Structural Expansion of Chalcogenido Tetrelates in Ionic Liquids by Incorporation of Sulfido Antimonate Units

Abstract

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.

Robust and Flexible Thioantimonate Materials for Cs+ Remediation with Distinctive Structural Transformation: A Clear Insight into the Ion-Exchange Mechanism

“…Each Sb atom is coordinated by three adjacent S atoms forming a {SbS 3 } trigonal pyramid. The Sb–S bond lengths scatter over a range from 2.344 to 2.523 Å, and corresponding S–Sb–S angles are in the range of 79.49–100.67° (Table S2), comparable to those of reported thioantimonates. − {Sb(1)­S 3 }, {Sb(2)­S 3 }, and {Sb(3)­S 3 } units are joined together via corner-sharing to form a trinuclear {Sb 3 S 6 } cluster, while one {Sb(5)­S 3 } and two {Sb(4)­S 3 } units are joined together via corner-sharing to give a linear trinuclear {Sb 3 S 7 } unit (Figure S2a). Alternating arrangements of two {Sb 3 S 6 } clusters and two {Sb 3 S 7 } units result in a 10-membered {Sb 10 S 10 } ring containing 10 {SbS 3 } units, whose cross section is 12.495 × 12.495 Å 2 (Figure S2a).…”

Exploration of metal sulfide syntheses and the dissolution process of antimony sulfide in phosphonium-based ionic liquids

“…Dehnen et al , for example, isolated various thio- and oxothiostannates, selenogermanates and -stannates including cations of the imidazolium-based ILs. 22,23,27–30 Among them, the most prominent compound contains the supersphere anion [Ge 24 Sn 36 Se 132 ]. 24–31,32 But also a new modification of K 2 Sn 2 S 5 was accessible, which obviously does not include the IL used.…”

“…22,23,27–30 Among them, the most prominent compound contains the supersphere anion [Ge 24 Sn 36 Se 132 ]. 24–31,32 But also a new modification of K 2 Sn 2 S 5 was accessible, which obviously does not include the IL used. 33…”

The Layered Semiconductor Cu(Sb2S3)[AlCl4]

“…[2][3][4][5][6][9][10][11][12][13][14]) have shown, that ILs promote the formation of complex, typically charged units in solution but also their crystallization. [12,[15][16][17][18][19] In particular, the IL-based synthesis of heavier chalcogenides is intricate. One approach is to use precursors.…”