Chalkogenide-based Ionic Liquids in the Synthesis of Metal Chalcogenide and Interchalcogenide Materials near Room Temperature

该项目研究了由氢硫族化合物[EH]、三甲基硅硫族化合物[E- tms]或多硫族化合物[Ex] （E = S, Se, Te）的硫基阴离子组成的离子液体（IL）在合成选定的2D和3d金属硫族化合物或多硫族化合物和间硫族材料中的应用。这项研究将证明使用这种高活性合成子进行硫转移的明显好处，它结合了易于获取、纯度最高、在有机共溶剂中的完美溶解度、低熔点（在某些情况下）和对亲电试剂和路易斯酸的最高反应性。第一种策略是在离子液体Cat [EH] （E = S, Se）中对选定的金属有机化合物和酰胺进行原解反应，第二种补充策略是对溶解在Cat [E- tms]和Cat [EH] ILs中的金属卤化物进行阴离子复分解。在这方面，计划将选定的p嵌段金属前体化合物Ga(III), In(III), In（II）和Sn（II）与选定的f嵌段元素前体Ln（II）和Ln（III）的反应性模式进行比较。新一类热不稳定的硫族有机金属酸盐[(RxM)yEz]n- （M = Ga, In， La和Ln； E = S, Se）和三甲基硅基硫族金属酸盐[M(E- tms)4]- (M = Ga, In, La)将会得到。它们是在室温或略高于室温的条件下转化为半导体材料ME、M2S3和ME2的不稳定中间体。室温IL反应可以分离出新的锡（II）和锡（IV）前体化合物Cat[SnE2]和Sn(E- tms)4 (E = S, Se)，等待它们缩合成SnE和SnE2半导体材料。[NH4]2[MoS4]与甲基碳酸盐ILs Cat[MeCO3]的反应提供了获得中间体Cat2[MoS4]的途径，这些中间体计划通过两种策略转化为MoS2: 1)在IL通量中热解，2)与亲电试剂反应，然后还原消除二硫化物RSSR。第三种策略是研究Cat[SH]或Cat[S-TMS] il中[MoX4]复合物的硫解。最后，探讨了硫族化合物在低温合成富硫多硫族化合物、间硫族化合物和间硫族材料中的应用价值。

The project investigates the application of ionic liquids (IL) comprising chalcogen-based anions of the hydrochalcogenide [EH], trimethylsilylchalcogenide [E-TMS] or polychalcogenide type [Ex] (E = S, Se, Te) in the synthesis of selected 2D- and 3D-metal chalcogenide or poly- and interchalcogenide materials. This research will demonstrate a clear benefit of using such highly reactive synthons for chalcogen transfer, that combine easy access, highest purity, perfect solubility in organic co-solvents, low melting points (in some cases) and highest reactivity towards electrophiles and Lewis acids. A first strategy follows up protolysis reactions of selected metal organyls and amides in ionic liquids Cat [EH] (E = S, Se), a second complementary strategy the anion metathesis of metal halides dissolved in Cat [E-TMS] and Cat [EH] ILs. In this respect, selected metal precursor compounds of the p-block, Ga(III), In(III), In(II) and Sn(II), are planned to be compared in their reactivity pattern with selected precursors of the f-block elements, Ln(II) and Ln(III). New classes of thermally labile chalcogenido organometallates [(RxM)yEz]n- (M = Ga, In, La and Ln; E = S, Se) and of trimethylsilylchalcogenido-metallates [M(E-TMS)4]- (M = Ga, In, La) will be accessible. They are labile intermediates in their conversion into semiconducting materials ME, M2S3 and ME2 at room temperature or slightly above. Room temperature IL reactions allow the isolation of novel tin(II) and tin(IV) precursor compounds, Cat[SnE2] and Sn(E-TMS)4 (E = S, Se), awaiting their condensation to SnE and SnE2 semiconducting materials. Reaction of [NH4]2[MoS4] with methylcarbonate ILs Cat[MeCO3] offers access to intermediates Cat2[MoS4], that are planned to be converted to MoS2 via two strategies: 1) thermolyis in a IL flux and 2) reaction with electrophiles followed by reductive elimination of disulfides RSSR. A third strategy investigates the thiolysis of [MoX4] complexes in Cat[SH] or Cat[S-TMS] ILs. Finally, the benefit of chalcogenide ILs in low-temperature syntheses of chalcogen-rich polychalcogenide, interchalcogenide and interchalcogen materials is planned to be explored.