Incorporation of Mn(II) and Fe(II) into uranyl carboxyphosphonates

Journal Article · · Crystal Growth and Design

DOI:https://doi.org/10.1021/cg200127a· OSTI ID:1066002

Alsobrook, Andrea N. ^[1]; Alekseev, Evgeny V. ^[2]; Depmeier, Wulf ^[2]; Albrecht-Schmitt, Thomas E. ^[1]

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1. Univ. of Notre Dame, IN (United States). Dept. of Civil Engineering and Geological Sciences and Dept. of Chemistry and Biochemistry
2. Univ. zu Kiel (Germany)

Five heterobimetallic U(VI)/M(II) (M = Mn, Fe) carboxyphosphonates have been synthesized under mild hydrothermal conditions by reacting UO₃, triethyl phosphonoacetate, with either Mn(II) or Fe(II) acetate. The manganese reactions yield Mn₂[(UO₂)₆(PO₃CH₂CO₂)₃O₃(OH)(H₂O)₂]·16H₂O (MnUPAA-1) and [Mn(H₂O)₆][Mn(H₂O)₅Mn₂(UO₂)₅(PO₃CH₂CO₂)₆(H₂O)]·5.75H₂O (MnUPAA-2). The addition of boric acid, which lowers the crystallization temperature, allows for the production of a third product, [Mn(H₂O)₄]₂(UO₂)₃(PO₃CH₂CO₂)₂O₂ (MnUPAA-3). The iron-containing reactions yield [Fe(H₂O)₆][UO₂(PO₃CH₂CO₂)]₂·8H₂O (FeUPAA-1) and [Fe(H₂O)₆][UO₂(PO₃CH₂CO₂)H₂O]₂·4H₂O (FeUPAA-2). Four of these five compounds crystallize in low-symmetry space groups; whereas MnUPAA-1 crystallizes in the cubic space group Im3⁻ and possesses a remarkably complex open-framework structure containing both UO₇ pentagonal bipyramids and UO₈ hexagonal bipyramids. MnUPAA-3 adopts a one-dimensional uranium oxide topology that contains both UO₆ tetragonal bipyramids and UO₇ pentagonal bipyramids. The remaining three compounds solely contain UO₇ pentagonal bipyramids.

• Research Organization: Energy Frontier Research Centers (EFRC); Materials Science of Actinides (MSA)
• Sponsoring Organization: USDOE
• DOE Contract Number: SC0001089
• OSTI ID: 1066002
• Journal Information: Crystal Growth and Design, Journal Name: Crystal Growth and Design Journal Issue: 6 Vol. 11; ISSN 1528-7483
• Publisher: American Chemical Society
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
nuclear (including radiation effects)
materials and chemistry by design
synthesis (novel materials)
synthesis (self-assembly)