Journal article
Synthesis and spectroscopic characterization of actinyl(VI) tetrahalide coordination compounds containing 2, 2′-bipyridine
Inorganica Chimica Acta, Vol.508(C), p.119628
08/01/2020
DOI: 10.1016/j.ica.2020.119628
Abstract
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•Synthesis of three new actinide halide complexes using slow evaporation.•Characterization of the complexes via single crystal X-ray diffraction, Raman spectroscopy, and IR spectroscopy.•Protonation of 2,2′-bipyridine introduces structural changes resulting in increased supramolecular assembly sites.•Calculation of force constants for the uranyl cation provides information on relative bond strength.
A series of three new actinide tetrahalide coordination compounds containing 2,2′-bipyridinium (H2bpy) have been synthesized by room temperature evaporation and characterized via single crystal X-ray diffraction, Raman spectroscopy, and infrared spectroscopy. The solid-state compounds (Np1, U1, and U2) contain the AnO22+ cation coordinated to four halide (chloride or bromide) atoms to form the anionic tetrahalide molecular unit [AnO2X4]2− (X = Cl, Br) and are charge balanced by the 2,2′-bipyridinium cations that engage in electrostatic interactions with the actinyl complex. Np1(N2C10H10)[NpO2Cl4] contains 2,2′-bipyridine in the cis conformation where both the nitrogen atoms are directed towards the [NpO2Cl4]2− monomer. Within U1(N2C10H9)[UO2Cl4], the 2,2′-bipyridine is in a trans conformation, and found in the same orientation in the isomorphous structure U2(N2C10H9)[UO2Br4]. The compounds were further characterized by vibrational spectroscopy with specific interest in the actinyl cation. Raman spectroscopy provided information on the actinyl symmetric stretch (ν1) whereas IR spectroscopy is used to determine the location of the asymmetric stretch (ν3). Spectral similarities are observed between the two isomorphous structures, but slight variations across the series of structures are found to be associated with bipyridine bands in the various conformations. Additional analysis of these vibrational features in U1 and U2 provided information on the actinyl force constants, allowing insight into the relative uranyl bond strength that was compared to similar tetrahalide compounds.
Details
- Title: Subtitle
- Synthesis and spectroscopic characterization of actinyl(VI) tetrahalide coordination compounds containing 2, 2′-bipyridine
- Creators
- Mikaela M PyrchJay M WilliamsMaguire W KasperskiLindsey C ApplegateTori Z Forbes
- Resource Type
- Journal article
- Publication Details
- Inorganica Chimica Acta, Vol.508(C), p.119628
- Publisher
- Elsevier B.V
- DOI
- 10.1016/j.ica.2020.119628
- ISSN
- 0020-1693
- eISSN
- 1873-3255
- Grant note
- DOI: 10.13039/100000015, name: U.S. Department of Energy
- Language
- English
- Date published
- 08/01/2020
- Academic Unit
- Civil and Environmental Engineering; Chemistry; Core Research Facilities
- Record Identifier
- 9984216719102771
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