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1. Quaternary cerium( iv ) containing fluorides exhibiting Ce ₃ F ₁₆ sheets and Ce ₆ F ₃₀ frameworks

   https://doi.org/10.1039/d0dt00616e  

   Ayer, Gyanendra B.; Klepov, Vladislav V.; Pace, Kristen A.; zur Loye, Hans-Conrad (May 2020, Dalton Transactions)

   null (Ed.)

   A series of new Ce( iv ) based fluorides with two different compositions, Cs 2 MCe 3 F 16 (M = Ni 2+ , Co 2+ , Mn 2+ , and Zn 2+ ) and Na 3 MCe 6 F 30 (M = Al 3+ , Ga 3+ , Fe 3+ , and Cr 3+ ) were synthesized as high quality single crystals via a mild hydrothermal route. The compounds with the composition Cs 2 MCe 3 F 16 (M = Ni 2+ , Co 2+ , Mn 2+ , and Zn 2+ ) crystallize in the hexagonal crystal system with space group P 6 3 / mmc and are isotypic with the uranium analogs, whereas the Na 3 MCe 6 F 30 (M = Al 3+ , Ga 3+ , Fe 3+ , and Cr 3+ ) compounds crystallize in the trigonal space group P 3̄ c 1 and are isotypic with the uranium and thorium analogs Na x MM′ 6 F 30 (M′ = Th, U). The Cs 2 MCe 3 F 16 compounds exhibit a complex 3D crystal structure constructed of edge-sharing cerium trimers, in which all three Ce atoms share a common μ 3 -F unit. The Na 3 MCe 6 F 30 compounds are constructed of edge- and vertex-sharing cerium polyhedra connected to each other to form Ce 6 F 30 6− framework, which can accommodate only relatively smaller trivalent cations (M 3+ = Al 3+ , Ga 3+ , Fe 3+ , and Cr 3+ ) as compared to uranium and thorium analogs. Magnetic susceptibility measurements were carried out on the samples of Cs 2 MCe 3 F 16 (M = Ni 2+ and Co 2+ ), which exhibit paramagnetic behavior. 

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2. Medium‐Entropy Engineering of Magnetism in Layered Antiferromagnet Cu _x Ni _{2(1‐ x )} Cr _x P ₂ S ₆

   https://doi.org/10.1002/adfm.202418722  

   Upreti, Dinesh; Basnet, Rabindra; Sharma, M_M; Chhetri, Santosh_Karki; Acharya, Gokul; Nabi, Md_Rafique_Un; Sakon, Josh; Benamara, Mourad; Mortazavi, Mansour; Hu, Jin (December 2024, Advanced Functional Materials)

   Abstract Antiferromagnetic van der Waals‐typeM₂P₂X₆compounds provide a versatile material platform for studying 2D magnetism and relevant phenomena. Establishing ferromagnetism in 2D materials is technologically valuable. Though magnetism is generally tunable via a chemical way, it is challenging to induce ferromagnetism with isovalent chalcogen and bimetallic substitutions inM₂P₂X₆. Here, we report co‐substitution of Cu¹⁺and Cr³⁺for Ni²⁺in Ni₂P₂S₆, creating Cu_xNi_2(1‐x)Cr_xP₂S₆medium‐entropy alloys spanning a full substitution range (x= 0 to 1). Such substitution strategy leads to a unique evolution in crystal structure and magnetic phases that are distinct from traditional isovalent bimetallic doping, with Cu and Cr co‐substitution enhancing ferromagnetic correlations and generating a weak ferromagnetic phase in intermediate compositions. This aliovalent substitution strategy offers a universal approach for tuning layered magnetism in antiferromagnetic systems, which along with the potential for light‐matter interaction and high‐temperature ferroelectricity, can enable multifunctional device applications. 

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3. Ca ₂ Ga ₄ Ge ₆ and Ca ₃ Ga ₄ Ge ₆ : Synthesis, Structure, and Electronic Properties

   https://doi.org/10.1002/zaac.202100342  

   Hodge, Kelsey L; Davis, H Olivia; Koster, Karl G; Windl, Wolfgang; Moore, Curtis E; Goldberger, Joshua E (August 2022, Zeitschrift für anorganische und allgemeine Chemie)

