A Strategy for the Preparation of Thioantimonates Based on the Concept of Weak Acids and Corresponding Strong Bases

Abstract

By following a new synthetic approach, which is based on the in situ formation of a basic medium by the reaction between the strong base Sb(V)S4 (3-) and the weak acid H2 O, it was possible to prepare three layered thioantimonate(III) compounds of composition [TM(2,2'-bipyridine)3 ][Sb6 S10 ] (TM=Ni, Fe) and [Ni(4,4'-dimethyl-2,2'-bipyridine)3 ][Sb6 S10 ] under hydrothermal conditions featuring two different thioantimonate(III) network topologies. The antimony source, Na3 SbS4 ⋅ 9 H2 O, undergoes several decomposition reactions and produces the Sb(III) S3 species, which condenses to generate the layered anion. The application of transition-metal complexes avoids crystallization of dense phases. The reactions are very fast compared to conventional hydrothermal/solvothermal syntheses and are much less sensitive to changes of the reaction parameters.

Synthesis and crystal structure of (1,4,7,10-tetraazacyclododecane-κ4 N)(tetrasulfido-κ2 S 1,S 4)manganese(II)

“…Most of these compounds were synthesized by solvothermal reactions using the elements as reactands, which is a disadvantage for several reasons. Recently, we have found that many such compounds are more easily available if simple metal salts such as, for example, Schlippe's salt (Na 3 SbS 4 Á9H 2 O) or NaSbS 3 are used as starting materials (Anderer et al, 2014(Anderer et al, , 2016Danker et al, 2020). The major advantage of this approach is the fact that different SbS x species are present in solution, which in some cases allows the preparation of thioantimonates already at room temperature.…”

“…The major advantage of this approach is the fact that different SbS x species are present in solution, which in some cases allows the preparation of thioantimonates already at room temperature. The reactions in solution are complex, but it has been found that Schlippe's salt is unstable and forms different species such as, for example, [SbS 3 (Anderer et al, 2014;Long et al, 1970;Rammelsberg, 1841;Planer-Friedrich & Wilson, 2012;Planer-Friedrich & Scheinost, 2011;Mosselmans et al, 2000).…”

Formation and Reactivity of Organo‐Functionalized Tin Selenide Clusters

“…The chalcogenidometalate family encompasses ab road spectrum of compounds with amultitude of applications stemming from their tunable optoelectronic and semiconducting properties; [1][2][3][4][5][6] al arge subgroupof this family are the chalcogenidotetrelates. [7,8] Ac haracteristic feature of tin chalcogenide chemistry is the reoccurrence of topologies, such as the [Sn 3 E 4 ] defect-ah eterocubane unit (DC, E = S, Se), most often aggregated through further Ea toms into frameworks [9][10][11] -or the adamantane-like [Sn 4 E 6 ]t in sesquichalcogenide unit (AD), which is also knownf or af ew tin telluride clusters (E = Te ).…”

The Two‐Dimensional Anion [Sb6Se10]2–: Solvothermal Synthesis, Crystal Structure, and Properties of an Iron ­Selenidoantimonate(III) [Fe(phen)3]Sb6Se10

“…Organic hybrid thioantimonates(III) (aepH 2 )[Sb 6 S 10 ] (aep = 1‐(2‐aminoethyl)‐piperazine),40 [(dach)(dachH 2 )][Sb 6 S 10 ] (dach = trans‐1, 2‐diaminocyclohexane),41 and (Ph 4 P) 2 [Sb 6 S 10 ] 42 contain the 1D chain‐like [Sb 6 S 10 ] 2– anion, which is constructed by SbS 3 and SbS 4 units. The 2D [Sb 6 S 10 ] 2– anion with Sb 2 S 2 , Sb 4 S 4 , and Sb 7 S 7 hetero‐rings in [ TM (bipy) 3 ][Sb 6 S 10 ] ( TM = Ni, Fe; bipy = 2, 2′‐bipyridine) is composed of SbS 3 and SbS 4 units 43…”