Hexacoordinate Actinide(IV) Compounds: Benchmark Complexes for Magnetism and Electronic Structure Analysis.
4 affiliations
- 1Helmholtz-Zentrum Dresden - Rossendorf , Institute of Resource Ecology, Bautzner Landstraße 400, Dresden01328, Germany.
- 2The Rossendorf Beamline at ESRF - The European Synchrotron, CS40220, Grenoble Cedex 938043, France.
- 3RWTH Aachen University, Institute of Inorganic Chemistry, Landoltweg 1, Aachen52074, Germany.
- 4Brandenburg University of Technology Cottbus-Senftenberg, Institute of Materials Chemistry, Senftenberg01968, Germany.
Abstract
Two series of actinide tetrachloride complexes with the monodentate carboxylic amide ligands phthalimidine (H-phthal) and 2-pyridone (HPyO) of the general formula [AnIVCl4(L)2] (An = U, Np, Pu) were synthesized and characterized in the solid state and in solution. SC-XRD analysis revealed an octahedral coordination environment with trans orientation of either H-phthal or HPyO in all cases, with and without THF molecules hydrogen-bonded to the NH group of the ligands. In the case of [NpCl4(H-phthal)2], the absence of THF leads to a significant distortion of the coordination geometry around the metal, including the shortest Np-Cl bonds observed so far (2.4394(8) Å). A quantum chemical bonding analysis (QTAIM) showed that the main bonding interaction is found between the actinide and chloride ligands, with the amides rather loosely bound. Despite their unusually low coordination number, the complexes were found to be stable, even in coordinating solvents. This allowed for an in-depth analysis of their 1H and 13C NMR spectroscopy. Due to their pseudoD4h symmetry in the first coordination sphere, these complexes are excellent model systems to analyze their electronic structure and magnetic properties. We applied SQUID magnetometry to extract magnetic properties (μeff) and crystal field parameters ( Bqk, Wybourne) in combination with quantum chemical calculations, which allows for the comprehensive description of the electronic ground state from an experimental and theoretical point of view.
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BibTeX
@article{sawallisch2026hexacoordinate,
title = {{Hexacoordinate Actinide(IV) Compounds: Benchmark Complexes for Magnetism and Electronic Structure Analysis.}},
author = {Till Sawallisch and Dennis Grödler and Adrian Näder and Clara L Silva and Peter Kaden and Michael Patzschke and Lucia Amidani and Kristina O Kvashnina and Solveig Pospiech and Jan van Leusen and Moritz Schmidt and Thorsten Stumpf and Robert Gericke},
journal = {Journal of the American Chemical Society},
year = {2026},
month = oct,
doi = {10.1021/jacs.6c09492},
url = {https://europepmc.org/article/MED/42912261},
note = {CC BY},
}
RIS
TY - JOUR
TI - Hexacoordinate Actinide(IV) Compounds: Benchmark Complexes for Magnetism and Electronic Structure Analysis.
AU - Till Sawallisch
AU - Dennis Grödler
AU - Adrian Näder
AU - Clara L Silva
AU - Peter Kaden
AU - Michael Patzschke
AU - Lucia Amidani
AU - Kristina O Kvashnina
AU - Solveig Pospiech
AU - Jan van Leusen
AU - Moritz Schmidt
AU - Thorsten Stumpf
AU - Robert Gericke
PY - 2026
DA - 2026/10/01
JO - Journal of the American Chemical Society
DO - 10.1021/jacs.6c09492
UR - https://europepmc.org/article/MED/42912261
AB - Two series of actinide tetrachloride complexes with the monodentate carboxylic amide ligands phthalimidine (H-phthal) and 2-pyridone (HPyO) of the general formula [AnIVCl4(L)2] (An = U, Np, Pu) were synthesized and characterized in the solid state and in solution. SC-XRD analysis revealed an octahedral coordination environment with trans orientation of either H-phthal or HPyO in all cases, with and without THF molecules hydrogen-bonded to the NH group of the ligands. In the case of [NpCl4(H-phthal)2], the absence of THF leads to a significant distortion of the coordination geometry around the metal, including the shortest Np-Cl bonds observed so far (2.4394(8) Å). A quantum chemical bonding analysis (QTAIM) showed that the main bonding interaction is found between the actinide and chloride ligands, with the amides rather loosely bound. Despite their unusually low coordination number, the complexes were found to be stable, even in coordinating solvents. This allowed for an in-depth analysis of their 1H and 13C NMR spectroscopy. Due to their pseudoD4h symmetry in the first coordination sphere, these complexes are excellent model systems to analyze their electronic structure and magnetic properties. We applied SQUID magnetometry to extract magnetic properties (μeff) and crystal field parameters ( Bqk, Wybourne) in combination with quantum chemical calculations, which allows for the comprehensive description of the electronic ground state from an experimental and theoretical point of view.
SN - 0002-7863
SN - 1520-5126
ER -