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

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
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
Externally published	Yes

Funding

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

Funders	Funder number
DOPO
TEAS
National Science Foundation	CHE 1625543
National Institutes of Health	F05TW002183
U.S. Department of Energy	DE‐SC002183, DE‐FG02‐13ER16414, DE‐SC0008479
Basic Energy Sciences
Chemical Sciences, Geosciences, and Biosciences Division

Keywords

californium
electronic structure analysis
f-element
radiolysis

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10.1002/chem.202001904

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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.",

keywords = "californium, electronic structure analysis, f-element, radiolysis",

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doi = "10.1002/chem.202001904",

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T1 - Evidence of Alpha Radiolysis in the Formation of a Californium Nitrate Complex

AU - Galley, Shane S.

AU - Gaggioli, Carlo Alberto

AU - Zeller, Matthias

AU - Celis-Barros, Cristian

AU - Albrecht-Schmitt, Thomas E.

AU - Gagliardi, Laura

AU - Bart, Suzanne C.

PY - 2020/7/22

Y1 - 2020/7/22

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.

AB - 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.

KW - californium

KW - electronic structure analysis

KW - f-element

KW - radiolysis

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SP - 8885

EP - 8888

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 41

ER -

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

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Keywords

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