The Redox Behavior of Rare Earth Elements

Cicconi, Maria Rita; Losq, Charles Le; Henderson, Grant S.; Neuville, Daniel R.

doi:10.1002/9781119473206.ch19

Cited by 7 publications

(4 citation statements)

References 89 publications

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“…While these metals are all rare earth elements, there can be marked differences in coordination number and the nature of metal–ligand interactions . Additionally, redox potential differences between these metals can lead to different properties. , Our group recently reported the first example of Group 3 metals for alkyl–alkyl cross-coupling catalysis enabled by a redox-active ligand (Figure a) . Cross-coupling is incredibly important due to its necessity to construct molecules of medicinal importance that have C(sp 3 ) character. − Follow up studies correlated redox potential across different Group 3 and 4 d 0 metals with rates of reactivity .…”

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confidence: 99%

“…31 Additionally, redox potential differences between these metals can lead to different properties. 32,33 Our group recently reported the first example of Group 3 metals for alkyl−alkyl cross-coupling catalysis enabled by a redox-active ligand (Figure 1a). 34 Cross-coupling is incredibly important due to its necessity to construct molecules of medicinal importance that have C(sp 3 ) character.…”

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confidence: 99%

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One- and Two-Electron Redox Catalysis with Lutetium Enabled by a Tris(Amido) Redox-Active Ligand

et al. 2023

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Recently rare earth elements have been used to catalyze alkyl–alkyl cross coupling and other organic transformations. Herein we report the synthesis and characterization of a tris(amido) Lu complex, 1-Lu, analogous to the Sc and Y rare earth complexes known to participate in these transformations. Complex 1-Lu displays similar solid state structural properties as its Group 3 congeners, but EPR spectroscopy reveals differing behavior. 1-Lu also was found to break the trends of reaction rates related to oxidation potential and is able to catalyze an alkyl–alkyl cross-coupling reaction faster than the Sc and Y analogs. The complex 1-Lu was also demonstrated to participate in two-electron redox catalysis.

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confidence: 99%

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One- and Two-Electron Redox Catalysis with Lutetium Enabled by a Tris(Amido) Redox-Active Ligand

et al. 2023

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“…This band is attributed to Eu 2+ species (Figure 5C), and is not present in the peralkaline composition. Based on previous studies dedicated to the redox behavior of Eu in silicate glasses, the presence of reduced species in this polymerized sample is expected [34,35].…”

Section: Eu-doped Pristine Glassesmentioning

confidence: 80%

Photoluminescence Study of Undoped and Eu-Doped Alkali-Niobate Aluminosilicate Glasses and Glass-Ceramics

Cicconi,

Deng,

Otsuka

et al. 2024

Materials

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In this study, the photoluminescence (PL) behavior of two aluminosilicate glass series containing alkali-niobates ranging from 0.4 to 20 mol% was investigated. The glasses exhibit an intense visible emission centered at ~18,400 cm−1 for the peralkaline series and at higher energies (~19,300 cm−1) for the metaluminous glasses. However, the photoluminescence emission intensity varies significantly with the niobate content and the bulk chemistry. PL and fluorescence lifetime measurements indicate that the broad emission bands result from the overlap of different niobate populations, whose distribution changes with niobate content. The distinct PL behavior in the two glass series was related to the structural evolution of the niobate units upon niobium addition. An enhancement of the visible emission was observed for a higher fraction of distorted [NbO6] units. Eu-doping was carried out as a structural probe of the glass network, and also to determine if these glasses could be used as potential rare earth element (REE) activators. The crystal field strength around Eu ions is strongly dependent on the bulk chemistry and the niobate content. Furthermore, the peralkaline series showed energy transfer from the host [NbO6] to Eu3+, confirming the feasibility of exploring niobate glasses and glass-ceramics as lanthanide ion-activated luminescent materials. In addition, glass-ceramics (GCs) containing alkali-niobate phases with a perovskite-like structure were developed and studied to verify the optical performance of these materials. It was verified that the bulk chemistry influences crystallization behavior, and also the photoluminescence response. The transparent GC from the metaluminous series exhibits a quenching of the Eu3+ emission, whereas an enhanced emission intensity is observed for the peralkaline GC. The latter shows a strong excitation-dependent PL emission, suggesting energy transfer and migration of electronic excitation from one Eu population to another. Additionally, Eu3+ emissions arising from the D15 and D25 excited states were observed, highlighting the low phonon energy achievable in niobo-aluminosilicate hosts.

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“…REE are a group of metals that includes lanthanides (f-block elements with atomic numbers from 57 to 71), scandium and yttrium [1,2], which demonstrate very similar chemical behaviour due to their ordinary trivalent state. REE have been extensively studied in geochemistry, serving as indicators of the terrestrial or marine provenance of rocks and suspended matter [3][4][5][6], as a proxy for redox conditions in paleogeography and paleoceanography [7][8][9][10][11][12][13][14], or as tracers of water masses and their circulation [15][16][17][18][19][20][21].…”

Section: Introductionmentioning

confidence: 99%

Rare Earth Elements in Shells of Black Sea Molluscs: Anomalies and Biogeochemical Implications

Kapranov,

Ryabushko,

Dikareva

et al. 2024

JMSE

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Rare earth elements (REE) are a class of increasingly used high-tech product components and new emerging environmental pollutants, which are accumulated, in particular, in marine biota. In this study, REE contents were estimated in shells of several molluscs common in the Black Sea. The summed REE contents in mollusc shells decreased in the following order of species: Magallana gigas = Anadara kagoshimensis > Flexopecten glaber ponticus ≥ Rapana venosa > Mytilus galloprovincialis, ranging from 0.46 to 1.9 mg·kg−1. Canonical analysis of principal coordinates allowed for the correct identification of species based on the REE composition in no fewer than 67% of the samples. The mollusc shells were anomalously enriched in Sc, Y, La, Eu and Tb, most likely due to anthropogenic contamination. The Y/Ho ratios in all samples were represented by two fit values: 23.2 (chondritic) and 67.6 (superchondritic, mainly associated with A. kagoshimensis). A new universal relationship linking the contents of three light and heavy REE in Black Sea mollusc shells was proposed: Ce0.3 Er0.7⁄Yb = 2.00 ± 0.46 (mean ± standard deviation).

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The Redox Behavior of Rare Earth Elements

Cited by 7 publications

References 89 publications

One- and Two-Electron Redox Catalysis with Lutetium Enabled by a Tris(Amido) Redox-Active Ligand

One- and Two-Electron Redox Catalysis with Lutetium Enabled by a Tris(Amido) Redox-Active Ligand

Photoluminescence Study of Undoped and Eu-Doped Alkali-Niobate Aluminosilicate Glasses and Glass-Ceramics

Rare Earth Elements in Shells of Black Sea Molluscs: Anomalies and Biogeochemical Implications

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