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

Abstract

Ionic liquids (ILs), especially task-specific ILs, are capable of dissolving various solids at moderate temperatures without the need for special reaction vessels. Direct synthesis of binary sulfides of B, Bi,...

The Layered Semiconductor Cu(Sb2S3)[AlCl4]

“…The substantial difference between the structure of Sb 2 S 3 and the Sb 2 S 3 partial structure in Cu(Sb 2 S 3 )[AlCl 4 ] (see below) suggests that molecular fragments form under ionothermal reaction conditions. This assumption is supported by a recent report on the activation of Sb 2 S 3 by phosphonium‐ and imidazolium‐based ILs already at 100 °C [31] …”

“…This assumption is supported by a recent report on the activation of Sb 2 S 3 by phosphonium-and imidazolium-based ILs already at 100 °C. [31] Crystal structure X-ray diffraction on a single-crystal of Cu(Sb 2 S 3 )[AlCl 4 ] revealed an orthorhombic structure in the space group Pnma (no. 62) with four formula unit per unit cell and lattice parameters a = 1834.1(3) pm, b = 1081.0(2) pm, c = 579.9(1) pm, and V = 1149.7(3) • 10 6 pm 3 at 296(2) K. The atomic parameters are listed in Table S2, selected interatomic distance can be found in Table 1.…”

“…[31] Particularly using Lewis-acidic imidazolium ILs, such as [BMIm]Cl•nAlCl 3 (n = 1-5), enabled the synthesis of large antimony-chalcogen polycations. [13,14,31,32] Among them are spiro-dicubanes [Sb 7 Ch 8 X 2 ] 3 + with Ch = S, Se and X = Cl, Br, [13,14] the spiro-tetracubane [Sb 13 Se 16 Br 2 ] 5 + , [13] the polycyclic cation [Sb 10 Se 10 ] 2 + including two realgar-like cages, [32] and the catena-polycation ∞ 1 Sb 2 Se 2 ½ �. [33] However, these compounds were in most cases synthesized by reaction of the elements.…”

“…Sb 2 S 3 can be dissolved, without evolution of H 2 S, in phosphonium‐ as well as imidazolium‐based ILs at temperatures between 100 and 160 °C, the latter being the much more efficient solvents [31] . Particularly using Lewis‐acidic imidazolium ILs, such as [BMIm]Cl⋅ n AlCl 3 ( n =1–5), enabled the synthesis of large antimony‐chalcogen polycations [13,14,31,32] . Among them are spiro ‐dicubanes [Sb 7 Ch 8 X 2 ] 3+ with Ch =S, Se and X =Cl, Br, [13,14] the spiro ‐tetracubane [Sb 13 Se 16 Br 2 ] 5+ , [13] the polycyclic cation [Sb 10 Se 10 ] 2+ including two realgar‐like cages, [32] and the catena ‐polycation [33] .…”

“…In contrast, Bi 2 S 3 dissolves at 180 to 200 °C in Lewis‐acidic ILs [BMIm]Cl⋅ n AlCl 3 ( n =3.6–4.3) [2–4,8,30] . Sb 2 S 3 can be dissolved, without evolution of H 2 S, in phosphonium‐ as well as imidazolium‐based ILs at temperatures between 100 and 160 °C, the latter being the much more efficient solvents [31] . Particularly using Lewis‐acidic imidazolium ILs, such as [BMIm]Cl⋅ n AlCl 3 ( n =1–5), enabled the synthesis of large antimony‐chalcogen polycations [13,14,31,32] .…”