Comparative investigation of N donor ligand-lanthanide complexes from the metal and ligand point of view
International audience N-donor ligands such as n-Pr-BTP (2,6-bis(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine) studied here preferentially bind An(III) over Ln(III) in liquid-liquid separation of trivalent ac-tinides from spent nuclear fuel. The chemical and physical processes responsible for this selec...
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ftunivnantes:oai:HAL:hal-01572871v1 2023-05-15T17:53:54+02:00 Comparative investigation of N donor ligand-lanthanide complexes from the metal and ligand point of view Pruessmann, T. Denecke, M. A. Geist, A. Rothe, J. Lindqvist-Reis, P. Loeble, M. Breher, F. Batchelor, D. R. Apostolidis, C. Walter, O. Caliebe, W. Kvashnina, K. Jorissen, K. Kas, J. J. Rehr, J. J. Vitova, T. Karlsruhe Inst Technol, POB 3640, D-76021 Karlsruhe, Germany JRC Institute for Transuranium Elements Karlsruhe (ITU ) European Commission - Joint Research Centre Karlsruhe (JRC) HASYLAB, D-22603 Hamburg, Germany European Synchrotron Radiation Facility (ESRF) Department of Physics Seattle University of Washington Seattle Beijing, China 2012-07-22 https://hal.archives-ouvertes.fr/hal-01572871 https://hal.archives-ouvertes.fr/hal-01572871/document https://hal.archives-ouvertes.fr/hal-01572871/file/J_Phys_Conf_Series_430_012115.pdf https://doi.org/10.1088/1742-6596/430/1/012115 en eng HAL CCSD info:eu-repo/semantics/altIdentifier/doi/10.1088/1742-6596/430/1/012115 hal-01572871 https://hal.archives-ouvertes.fr/hal-01572871 https://hal.archives-ouvertes.fr/hal-01572871/document https://hal.archives-ouvertes.fr/hal-01572871/file/J_Phys_Conf_Series_430_012115.pdf doi:10.1088/1742-6596/430/1/012115 info:eu-repo/semantics/OpenAccess 15th International Conference on X-Ray Absorption Fine Structure (XAFS) https://hal.archives-ouvertes.fr/hal-01572871 15th International Conference on X-Ray Absorption Fine Structure (XAFS), Jul 2012, Beijing, China. 5 p., ⟨10.1088/1742-6596/430/1/012115⟩ [PHYS]Physics [physics] info:eu-repo/semantics/conferenceObject Conference papers 2012 ftunivnantes https://doi.org/10.1088/1742-6596/430/1/012115 2022-09-20T23:06:41Z International audience N-donor ligands such as n-Pr-BTP (2,6-bis(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine) studied here preferentially bind An(III) over Ln(III) in liquid-liquid separation of trivalent ac-tinides from spent nuclear fuel. The chemical and physical processes responsible for this selectivity are not yet well understood. We present systematic comparative near-edge X-ray absorption structure (XANES) spectroscopy investigations at the Gd L-3 edge of [GdBTP3](NO3)(3), [Gd(BTP)(3)](OTf)(3), Gd(NO3)(3), Gd(OTf)(3) and N K edge of [Gd(BTP)(3)](NO3)(3), Gd(NO3)(3) complexes. The pre-edge absorption resonance in Gd L3 edge high-energy resolution X-ray absorption near edge structure spectra (HR-XANES) is explained as arising from 2p(3/2) -> 4f/5d electronic transitions by calculations with the FEFF9.5 code. Experimental evidence is found for higher electronic density on Gd in [Gd(BTP)(3)](NO3)(3) and [Gd(BTP)(3)](OTf)(3) compared to Gd in Gd(NO3)(3) and Gd(OTf)(3), and on N in [Gd(BTP)(3)](NO3)(3) compared to n-Pr-BTP. The origin of the pre-edge structure in the N K edge XANES is explained by density functional theory (DFT) with the ORCA code. Results at the N K edge suggest a change in ligand orbital occupancies and mixing upon complexation but further work is necessary to interpret observed spectral variations Conference Object Orca Université de Nantes: HAL-UNIV-NANTES Journal of Physics: Conference Series 430 012115 |
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Open Polar |
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Université de Nantes: HAL-UNIV-NANTES |
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ftunivnantes |
language |
English |
topic |
[PHYS]Physics [physics] |
spellingShingle |
[PHYS]Physics [physics] Pruessmann, T. Denecke, M. A. Geist, A. Rothe, J. Lindqvist-Reis, P. Loeble, M. Breher, F. Batchelor, D. R. Apostolidis, C. Walter, O. Caliebe, W. Kvashnina, K. Jorissen, K. Kas, J. J. Rehr, J. J. Vitova, T. Comparative investigation of N donor ligand-lanthanide complexes from the metal and ligand point of view |
