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Mixed-Valence NpV/AnVI Molybdate Complexes with Single-Charge Outer-Sphere Cations.

Mikhail S Grigoriev1, Iraida A Charushnikova1, Nina A Budantseva1

  • 1Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Moscow 119071, Russian Federation.

Inorganic Chemistry
|July 28, 2023
PubMed
Summary

Five new mixed-valence neptunium/actinide molybdates were synthesized and structurally characterized. These compounds exhibit diverse structures, including anionic layers and 3D frameworks, with pentagonal bipyramidal coordination for Np and An atoms.

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Area of Science:

  • Inorganic Chemistry
  • Radiochemistry
  • Materials Science

Background:

  • Mixed-valence actinide compounds are crucial for understanding complex electronic and structural properties.
  • Molybdates offer a versatile framework for incorporating various metal ions, including actinides.

Purpose of the Study:

  • To synthesize and characterize novel mixed-valence neptunium (Np) and actinide (An) molybdates.
  • To elucidate the structural diversity and coordination chemistry of these new compounds.
  • To investigate the structural basis of mixed-valence states in actinide molybdates.

Main Methods:

  • Synthesis of five new mixed-valence NpV/AnVI molybdates.
  • Single-crystal X-ray diffraction for structural characterization.
  • UV-visible and Infrared (IR) spectroscopy for chemical analysis.

Main Results:

  • Five compounds with compositions [C(NH2)3]3[(NpVO2)(NpVIO2)(MoO4)3(H2O)]·H2O (1), [C(NH2)3]3[(NpVO2)(NpVIO2)(MoO4)3(H2O)]·3H2O (2), Na3[(NpVO2)(PuVIO2)(MoO4)3(H2O)]·nH2O (3), Na6[(NpVO2)2(UVIO2)(MoO4)5]·13H2O (4), and LiNa2[(NpVO2)(NpVIO2)2(MoO4)4(H2O)]·4H2O (5) were synthesized.
  • The NpV and AnVI atoms exhibit pentagonal bipyramidal coordination polyhedra.
  • Structures 1-3 feature anionic layers with varying arrangements, while structure 4 also contains anionic layers with a different composition. Compound 5 displays a 3D structure.

Conclusions:

  • The study successfully synthesized and characterized novel mixed-valence neptunium and actinide molybdates.
  • The diverse structural motifs highlight the versatility of molybdate frameworks in accommodating different actinide oxidation states.
  • Spectroscopic data provide further characterization of these unique inorganic compounds.