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![EDX map of the solid reaction products from the synthesis in [P66614]Cl after 16 h at 200 °C. Left: Au+2 Te; particle with unreacted gold in a shell of AuTe2. Right: 2 Ag+Te; even large particles show homogenous distribution of silver and tellurium in the molar ratio 2 : 1.](publication/345546084/figure/fig2/AS:11431281181916697@1692218639835/EDX-map-of-the-solid-reaction-products-from-the-synthesis-in-P66614Cl-after-16h-at.png)
EDX map of the solid reaction products from the synthesis in [P66614]Cl after 16 h at 200 °C. Left: Au+2 Te; particle with unreacted gold in a shell of AuTe2. Right: 2 Ag+Te; even large particles show homogenous distribution of silver and tellurium in the molar ratio 2 : 1.
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![EDX map of the solid reaction products from the synthesis in [P66614]Cl...](publication/345546084/figure/fig2/AS:11431281181916697@1692218639835/EDX-map-of-the-solid-reaction-products-from-the-synthesis-in-P66614Cl-after-16h-at_Q320.jpg)
![PXRD patterns of Ag2Te from 2 Ag+Te with [P66614]Cl. 60 °C is the...](publication/345546084/figure/fig3/AS:11431281181897546@1692218640457/PXRD-patterns-of-Ag2Te-from-2Ag-Te-with-P66614Cl-60C-is-the-lowest-temperature-at_Q320.jpg)
![Section of the ³¹P‐NMR spectrum of commercial [P66614]Cl. The frame is...](publication/345546084/figure/fig4/AS:11431281181916699@1692218641713/Section-of-the-P-NMR-spectrum-of-commercial-P66614Cl-The-frame-is-zoomed-in-on-one_Q320.jpg)
![³¹P‐NMR spectra of the IL (a) of [P66614]Cl after the reaction with...](publication/345546084/figure/fig5/AS:11431281181897549@1692218642142/P-NMR-spectra-of-the-IL-a-of-P66614Cl-after-the-reaction-with-tellurium-and-b_Q320.jpg)
The low temperature syntheses of AuTe2 and Ag2Te starting from the elements were investigated in the ionic liquids (ILs) [BMIm]X and [P66614]Z ([BMIm]+=1‐butyl‐3‐methylimidazolium; X = Cl, [HSO4]−, [P66614]+ = trihexyltetradecylphosphonium; Z = Cl−, Br−, dicyanamide [DCA]−, bis(trifluoromethylsulfonyl)imide [NTf2]−, decanoate [dec]−, acetate [OAc]−...
Citations
... According to the literature, the reaction in bulk form between silver and tellurium occurs at 475 °C [24], while the reaction between gold and tellurium is reported at 300-500 °C [27]. In the case of thin films, we studied the growth in the temperature range of 100-350 °C for the downstream furnace under an isobaric condition (pressure of 1 atm/760 torr) and with a 10 sccm Ar/H2 flux (H2 4% vol.) as a carrier gas. ...
... As a result, the control of the reaction product in the CVD system is more complicated in the case of silver tellurization experiments rather than the gold ones. We have According to the literature, the reaction in bulk form between silver and tellurium occurs at 475 • C [24], while the reaction between gold and tellurium is reported at 300-500 • C [27]. In the case of thin films, we studied the growth in the temperature range of 100-350 • C for the downstream furnace under an isobaric condition (pressure of 1 atm/760 torr) and with a 10 sccm Ar/H 2 flux (H 2 4% vol.) as a carrier gas. ...
Developing a method for the growth of ultrathin metal chalcogenides, potentially targeting the two-dimensional (2D) limit, has a pivotal impact on various nanotechnological device applications. Here, we employed a vapor deposition scheme, based on tellurization, to induce the heterogenous chemical reaction between solid Ag and Au precursors, in the form of ultrathin films, and Te vapors. We characterized the morphological and structural properties of the grown tellurides by using atomic force microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy and X-ray diffraction techniques. The developed tellurization methodology provides a key advancement in the picture of growing ultrathin noble metal tellurides and holds great potential for applications in different technological fields.
