No description available.

The research on phosphorus-chalcogen compounds enjoys a long tradition in the field of inorganic chemistry, which has led to applications such as strike-anywhere matches, precursors for metal chalcogenide thin films and versatile reagents in organic synthesis. Whereas a wide range of phosphorus-sulfur and -selenium systems is known, the literature lacks information about compounds incorporating phosphorus-tellurium bonds. This thesis describes fundamental studies that develop the basic understanding of the synthesis of phosphorus-tellurium systems and the structural characteristics of these species. The focus will be on cyclic structural motifs as these offer novel bonding modes and often an interesting reactivity. In addition, the novel compounds are compared with the properties of the sulfur and selenium analogues. Three different approaches were developed to stabilise and study compounds incorporating phosphorus-tellurium bonds: a) Stabilisation of binary organophosphorus-tellurium heterocycles by bulky substituents, b) the utilisation of P₂N₂ rings based on the dianions [{EP(NtBu)(μ-NtBu)}₂]²⁻ (E = S, Se, Te) and c) the peri-substitution of phosphorus and tellurium atoms on an acenaphthene backbone. The use of sterically demanding substituents led to the isolation of the first series of structurally characterised organophosphorus(III)-tellurium heterocycles of the type (RP)[sub]nTe[sub]m including three- to six-membered ring systems. The mild oxidation of [{EP(NtBu)(μ-NtBu)}₂]²⁻ (E = S, Se, Te) with iodine yielded macrocyclic (S, Se) or oligomeric systems (Te). Furthermore, a collection of novel P₂N₂-supported phosphorus-chalcogen heterocycles incorporating main group elements was synthesised employing [{EP(NtBu)(μ-NtBu)}₂]²⁻ (E = S, Se, Te) in metathetical reactions with main group element halides. Extension of this approach to transition metal halides generated some unusual metallocycles, as well as macrocycles and ladders incorporating coinage metals. The first peri-substituted phosphorus-tellurium species were studied regarding their interatomic and intermolecular forces. Systems of the general formula RTe–Acenap–P(iPr)₂ were shown to exhibit extensive through-space spin-spin coupling. In addition, the influence of oxidation and complexation on these interactions was investigated and the formation of peri-substituted phosphorus-tellurium cations exhibiting P–Te bonds was observed.

Current electrochemical energy storage systems are not sufficient to meet ever-rising energy storage requirements of emerging technologies. Hence, development of alternative electrode materials is inevitable. This thesis aims to establish novel electrode materials demonstrating both high energy and power density with prolonged cycle life derived from fundamental understandings on electrochemical reactions of chalcogens, such as sulfur (S) and selenium (Se). First, the effects of the pore size distribution, pore volume and specific surface area of porous carbons on the temperature-dependent electrochemical performance of S-infiltrated carbon cathodes in electrolytes having different salt concentrations are investigated. Additionally, the carbide derived carbon (CDC) synthesis temperature, electrolyte composition, and electrochemical S utilization have been correlated. The effects of thin Li-ion permeable but polysulfide non-permeable Al2O3 layer coating on the surface of S infiltrated carbon cathode are also examined. Similar with S studies, Se infiltrated ordered meso- and microporous CDC composites are prepared and the correlations between pore structure designing and electrolyte molarity are explored. Finally, this thesis demonstrates a simple process to form a protective solid electrolyte layer on the Se cathode surface in-situ. This technique adopts fluoroethylene carbonate to convert into a layer that remains permeable to Li ions, but prevents transport of polyselenides. As a whole, the correlations of multiple cell parameters, such as the cathode structure, the electrolyte composition, and operating temperature on the performances of lithium-chalcogen batteries are discussed.

