Welcome to the new version of CaltechAUTHORS. Login is currently restricted to library staff. If you notice any issues, please email coda@library.caltech.edu
Published January 2015 | Published
Journal Article Open

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

Files

Breshears_2015p49.pdf
Files (854.5 kB)
Name Size Download all
md5:cccafd1d193600fd72aa6ccf0d338075
854.5 kB Preview Download

Additional details

Created:
August 22, 2023
Modified:
October 20, 2023