   Abstract During the search for transition metal‐free alkyne hydrogenation catalysts, two new ternary Ca−Ga−Ge phases, Ca₂Ga₄Ge₆(Cmc2₁, a=4.1600(10) Å, b=23.283(5) Å, c=10.789(3) Å) and Ca₃Ga₄Ge₆(C2/m, a=24.063(2) Å, b=4.1987(4) Å, c=10.9794(9) Å, β=91.409(4)°), were discovered. These compounds are isostructural to the previously established Yb₂Ga₄Ge₆and Yb₃Ga₄Ge₆analogues, and according to Zintl‐Klemm counting rules, consist of anionic [Ga₄Ge₆]⁴⁻and [Ga₄Ge₆]⁶⁻frameworks in which every Ga and Ge atom would have a formal octet with no Ga−Ga or Ga−Ge π‐bonding. These compounds are metallic, based on temperature dependent electrical resistivity and thermopower measurements for Ca₃Ga₄Ge₆, along with density functional theory calculations for both phases. Unlike the highly active 13‐layer trigonal CaGaGe phase, these new compounds exhibit minimal activity in the semi/full alkyne hydrogenation of phenylacetylene, which is consistent with previous observations that the lack of a formal octet for framework atoms is essential for catalysis in these Zintl‐Klemm compounds. 

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4. New germanate and mixed cobalt germanate salt inclusion materials: [(Rb ₆ F)(Rb ₄ F)][Ge ₁₄ O ₃₂ ] and [(Rb ₆ F)(Rb _3.1 Co _0.9 F _0.96 )][Co _3.8 Ge _10.2 O ₃₀ F ₂ ]

   https://doi.org/10.1039/D0CE01099E  

   Carone, Darren; Usman, Mohammad; Klepov, Vladislav V.; Smith, Mark D.; Kocevski, Vancho; Besmann, Theodore M.; zur Loye, Hans-Conrad (December 2020, CrystEngComm)

   null (Ed.)

   Single crystals of two new germanates, [(Rb 6 F)(Rb 4 F)][Ge 14 O 32 ] and [(Rb 6 F)(Rb 3.1 Co 0.9 F 0.96 )][Co 3.8 Ge 10.2 O 30 F 2 ], were synthesized via high temperature RbCl/RbF flux growth. Both compounds crystallize in the cubic space group F 4̄3 m and possess the germanium framework of the previously reported salt inclusion material (SIM), [(Cs 6 F)(Cs 3 AgF)][Ge 14 O 32 ], related to the Ge 7 O 16 zeolitic family. These materials demonstrate the ability to accommodate a variety of salt-inclusions, and exhibit chemical flexibility enabling modifications of the framework through incorporation of Co. Alteration of the salt-inclusion led to intrinsic luminescence of [(Rb 6 F)(Rb 4 F)][Ge 14 O 32 ] while modification of the framework resulted in an unanticipated Rb/Co salt/inclusion in [(Rb 6 F)(Rb 3.1 Co 0.9 F 0.96 )][Co 3.8 Ge 10.2 O 30 F 2 ]. Fluorescence measurements were performed on [(Rb 6 F)(Rb 4 F)][Ge 14 O 32 ]. First-principles calculations in the form of density functional theory (DFT) were performed for [(Rb 6 F)(Rb 3.1 Co 0.9 F 0.96 )][Co 3.8 Ge 10.2 O 30 F 2 ] to elucidate its electronic and magnetic properties, and stability at 0 K. 

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5. Why Mg ₂ IrH ₆ Is Predicted to Be a High‐Temperature Superconductor, But Ca ₂ IrH ₆ Is Not

   https://doi.org/10.1002/anie.202412687  

   Wang, Xiaoyu; Pickett, Warren E; Hutcheon, Michael; Prasankumar, Rohit P; Zurek, Eva (December 2024, Angewandte Chemie International Edition)

   Abstract The X₂MH₆family, consisting of an electropositive cation Xⁿ⁺and a main group metal M octahedrally coordinated by hydrogen, have been identified as promising templates for high‐temperature conventional superconductivity. Herein, we analyze the electronic structure of two members of this family, Mg₂IrH₆and Ca₂IrH₆, showing why the former may possess superconducting properties rivaling those of the cuprates, whereas the latter does not. Within Mg₂IrH₆the vibrations of the anions IrH₆⁴⁻anions are key for the superconducting mechanism, and they induce coupling in the set of orbitals, which are antibonding between the H 1sand the Ir or orbitals. Because calcium possesses low‐lyingd‐orbitals, →Cadback‐donation is preferred, quenching the superconductivity. Our analysis explains why high critical temperatures were only predicted for second or third row X metal atoms, and may provide rules for identifying likely high‐temperature superconductors in other systems where the antibonding anionic states are filled. 

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