazenby, R. A., Gibson, J. K., Baumbach, R. E., Páez-Hernández, D., Neidig, M. L., & Albrecht-Schönzart, T. E. (2021). Creation of an unexpected plane of enhanced covalency in cerium(III) and berkelium(III) terpyridyl complexes. Nature Communications, 12(1), Article 7230. https://doi.org/10.1038/s41467-021-27576-y

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

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{\textquoteright}-(4-nitrophenyl)-2,2{\textquoteright}:6{\textquoteright},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.",

author = "Gaiser, {Alyssa N.} and Cristian Celis-Barros and White, {Frankie D.} and Beltran-Leiva, {Maria J.} and Sperling, {Joseph M.} and Salpage, {Sahan R.} and Poe, {Todd N.} and {Gomez Martinez}, Daniela and Tian Jian and Wolford, {Nikki J.} and Jones, {Nathaniel J.} and Ritz, {Amanda J.} and Lazenby, {Robert A.} and Gibson, {John K.} and Baumbach, {Ryan E.} and Day{\'a}n P{\'a}ez-Hern{\'a}ndez and Neidig, {Michael L.} and Albrecht-Sch{\"o}nzart, {Thomas E.}",

note = "Publisher Copyright: {\textcopyright} 2021, The Author(s).",

year = "2021",

month = dec,

doi = "10.1038/s41467-021-27576-y",

language = "English",

volume = "12",

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Gaiser, AN, Celis-Barros, C , White, FD, Beltran-Leiva, MJ, Sperling, JM, Salpage, SR, Poe, TN, Gomez Martinez, D, Jian, T, Wolford, NJ, Jones, NJ, Ritz, AJ, Lazenby, RA, Gibson, JK, Baumbach, RE, Páez-Hernández, D, Neidig, ML & Albrecht-Schönzart, TE 2021, 'Creation of an unexpected plane of enhanced covalency in cerium(III) and berkelium(III) terpyridyl complexes', Nature Communications, vol. 12, no. 1, 7230. https://doi.org/10.1038/s41467-021-27576-y

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T1 - Creation of an unexpected plane of enhanced covalency in cerium(III) and berkelium(III) terpyridyl complexes

AU - Gaiser, Alyssa N.

AU - Celis-Barros, Cristian

AU - White, Frankie D.

AU - Beltran-Leiva, Maria J.

AU - Sperling, Joseph M.

AU - Salpage, Sahan R.

AU - Poe, Todd N.

AU - Gomez Martinez, Daniela

AU - Jian, Tian

AU - Wolford, Nikki J.

AU - Jones, Nathaniel J.

AU - Ritz, Amanda J.

AU - Lazenby, Robert A.

AU - Gibson, John K.

AU - Baumbach, Ryan E.

AU - Páez-Hernández, Dayán

AU - Neidig, Michael L.

AU - Albrecht-Schönzart, Thomas E.

PY - 2021/12

Y1 - 2021/12

N2 - 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.

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

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