Systematic study on anion–cation interactions via doubly ionic H-bonds in 1,3-dimethylimidazolium salts comprising chalcogenolate anions MMIm [ER] (E = S, Se; R = H, tBu, SiMe3)

Guschlbauer, Jannick; Vollgraff, Tobias

doi:10.1039/c9dt01586h

Cited by 7 publications

(8 citation statements)

References 25 publications

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“…The C−S−Se bond angle in the former, amounting to 106.99( 14 During our search for crystal structures in the CCDC similar to the title compound, we were surprised by the paucity of terminal, singly bound selenide species that are not stabilized by an adjacent carbon−carbon double bond. One of the rare examples is a tert-butylselenide salt; 22 another one is a trifluoromethyl selenide salt, 23 and a third one is the more exotic [PPN][Se 5 C(Se)COMe] compound. 24 The title compound takes the fourth place in this series.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Synthesis, Isolation, and Characterization of a Phenylsulfane-Selenolate Compound

Jungen

Chen

2020

Inorg. Chem.

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The first example of a stable phenylsulfaneselenoate species was synthesized in a one-step process and isolated as the tetraphenylphosphonium salt [PPh4][PhSSe] as indicated by X-ray crystal structure analysis. Electrospray ionization mass spectrometry and NMR studies in solution showed the compound to enter a complex system of equilibria when dissolved. Computations suggested a high barrier for rotation around the C-S bond, indicating a π-system conjugated over the whole molecule. In general, the compound is closely related to the recently isolated [PPh4][PhS2] perthiolate salt.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Synthesis, Isolation, and Characterization of a Phenylsulfane-Selenolate Compound

Jungen

Chen

2020

Inorg. Chem.

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“…Besides coulombic interactions, hydrogen bonds and anion cation pi‐interactions greatly determine the thermal behaviour of ILs, e. g. the rather surprising sublimation and condensation of chalcogenide based ILs with dialkylimidazolium cation [4] . In order to better understand the thermal stability of such ILs and their chemical and physical behaviour, anion‐cation interactions in the crystalline and liquid phase were experimentally investigated by XRD and NMR analyses and correlated with the number and strength of anion‐cation hydrogen bonds [18] . With this basic insight ahead, we draw our attention towards coordination chemistry.…”

Section: Syntheses Of Metal Chalcogenide Materials Near Room Temperaturementioning

confidence: 99%

“…[4] In order to better understand the thermal stability of such ILs and their chemical and physical behaviour, anion-cation interactions in the crystalline and liquid phase were experimentally investigated by XRD and NMR analyses and correlated with the number and strength of anion-cation hydrogen bonds. [18] With this basic insight ahead, we draw our attention towards coordination chemistry. Homoleptic neutral complexes [M-(EÀ H) n ] or [M(E-SiMe 3 ) n ] were unknown.…”

Section: Targeting Precursors For 2d Metal Chalcogenide Materialsmentioning

confidence: 99%

“…The noncrystalline black precipitate from this three-component organic salt mix gave, after washing and annealing steps, microcrystalline quaternary chalcogenide material CZTS. [18] Although further optimization is needed in order to get absolutely phase pure CZTS with ILs of smaller and cheaper cations, this study might be seen as fundamental investigation of an optional sol-geltype condensation approach towards such multinary heavy chalcogenide materials. The challenge is to slow down the thermodynamically favoured precipitation of phase separated binary chalcogenides by organic IL cations.…”

Section: Approaching Pv Materials Cu 2 Znsn(s X Se 1à X ) 4 (Czts)mentioning

confidence: 99%

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Heavy Chalcogenide‐Based Ionic Liquids in Syntheses of Metal Chalcogenide Materials near Room Temperature

Guschlbauer

2021

ChemistryOpen

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This minireview describes two strategically different and unexplored approaches to use ionic liquids (IL) containing weakly solvated and highly reactive chalcogenide anions [E‐SiMe3]− and [E−H]− of the heavy chalcogens (E=S, Se, Te) in materials synthesis near room temperature. The first strategy involves the synthesis of unprecedented trimethylsilyl chalcogenido metalates Cat+[M(E‐SiMe3)n]− (Cat=organic IL cation) of main group and transition metals (M=Ga, In, Sn, Zn, Cu, Ag, Au). These fully characterized homoleptic metalates serve as thermally metastable precursors in low‐temperature syntheses of binary, ternary and even quaternary chalcogenide materials such as CIGS and CZTS relevant for semiconductor and photovoltaics (PV) applications. Furthermore, thermally and protolytically metastable coinage metalates Cat+[M(ESiMe3)2]− (M=Cu, Ag, Au; E=S, Se) are accessible. Finally, the use of precursors BMPyr[E‐SiMe3] (E=Se,Te; BMPyr=1‐butyl‐1‐methylpyrrolidinium) as sources of activated selenium and tellurium in the synthesis of high‐grade thermoelectric nanoparticles Bi2Se3 and Bi2Te3 is shortly highlighted. The second synthesis strategy involves the metalation of ionic liquids Cat[S−H] and Cat[Se−H] by protolytically highly active metal alkyls or amides RnM. This rather general approach towards unknown chalcogenido metalates Catm[Rn‐1M(E)]m (E=S, Se) will be demonstrated in a research paper following this short review head‐to‐tail.

