Altering the spectroscopy, electronic structure, and bonding of organometallic curium(III) upon coordination of 4,4′−bipyridine

Brian N. Long; María J. Beltrán-Leíva; Joseph M. Sperling; Todd N. Poe; Cristian Celis-Barros; Thomas E. Albrecht-Schönzart

doi:10.1038/s41467-023-39481-7

Altering the spectroscopy, electronic structure, and bonding of organometallic curium(III) upon coordination of 4,4′−bipyridine

Brian N. Long, María J. Beltrán-Leíva, Joseph M. Sperling, Todd N. Poe, Cristian Celis-Barros, Thomas E. Albrecht-Schönzart

Research output: Contribution to journal › Article › peer-review

5 Scopus citations

Abstract

Structural and electronic characterization of (Cp′₃Cm)₂(μ−4,4′−bpy) (Cp′ = trimethylsilylcyclopentadienyl, 4,4′−bpy = 4,4′−bipyridine) is reported and provides a rare example of curium−carbon bonding. Cp′₃Cm displays unexpectedly low energy emission that is quenched upon coordination by 4,4′−bipyridine. Electronic structure calculations on Cp′₃Cm and (Cp′₃Cm)₂(μ−4,4′−bpy) rule out significant differences in the emissive state, rendering 4,4′−bipyridine as the primary quenching agent. Comparisons of (Cp′₃Cm)₂(μ−4,4′−bpy) with its samarium and gadolinium analogues reveal atypical bonding patterns and electronic features that offer insights into bonding between carbon with f-block metal ions. Here we show the structural characterization of a curium−carbon bond, in addition to the unique electronic properties never before observed in a curium compound.

Original language	English
Article number	3774
Journal	Nature Communications
Volume	14
Issue number	1
DOIs	https://doi.org/10.1038/s41467-023-39481-7
State	Published - Dec 2023
Externally published	Yes

Funding

This study was completed under the Department of Energy Office of Science, Basic Energy Sciences, DOE-BES Heavy Elements Chemistry award number DE-FG02-13ER16414 (TEAS). We would like to thank Oak Ridge National Laboratory for providing the248Cm. Additionally, we would like to extend our gratitude to Professor Cory J. Windorff for his help and insight into organometallic actinide chemistry, as well as our radiation safety officers, Ashley Gray and Jason Johnson, for their efforts in our program. This study was completed under the Department of Energy Office of Science, Basic Energy Sciences, DOE-BES Heavy Elements Chemistry award number DE-FG02-13ER16414 (TEAS). We would like to thank Oak Ridge National Laboratory for providing the Cm. Additionally, we would like to extend our gratitude to Professor Cory J. Windorff for his help and insight into organometallic actinide chemistry, as well as our radiation safety officers, Ashley Gray and Jason Johnson, for their efforts in our program. 248

Funders	Funder number
TEAS
Office of Science
Basic Energy Sciences	DE-FG02-13ER16414
Oak Ridge National Laboratory

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title = "Altering the spectroscopy, electronic structure, and bonding of organometallic curium(III) upon coordination of 4,4′−bipyridine",

abstract = "Structural and electronic characterization of (Cp′3Cm)2(μ−4,4′−bpy) (Cp′ = trimethylsilylcyclopentadienyl, 4,4′−bpy = 4,4′−bipyridine) is reported and provides a rare example of curium−carbon bonding. Cp′3Cm displays unexpectedly low energy emission that is quenched upon coordination by 4,4′−bipyridine. Electronic structure calculations on Cp′3Cm and (Cp′3Cm)2(μ−4,4′−bpy) rule out significant differences in the emissive state, rendering 4,4′−bipyridine as the primary quenching agent. Comparisons of (Cp′3Cm)2(μ−4,4′−bpy) with its samarium and gadolinium analogues reveal atypical bonding patterns and electronic features that offer insights into bonding between carbon with f-block metal ions. Here we show the structural characterization of a curium−carbon bond, in addition to the unique electronic properties never before observed in a curium compound.",

author = "Long, {Brian N.} and Beltr{\'a}n-Le{\'i}va, {Mar{\'i}a J.} and Sperling, {Joseph M.} and Poe, {Todd N.} and Cristian Celis-Barros and Albrecht-Sch{\"o}nzart, {Thomas E.}",

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AU - Beltrán-Leíva, María J.

AU - Sperling, Joseph M.

AU - Poe, Todd N.

AU - Celis-Barros, Cristian

AU - Albrecht-Schönzart, Thomas E.

PY - 2023/12

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N2 - Structural and electronic characterization of (Cp′3Cm)2(μ−4,4′−bpy) (Cp′ = trimethylsilylcyclopentadienyl, 4,4′−bpy = 4,4′−bipyridine) is reported and provides a rare example of curium−carbon bonding. Cp′3Cm displays unexpectedly low energy emission that is quenched upon coordination by 4,4′−bipyridine. Electronic structure calculations on Cp′3Cm and (Cp′3Cm)2(μ−4,4′−bpy) rule out significant differences in the emissive state, rendering 4,4′−bipyridine as the primary quenching agent. Comparisons of (Cp′3Cm)2(μ−4,4′−bpy) with its samarium and gadolinium analogues reveal atypical bonding patterns and electronic features that offer insights into bonding between carbon with f-block metal ions. Here we show the structural characterization of a curium−carbon bond, in addition to the unique electronic properties never before observed in a curium compound.

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Altering the spectroscopy, electronic structure, and bonding of organometallic curium(III) upon coordination of 4,4′−bipyridine

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