Metal chalcogenides (sulfides, selenides and tellurides) are materials of current interest due to their peculiar properties such as optoelectronic, magnetooptic, thermoelectric and piezoelectric displays. These semiconducting materials have potential applications in solar cell devices, infrared detectors and ambient thermoelectric generators. Previously, these materials have been deposited by multiple-source precursor route with several problems associated with this technique. This work describes the synthesis of metal complexes (Zn, Cd, Fe, Ni, Pd, Pt) using the imidodichalcogenodiphosphinate ligand (Woollins ligand). Their thermal decomposition together with structural and spectroscopy analysis was carried out. The complexes were used as single source precursors for the deposition of cadmium selenide, cadmium phosphide, cadmium sulfide, zinc selenide, iron selenide and the tellurides of nickel, palladium, platinum and iron as thin films and powders. These were deposited by AACVD and pyrolysis. The deposited thin films and powders were characterised by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), energy dispersive analysis of X-rays (EDAX), X-ray photoelectron spectroscopy (XPS) and superconducting quantum interference device (SQUID). The cadmium complexes [Cd{iPr2P(Se)NP(Se)iPr2}2] and [Cd{iPr2P(S)NP(Se)iPr2}2] deposited the mixture of hexagonal CdSe and monoclinic Cd2P3 films at the flow rate of 160 sccm at 475 and 500 °C. At the flow rate of 240 sccm, only hexagonal CdSe was deposited from [Cd{iPr2P(Se)NP(Se)iPr2}2] at all temperatures. Hexagonal CdS and the mixture of orthorhombic Cd6P7/cubic Cd7P10 were deposited from [Cd{iPr2P(S)NP(S)iPr2}2]. The zinc complexes [Zn{iPr2P(Se)NP(Se)iPr2}2] and [Zn{iPr2P(S)NP(Se)iPr2}2] both deposited cubic ZnSe at all temperatures with the flow rates of 160 and 240 sccm. The iron complexes [Fe{(SePPh2)2N}2] and [Fe{(SePPh2NPPh2S)2N}2] deposited orthorhombic FeSe2 mixed with monoclinic Fe3Se4 by pyrolysis at 500 and 550 °C. An unresolved pattern was observed from the complex [Fe{(SePPh2NPPh2S)2N}2] at 550 °C. XPS analysis of the deposited FeSe2 showed the surface oxidation of the material, while the magnetic measurements on the sample using SQUID confirmed its ferromagnetic properties. The telluride complexes of nickel, palladium, platinum and iron deposited the metal telluride respectively as: hexagonal NiTe, hexagonal PdTe, hexagonal PtTe2 (mixed with rhombohedral PtTe) and hexagonal FeTe2. Conductivity studies on NiTe and PdTe revealed them to be insulators, while the magnetic measurements on FeTe2 indicated its antiferromagnetic behaviour.

This dissertation summarizes my research in the Nuckolls group on two projects, with a central theme of achieving control of electronic coupling in various nanoscale systems. The two studies of interest aim at the study of emerging properties from alkali-doping of polyaromatic hydrocarbons (PAH), and the synthesis of novel metal chalcogen molecular clusters. Chapter 1 is divided into two parts. Part one provides a brief history of the forces we associate with bond formation. We will learn that although defining a “chemical bond” is helpful, it is limited to our incomplete understanding of what forces contribute to its existence. The behavior of an electron in externally applied magnetic fields will be discussed, where the collective behavior of electrons in a material can be measured, showing a myriad of emerging properties. The known superconducting alkali-doped PAHs are introduced, followed by the unresolved problems of reproducibility and lack of structural data to accompany superconducting samples. Finally, the proximity of AFM to superconductivity is discussed, which could give us insights on further exploration of hight temperature organic superconductors. Part two introduces atomically precise clusters of atoms, also knows as superatoms. Various synthetic approaches to create metal chalcogenide superatoms are introduced. Next, a closer look into the cobalt selenide core, [Co6Se8], is presented. The ability to selectively substitute the ligands on this superatom, achieves dimensional control. The subunit can be seen as a 0-dimensional subunit, where it readily gives away its electrons. Furthermore, assembly of the clusters into 1-, 2-, and 3-dimensional structures is described. Chapter 2 introduces a novel approach to acquire phase pure alkali-doped PAHs, p-terphenyl specifically. Previous reports of solution-processed doping of PAH have inspired highly reliable synthesis of these salts, by employing a chelating agent to stabilize the alkali metal. The first half of chapter 2 analyzes one such crystal in detail, describing emerging AFM fluctuations. The AFM coupling between nearest neighboring p-terphenyls occurs in all three crystallographic directions. Interestingly, this coupling can be seen as an unconventional bond between two terphenyl units along the hard axis, and resembles resonance structures seen in polyacetylene. The second half of the chapter further investigates the novel method, obtaining a library of alkali-doped p-terphenyls. This approach allows for selective variation of either the alkali-metal, the chelating agent, or the electronic structure of p-terphenyl. Obtaining nearly a dozen structures allows for a study of trends of doping level and accompanied magnetic properties. Lastly, Chapter 3 proves a new mechanism for ligand substitution of cobalt selenide superatomic clusters, using an easily removable carbene as the ligand. This approach grants access to new surface ligands and core shapes to expand the properties of these superatoms. Through this approach, larger atomically precise materials can be targeted, giving rise to new types of electronic properties.

