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- ItemSyntheses, crystal structure and magnetic properties of Tl9RETe6 (RE = Ce, Sm, Gd)(Basel : MDPI AG, 2020) Isaeva, A.; Schönemann, R.; Doert, T.The three compounds Tl9RETe6 with RE = Ce, Sm, Gd were synthesized from the elements at 1020 K. Their isostructural crystal structures are ordered derivatives of the Tl5Te3 type with rare-earth metal and thallium occupying different Wyckoff positions. The structures can be understood as charge-ordered in accordance with the Zintl-Klemm concept: 9 Tl+ + RE3+ + 6 Te2-. DFT calculations for Tl9GdTe6, however, result in a low, but finite density of states at the Fermi level. Magnetic data confirm trivalent Gd, but indicate a small amount of Ce4+ in Tl9CeTe6; no indications for long-range magnetic order was found down to T = 2 K.
- ItemNew Low-Melting Triply Charged Homoleptic Cr(III)-Based Ionic Liquids in Comparison to Their Singly Charged Heteroleptic Analogues(Basel : MDPI AG, 2021) Peppel, Tim; Köckerling, MartinA series of new low-melting triply charged homoleptic Cr(III)-based ionic liquids of the general formula (RMIm)3[Cr(NCS)6] (R = methyl, ethyl, n-butyl, benzyl) is reported. Their syntheses and properties are described in comparison to their singly charged heteroleptic analogues of the general formula (RMIm)[Cr(NCS)4L2] (R = methyl, ethyl, n-butyl, benzyl; L = pyridine, γ-picoline). In total, sixteen new Reineckate related salts with large imidazolium cations are described. Out of these, five compounds were crystallized, and their structures determined by single-crystal X-ray structure analyses. They all consisted of discrete anions and cations with octahedrally coordinated Cr(III) ions. In the structures, various hydrogen contacts interconnect the entities to build up hydrogen bonded networks. Thermal investigations showed relatively low melting points for the homoleptic complexes. The compounds with the [Cr(NCS)6]3− anion melt without decomposition and are stable up to 200 K above their melting points. The complex salts with the [Cr(NCS)4L2]− anion, in contrast, start to decompose and lose L molecules (Pyr or Pic) already at the melting point.