Open AccessIn situ beam reduction of Pu(IV) and Bk(IV) as a route to trivalent transuranic coordination complexes with hydroxypyridinone chelators
Author(s) -
Carter Korey P.,
Wacker Jennifer N.,
Smith Kurt F.,
Deblonde Gauthier J.-P.,
Moreau Liane M.,
Rees Julian A.,
Booth Corwin H.,
Abergel Rebecca J.
Publication year - 2022
Publication title -
journal of synchrotron radiation
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.172
H-Index - 99
ISSN - 1600-5775
DOI - 10.1107/s1600577522000200
Subject(s) - xanes , actinide , x ray absorption spectroscopy , chemistry , oxidation state , extended x ray absorption fine structure , plutonium , absorption spectroscopy , radiochemistry , crystallography , spectroscopy , inorganic chemistry , metal , organic chemistry , physics , quantum mechanics
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—O HOPO 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 5 f covalency and heterogeneity across the actinide series.