From yellow to black

Dramatic changes between cerium(IV) and plutonium(IV) molybdates

Justin N. Cross, Patrick M. Duncan, Eric Villa, Matthew J. Polinski, Jean Marie Babo, Evgeny V. Alekseev, Corwin H. Booth, Thomas E. Albrecht-Schmitt

Research output: Contribution to journalArticle

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Abstract

Hydrothermal reactions of CeCl3 and PuCl3 with MoO3 and Cs2CO3 yield surprisingly different results. Ce3Mo6O24(H2O)4 crystallizes as bright yellow plates (space group C2/c, a = 12.7337(7) Å, b = 22.1309(16) Å, c = 7.8392(4) Å, β = 96.591(4), V = 2194.6(2) Å3), whereas CsPu3Mo6O 24(H2O) crystallizes as semiconducting black-red plates (space group C2/c, a = 12.633(5) Å, b = 21.770(8) Å, c = 7.743(7) Å, β = 96.218(2), V = 2117(2) Å3). The topologies of the two compounds are similar, with channel structures built from disordered Mo(VI) square pyramids and (RE)O8 square antiprisms (RE = Ce(IV), Pu(IV)). However, the Pu(IV) compound contains Cs+ in its channels, while the channels in Ce3Mo6O24(H 2O)4 contain water molecules. Disorder and an ambiguous oxidation state of Mo lead to the formula CsPu3Mo6O 24(H2O), where one Mo site is Mo(V) and the rest are Mo(VI). X-ray absorption near-edge structure (XANES) experiments were performed to investigate the source of the black color of CsPu3Mo 6O24(H2O). These experiments revealed Pu to be tetravalent, while the strong pre-edge absorption from the distorted molybdate anions leaves the oxidation state ambiguous between Mo(V) and Mo(VI).

Original languageEnglish
Pages (from-to)2769-2775
Number of pages7
JournalJournal of the American Chemical Society
Volume135
Issue number7
DOIs
StatePublished - Feb 20 2013
Externally publishedYes

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Cerium
Plutonium
Oxidation
X ray absorption
Anions
Negative ions
Color
Experiments
Topology
X-Rays
Hydrogen
Molecules
Water
molybdate
cerous chloride
molybdenum trioxide

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Cross, J. N., Duncan, P. M., Villa, E., Polinski, M. J., Babo, J. M., Alekseev, E. V., ... Albrecht-Schmitt, T. E. (2013). From yellow to black: Dramatic changes between cerium(IV) and plutonium(IV) molybdates. Journal of the American Chemical Society, 135(7), 2769-2775. https://doi.org/10.1021/ja311910h

From yellow to black : Dramatic changes between cerium(IV) and plutonium(IV) molybdates. / Cross, Justin N.; Duncan, Patrick M.; Villa, Eric; Polinski, Matthew J.; Babo, Jean Marie; Alekseev, Evgeny V.; Booth, Corwin H.; Albrecht-Schmitt, Thomas E.

In: Journal of the American Chemical Society, Vol. 135, No. 7, 20.02.2013, p. 2769-2775.

