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 journalArticlepeer-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 languageEnglish
Article number3774
JournalNature Communications
Volume14
Issue number1
DOIs
StatePublished - Dec 2023
Externally publishedYes

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

FundersFunder number
TEAS
Office of Science
Basic Energy SciencesDE-FG02-13ER16414
Oak Ridge National Laboratory

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