Theoretical Investigation of the Te₄Br₂ Molecule in Ionic Liquids

Abstract

Material synthesis in ionic liquids, at or near room temperature, is currently a subject of immense academic interest. In order to illuminate molecular‐level details and the underlying chemistry, we carried out molecular simulations of a single Te4Br2 molecule dissolved in the ionic liquid 1‐ethyl‐3‐methylimidazolium chloride, as well as in the ionic liquid mixed with aluminum chloride. Although the ethyl side chain is much too short to show detailed microheterogeneity, significant structuring with the small chloride anions is seen in case of the pure ionic liquid. In the case of the mixture, formation of larger anionic clusters is distinctly observed and analyzed. Due to the tendency of ionic liquids to dissociate, there is a pronounced shift to elongated Te–Br distances in both investigated solvents. However, only in the AlCl3‐containing liquid, we observe the reaction of the open chain‐like Te4Br2 molecule to a closed square‐like Te4Br+ and AlCl3Br– ion. The molecular arrangement of the [Te4]2+ unit shows negligible deviation from that in the experimental crystal structure.

First examples of organosilica-based ionogels: synthesis and electrochemical behavior

“…Computational methodology. The ab initio molecular dynamics (AIMD) simulations in which the forces are calculated from the electronic structure on the fly were carried out as described previously [ 41 ] using the cp2k program packages [ 42 ]. AIMD simulation was started from a classical molecular dynamics simulation snapshot of 32 ion pairs of [BmimSO 3 H][PTS] under periodic boundary conditions.…”

Lewis Acidic Ionic Liquids

“…3 towards tetrahedral [AlX 4 ] -, thus leading to crystallization [148]. The role of chloroaluminate(III) anions was studied computationally by Kirchner and co-workers [149] . The ellipsoids are at 90% probability level [153] 3 Liquid Coordination Complexes (LCCs)…”

ADUC Prizes: U.‐P. Apfel, P. Heretsch, O. Hollóczki / Carl Duisberg Memorial Award: B. Morandi / Elected to the Académie des Sciences: E. Charpentier, J. Cossy, I. Marek / Max Delbrück Junior Prize: S. Disch / Novartis Early Career Award: B. Morandi and R. R. Knowles

“…Hollóczki's research interests include the use of static DFT and ab initio calculations as well as molecular dynamics simulations for the theoretical investigation of catalyst systems, as well as the design of liquids that function as both solvent and catalyst/reagent. He is co‐author of a report in the Zeitschrift für anorganische und allgemeine Chemie on a theoretical investigation of Te 4 Br 2 in ionic liquids, and he has reported in Angewandte Chemie on the mechanism of azolium ion catalysis …”