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Incipient class II mixed valency in a plutonium solid-state compound

Journal Article · · Nature Chemistry
DOI:https://doi.org/10.1038/nchem.2777· OSTI ID:2346155
 [1];  [2];  [2];  [2];  [3];  [2];  [2];  [2];  [4];  [3]
  1. Florida State Univ., Tallahassee, FL (United States); Florida State University
  2. Florida State Univ., Tallahassee, FL (United States)
  3. Florida State Univ., Tallahassee, FL (United States). National High Magnetic Field Lab. (MagLab)
  4. Institut National des Sciences Appliquées (France)
+ Show Author Affiliations

Electron transfer in mixed-valent transition-metal complexes, clusters and materials is ubiquitous in both natural and synthetic systems. The degree to which intervalence charge transfer (IVCT) occurs, dependent on the degree of delocalization, places these within class II or III of the Robin–Day system. In contrast to the d-block, compounds of f-block elements typically exhibit class I behaviour (no IVCT) because of localization of the valence electrons and poor spatial overlap between metal and ligand orbitals. Here, in this paper, we report experimental and computational evidence for delocalization of 5f electrons in the mixed-valent PuIII/PuIV solid-state compound, Pu3(DPA)5(H2O)2 (DPA = 2,6-pyridinedicarboxylate). The properties of this compound are benchmarked by the pure PuIII and PuIV dipicolinate complexes, [PuIII(DPA)(H2O)4]Br and PuIV(DPA)2(H2O)3·3H2O, as well as by a second mixed-valent compound, PuIII[PuIV(DPA)3H0.5]2, that falls into class I instead. Metal-to-ligand charge transfer is involved in both the formation of Pu3(DPA)5(H2O)2 and in the IVCT.

Research Organization:
Florida State Univ., Tallahassee, FL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0010677; SC0010677
OSTI ID:
2346155
Alternate ID(s):
OSTI ID: 1535050
Journal Information:
Nature Chemistry, Journal Name: Nature Chemistry Journal Issue: 9 Vol. 9; ISSN 1755-4330
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English

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Origins of the odd optical observables in plutonium and americium tungstates journal January 2019

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