[UF6]2−: A Molecular Hexafluorido Actinide(IV) Complex with Compensating Spin and Orbital Magnetic Moments

Kasper Steen Pedersen; Katie R. Meihaus; Andrei Rogalev; Fabrice Wilhelm; Daniel Aravena; Martín Amoza; Eliseo Ruiz; Jeffrey R. Long; Jesper Bendix; Rodolphe Clérac

doi:10.1002/ange.201905056

[UF₆]²⁻: A Molecular Hexafluorido Actinide(IV) Complex with Compensating Spin and Orbital Magnetic Moments

Kasper Steen Pedersen^*
, Katie R. Meihaus
, Andrei Rogalev
, Fabrice Wilhelm
, Daniel Aravena
, Martín Amoza
, Eliseo Ruiz
, Jeffrey R. Long
, Jesper Bendix
, Rodolphe Clérac

^*Corresponding author for this work

Department of Chemistry

University of California at Berkeley
University of Copenhagen
The European Synchrotron
Universidad de Santiago de Chile
Universitat de Barcelona
Université de Bordeaux

Research output: Contribution to journal › Journal article › Research › peer-review

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Abstract

The first structurally characterized hexafluorido complex of a tetravalent actinide ion, the [UF₆]²⁻ anion, is reported in the (NEt₄)₂[UF₆]⋅2 H₂O salt (1). The weak magnetic response of 1 results from both U^IV spin and orbital contributions, as established by combining X‐ray magnetic circular dichroism (XMCD) spectroscopy and bulk magnetization measurements. The spin and orbital moments are virtually identical in magnitude, but opposite in sign, resulting in an almost perfect cancellation, which is corroborated by ab initio calculations. This work constitutes the first experimental demonstration of a seemingly non‐magnetic molecular actinide complex carrying sizable spin and orbital magnetic moments.

Original language	English
Journal	Angewandte Chemie
Volume	131
Issue number	44
Pages (from-to)	15797-15801
Number of pages	6
ISSN	0044-8249
DOIs	https://doi.org/10.1002/ange.201905056
Publication status	Published - 2019

Keywords

Electronic structure
Fluorides
Magnetic properties
Uranium
X-ray spectroscopy

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title = "[UF6]2−: A Molecular Hexafluorido Actinide(IV) Complex with Compensating Spin and Orbital Magnetic Moments",

abstract = "The first structurally characterized hexafluorido complex of a tetravalent actinide ion, the [UF6]2− anion, is reported in the (NEt4)2[UF6]⋅2 H2O salt (1). The weak magnetic response of 1 results from both UIV spin and orbital contributions, as established by combining X‐ray magnetic circular dichroism (XMCD) spectroscopy and bulk magnetization measurements. The spin and orbital moments are virtually identical in magnitude, but opposite in sign, resulting in an almost perfect cancellation, which is corroborated by ab initio calculations. This work constitutes the first experimental demonstration of a seemingly non‐magnetic molecular actinide complex carrying sizable spin and orbital magnetic moments.",

keywords = "Electronic structure, Fluorides, Magnetic properties, Uranium, X-ray spectroscopy",

author = "Pedersen, \{Kasper Steen\} and Meihaus, \{Katie R.\} and Andrei Rogalev and Fabrice Wilhelm and Daniel Aravena and Mart{\'i}n Amoza and Eliseo Ruiz and Long, \{Jeffrey R.\} and Jesper Bendix and Rodolphe Cl{\'e}rac",

year = "2019",

doi = "10.1002/ange.201905056",

language = "English",

volume = "131",

pages = "15797--15801",

journal = "Angewandte Chemie",

issn = "0044-8249",

publisher = "Wiley-Blackwell",

number = "44",

}

TY - JOUR

T1 - [UF6]2−: A Molecular Hexafluorido Actinide(IV) Complex with Compensating Spin and Orbital Magnetic Moments

AU - Pedersen, Kasper Steen

AU - Meihaus, Katie R.

AU - Rogalev, Andrei

AU - Wilhelm, Fabrice

AU - Aravena, Daniel

AU - Amoza, Martín

AU - Ruiz, Eliseo

AU - Long, Jeffrey R.

AU - Bendix, Jesper

AU - Clérac, Rodolphe

PY - 2019

Y1 - 2019

N2 - The first structurally characterized hexafluorido complex of a tetravalent actinide ion, the [UF6]2− anion, is reported in the (NEt4)2[UF6]⋅2 H2O salt (1). The weak magnetic response of 1 results from both UIV spin and orbital contributions, as established by combining X‐ray magnetic circular dichroism (XMCD) spectroscopy and bulk magnetization measurements. The spin and orbital moments are virtually identical in magnitude, but opposite in sign, resulting in an almost perfect cancellation, which is corroborated by ab initio calculations. This work constitutes the first experimental demonstration of a seemingly non‐magnetic molecular actinide complex carrying sizable spin and orbital magnetic moments.

AB - The first structurally characterized hexafluorido complex of a tetravalent actinide ion, the [UF6]2− anion, is reported in the (NEt4)2[UF6]⋅2 H2O salt (1). The weak magnetic response of 1 results from both UIV spin and orbital contributions, as established by combining X‐ray magnetic circular dichroism (XMCD) spectroscopy and bulk magnetization measurements. The spin and orbital moments are virtually identical in magnitude, but opposite in sign, resulting in an almost perfect cancellation, which is corroborated by ab initio calculations. This work constitutes the first experimental demonstration of a seemingly non‐magnetic molecular actinide complex carrying sizable spin and orbital magnetic moments.

KW - Electronic structure

KW - Fluorides

KW - Magnetic properties

KW - Uranium

KW - X-ray spectroscopy

U2 - 10.1002/ange.201905056

DO - 10.1002/ange.201905056

M3 - Journal article

SN - 0044-8249

VL - 131

SP - 15797

EP - 15801

JO - Angewandte Chemie

JF - Angewandte Chemie

IS - 44

ER -