... 93 Nb NMR has been reported for the characterization of ILs containing peroxoniobate anions [32]. 125 Te NMR chemical shifts have been reported to characterize the reaction of trialkylphosphonium cation in the IL, [P 66614 ]Cl with elemental tellurium [33], and to identify the formation of polycationic clusters [Te 8 ][NTf 2 ] 2 in ILs [34]. 127 I NMR chemicals shifts and linewidths have been used to identify the formation of polyiodides and probe local environment in iodide-based ILs, [C n mim][I] (with n = 1, 2, 3, 4, 6, and 12) [35]. ...
This review presents recent developments in the application of NMR spectroscopic techniques in the study of ionic liquids. NMR has been the primary tool not only for the structural characterization of ionic liquids, but also for the study of dynamics. The presence of a host of NMR active nuclei in ionic liquids permits widespread use of multinuclear NMR experiments. Chemical shifts and multinuclear coupling constants are used routinely for the structure elucidation of ionic liquids and of products formed by their covalent interactions with other materials. Also, the availability of a multitude of NMR techniques has facilitated the study of dynamical processes in them. These include the use of NOESY to study inter-ionic interactions, pulsed-field gradient techniques for probing transport properties, and relaxation measurements to elucidate rotational dynamics. This review will focus on the application of each of these techniques to investigate ionic liquids.
... [22,23] Below 100°C, the activation of tellurium in phosphonium ILs proceeded without the formation of R 3 PÀ Te and thus preserving the IL. [24] [P 66614 ]Cl, subsequent reaction of the solution with silver or gold yielded the respective metal tellurides. [24] These results indicate a temperature-and anion-specific behavior of phosphonium ILs, especially when the anion can be considered as a base. ...
... [24] [P 66614 ]Cl, subsequent reaction of the solution with silver or gold yielded the respective metal tellurides. [24] These results indicate a temperature-and anion-specific behavior of phosphonium ILs, especially when the anion can be considered as a base. The color of the solutions suggests the formation of oligotellurides in the IL. ...
... When testing various phosphonium-based ionic liquids for the synthesis of silver and gold tellurides, starting from the elements, some ionic liquids containing the anions [DCA] À , [dec] À or [OAc] À showed insufficient reaction to tellurides but strong red coloration of the liquid phase. [24] After addition of EtOH, DCM or THF, the solution turned into a brownish-black suspension of tellurium particles. The red reaction mixtures of ionic liquids were found to be stable over the long term under inert conditions after all solid components had been separated (see Figure S1 in Supporting Information). ...
Elemental tellurium readily dissolves in ionic liquids (ILs) based on tetraalkylphosphonium cations even at temperatures below 100 °C. In the case of ILs with acetate, decanoate, or dicyanamide anions, dark red to purple colored solutions form. A study combining NMR, UV‐Vis and Raman spectroscopy revealed the formation of tellurium anions (Ten)²⁻ with chain lengths up to at least n=5, which are in dynamic equilibrium with each other. Since external influences could be excluded and no evidence of an ionic liquid reaction was found, disproportionation of the tellurium is the only possible dissolution mechanism. Although the spectroscopic detection of tellurium cations in these solutions is difficult, the coexistence of tellurium cations, such as (Te4)²⁺ and (Te6)⁴⁺, and tellurium anions could be proven by cyclic voltammetry and electrodeposition experiments. DFT calculations indicate that electrostatic interactions with the ions of the ILs are sufficient to stabilize both types of tellurium ions in solution.
... To date,t here are only af ew case studies on the detailed reaction mechanisms. [16,[41][42][43][44][45] In comparison, the chemical reactivity of ILs in organic synthesis has been discussed in several reviews. [35,[46][47][48] Herein, we attempt to systematically and comprehensively summarize this fascinating research area from the point of view of inorganic synthesis based on the chemical reactions of ILs or DESs.Itincludes reactions of metal-containing ILs, fluorine-containing ILs,b asic ILs,c halcogen-containing ILs, and DESs.Moreover,reactions of ILs whose cations,anions, or both are incorporated into the final products are also included. ...
Ionic liquids and deep eutectic solvents are of growing interest as solvents for the resource‐efficient synthesis of inorganic materials. This Review covers chemical reactions of various deep eutectic solvents and types of ionic liquids, including metal‐containing ionic liquids, [BF4]⁻‐ or [PF6]⁻‐based ionic liquids, basic ionic liquids, and chalcogen‐containing ionic liquids. Cases in which cations, anions, or both are incorporated into the final products are also included. The purpose of this Review is to raise caution about the chemical reactivity of ionic liquids and deep eutectic solvents and to establish a guide for their proper use.