A reação de Morita-Baylis-Hillman (MBH) consiste em uma poderosa transformação química, podendo levar à formação de importantes blocos de construção em síntese orgânica. No entanto, a reação de MBH apresenta sérias limitações, principalmente no que diz respeito ao tempo reacional, ao uso de aceptores de Michael β-substituídos e à necessidade de eletrófilos secundários extremamente elétron-deficientes. Dentro desta temática, o presente trabalho investiga uma metodologia tricomponente do tipo Michael-aldol mediada por organocalcogenolatos metálicos, dando origem a adutos de MBH β-organocalcogeno funcionalizados como produto. Nestes estudos foram avaliados diferentes organocalcogenolatos metálicos (S, Se e Te), bem como diferentes aceptores de Michael (eletrófilo primário) e aldeídos (eletrófilo secundário) frente à metodologia. Tal estudo tornou possível a obtenção da (±)-Acaterina, um produto natural biologicamente ativo, em uma única etapa reacional, sendo a síntese mais curta e de maior rendimento até então relatada. Além disso, a metodologia tricomponente foi adaptada à adição de um terceiro eletrófilo no meio reacional, tornando possível a obtenção de derivados de adutos de MBH (ésteres, éteres de silício e carbonatos) também de maneira one-pot (reação tetra-componente do tipo Michael-aldol-O-funcionalização/eliminação de selenóxido). Investigando possíveis novas aplicações dos derivados de MBH produzidos, foi estudada a enolização de ésteres derivados de adutos de MBH onde se observou comportamento nucleofílico do LDA bem como de outras bases fortes. Utilizando cálculos computacionais baseados em DFT, uma coordenada de reação foi calculada para um dos sistemas nos quais LDA foi empregado e, o resultado teórico obtido está de acordo com os resultados obtidos experimentalmente. / The Morita-Baylis-Hillman reaction consists on a powerfull chemical transformation, leading to important building blocks in organic synthesis. However, the MBH presents some serious drawbacks, specially in respect to reactional time, the use of β- substituted Michael acceptors and the need for highly electron-deficient secondary electrophiles. Within this issue, the present work aims the investigation of a tricomponent Michael-aldol reaction mediated by metallic organochalcogenolates, leading to β-organochalcogen functionalized MBH adducts as products. In these studies the behavior of different metallic organochalcogenolates as well as different Michael acceptors (primary electrophile) and aldehydes (secondary electrophiles) were evaluated towards the methodology. Within this study it was possible to synthesize (±)-Acaterin, a natural bioactive compound, in a single reactional step, consisting in the shortest and higher yielding protocol related so far. Moreover, the tricomponent methodology was adapted to the addition of a third electrophile into the reactional media, allowing the preparation of MBH derivatives (esters, silicon ethers and carbonates) also in an one-pot manner (Michael-aldol-O-functionalization/selenoxide elimination four-component reaction). Investigating possible new applications of the produced MBH derivatives, the enolization of MBH esters was studied and a nucleophilic behavior was observed for LDA and for other strong bases. By means of DFT-based computational calculations, a reaction coordinate was calculated for a LDA-based enolization system and the obtained theoretical results are in agreement with the experimentally obtained results.

