Synthesis and spectroscopy of new plutonium(III) and -(IV) molybdates: Comparisons of electronic characteristics

Justin N. Cross; Samantha K. Cary; Jared T. Stritzinger; Matthew J. Polinski; Thomas E. Albrecht Schmitt

doi:10.1021/ic403116r

Synthesis and spectroscopy of new plutonium(III) and -(IV) molybdates: Comparisons of electronic characteristics

Justin N. Cross, Samantha K. Cary, Jared T. Stritzinger, Matthew J. Polinski, Thomas E. Albrecht Schmitt

Research output: Contribution to journal › Article › peer-review

8 Scopus citations

Abstract

Synthesis of a plutonium(III) molybdate bromide, PuMoO₄Br(H ₂O), has been accomplished using hydrothermal techniques in an inert-atmosphere glovebox. The compound is green in color, which is in stark contrast to the typical blue color of plutonium(III) complexes. The unusual color arises from the broad charge transfer (CT) spanning from approximately 300 to 500 nm in the UV-vis-near-IR spectra. Repeating the synthesis with an increase in the reaction temperature results in the formation of a plutonium(IV) molybdate, Pu₃Mo₆O₂₄(H₂O) ₂, which also has a broad CT band and red-shifted f-f transitions. Performing an analogous reaction with neodymium produced a completely different product, [Nd(H₂O)₃][NdMo₁₂O₄₂] ·2H₂O, which is built of Silverton-type polyoxometallate clusters.

Original language	English
Pages (from-to)	3148-3152
Number of pages	5
Journal	Inorganic Chemistry
Volume	53
Issue number	6
DOIs	https://doi.org/10.1021/ic403116r
State	Published - Mar 17 2014
Externally published	Yes

Funding

Funders	Funder number
U.S. Department of Energy	DE-SC0001089

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10.1021/ic403116r

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title = "Synthesis and spectroscopy of new plutonium(III) and -(IV) molybdates: Comparisons of electronic characteristics",

abstract = "Synthesis of a plutonium(III) molybdate bromide, PuMoO4Br(H 2O), has been accomplished using hydrothermal techniques in an inert-atmosphere glovebox. The compound is green in color, which is in stark contrast to the typical blue color of plutonium(III) complexes. The unusual color arises from the broad charge transfer (CT) spanning from approximately 300 to 500 nm in the UV-vis-near-IR spectra. Repeating the synthesis with an increase in the reaction temperature results in the formation of a plutonium(IV) molybdate, Pu3Mo6O24(H2O) 2, which also has a broad CT band and red-shifted f-f transitions. Performing an analogous reaction with neodymium produced a completely different product, [Nd(H2O)3][NdMo12O42] ·2H2O, which is built of Silverton-type polyoxometallate clusters.",

author = "Cross, {Justin N.} and Cary, {Samantha K.} and Stritzinger, {Jared T.} and Polinski, {Matthew J.} and {Albrecht Schmitt}, {Thomas E.}",

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T1 - Synthesis and spectroscopy of new plutonium(III) and -(IV) molybdates

T2 - Comparisons of electronic characteristics

AU - Cross, Justin N.

AU - Cary, Samantha K.

AU - Stritzinger, Jared T.

AU - Polinski, Matthew J.

AU - Albrecht Schmitt, Thomas E.

PY - 2014/3/17

Y1 - 2014/3/17

N2 - Synthesis of a plutonium(III) molybdate bromide, PuMoO4Br(H 2O), has been accomplished using hydrothermal techniques in an inert-atmosphere glovebox. The compound is green in color, which is in stark contrast to the typical blue color of plutonium(III) complexes. The unusual color arises from the broad charge transfer (CT) spanning from approximately 300 to 500 nm in the UV-vis-near-IR spectra. Repeating the synthesis with an increase in the reaction temperature results in the formation of a plutonium(IV) molybdate, Pu3Mo6O24(H2O) 2, which also has a broad CT band and red-shifted f-f transitions. Performing an analogous reaction with neodymium produced a completely different product, [Nd(H2O)3][NdMo12O42] ·2H2O, which is built of Silverton-type polyoxometallate clusters.

AB - Synthesis of a plutonium(III) molybdate bromide, PuMoO4Br(H 2O), has been accomplished using hydrothermal techniques in an inert-atmosphere glovebox. The compound is green in color, which is in stark contrast to the typical blue color of plutonium(III) complexes. The unusual color arises from the broad charge transfer (CT) spanning from approximately 300 to 500 nm in the UV-vis-near-IR spectra. Repeating the synthesis with an increase in the reaction temperature results in the formation of a plutonium(IV) molybdate, Pu3Mo6O24(H2O) 2, which also has a broad CT band and red-shifted f-f transitions. Performing an analogous reaction with neodymium produced a completely different product, [Nd(H2O)3][NdMo12O42] ·2H2O, which is built of Silverton-type polyoxometallate clusters.

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JO - Inorganic Chemistry

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Synthesis and spectroscopy of new plutonium(III) and -(IV) molybdates: Comparisons of electronic characteristics

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