In situ beam reduction of Pu(IV) and Bk(IV) as a route to trivalent transuranic coordination complexes with hydroxypyridinone chelators

Autor: 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
Jazyk: angličtina
Rok vydání: 2022
Předmět:
Zdroj: Journal of Synchrotron Radiation, Vol 29, Iss 2, Pp 315-322 (2022)
Druh dokumentu: article
ISSN: 1600-5775
16005775
DOI: 10.1107/S1600577522000200
Popis: 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.
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