Structure and spectroscopy of uranyl and thorium complexes with substituted phosphine oxide ligands
Abstract
Phosphine oxide ligands are important in the chemistry of the nuclear fuel cycle. We have synthesized and characterized a series of phosphine oxide ligands with polycyclic aromatic hydrocarbon (PAH) groups to enhance the spectroscopic features of uranyl, UO_2^(2+), and to make detection more efficient. Complexation of OPPh_2R, R = C_(10)H_7 (naphthyl); C_(14)H_9 (phenanthrenyl); C_(14)H_9 (anthracenyl); and C_(16)H_9 (pyrenyl), to UO_2(NO_3)_2 afforded the eight-coordinate complexes, UO_2(NO_3)_2(OPPh_2R)_2. An eleven-coordinate complex, Th(NO_3)_4[OPPh_2(C_(14)H_9)]_3, C_(14)H_9 = phenanthrenyl, was structurally characterized, and was found to be the first thorium compound isolated with three phosphine oxide ligands bound. The phosphine oxide ligands were not fluorescent but the anthracenyl-substituted ligand showed broad, red-shifted emission at approximately 50 nm relative to typical anthracene, making this ligand set a possibility for use in detection. The synthesis and spectroscopy of the uranyl and thorium complexes are presented.
Additional Information
© 2014 by Walter de Gruyter GmbH. Received May 27, 2014; accepted September 11, 2014. This material is based upon work supported by the U.S. Department of Homeland Security under Grant Award Number, 2012-DN-130-NF0001-02. The views and conclusions contained in this document are those of the authors and should not be interpreted as necessarily representing the official policies, either expressed or implied, of the U.S. Department of Homeland Security. We also acknowledge the Nuclear Regulatory Commission (NRC) Faculty Development Award for financial support.Attached Files
Published - Breshears_2015p49.pdf
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Additional details
- Eprint ID
- 55069
- Resolver ID
- CaltechAUTHORS:20150220-141447707
- 2012-DN-130-NF0001-02
- Department of Homeland Security
- Nuclear Regulatory Commission (NRC)
- Created
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2015-02-23Created from EPrint's datestamp field
- Updated
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2021-11-10Created from EPrint's last_modified field