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Molecular and electronic structure of terminal and alkali metal-capped uranium(V) nitride complexes

King, David M.; Cleaves, Peter A.; Wooles, Ashley J.; Gardner, Benedict. M.; Chilton, Nicholas F.; Tuna, Floriana; Lewis, William; McInnes, Eric J.L.; Liddle, Stephen T.

Authors

David M. King

Peter A. Cleaves

Ashley J. Wooles

Benedict. M. Gardner

Nicholas F. Chilton

Floriana Tuna

William Lewis

Eric J.L. McInnes

Stephen T. Liddle



Abstract

Determining the electronic structure of actinide complexes is intrinsically challenging because inter-electronic repulsion, crystal field, and spin–orbit coupling effects can be of similar magnitude. Moreover, such efforts have been hampered by the lack of structurally analogous families of complexes to study. Here we report an improved method to U≡N triple bonds, and assemble a family of uranium(V) nitrides. Along with an isoelectronic oxo, we quantify the electronic structure of this 5f1 family by magnetometry, optical and electron paramagnetic resonance (EPR) spectroscopies and modelling. Thus, we define the relative importance of the spin–orbit and crystal field interactions, and explain the experimentally observed different ground states. We find optical absorption linewidths give a potential tool to identify spin–orbit coupled states, and show measurement of UV···UV super-exchange coupling in dimers by EPR. We show that observed slow magnetic relaxation occurs via two-phonon processes, with no obvious correlation to the crystal field.

Citation

King, D. M., Cleaves, P. A., Wooles, A. J., Gardner, B. M., Chilton, N. F., Tuna, F., …Liddle, S. T. (in press). Molecular and electronic structure of terminal and alkali metal-capped uranium(V) nitride complexes. Nature Communications, 7(13773), https://doi.org/10.1038/ncomms13773

Journal Article Type Article
Acceptance Date Oct 31, 2016
Online Publication Date Oct 20, 2016
Deposit Date Jan 17, 2017
Publicly Available Date Jan 17, 2017
Journal Nature Communications
Electronic ISSN 2041-1723
Publisher Nature Publishing Group
Peer Reviewed Peer Reviewed
Volume 7
Issue 13773
DOI https://doi.org/10.1038/ncomms13773
Public URL http://eprints.nottingham.ac.uk/id/eprint/39893
Publisher URL http://www.nature.com/articles/ncomms13773
Copyright Statement Copyright information regarding this work can be found at the following address: http://creativecommons.org/licenses/by/4.0

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Copyright Statement
Copyright information regarding this work can be found at the following address: http://creativecommons.org/licenses/by/4.0





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