... To date, there are only a few case studies on the detailed reaction mechanisms. [16,[41][42][43][44][45] In comparison, the chemical reactivity of ILs in organic synthesis has been discussed in several reviews. [35,[46][47][48] Herein, we attempt to systematically and comprehensively summarize this fascinating research area from the point of view of inorganic synthesis based on the chemical reactions of ILs or DESs. ...
Ionic liquids and deep eutectic solvents are of growing interest as solvents for the resource‐efficient synthesis of inorganic materials. This review covers such chemical reactions of various deep eutectic solvents and types of ionic liquids, including metal‐containing ionic liquids, [BF 4 ] – or [PF 6 ] – ‐based ionic liquids, basic ionic liquids, and chalcogen‐containing ionic liquids. This includes cases, in which cations or anions or both are incorporated into the final products. The purpose of this review is to raise caution on the chemical reactivity of ionic liquids and deep eutectic solvents and to establish a guide for their proper use.
The dissolution of gray selenium in tetraalkylphosphonium acetate ionic liquids was investigated by UV-vis, NMR, and Raman spectroscopy as well as quantum chemical calculations and electrochemical methods. Acetate anions and tetraalkylphosphonium cations facilitate the formation and stabilization of oligoselenides Sen2- and cationic Se species in the ionic liquid phase. Chemical exchange of selenium atoms was demonstrated by variable-temperature 77Se NMR experiments. Additionally, uncharged cycloselenium molecules exist at high selenium concentrations. Upon dilution with ethanol, amorphous red selenium precipitates from the solution. Moreover, crystalline Se1-xTex solid solutions precipitate when elemental tellurium is added to the mixture as confirmed by powder X-ray diffraction and Raman spectroscopy.
Ionic liquids (ILs) are able to activate elements that are insoluble in common solvents. Here, the synthesis of binary antimony compounds directly from elements was explored. The 12 elements Ti–Cu, Al, Ga, In, and Te, known to form binary compounds with Sb, were reacted with Sb in [P 66614 ]Cl under inert conditions in a closed glass flask with vigorous stirring for 16 h at 200 °C. This was immediately successful in four cases and resulted in the formation of NiSb, InSb, Cu 2 Sb and Sb 2 Te 3 . The applied reaction temperature is several hundred degrees below the temperatures required for solvent‐free conversions. Compared to reactions based on diffusion in the solid state, reaction times are much shorter. The IL is not consumed and can be recycled. Since the reaction with Cu showed almost complete conversion, the influences of reaction time, temperature and medium were further investigated. Among the tested imidazolium ILs ([BMIm]Cl, [BMIm][OAc], [BDMIm]Cl) and phosphonium ILs ([P 66614 ] X , X = Cl – , [DCA] – , [OAc] – , [NTf 2 ] – ), those with chloride anion yielded the best results. In a diffusion experiment, Cu 2 Sb formed on the copper, which indicates that antimony forms mobile species in these ILs. Supplemental crystal structure data of (As 3 S 4 )[AlCl 4 ], which was ionothermally synthesized from As and S, are reported.
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, Ge, Mo, Cu, Au, Sn, In, Ti, V, Fe, Co, Ga, Ni, Al, Zn, and Sb in [P66614]Cl was tested at 100 °C, i.e. below the melting point of sulfur. Under these conditions, substantial sulfide formation occurred only for nickel (Ni3S4, Ni3S2, NiS) and copper (Cu2S, CuS). Sb showed no formation of crystalline sulfide, but after addition of EtOH, an orange material precipitated which was identified as amorphous metastibnite. Subsequently, the dissolution of antimony sulfide (Sb2S3), the main source of antimony production, in the phosphonium-based ILs [P66614][OAc] and [P66614]Cl at 100 °C was studied in detail. The dissolution proceeds without H2S evolution, and amorphous Sb2S3 can be precipitated from these solutions. Heating Sb2S3 in the Lewis-acidic IL [BMIm]Cl·4.7AlCl3 led to the crystallization of [Sb13S16Cl2][AlCl4]5, which contains a new quadruple heterocubane cation.
