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1. In situ Raman investigation of Dy complexation in Cl-bearing aqueous solutions at 20–300 °C

   https://doi.org/10.1039/D4DT02170C  

   Smith-Schmitz, Sarah E; Hurtig, Nicole C; Gysi, Alexander P (March 2025, Dalton Transactions)

   The firstin situRaman spectroscopic measurements of Dy speciation in hydrothermal fluids to 300 °C indicate that the Dy³⁺aqua ion (v_1,Dy–O) is stable in acidic DyCl₃solutions up to 200 °C above which Dy chloride complexes (v_Dy–Cl) predominate. 

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2. Chelator‐Assisted Precipitation‐Based Separation of the Rare Earth Elements Neodymium and Dysprosium from Aqueous Solutions

   https://doi.org/10.1002/anie.202410233  

   Gao, Yangyang; Licup, Gerra L; Bigham, Nicholas P; Cantu, David C; Wilson, Justin J (September 2024, Angewandte Chemie International Edition)

   Abstract The rare earth elements (REEs) are critical resources for many clean energy technologies, but are difficult to obtain in their elementally pure forms because of their nearly identical chemical properties. Here, an analogue of macropa, G‐macropa, was synthesized and employed for an aqueous precipitation‐based separation of Nd³⁺and Dy³⁺. G‐macropa maintains the same thermodynamic preference for the large REEs as macropa, but shows smaller thermodynamic stability constants. Molecular dynamics studies demonstrate that the binding affinity differences of these chelators for Nd³⁺and Dy³⁺is a consequence of the presence or absence of an inner‐sphere water molecule, which alters the donor strength of the macrocyclic ethers. Leveraging the small REE affinity of G‐macropa, we demonstrate that within aqueous solutions of Nd³⁺, Dy³⁺, and G‐macropa, the addition of HCO₃⁻selectively precipitates Dy₂(CO₃)₃, leaving the Nd³⁺−G‐macropa complex in solution. With this method, remarkably high separation factors of 841 and 741 are achieved for 50 : 50 and 75 : 25 mixtures. Further studies involving Nd³⁺:Dy³⁺ratios of 95 : 5 in authentic magnet waste also afford an efficient separation as well. Lastly, G‐macropa is recovered via crystallization with HCl and used for subsequent extractions, demonstrating its good recyclability. 

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3. Lanthanide Identity Governs Guest‐Induced Dimerization in Ln ^III [15‐MC _N(L‐pheHA) ‐5]) ³⁺ Metallacrowns

   https://doi.org/10.1002/chem.202103263  

   Sgarlata, Carmelo; Schneider, Bernadette_L; Zito, Valeria; Migliore, Rossella; Tegoni, Matteo; Pecoraro, Vincent_L; Arena, Giuseppe (November 2021, Chemistry – A European Journal)

   Abstract Series of lanthanide‐containing metallic coordination complexes are frequently presented as structurally analogous, due to the similar chemical and coordinative properties of the lanthanides. In the case of chiral (Ln^III[15‐MC_N(L‐pheHA)‐5])³⁺metallacrowns (MCs), which are well established supramolecular hosts, the formation of dimers templated by a dicarboxylate guest (muconate) in solution of neutral pH is herein shown to have a unique dependence on the identity of the MC's central lanthanide. Calorimetric data and nuclear magnetic resonance diffusion studies demonstrate that MCs containing larger or smaller lanthanides as the central metal only form monomeric host‐guest complexes whereas analogues with intermediate lanthanides (for example, Eu, Gd, Dy) participate in formation of dimeric host‐guest‐host compartments. The driving force for the dimerization event across the series is thought to be a competition between formation of highly stable MCs (larger lanthanides) and optimally linked bridging guests (smaller lanthanides). 

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4. Structure and Oxidation States of Giant Unit Cell Compound Dy _117+x Fe _57–y Sn _112–z

   https://doi.org/10.1002/zaac.201700321  

   Brown, Alexander T.; Barron, Keaton G.; Salazar, Bryan G.; Kirby, Parker; McCandless, Gregory T.; Walker, Amy V.; Chan, Julia Y. (November 2017, Zeitschrift für anorganische und allgemeine Chemie)

   Motivated by the complex structure and properties of giant unit cell intermetallic compounds, a new isostructural Fe analogue of the Dy₁₁₇Co₅₇Sn₁₁₂structure type was synthesized. Single crystals of Dy₁₂₂Fe₅₅Sn₁₀₁were grown at 1260 °C via a Dy–Fe eutectoid flux. The Fe analogue also adopts the space groupFm3mwith lattice parametersa= 29.914(9) Å,V= 26769(23) ų, andZ= 4. Dy₁₂₂Fe₅₅Sn₁₀₁has a large cell volume, structural complexity, and consists of seven Dy, eight Fe, and ten Sn unique crystallographic sites. There are fifteen fully occupied atomic positions, three unique pairs of alternating atomic positions with positional disorder, and seven partially occupied atomic sites. Within this complex unit cell, only approximately half the unique atomic positions are fully occupied with the remainder of the atoms either positionally or occupationally disordered. X‐ray photoelectron spectroscopy indicates that the compound contains Dy³⁺, Fe⁰, Fe²⁺, Sn⁰, and Sn⁴⁺. 

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5. Axial Elongation of Mononuclear Lanthanide Metallocenophanes: Magnetic Properties of Dysprosium‐ and Terbium‐[1]Ruthenocenophane Complexes

   https://doi.org/10.1002/anie.202003759  

   Risica, Gabrielle M.; Vieru, Veacheslav; Wilkins, Branford O.; Latendresse, Trevor P.; Reibenspies, Joseph H.; Bhuvanesh, Nattamai S.; Wylie, Gregory P.; Chibotaru, Liviu F.; Nippe, Michael (May 2020, Angewandte Chemie International Edition)

   Abstract We report the first f‐block‐ruthenocenophane complexes1(Dy) and2(Tb) and provide a comparative discussion of their magnetic structure with respect to earlier reported ferrocenophane analogues. While axial elongation of the rare trigonal‐prismatic geometry stabilizes the magnetic ground state in the case of Dy³⁺and results in a larger barrier to magnetization reversal (U), a decrease inUis observed for the case of Tb³⁺. 

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