Bi2S3 was dissolved in the presence of either AuCl/PtCl2 or AgCl in the ionic liquids [BMIm]Cl ⋅ xAlCl3 (BMIm=1‐n‐butyl‐3‐methylimidazolium; x=4–4.3) through annealing the mixtures at 180 or 200 °C. Upon cooling to room temperature, orange, air‐sensitive crystals of [BMIm](Bi4S4)[AlCl4]5 (1) or Ag(Bi7S8)[S(AlCl3)3]2[AlCl4]2 (2) precipitated, respectively. 1 did not form in the absence of AuCl/PtCl2, suggesting an essential role of the metal cations. X‐ray diffraction on single‐crystals of 1 revealed a monoclinic crystal structure that contains (Bi4S4)4+ heterocubanes and [AlCl4]− tetrahedra as well as [BMIm]+ cations. The intercalation of the ionic liquid was confirmed via solid state NMR spectroscopy, revealing unusual coupling behavior. The crystal structure of 2 consists of (Bi7S8)5+ spiro‐dicubanes, [S(AlCl3)3]2− tetrahedra triples, isolated [AlCl4]− tetrahedra, and heavily disordered silver(I) cations. No cation ordering took place in 2 upon slow cooling to 100 K.

We present a colloidal synthesis of quaternary Cu–Zn–In–S (CZIS) nanoplatelets (NPLs) by means of partial cation exchange. Starting with the synthesis of highly monodisperse binary CuS NPLs with lateral dimensions of ∼64 nm and thickness of ∼5 nm, we further performed a cation exchange reaction in which copper was partly replaced by indium, leading to Cu–In–S NPLs. To enhance the stability of the resulting NPLs and to improve their optical properties, we carried out the ZnS shell growth via both the heterogeneous nucleation of ZnS on the NPLs and via partial cation exchange on the surface of the particles. The latter reaction resulted, however, in rather an alloyed than the core/shell structure, whereas the reaction between zinc and sulfur precursors yielded unusual cookie-like hexagonal shaped structure, in which ZnS trigonal extensions grew only on one of the basal planes of the plates along the thickness direction. Upon ZnS growth, the lateral dimensions of the resulting core/shell CZIS/ZnS and alloyed CZIS NPLs distinctly increased to ∼80 and ∼75 nm, respectively. The analysis of the optical properties of the alloyed CZIS NPLs showed photoluminescence (PL) in the range from 780 to 820 nm depending on the reaction time and temperature. This PL signal originated mainly from small nanoparticles formed as a byproduct in the synthesis. In contrast to the alloyed NPLs, PL measurements of the core/shell CZIS/ZnS platelets showed a weak emission in the near-infrared region (PL maximum at approx. 1110 nm), which so far has rarely been reported for the copper chalcogenide-based two-dimensional structures.

The mechanism of the synthesis of copper(i) phosphide (CuP) in the ionic liquid (IL) trihexyl(tetradecyl)phosphonium chloride ([P][Cl]) was investigated. The phosphide formation is promoted by a transformation of red phosphorus (P) into mobile P molecules and a surface activation of copper caused by the IL including the Brønsted acidic impurity. The surface activation is important to obtain a quantitative product yield. Moreover, we demonstrate that single-phase CuP can also be synthesized in the nitrogen-based IL tetrabutylammonium chloride ([N][Cl]). Further substitution of the anion of the IL using tetrabutylammonium bromide ([N][Br]) or the complete replacement of the IL by a deep eutectic solvent consisting of adipic acid and betaine do not lead to single-phase CuP. Therefore, the nature of the anions present in the IL also seems to be relevant for the convenient phosphidization reaction.

Hydrothermal synthesis of ZSM-5 is an often applied but incompletely understood procedure. In comparison to current research efforts that aim to produce complex micro-mesoporous catalysts for the conversion of biogenic and bulky hydrocarbons, this work focuses on the dependency between Si/Al ratio and zeolite morphology of microporous ZSM-5 to understand and to control the synthesis process. In two series of time dependent crystallization, kinetics were analyzed at Si/Al ratio 20 and 100 to optimize the crystallization time. Subsequently, zeolites with different Si/Al ratio were obtained and character-ized. The results show a transition from a slow dissolutionrecrystallization process to a fast solid-state-transformation with increasing Si/Al ratio. This is followed by a switching morphology from clusters of small agglomerates to bigger spherical particles. Respective acid site density and zeolite morphology determine local residence time, hydride transfer behavior and finally selectivity towards aromatics and higher hydrocarbons during methanol conversion. This background should provide control of even more complex syntheses of porous catalysts.