Imidazolium-based ionic liquids served to selectively methylate terminal chalcogenide ligands of chalcogenidometalate clusters [Sn10S16O4(SMe)4]4−, [Mn4Sn4Se13(SeMe)4]6−, and [Hg6Te10(TeMe)2]6−.

Clusters containing tin atoms show a huge variety of molecular structures, chemical as well as physical properties.

Supertetrahedral clusters have been reported in two generally different types so far:one type possessing an organic ligand shell, no or lowc harges,a nd high solubility,w hile the other cluster type is ligand-free with usually high charges and low or no solubility in common solvents.T he latter is atremendous disadvantage regarding further use of the clusters in solution. However,a so rganic substituents usually broaden the HOMO-LUMO gaps,w hichc annot be overcompensated by the (limited) cluster sizes,afull organic shielding comes along with drawbacks regarding opto-electronic properties.We therefore sought to find aw ay of generating soluble clusters with am inimum number of organic substituents.H ere,w e present the synthesis and full characterization of two salts of [Sn 10 O 4 S 16 (SBu) 4 ] 4À that are high soluble in CH 2 Cl 2 or CH 3 CN, which includes first NMR and mass spectra obtained from solutions of such salts with mostly inorganic supertetrahedral clusters.The optical absorption properties of this new class of compounds indicates nearly unaffected band gaps.T he synthetic approach and the spectroscopic findings were rationalized and explained by means of high-level quantum chemical studies.

A new salt of the alkylated oxo‐thio stannate cluster [Sn10O4S16(SMe)4]4–, (C4C4C1Im)4[Sn10O4S16(SMe)4] (1), was obtained by ionothermal treatment of K4[SnS4]·4H2O. The reaction was carried out in the ionic liquid 1,3‐dibutyl‐2‐methylimidazolium chloride, (C4C4C1Im)Cl, which proved to be non‐innocent against the chalcogenido metallate species in the reaction mixture. In continuation of our first studies on alkylation of very weakly nucleophilic chalcogenido metalate anions, this study served to prove that an N‐bonded alkyl group is selectively released from the imidazolium cation of the ionic liquid, and it served to show that methylation is favored over butylation. The title compound is one of the rare cases, in which the cations of the salt, which stem from the ionic liquid, could be crystallographically determined without problems.

as an interdisciplinary research line of chemistry, physics, and materials engineering. [1,2] Numerous scientific efforts have focused on designing new materials with the desired electronic and magnetic features by tuning the chemical composition, structural parameters, and physical modifications. [3,4] In recent years, defect variant structures have been considered as promising candidates to provide new, targeted properties and property combinations. The interdependence of magnetic and electronic structures to the partial vacancies on anion positions has been reported for a few ferrite and ferrate compounds indicating significant effects of vacancies on the Fermi level, orbital splitting, and geometrical interactions in the crystal structure, thereby changing the magnetization and the ionic conductivity. [5,6] The change in properties originates from the different vacancies of isolated cations and anions, as well as defects in the complex anionic motifs. For compounds including iron, depending on the structure, the iron vacancies can be considered either as vacancies of single cations, or as defects in the anionic motifs. Although the impact of iron The multigram synthesis of K 2 [Fe 3 S 4 ] starting from K 2 S and FeS is presented, and its electronic and magnetic properties are investigated. The title compound obtains a defect variant of the K[Fe 2 Se 2 ] structure type. Dielectric and impedance measurements indicate a dielectric constant of 1120 at 1 kHz and an outstanding ionic conductivity of 24.37 mS cm -1 at 295 K, which is in the range of the highest reported value for potential solid-state electrolytes for potassium-ion batteries. The Seebeck coefficient of the n-type conductor amounts to −60 µV K −1 at 973 K. The mismatch of the measured electrical resistivity and the predicted metal-like band structure by periodic quantum chemical calculations indicates Mott insulating behavior. Magnetometry demonstrates temperature-dependent, large exchange bias fields of 35 mT, as a consequence of the coexistence of spin glass and antiferromagnetic orderings due to the iron vacancies in the lattice. In addition, the decreasing training effects of 34% in the exchange bias are identified at temperatures lower than 20 K. These results demonstrate the critical role of iron vacancies in tuning the electronic and magnetic properties and a multifunctional material from abundant and accessible elements.

Multinary chalcogenido (semi)metalate salts exhibit finely tunable optical properties based on the combination of metal and chalcogenide ions in their polyanionic substructure. Here, we present the structural expansion of chalcogenido germanate(IV) or stannate(IV) architectures with SbIII, which clearly affects the vibrational and optical absorption properties of the solid compounds. For the synthesis of the title compounds, [K4(H2O)4][Ge4S10] or [K4(H2O)4][SnS4] were reacted with SbCl3 under ionothermal conditions in imidazolium‐based ionic liquids. Salt metathesis at relatively low temperatures (120 °C or 150 °C) enabled the incorporation of (formally) Sb3+ ions into the anionic substructure of the precursors, and their modification to form (Cat)16[Ge2Sb2S7]6[GeS4] (1) and (Cat)6[Sn10O4S20][Sb3S4]2 (2 a and 2 b), wherein Cat=(C4C1C1Im)+ (1 and 2 a) or (C4C1C2Im)+ (2 b). In 1, germanium and antimony atoms are combined to form a rare noradamantane‐type ternary molecular anion, six of which surround an {GeS4} unit in a highly symmetric secondary structure, and finally crystallize in a diamond‐like superstructure. In 2, supertetrahedral oxo‐sulfido stannate clusters are generated, as known from the ionothermal treatment of the stannate precursor alone, yet, linked here into unprecedented one‐dimensional strands with {Sb3S4} units as linkers. We discuss the single‐crystal structures of these uncommon salts of ternary and quaternary chalcogenido (semi)metalate anions, as well as their Raman and UV‐visible spectra.

One- and two-dimensional networks of alkali metal ions and silicon-based ligands were synthesised and structurally characterised.

Two types of layered sulfido stannates or a molecular cluster compound are obtained upon ionothermal treatment of the simple sulfido stannate salt K4[SnS4] ·  4H2O that is based on binary tetrahedral [SnS4]4− anions. The formation of the respective products, novel compounds (C4C1C1Im)2[Sn3S7] (1 a), (C4C1C2Im)2[Sn3S7] (1 b), and (C4C1C2Im)2[Sn4S9] (2) with layered anionic substructures, or the recently reported compound (C4C1C1Im)4+x[Sn10O4S16(SMe)4][An]x (A) comprising a molecular cluster anion, is controlled by both the choice of the ionic liquid cation and the reaction temperature. We report the scale‐up of the syntheses by a factor of 100 with regard to other reported ionothermal syntheses of related compounds, and a procedure of how to isolate them in phase‐pure form – both being rare observations in chalcogenido stannate chemistry in ionic liquids. Moreover, the synthesis of compound 1 a can be achieved by rapid cation exchange starting out from 1 b, which has not been reported for organic cations in any chalcogenido stannate salt to date.