Molecular and electronic structure of terminal and alkali metal-capped uranium(V) nitride complexes
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 complexe...
| Main Authors: | , , , , , , , , |
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| Format: | Article |
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Nature Publishing Group
2016
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| Online Access: | https://eprints.nottingham.ac.uk/39893/ |
| _version_ | 1848795939906519040 |
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| author | 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. |
| author_facet | 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. |
| author_sort | King, David M. |
| building | Nottingham Research Data Repository |
| collection | Online Access |
| description | 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. |
| first_indexed | 2025-11-14T19:40:04Z |
| format | Article |
| id | nottingham-39893 |
| institution | University of Nottingham Malaysia Campus |
| institution_category | Local University |
| last_indexed | 2025-11-14T19:40:04Z |
| publishDate | 2016 |
| publisher | Nature Publishing Group |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | nottingham-398932020-05-04T18:16:16Z https://eprints.nottingham.ac.uk/39893/ 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. 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. Nature Publishing Group 2016-10-20 Article PeerReviewed King, David M., Cleaves, Peter A., Wooles, Ashley J., Gardner, Benedict. M., Chilton, Nicholas F., Tuna, Floriana, Lewis, William, McInnes, Eric J.L. and Liddle, Stephen T. (2016) Molecular and electronic structure of terminal and alkali metal-capped uranium(V) nitride complexes. Nature Communications, 7 (13773). pp. 1-14. ISSN 2041-1723 http://www.nature.com/articles/ncomms13773 doi:10.1038/ncomms13773 doi:10.1038/ncomms13773 |
| spellingShingle | 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. Molecular and electronic structure of terminal and alkali metal-capped uranium(V) nitride complexes |
| title | Molecular and electronic structure of terminal and alkali metal-capped uranium(V) nitride complexes |
| title_full | Molecular and electronic structure of terminal and alkali metal-capped uranium(V) nitride complexes |
| title_fullStr | Molecular and electronic structure of terminal and alkali metal-capped uranium(V) nitride complexes |
| title_full_unstemmed | Molecular and electronic structure of terminal and alkali metal-capped uranium(V) nitride complexes |
| title_short | Molecular and electronic structure of terminal and alkali metal-capped uranium(V) nitride complexes |
| title_sort | molecular and electronic structure of terminal and alkali metal-capped uranium(v) nitride complexes |
| url | https://eprints.nottingham.ac.uk/39893/ https://eprints.nottingham.ac.uk/39893/ https://eprints.nottingham.ac.uk/39893/ |