topic_facet |
[PHYS]Physics [physics] |
description |
International audience N-donor ligands such as n-Pr-BTP (2,6-bis(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine) studied here preferentially bind An(III) over Ln(III) in liquid-liquid separation of trivalent ac-tinides from spent nuclear fuel. The chemical and physical processes responsible for this selectivity are not yet well understood. We present systematic comparative near-edge X-ray absorption structure (XANES) spectroscopy investigations at the Gd L-3 edge of [GdBTP3](NO3)(3), [Gd(BTP)(3)](OTf)(3), Gd(NO3)(3), Gd(OTf)(3) and N K edge of [Gd(BTP)(3)](NO3)(3), Gd(NO3)(3) complexes. The pre-edge absorption resonance in Gd L3 edge high-energy resolution X-ray absorption near edge structure spectra (HR-XANES) is explained as arising from 2p(3/2) -> 4f/5d electronic transitions by calculations with the FEFF9.5 code. Experimental evidence is found for higher electronic density on Gd in [Gd(BTP)(3)](NO3)(3) and [Gd(BTP)(3)](OTf)(3) compared to Gd in Gd(NO3)(3) and Gd(OTf)(3), and on N in [Gd(BTP)(3)](NO3)(3) compared to n-Pr-BTP. The origin of the pre-edge structure in the N K edge XANES is explained by density functional theory (DFT) with the ORCA code. Results at the N K edge suggest a change in ligand orbital occupancies and mixing upon complexation but further work is necessary to interpret observed spectral variations |
author2 |
Karlsruhe Inst Technol, POB 3640, D-76021 Karlsruhe, Germany JRC Institute for Transuranium Elements Karlsruhe (ITU ) European Commission - Joint Research Centre Karlsruhe (JRC) HASYLAB, D-22603 Hamburg, Germany European Synchrotron Radiation Facility (ESRF) Department of Physics Seattle University of Washington Seattle |
format |
Conference Object |
author |
Pruessmann, T. Denecke, M. A. Geist, A. Rothe, J. Lindqvist-Reis, P. Loeble, M. Breher, F. Batchelor, D. R. Apostolidis, C. Walter, O. Caliebe, W. Kvashnina, K. Jorissen, K. Kas, J. J. Rehr, J. J. Vitova, T. |
author_facet |
Pruessmann, T. Denecke, M. A. Geist, A. Rothe, J. Lindqvist-Reis, P. Loeble, M. Breher, F. Batchelor, D. R. Apostolidis, C. Walter, O. Caliebe, W. Kvashnina, K. Jorissen, K. Kas, J. J. Rehr, J. J. Vitova, T. |
author_sort |
Pruessmann, T. |
title |
Comparative investigation of N donor ligand-lanthanide complexes from the metal and ligand point of view |
title_short |
Comparative investigation of N donor ligand-lanthanide complexes from the metal and ligand point of view |
title_full |
Comparative investigation of N donor ligand-lanthanide complexes from the metal and ligand point of view |
title_fullStr |
Comparative investigation of N donor ligand-lanthanide complexes from the metal and ligand point of view |
title_full_unstemmed |
Comparative investigation of N donor ligand-lanthanide complexes from the metal and ligand point of view |
title_sort |
comparative investigation of n donor ligand-lanthanide complexes from the metal and ligand point of view |
publisher |
HAL CCSD |
publishDate |
2012 |
url |
https://hal.archives-ouvertes.fr/hal-01572871 https://hal.archives-ouvertes.fr/hal-01572871/document https://hal.archives-ouvertes.fr/hal-01572871/file/J_Phys_Conf_Series_430_012115.pdf https://doi.org/10.1088/1742-6596/430/1/012115 |
op_coverage |
Beijing, China |
genre |
Orca |
genre_facet |
Orca |
op_source |
15th International Conference on X-Ray Absorption Fine Structure (XAFS) https://hal.archives-ouvertes.fr/hal-01572871 15th International Conference on X-Ray Absorption Fine Structure (XAFS), Jul 2012, Beijing, China. 5 p., ⟨10.1088/1742-6596/430/1/012115⟩ |
op_relation |
info:eu-repo/semantics/altIdentifier/doi/10.1088/1742-6596/430/1/012115 hal-01572871 https://hal.archives-ouvertes.fr/hal-01572871 https://hal.archives-ouvertes.fr/hal-01572871/document https://hal.archives-ouvertes.fr/hal-01572871/file/J_Phys_Conf_Series_430_012115.pdf doi:10.1088/1742-6596/430/1/012115 |
op_rights |
info:eu-repo/semantics/OpenAccess |
op_doi |
https://doi.org/10.1088/1742-6596/430/1/012115 |
container_title |
Journal of Physics: Conference Series |
container_volume |
430 |
container_start_page |
012115 |
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1766161614092894208 |