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1. Thermodynamic assessment of BaO–Ln ₂ O ₃ (Ln = La, Pr, Eu, Gd, Er) systems

   https://doi.org/10.1111/jace.17060  

   Gong, Weiping; Liu, Yanzhi; Xie, Yun; Zhao, Zhenting; Ushakov, Sergey V.; Navrotsky, Alexandra (February 2020, Journal of the American Ceramic Society)

   Abstract Heat capacities and enthalpies of formation of BaGd₂O₄were determined by high‐temperature differential scanning calorimetry and high‐temperature oxide melt solution calorimetry, respectively. Thermodynamic stability of BaLn₂O₄compounds increases with decreasing Ln³⁺ionic radius. Previously reported data on BaNd₂O₄and BaSm₂O₄corroborate this trend. Missing data for compounds in BaO–Ln₂O₃(Ln = La, Pr, Eu, Er) systems were estimated from established relations, thermodynamic assessment was performed, and binary phase diagrams were calculated. 

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2. Synthesis of Ln ^II ‐in‐Cryptand Complexes by Chemical Reduction of Ln ^III ‐in‐Cryptand Precursors: Isolation of a Nd ^II ‐in‐Cryptand Complex

   https://doi.org/10.1002/anie.202006393  

   Huh, Daniel N.; Ciccone, Sierra R.; Bekoe, Samuel; Roy, Saswata; Ziller, Joseph W.; Furche, Filipp; Evans, William J. (June 2020, Angewandte Chemie International Edition)

   Abstract Lanthanide triflates have been used to incorporate Nd^IIIand Sm^IIIions into the 2.2.2‐cryptand ligand (crypt) to explore their reductive chemistry. The Ln(OTf)₃complexes (Ln=Nd, Sm; OTf=SO₃CF₃) react with crypt in THF to form the THF‐soluble complexes [Ln^III(crypt)(OTf)₂][OTf] with two triflates bound to the metal encapsulated in the crypt. Reduction of these Ln^III‐in‐crypt complexes using KC₈in THF forms the neutral Ln^II‐in‐crypt triflate complexes [Ln^II(crypt)(OTf)₂]. DFT calculations on [Nd^II(crypt)]²⁺], the first Nd^IIcryptand complex, assign a 4f⁴electron configuration to this ion. 

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3. Three derivatives of phenacyldiphenylphosphine oxide: influence of aromatic and alkyl substituents on the luminescence sensitization of four Ln(NO ₃ ) ₃ salts

   https://doi.org/10.1039/d3dt03556e  

   Sands, Georgia G; Cook, Alyssa K; Delabbio, Angelina; Fuhrer, Tim; Bailey, Matthew D; Leach, Erin G; Purosky, Isabella R; Biros, Shannon M (February 2024, Dalton Transactions)

   Four β-carbonylphosphine oxide compounds were complexed with four Ln(NO₃)₃salts (Ln = Sm, Eu, Tb, Dy). The Ln–ligand complexes were characterized in the solid state (IR, CHN) and as solutions in acetonitrile (NMR, LR-MS, photophysical properties). 

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4. 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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5. Evaluating electrochemical accessibility of 4f ⁿ 5d ¹ and 4f ⁿ⁺¹ Ln( ii ) ions in (C ₅ H ₄ SiMe ₃ ) ₃ Ln and (C ₅ Me ₄ H) ₃ Ln complexes

   https://doi.org/10.1039/D1DT02427B  

   Trinh, Michael T.; Wedal, Justin C.; Evans, William J. (October 2021, Dalton Transactions)

   The reduction potentials (reported vs. Fc + /Fc) for a series of Cp′ 3 Ln complexes (Cp′ = C 5 H 4 SiMe 3 , Ln = lanthanide) were determined via electrochemistry in THF with [ n Bu 4 N][BPh 4 ] as the supporting electrolyte. The Ln( iii )/Ln( ii ) reduction potentials for Ln = Eu, Yb, Sm, and Tm (−1.07 to −2.83 V) follow the expected trend for stability of 4f 7 , 4f 14 , 4f 6 , and 4f 13 Ln( ii ) ions, respectively. The reduction potentials for Ln = Pr, Nd, Gd, Tb, Dy, Ho, Er, and Lu, that form 4f n 5d 1 Ln( ii ) ions ( n = 2–14), fall in a narrow range of −2.95 V to −3.14 V. Only cathodic events were observed for La and Ce at −3.36 V and −3.43 V, respectively. The reduction potentials of the Ln( ii ) compounds [K(2.2.2-cryptand)][Cp′ 3 Ln] (Ln = Pr, Sm, Eu) match those of the Cp′ 3 Ln complexes. The reduction potentials of nine (C 5 Me 4 H) 3 Ln complexes were also studied and found to be 0.05–0.24 V more negative than those of the Cp′ 3 Ln compounds. 

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