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

硫族化物基离子液体在近室温合成金属硫族化物和硫族化物间材料中的应用

• 批准号: 376983425
• 负责人: Professor Dr. Jörg Sundermeyer
• 金额: --
• 依托单位: AG Sundermeyer
• 依托单位国家: 德国
• 项目类别: Priority Programmes
• 财政年份: 2017
• 资助国家: 德国
• 起止时间: 2016-12-31 至 2020-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/376983425?language=en
• 关键词: Chalkogenide; based; Ionic; Liquids; Synthesis

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.

该项目研究了离子液体（IL）在合成选定的2D和3D金属硫属化物或多和间硫属化物材料中的应用，所述离子液体包括氢硫属化物[EH]、三甲基甲硅烷基硫属化物[E-TMS]或多硫属化物类型[Ex]（E = S、Se、Te）的硫属化物基阴离子。该研究将证明使用这种高反应性的硫族转移离子的明显益处，其结合了联合收割机容易获得、最高纯度、在有机共溶剂中的完美溶解度、低熔点（在某些情况下）以及对亲电体和刘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）中进行所选金属有机化合物和酰胺的质子分解反应，第二种补充策略是溶解在Cat [E-TMS]和Cat [EH] IL中的金属卤化物的阴离子复分解反应。在这方面，计划将p区的所选金属前体化合物Ga（III）、In（III）、In（II）和Sn（II）的反应性模式与f区元素Ln（II）和Ln（III）的所选前体进行比较。新的热不稳定的硫族有机金属化物[（RxM）yEz]n-（M = Ga，In，La和Ln; E = S，Se）和三甲基甲硅烷基硫族金属化物[M（E-TMS）4]-（M = Ga，In，La）将是可获得的。它们在室温或稍高温度下转化为半导体材料ME、M2 S3和ME 2时是不稳定的中间体。室温IL反应允许分离新型锡（II）和锡（IV）前体化合物Cat[SnE 2]和Sn（E-TMS）4（E = S，Se），等待它们缩合成SnE和SnE 2半导体材料。[NH 4]2[MoS 4]与碳酸甲酯离子液体Cat[MeCO 3]的反应提供了获得中间体Cat 2 [MoS 4]的途径，其计划通过两种策略转化为MoS 2：1）热交换器处于离子液体通量中，2）与亲电试剂反应，然后还原消除二硫化物RSSR。第三种策略研究Cat[SH]或Cat[S-TMS] IL中[MoX 4]复合物的硫解。最后，硫族化物离子液体在低温合成富含硫族元素的多硫族化物、硫族化物间和硫族化物间材料中的益处计划被探索。