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“…Besides application in classic solid state chemistry, ILs can be used as reaction media to prepare (oligomeric) metal complexes, metal organic frameworks, coordination polymers [25–35] or cluster compounds incorporating main group elements [36–41] . Within SPP 1708, the synthesis of intermetallic cluster and nanoparticles, [3,42–56] the controlled synthesis of polyanions and cations, [57–61] solvent‐free chalcogenidometal‐containing materials, [62–75] deposition of nanocrystalline materials, [76–80] ionic liquids as precursors for inorganic materials, [81–83] ionic‐liquid‐modified hybrid materials, [84–87] as well as the low‐temperature synthesis of thermoelectric materials [88–92] were investigated. Moreover, theoretical [93–106] and solubility [107–114] aspects during the synthesis process were studied.…”

Section: Introductionmentioning

confidence: 99%

Pseudohalogen Chemistry in Ionic Liquids with Non‐innocent Cations and Anions

et al. 2020

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Within the second funding period of the SPP 1708 “Material Synthesis near Room Temperature”,which started in 2017, we were able to synthesize novel anionic species utilizing Ionic Liquids (ILs) both, as reaction media and reactant. ILs, bearing the decomposable and non‐innocent methyl carbonate anion [CO3Me]−, served as starting material and enabled facile access to pseudohalide salts by reaction with Me3Si−X (X=CN, N3, OCN, SCN). Starting with the synthesized Room temperature Ionic Liquid (RT‐IL) [nBu3MeN][B(OMe)3(CN)], we were able to crystallize the double salt [nBu3MeN]2[B(OMe)3(CN)](CN). Furthermore, we studied the reaction of [WCC]SCN and [WCC]CN (WCC=weakly coordinating cation) with their corresponding protic acids HX (X=SCN, CN), which resulted in formation of [H(NCS)2]− and the temperature labile solvate anions [CN(HCN)n]− (n=2, 3). In addition, the highly labile anionic HCN solvates were obtained from [PPN]X ([PPN]=μ‐nitridobis(triphenylphosphonium), X=N3, OCN, SCN and OCP) and HCN. Crystals of [PPN][X(HCN)3] (X=N3, OCN) and [PPN][SCN(HCN)2] were obtained when the crystallization was carried out at low temperatures. Interestingly, reaction of [PPN]OCP with HCN was noticed, which led to the formation of [P(CN)2]−, crystallizing as HCN disolvate [PPN][P(CN⋅HCN)2]. Furthermore, we were able to isolate the novel cyanido(halido) silicate dianions of the type [SiCl0.78(CN)5.22]2− and [SiF(CN)5]2− and the hexa‐substituted [Si(CN)6]2− by temperature controlled halide/cyanide exchange reactions. By facile neutralization reactions with the non‐innocent cation of [Et3HN]2[Si(CN)6] with MOH (M=Li, K), Li2[Si(CN)6] ⋅ 2 H2O and K2[Si(CN)6] were obtained, which form three dimensional coordination polymers. From salt metathesis processes of M2[Si(CN)6] with different imidazolium bromides, we were able to isolate new imidazolium salts and the ionic liquid [BMIm]2[Si(CN)6]. When reacting [Mes(nBu)Im]2[Si(CN)6] with an excess of the strong Lewis acid B(C6F5)3, the voluminous adduct anion {Si[CN⋅B(C6F5)3]6}2− was obtained.

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Systematic study on anion–cation interactions via doubly ionic H-bonds in 1,3-dimethylimidazolium salts comprising chalcogenolate anions MMIm [ER] (E = S, Se; R = H, tBu, SiMe₃)

Abstract: We present convenient syntheses of so far inaccessible, crystalline and highly pure 1,3-dialkylimidazolium salts with extremely nucleophilic thiolate and selenolate anions [ER]− (R = H, tBu, SiMe3).

Cited by 7 publications

References 25 publications

Synthesis, Isolation, and Characterization of a Phenylsulfane-Selenolate Compound

Synthesis, Isolation, and Characterization of a Phenylsulfane-Selenolate Compound

Heavy Chalcogenide‐Based Ionic Liquids in Syntheses of Metal Chalcogenide Materials near Room Temperature

Pseudohalogen Chemistry in Ionic Liquids with Non‐innocent Cations and Anions

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