Research output: Contribution to journalArticle

Cross, JN, Duncan, PM, Villa, E, Polinski, MJ, Babo, JM, Alekseev, EV, Booth, CH & Albrecht-Schmitt, TE 2013, 'From yellow to black: Dramatic changes between cerium(IV) and plutonium(IV) molybdates', Journal of the American Chemical Society, vol. 135, no. 7, pp. 2769-2775. https://doi.org/10.1021/ja311910h
Cross, Justin N. ; Duncan, Patrick M. ; Villa, Eric ; Polinski, Matthew J. ; Babo, Jean Marie ; Alekseev, Evgeny V. ; Booth, Corwin H. ; Albrecht-Schmitt, Thomas E. / From yellow to black : Dramatic changes between cerium(IV) and plutonium(IV) molybdates. In: Journal of the American Chemical Society. 2013 ; Vol. 135, No. 7. pp. 2769-2775.
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title = "From yellow to black: Dramatic changes between cerium(IV) and plutonium(IV) molybdates",
abstract = "Hydrothermal reactions of CeCl3 and PuCl3 with MoO3 and Cs2CO3 yield surprisingly different results. Ce3Mo6O24(H2O)4 crystallizes as bright yellow plates (space group C2/c, a = 12.7337(7) {\AA}, b = 22.1309(16) {\AA}, c = 7.8392(4) {\AA}, β = 96.591(4), V = 2194.6(2) {\AA}3), whereas CsPu3Mo6O 24(H2O) crystallizes as semiconducting black-red plates (space group C2/c, a = 12.633(5) {\AA}, b = 21.770(8) {\AA}, c = 7.743(7) {\AA}, β = 96.218(2), V = 2117(2) {\AA}3). The topologies of the two compounds are similar, with channel structures built from disordered Mo(VI) square pyramids and (RE)O8 square antiprisms (RE = Ce(IV), Pu(IV)). However, the Pu(IV) compound contains Cs+ in its channels, while the channels in Ce3Mo6O24(H 2O)4 contain water molecules. Disorder and an ambiguous oxidation state of Mo lead to the formula CsPu3Mo6O 24(H2O), where one Mo site is Mo(V) and the rest are Mo(VI). X-ray absorption near-edge structure (XANES) experiments were performed to investigate the source of the black color of CsPu3Mo 6O24(H2O). These experiments revealed Pu to be tetravalent, while the strong pre-edge absorption from the distorted molybdate anions leaves the oxidation state ambiguous between Mo(V) and Mo(VI).",
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AU - Cross, Justin N.

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AU - Polinski, Matthew J.

AU - Babo, Jean Marie

AU - Alekseev, Evgeny V.

AU - Booth, Corwin H.

AU - Albrecht-Schmitt, Thomas E.

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N2 - Hydrothermal reactions of CeCl3 and PuCl3 with MoO3 and Cs2CO3 yield surprisingly different results. Ce3Mo6O24(H2O)4 crystallizes as bright yellow plates (space group C2/c, a = 12.7337(7) Å, b = 22.1309(16) Å, c = 7.8392(4) Å, β = 96.591(4), V = 2194.6(2) Å3), whereas CsPu3Mo6O 24(H2O) crystallizes as semiconducting black-red plates (space group C2/c, a = 12.633(5) Å, b = 21.770(8) Å, c = 7.743(7) Å, β = 96.218(2), V = 2117(2) Å3). The topologies of the two compounds are similar, with channel structures built from disordered Mo(VI) square pyramids and (RE)O8 square antiprisms (RE = Ce(IV), Pu(IV)). However, the Pu(IV) compound contains Cs+ in its channels, while the channels in Ce3Mo6O24(H 2O)4 contain water molecules. Disorder and an ambiguous oxidation state of Mo lead to the formula CsPu3Mo6O 24(H2O), where one Mo site is Mo(V) and the rest are Mo(VI). X-ray absorption near-edge structure (XANES) experiments were performed to investigate the source of the black color of CsPu3Mo 6O24(H2O). These experiments revealed Pu to be tetravalent, while the strong pre-edge absorption from the distorted molybdate anions leaves the oxidation state ambiguous between Mo(V) and Mo(VI).

AB - Hydrothermal reactions of CeCl3 and PuCl3 with MoO3 and Cs2CO3 yield surprisingly different results. Ce3Mo6O24(H2O)4 crystallizes as bright yellow plates (space group C2/c, a = 12.7337(7) Å, b = 22.1309(16) Å, c = 7.8392(4) Å, β = 96.591(4), V = 2194.6(2) Å3), whereas CsPu3Mo6O 24(H2O) crystallizes as semiconducting black-red plates (space group C2/c, a = 12.633(5) Å, b = 21.770(8) Å, c = 7.743(7) Å, β = 96.218(2), V = 2117(2) Å3). The topologies of the two compounds are similar, with channel structures built from disordered Mo(VI) square pyramids and (RE)O8 square antiprisms (RE = Ce(IV), Pu(IV)). However, the Pu(IV) compound contains Cs+ in its channels, while the channels in Ce3Mo6O24(H 2O)4 contain water molecules. Disorder and an ambiguous oxidation state of Mo lead to the formula CsPu3Mo6O 24(H2O), where one Mo site is Mo(V) and the rest are Mo(VI). X-ray absorption near-edge structure (XANES) experiments were performed to investigate the source of the black color of CsPu3Mo 6O24(H2O). These experiments revealed Pu to be tetravalent, while the strong pre-edge absorption from the distorted molybdate anions leaves the oxidation state ambiguous between Mo(V) and Mo(VI).

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