A reação de Morita-Baylis-Hillman (MBH) consiste em uma poderosa transformação química, podendo levar à formação de importantes blocos de construção em síntese orgânica. No entanto, a reação de MBH apresenta sérias limitações, principalmente no que diz respeito ao tempo reacional, ao uso de aceptores de Michael β-substituídos e à necessidade de eletrófilos secundários extremamente elétron-deficientes. Dentro desta temática, o presente trabalho investiga uma metodologia tricomponente do tipo Michael-aldol mediada por organocalcogenolatos metálicos, dando origem a adutos de MBH β-organocalcogeno funcionalizados como produto. Nestes estudos foram avaliados diferentes organocalcogenolatos metálicos (S, Se e Te), bem como diferentes aceptores de Michael (eletrófilo primário) e aldeídos (eletrófilo secundário) frente à metodologia. Tal estudo tornou possível a obtenção da (±)-Acaterina, um produto natural biologicamente ativo, em uma única etapa reacional, sendo a síntese mais curta e de maior rendimento até então relatada. Além disso, a metodologia tricomponente foi adaptada à adição de um terceiro eletrófilo no meio reacional, tornando possível a obtenção de derivados de adutos de MBH (ésteres, éteres de silício e carbonatos) também de maneira one-pot (reação tetra-componente do tipo Michael-aldol-O-funcionalização/eliminação de selenóxido). Investigando possíveis novas aplicações dos derivados de MBH produzidos, foi estudada a enolização de ésteres derivados de adutos de MBH onde se observou comportamento nucleofílico do LDA bem como de outras bases fortes. Utilizando cálculos computacionais baseados em DFT, uma coordenada de reação foi calculada para um dos sistemas nos quais LDA foi empregado e, o resultado teórico obtido está de acordo com os resultados obtidos experimentalmente. / The Morita-Baylis-Hillman reaction consists on a powerfull chemical transformation, leading to important building blocks in organic synthesis. However, the MBH presents some serious drawbacks, specially in respect to reactional time, the use of β- substituted Michael acceptors and the need for highly electron-deficient secondary electrophiles. Within this issue, the present work aims the investigation of a tricomponent Michael-aldol reaction mediated by metallic organochalcogenolates, leading to β-organochalcogen functionalized MBH adducts as products. In these studies the behavior of different metallic organochalcogenolates as well as different Michael acceptors (primary electrophile) and aldehydes (secondary electrophiles) were evaluated towards the methodology. Within this study it was possible to synthesize (±)-Acaterin, a natural bioactive compound, in a single reactional step, consisting in the shortest and higher yielding protocol related so far. Moreover, the tricomponent methodology was adapted to the addition of a third electrophile into the reactional media, allowing the preparation of MBH derivatives (esters, silicon ethers and carbonates) also in an one-pot manner (Michael-aldol-O-functionalization/selenoxide elimination four-component reaction). Investigating possible new applications of the produced MBH derivatives, the enolization of MBH esters was studied and a nucleophilic behavior was observed for LDA and for other strong bases. By means of DFT-based computational calculations, a reaction coordinate was calculated for a LDA-based enolization system and the obtained theoretical results are in agreement with the experimentally obtained results.

In the presented work, first principle studies on electronic structure, stability, and magnetic properties of metal chalcogenide, CrnTem clusters have been carried out within a density functional framework using generalized gradient functions to incorporate the exchange and correlation effects. The energetic and electronic stability was investigated, and it was found that they are not always correlated as seen in the cluster Cr6Te8 which has smaller gap between its HOMO (Highest Occupied Molecular Orbital) and LUMO (Lowest Unoccupied Molecular Orbital) and a high electron affinity of 3.39 eV indicating lower electronic stability whereas higher fragmentation energy indicating energetic stability. The high electron affinity shows that the stability of Cr6Te8 cluster can be enhanced by adding charge donating ligands including PEt3 to form stable Cr6Te8(PEt3)6 clusters as seen in experiments. The other cluster of interest was Cr4Te6 in which energetic stability was accompanied with electronic inertness marked by its large HOMO-LUMO gap, non-magnetic ground state and high fragmentation energy.

