Journal article
Influence of heterocyclic N-donors on the structural topologies and vibrational spectra of uranyl selenate phases
Journal of solid state chemistry, Vol.304, p.122619
12/2021
DOI: 10.1016/j.jssc.2021.122619
Abstract
Uranyl (U(VI)O22+) selenate compounds represent a well-studied family of structures with diverse structural arrays. Differences in the overall topology and bonding with the uranyl cation combined with additional intermolecular interactions can lead to variation in the resulting spectroscopic signals. In the current study, we evaluated the structural chemistry and vibrational spectroscopy for uranyl selenates crystallized with heterocyclic N-donors. Five compounds ((C4H12N2)[(UO2)(SeO4)2(H2O)]·H2O (USe_pip), (C4H5N2)2[(UO2)(SeO4)2(H2O)] (USe_pyrdz), (C5H5N)2[(UO2)2(SeO4)3(H2O)] ∙ 3H2O (USe_pyrmd), (H3O)2(C4H5N2)2[(UO2)3(SeO4)5(H2O)]·H2O (USe_pyrz), and (C5H6N)2[(UO2)2(SeO4)3(H2O)] ∙ 3H2O (USe_pyr)) were characterized using X-ray diffraction (single-crystal and powder) and vibrational (Raman and IR) spectroscopy. Two one-dimensional (1-D) chain and three two-dimensional sheet (2-D) topologies were identified and classified based upon previous graphical representations. Overall, the arrangement of the heteroatoms could be linked to the hydrogen bonding network associated with the heterocycles and selenate anions. Vibrational spectra of the solid-state compounds were complex, with multiple bands associated with the uranyl cation, selenate anion, and heteroatoms. The ν1 symmetric stretching band of the uranyl was relatively consistent across all compounds, whereas differences were observed for the ν3 asymmetric band between the 1-D and 2-D structural topologies.
The impacts of hydrogen bonding between heterocyclic amines and uranyl selenate topologies were evaluated using X-ray diffraction and spectroscopic techniques. [Display omitted]
•Synthesis of five new U(VI) selenate complexes with heterocyclic N-donors.•Formation of two 1-D chain and 3 2-D sheet topologies with previously identified graphical representations.•Delineation of hydrogen bonding networks and comparison to other amine-templated uranyl selenate compounds.•Hydrogen bonding between the amine donor and selenate acceptor can lead to rational design of uranyl selenate materials.•Vibrational analysis indicates that the uranyl asymmetric stretch is impacted by hydrogen bonding.
Details
- Title: Subtitle
- Influence of heterocyclic N-donors on the structural topologies and vibrational spectra of uranyl selenate phases
- Creators
- James M WilliamsMikaela M PyrchDaniel K UnruhHaley LightfootTori Z Forbes
- Resource Type
- Journal article
- Publication Details
- Journal of solid state chemistry, Vol.304, p.122619
- DOI
- 10.1016/j.jssc.2021.122619
- ISSN
- 0022-4596
- eISSN
- 1095-726X
- Publisher
- Elsevier Inc
- Grant note
- DOI: 10.13039/100006151, name: Basic Energy Sciences, award: DE-SC0021420
- Language
- English
- Date published
- 12/2021
- Academic Unit
- Civil and Environmental Engineering; Core Research Facilities; Chemistry
- Record Identifier
- 9984216601502771
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