Evidence of Alpha Radiolysis in the Formation of a Californium Nitrate Complex

Shane S. Galley; Carlo Alberto Gaggioli; Matthias Zeller; Cristian Celis-Barros; Thomas E. Albrecht-Schmitt; Laura Gagliardi; Suzanne C. Bart

doi:10.1002/chem.202001904

Evidence of Alpha Radiolysis in the Formation of a Californium Nitrate Complex

Shane S. Galley, Carlo Alberto Gaggioli, Matthias Zeller, Cristian Celis-Barros, Thomas E. Albrecht-Schmitt, Laura Gagliardi, Suzanne C. Bart

Chemistry (Twin Cities)

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

7 Scopus citations

Abstract

Well-characterized complexes of transplutonium elements are scarce because of the experimental challenges of working with these elements and the rarity of the isotopes. This leads to a lack of structural and spectroscopic data needed to understand the nature of chemical bonds in these compounds. In this work, the synthesis of Cf(DOPO^q)₂(NO₃)(py) (DOPO^q=2,4,6,8-tetra-tert-butyl-1-oxo-1H-phenoxazin-9-olate; py=pyridine) is reported, in which the nitrate anion is hypothesized to form through the α-radiolysis-induced reaction of pyridine and/or the ligand. Computational analysis of the electronic structure of the complex reveals that the Cf^III–ligand interactions are largely ionic.

Original language	English (US)
Pages (from-to)	8885-8888
Number of pages	4
Journal	Chemistry - A European Journal
Volume	26
Issue number	41
DOIs	https://doi.org/10.1002/chem.202001904
State	Published - Jul 22 2020

Bibliographical note

Funding Information:
This work was funded by the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences of the U.S. Department of Energy through Grants DE‐SC0008479 (SCB), DE‐SC002183 (L.G.), and DE‐FG02‐13ER16414 (TEAS). This material is based upon work supported by the National Science Foundation through the Major Research Instrumentation Program under Grant No. CHE 1625543 (M.Z., X‐ray structure of Gd(DOPO)(NO)(py)). q 2 3

Publisher Copyright:
© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Keywords

californium
electronic structure analysis
f-element
radiolysis

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title = "Evidence of Alpha Radiolysis in the Formation of a Californium Nitrate Complex",

abstract = "Well-characterized complexes of transplutonium elements are scarce because of the experimental challenges of working with these elements and the rarity of the isotopes. This leads to a lack of structural and spectroscopic data needed to understand the nature of chemical bonds in these compounds. In this work, the synthesis of Cf(DOPOq)2(NO3)(py) (DOPOq=2,4,6,8-tetra-tert-butyl-1-oxo-1H-phenoxazin-9-olate; py=pyridine) is reported, in which the nitrate anion is hypothesized to form through the α-radiolysis-induced reaction of pyridine and/or the ligand. Computational analysis of the electronic structure of the complex reveals that the CfIII–ligand interactions are largely ionic.",

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author = "Galley, {Shane S.} and Gaggioli, {Carlo Alberto} and Matthias Zeller and Cristian Celis-Barros and Albrecht-Schmitt, {Thomas E.} and Laura Gagliardi and Bart, {Suzanne C.}",

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AU - Gagliardi, Laura

AU - Bart, Suzanne C.

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PY - 2020/7/22

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N2 - Well-characterized complexes of transplutonium elements are scarce because of the experimental challenges of working with these elements and the rarity of the isotopes. This leads to a lack of structural and spectroscopic data needed to understand the nature of chemical bonds in these compounds. In this work, the synthesis of Cf(DOPOq)2(NO3)(py) (DOPOq=2,4,6,8-tetra-tert-butyl-1-oxo-1H-phenoxazin-9-olate; py=pyridine) is reported, in which the nitrate anion is hypothesized to form through the α-radiolysis-induced reaction of pyridine and/or the ligand. Computational analysis of the electronic structure of the complex reveals that the CfIII–ligand interactions are largely ionic.

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Evidence of Alpha Radiolysis in the Formation of a Californium Nitrate Complex

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