Conselho Nacional de Desenvolvimento Científico e Tecnológico / This work presents a study related to the synthesis and characterization of a series of clusters with chacogen-metal bonds in which the metals are mercury, silver, cobalt, nickel, palladium, cadmium and zinc. The synthetic strategy is based on the combination a building block, bis-(phenyltellurium)mercury(II), (Hg(TePh)2), as the starting material, with a series of co-ligands and metal salts. In the synthesis of the fourteen clusters presented in this work, evidence of redistribution reactions was observed and, for some syntheses, disproportion reactions occurred concomitantly. In this study the following clusters were obtained: [Hg5(PhTe)7Br3]n;[Hg6(PhTe)15Te2Ag4]n; [Hg4(TePh)7IPy]n;[Hg4(SePh)7IPy]n;[Hg8(TePh)14Te(PPhMe2)2]·DMF; [Hg11(TePh)18Te2(Py)3]·Py2;[Hg6(PhTe16)Ag4];[Hg2(TePh)4Ag2(Cl2)]n; [Hg6(TePh)16Ag4Py4]·H2O;[Hg8Te(TePh)12Cl4]-2[Ni(DMF)6]+2; {[Zn(H2O)2(OH)2]@[Hg16(TePh)32]};[Pd2(TePh)2Cl2(PPh3)2]; [Hg8Te(TePh)12Cl4]-2[Co(DMF)6]+2 and {[Cd(H2O)2(OH)2]@[Hg16(TePh)32]}. The clusters were characterized by single crystal X-ray diffraction, elemental analysis and electron microscopy with X-ray dispersive energy spectroscopy. For some clusters, thermogravimetric analysis was carried out to test their stability. / Este trabalho apresenta um estudo relacionado com a síntese e caracterização de uma série de clusters contendo ligações de organocalcogenetos e metais de transição como mercúrio, prata, cobalto, níquel, paládio, cádmio e zinco. A metodologia de síntese baseou-se na utilização de um bloco de montagem básico, o bis(feniltelureto) de mercúrio (Hg(TePh)2), como material de partida e uma série de coligantes além de diferentes sais de metais. Na formação dos 14 clusters apresentados neste trabalho, houve evidências de reações de redistribuição e oxi-redução. Os clusters obtidos neste trabalho foram: [Hg5(PhTe)7Br3]n; [Hg6(PhTe)15Te2Ag4]n; [Hg4(TePh)7IPy]n; [Hg4(SePh)7IPy]n; [Hg8(TePh)14Te(PPhMe2)2]·DMF; [Hg11(TePh)18Te2(Py)3]·Py2; [Hg6(PhTe16)Ag4]; [Hg2(TePh)4Ag2(Cl2)]n; [Hg6(TePh)16Ag4Py4]·H2O; Hg8Te(TePh)12Cl4]-2[Ni(DMF)6]+2; {[Zn(H2O)2(OH)2]@[Hg16(TePh)32]}; [Pd2(TePh)2Cl2(PPh3)2]; [Hg8Te(TePh)12Cl4]-2[Co(DMF)6]+2 e {[Cd(H2O)2(OH)2]@[Hg16(TePh)32]}. Estruturalmente estes clusters foram caracterizados através da difração de raios-x em monocristal. Além disso, para todos os compostos incluem-se os resultados de análise elementar, espectroscopia de energia dispersiva de raios-x (EDX) e microscopia eletrônica de varredura. Para alguns dos clusters também foram realizados testes de estabilidade térmica através da análise de termogravimetria.

As the UN summit in September 2015 addressed with the Sustainable Development Goals (SDG), our planet faces great challenges.[1] Not only since then has the role of synthetic materials chemistry been discussed in this context.[2–16] This not only concerns the development of new materials with outstanding properties such as catalysts, materials for energy conversion, and cost-efficient energy converting and storage materials, but also a reduction of the energy consumption of established functional material syntheses. Therefore, new approaches addressing the three main categories to promote the potential for energy and resource efficiency have been proposed: lowering the temperature of the synthetic processes, improving the yield and purity of the materials, and reducing the amount of waste materials. In this context a number of low-temperature processes have been established, in which mainly solvents, i.e. amines and alcohols, are used in combination with previously synthesised precursors as the solubility of the starting materials limits their usability and most elements are not soluble in these solvents. Novel solvents like ionic liquids (ILs) showcase growing interest as they are considered particularly resource-efficient.[17,18] ILs are defined as liquids that are comprised entirely of ions, with melting points below 100 °C. Continuing on from the reported work in this field, this thesis focuses on investigating the ability of ILs in the syntheses for known chalcogenides at lower temperatures and the synthesis of new materials. The main focus lies on conversions with high atom economy, especially by starting from the elements and completely recycling the IL afterwards, and mechanistic studies elucidating the intermediate dissolved species. Furthermore, as imidazolium based ILs, and their derived LEWIS-acidic ILs [BMIm]Cl/nAlCl3 mixtures, have proven to be good crystallisation media in inorganic syntheses, and the class of mostly room-temperature liquid ILs (RTILs) based on phosphonium cations [P66614]Cl showcased the ability to dissolve red phosphorous, Pred, and the heavier chalcogens S, Se, and Te, this work mainly focuses on these two IL systems. This was also chosen as an in-depth understanding of the activation and resource-efficient synthesis of these chalcogenides has still not been established. As they are RTILs, they also made the characterisation