Academic Journal
In situ beam reduction of Pu(IV) and Bk(IV) as a route to trivalent transuranic coordination complexes with hydroxypyridinone chelators
| Title: | In situ beam reduction of Pu(IV) and Bk(IV) as a route to trivalent transuranic coordination complexes with hydroxypyridinone chelators |
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| Authors: | Korey P. Carter, Jennifer N. Wacker, Kurt F. Smith, Gauthier J.-P. Deblonde, Liane M. Moreau, Julian A. Rees, Corwin H. Booth, Rebecca J. Abergel |
| Source: | Journal of Synchrotron Radiation, Vol 29, Iss 2, Pp 315-322 (2022) |
| Publisher Information: | International Union of Crystallography, 2022. |
| Publication Year: | 2022 |
| Collection: | LCC:Nuclear and particle physics. Atomic energy. Radioactivity LCC:Crystallography |
| Subject Terms: | plutonium, berkelium, coordination complexes, x-ray absorption spectroscopy, periodicity, Nuclear and particle physics. Atomic energy. Radioactivity, QC770-798, Crystallography, QD901-999 |
| More Details: | The solution-state interactions of plutonium and berkelium with the octadentate chelator 3,4,3-LI(1,2-HOPO) (343-HOPO) were investigated and characterized by X-ray absorption spectroscopy, which revealed in situ reductive decomposition of the tetravalent species of both actinide metals to yield Pu(III) and Bk(III) coordination complexes. X-ray absorption near-edge structure (XANES) measurements were the first indication of in situ synchrotron redox chemistry as the Pu threshold and white-line position energies for Pu-343-HOPO were in good agreement with known diagnostic Pu(III) species, whereas Bk-343-HOPO results were found to mirror the XANES behavior of Bk(III)-DTPA. Extended X-ray absorption fine structure results revealed An—OHOPO bond distances of 2.498 (5) and 2.415 (2) Å for Pu and Bk, respectively, which match well with bond distances obtained for trivalent actinides and 343-HOPO via density functional theory calculations. Pu(III)- and Bk(III)-343-HOPO data also provide initial insight into actinide periodicity as they can be compared with previous results with Am(III)-, Cm(III)-, Cf(III)-, and Es(III)-343-HOPO, which indicate there is likely an increase in 5f covalency and heterogeneity across the actinide series. |
| Document Type: | article |
| File Description: | electronic resource |
| Language: | English |
| ISSN: | 1600-5775 16005775 |
| Relation: | http://scripts.iucr.org/cgi-bin/paper?S1600577522000200; https://doaj.org/toc/1600-5775 |
| DOI: | 10.1107/S1600577522000200 |
| Access URL: | https://doaj.org/article/751334af381145b599e45e43c75d7049 |
| Accession Number: | edsdoj.751334af381145b599e45e43c75d7049 |
| Database: | Directory of Open Access Journals |
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| ISSN: | 16005775 |
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| DOI: | 10.1107/S1600577522000200 |
| Published in: | Journal of Synchrotron Radiation |
| Language: | English |