Starting from fluoridosilicate precursors in neat cyanotrimethylsilane, Me3Si−CN, a series of different ammonium salts [R3NMe]+ (R=Et, nPr, nBu) with the novel [SiF(CN)5]2− and [Si(CN)6]2− dianions was synthesized in facile, temperature controlled F−/CN− exchange reactions. Utilizing decomposable, non‐innocent cations, such as [R3NH]+, it was possible to generate metal salts of the type M2[Si(CN)6] (M+=Li+, K+) via neutralization reactions with the corresponding metal hydroxides. The ionic liquid [BMIm]2[Si(CN)6] (m.p.=72 °C, BMIm=1‐butyl‐3‐methylimidazolium) was obtained by a salt metathesis reaction. All the synthesized salts could be isolated in good yields and were fully characterized.

Supertetrahedral chalcogenido (semi)metalate clusters have been in the focus of inorganic and materials chemistry for many years owing to a variety of outstanding physical and chemical properties. However, a critical drawback in the canon of studying corresponding compounds has been the lack of control in assembling the supertetrahedral units, which have been known as either highly charged monomeric cluster anions or lower charged, yet extended anionic substructures of linked clusters. The latter is the reason for the predominance of applications of such materials in heterogeneous environment, or their solubilization by organic shielding, which in turn was unfavorable regarding the optical properties. Recently, we reported a partial alkylation of such clusters, which allowed for a significantly enhanced solubility at a marginal impact on the optical gap. Herein we showcase the formation of finite cluster oligomers of supertetrahedral architectures by ionothermal syntheses. We were successful in generating the unprecedented dimers and tetramers of the [Ge 4 Se 10 ] 4– anion in salts with imidazolium-based ionic liquid counterions. The oligomers exhibit lower average negative charges and thus reduced electrostatic interactions between anionic clusters and cationic counterions. As a consequence, the salts readily dissolve in common solvents like DMF. Besides, the tetrameric [Ge 16 Se 36 ] 8– anion represents the largest discrete chalcogenide cluster of a group 14 element. We prove that undestroyed cluster oligomers can be transferred into solution by means of electrospray ionization (ESI) mass spectrometry and provide a full set of characteristics of the compounds including crystal structures and optical properties.

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.

Ausgehend von Fluoridosilikat-Vorstufen in reinem Cyantrimethylsilan, Me 3 Si-CN,w urde eine Reihe verschiedener Ammoniumsalze[ R 3 NMe] + (R = Et, n Pr, n Bu) mit den neuen [SiF(CN) 5 ] 2À -und [Si(CN) 6 ] 2À -Dianionen in einfachen, temperaturgesteuerten F À /CN À -Austauschreaktionen synthetisiert. Mit zersetzbaren, nicht-unschuldigen Kationen wie [R 3 NH] + konnten Metallsalzed es Typs M 2 [Si(CN) 6 ]( M + = Li + ,K + )d urchN eutralisationsreaktionen mit entsprechenden Metallhydroxiden hergestellt werden. Die ionische Flüssigkeit [BMIm] 2 [Si(CN) 6 ]( Schmp. = 72 8 8C) wurde durch eine Salzmetathesereaktion erhalten. Alle synthetisierten Salzekonnten in guten Ausbeuten isoliert und vollständig charakterisiert werden.

Adamantane-type organo-group 14 chalcogenide clusters were shown to possess extreme non-linear optical properties. Reactivity studies of corresponding organosilicon sulfide clusters towards copper and silver complexes indicate a replacement of exactly...