of the reactive and dissolved species by liquid state NMR, Raman, UV/Vis spectroscopy and electrochemical characterisation possible. This expands the knowledge of which main group elements and ore-like starting materials can be used in ionothermal synthesis. As a starting point the thermoelectrically interesting materials class of tellurides is addressed. The under normal conditions hard to dissolve element tellurium readily dissolves in phosphonium ILs with the cations [P66614]+ and [P4444]+. In ILs with carboxylate anions a deep purple hue of the IL already occurred by dissolving tellurium at temperatures of 60 °C. Investigations on the solutions in the acetate ILs revealed the formation of tellurium anions (Ten)2– with chain lengths up to at least n = 5, which are in a dynamic equilibrium with each other. Since external influences could be excluded and no evidence of an IL reaction was found, disproportionation of the tellurium is the only possible dissolution mechanism. However, the spectroscopic detection of tellurium cations in these solutions is difficult, but 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 in stabilizing both types of tellurium ions in solution.[19] In contrast, the acetate ILs show insufficient conversion in reactions of coin metals (Cu, Ag, Au) with tellurium to the corresponding tellurides, especially at low temperatures, however the chloride ILs successfully synthesise Cu2–xTe, CuTe, AuTe2 and Ag2Te. As the synthesis of the tellurides in neat ILs at temperatures down to 60 °C was only sufficient for the system Ag-Te, with a full conversion of the elements to Ag2Te, this was chosen as a model system for further investigations. Even at room temperature, a quantitative yield was achieved by using either 2 mol% of [P66614]Cl in dichloromethane or a planetary ball mill. The unexpected finding that phosphane-free [P66614]Cl also allows the quantitative synthesis of Ag2Te at 60°C implies an additional activation mechanism independent from the phosphane, which is yet unknown.[20] Subsequently, the manifoldly-used lighter chalcogen sulphur is tested for the synthesis of sulphides. Direct synthesis of binary sulphides 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 sulphur. Under these conditions, substantial sulphide formation occurred only for nickel (Ni3S4, Ni3S2, NiS) and copper (Cu2S, CuS). Sb showed no formation of crystalline sulphide, but after addition of EtOH, an orange material precipitated which was identified as amorphous metastibnite.[21] As generating these elements from their ores is highly energy consuming, direct dissolution experiments of the crystalline stibnite in [P66614][OAc] and Cl– were investigated and resulted in yellow solutions, from which the amorphous form can be precipitated upon exposure to EtOH air without any sign of decomposition of the IL. In particular, follow-up investigations were conducted on the solubility of Sb2S3 for follow-up chemistry in the LEWIS-acidic IL [BMIm]Cl · 4.7 AlCl3 at 160 °C which resulted in the formation of the novel chloride-terminated [Sb13S16Cl2]5+ quadruple-heterocubane cation-containing compound [Sb13S16Cl2][AlCl4]5.[21] Addition of CuCl in a slightly modified reaction resulted in the formation of the layered semiconductor Cu(Sb2S3)[AlCl4]. From this the AlCl3 can be leached by treatment with 0.1 molar hydrochloric acid, yielding a compound with the presumed composition Cu(Sb2S3)Cl.[22] As ILs showed to be able to activate elements that are insoluble in common solvents, and the formation of Sb2S3 from reactions mixtures of the elements raised the question of whether only the sulphur forms a mobile species or if antimony could additionally activated, the synthesis of binary antimony compounds directly from elements was explored as they are highly discussed as replacements for silicon-based semiconductors. Therefore the 12 elements Ti–Cu, Al, Ga, In, and Te, which are known to form binary compounds with Sb, were reacted with Sb in [P66614]Cl under inert conditions in a simple closed glass flask with vigorous stirring for 16 h at 200 °C. This resulted in the formation of NiSb, InSb, Cu2Sb and Sb2Te3. The applied reaction temperature is several hundred degrees below the temperatures required for solvent-free conversions. Compared to reactions based on diffusions 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. In a diffusion experiment, Cu2Sb formed on the copper, which indicates that antimony forms mobile species in these ILs. These systematic studies hence deliver a contribution to how ILs can help in the synthesis of new materials and how they can make a difference in the synthesis of inorganic materials as well in the context of “GREEN CHEMISTRY”. This can help in developing a more educated choice/toolbox of IL systems for reducing energy costs by reducing the temperature from high temperature inorganic syntheses to syntheses near room-temperature by using the elements as starting materials, with a high atom economy for the synthesis of known and new materials.