The crystal and coordination chemistry of neptunium in all its oxidation states: An expanded structural hierarchy of neptunium compounds

Gilson, Sara E.; Burns, Peter C.

doi:10.1016/j.ccr.2021.213994

Cited by 28 publications

(34 citation statements)

References 266 publications

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“…23 With increased concentrations, they noted up to six additional vibrational modes, but did not assign them to additional neptunyl species within the solution. Since these initial studies, AAIs have been readily observed within solid-state materials and a recent review by Gilson and Burns 30 noted that 48% of the reported Np(V) compounds were built on this bonding motif. Evaluation of AAI topologies for the Np(V) solids suggests that the extended arrays are composed of repeating motifs of dimeric, trimeric, and tetrameric subunits (Fig.…”

Section: Introductionmentioning

confidence: 99%

Use of vibrational spectroscopy to identify the formation of neptunyl–neptunyl interactions: a paired density functional theory and Raman spectroscopy study

et al. 2022

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Section: Introductionmentioning

confidence: 99%

Use of vibrational spectroscopy to identify the formation of neptunyl–neptunyl interactions: a paired density functional theory and Raman spectroscopy study

et al. 2022

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“…The observed chains of edge-sharing pentagonal bipyramids are common to several actinyl phases. 20,25 In the structural classification of uranium anion−sheet topologies, these edgeshared chains form one of the fundamental subunits of the topology. 31 However, these chains are often bridged together to form two-dimensional sheets through other anions, as is widely observed in uranium(VI) crystal chemistry, such as in the case of the uranyl silicate uranophane.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Infinite chains of pentagonal bipyramids are also common to neptunium(V) structures, as recently reviewed by Gilson and Burns. 20 The infinite zig-zagging chains observed here are identical with those formed by the edge-sharing, through the chloride bridges, pentagonal bipyramids observed in Cs[NpO 2 Cl 2 ]-H 2 O. 32 In the potassium structure, each chain of neptunium polyhedra is separated from the others by corresponding chains of K + counterions, which are bridged via interactions with the neptunium oxo and hydroxo groups along with two water molecules in the interstitial space forming distorted octahedra.…”

Section: ■ Introductionmentioning

confidence: 99%

Reactions of Neptunium(V) in Alkali-Metal Hydroxides

2021

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The preparation of two new neptunium hydroxide compounds synthesized in concentrated potassium and rubidium hydroxide is reported. The phases K 4 [(NpO 2 ) 2 (OH) 6 ]•4H 2 O and Rb 4 [(NpO 2 ) 4 (OH) 8 ]•2H 2 O were prepared and their chemical structures determined using single-crystal X-ray diffraction. Raman spectra of the compounds are also presented. The newly synthesized phases are structurally related to Np 2 O 5 and Na[NpO 2 (OH) 2 ]. The potassium-containing phase reported here consists of infinite chains of edge-sharing neptunium hydroxide polyhedra but lacking the cation−cation interactions (CCIs) observed in Np 2 O 5 and Na[NpO 2 (OH) 2 ]. Rb 4 [(NpO 2 ) 4 (OH) 8 ]•2H 2 O is a an expanded three-dimensional framework based on NpO 2 + CCIs like those observed in Np 2 O 5 and Na[NpO 2 (OH) 2 ]. Together these complexes begin to develop a structural series of neptunium(V) oxides and hydroxides of varying dimensionalities within the alkali-metal series. The potential roles of the alkali-metal cations and neptunyl(V) CCIs in directing the resulting structures are discussed.

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“…The +5 oxidation state of neptunium is more stable under oxidizing conditions than this oxidation state of any other actinide. AAIs are observed in approximately 48% of its extended crystal structures, resulting in a class of neptunium compounds distinct from those of any other actinide element . The unique chemistry of Np(V) may be exploited to synthesize MOFs containing unprecedented connectivity and unusual topologies and properties …”

mentioning

confidence: 99%

“…AAIs are observed in approximately 48% of its extended crystal structures, resulting in a class of neptunium compounds distinct from those of any other actinide element. 23 The unique chemistry of Np(V) may be exploited to synthesize MOFs containing unprecedented connectivity and unusual topologies and properties. 16 MOFs are increasingly being investigated for use in highly radioactive environments, in which their radiation resistance is essential.…”

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confidence: 99%

Unusual Metal–Organic Framework Topology and Radiation Resistance through Neptunyl Coordination Chemistry

et al. 2021

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A Np(V) neptunyl metal–organic framework (MOF) with rod-shaped secondary building units was synthesized, characterized, and irradiated with γ rays. Single-crystal X-ray diffraction data revealed an anionic framework containing infinite helical chains of actinyl–actinyl interaction (AAI)-connected neptunyl ions linked together through tetratopic tetrahedral organic ligands (NSM). NSM exhibits an unprecedented net, demonstrating that AAIs may be exploited to give new MOFs and new topologies. To probe its radiation stability, we undertook the first irradiation study of a transuranic MOF and its organic linker building block using high doses of γ rays. Diffraction and spectroscopic data demonstrated that the radiation resistance of NSM is greater than that of its linker building block alone. Approximately 6 MGy of irradiation begins to induce notable changes in the long- and short-range order of the framework, whereas 3 MGy of irradiation induces total X-ray amorphization and changes in the local vibrational bands of the linker building block.

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The crystal and coordination chemistry of neptunium in all its oxidation states: An expanded structural hierarchy of neptunium compounds

Cited by 28 publications

References 266 publications

Use of vibrational spectroscopy to identify the formation of neptunyl–neptunyl interactions: a paired density functional theory and Raman spectroscopy study

Use of vibrational spectroscopy to identify the formation of neptunyl–neptunyl interactions: a paired density functional theory and Raman spectroscopy study

Reactions of Neptunium(V) in Alkali-Metal Hydroxides

Unusual Metal–Organic Framework Topology and Radiation Resistance through Neptunyl Coordination Chemistry

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