A simple approach for the preparation of symmetrical quaternary ammonium bromides employing thiol–ene click chemistry is used to synthesize tetra(4-thiaalkyl)ammonium bromides. This approach allows the incorporation of a variety of alkyl moieties onto the nitrogen center with a one-step synthesis involving easy work-up, no side reactions and environmentally friendly reagents. To elucidate information regarding the behaviour of this novel class of compounds, comparisons to tetraalkylammonium analogues have been made. These include melting points, activity as phase-transfer catalysts, and conformational predictions from computational modelling. All results are consistent in indicating stronger bonding between the quaternary cation and the anion for the salts with 4-thiaalkyl chains as compared to those with n-alkyl chains.

Boronium (+3) cations, L4B3+, are rare and scarcely studied. But, thanks to their rigid tetrahedral shape and high cationic charge they may be promising tectons for creating hybrid organic-inorganic solids, especially since a single cation can serve as a nucleating center around which three anions can be assembled. However, the few boronium (+3) cations which have been reported are generally water-sensitive, a factor which is a potential impediment to the former endeavor (as is the case with many perovskite photovoltaics). Herein we report the synthesis and characterization (X-ray, NMR, DSC, TGA, CV) of multiple boronium (+3) salts, all of which are highly water stable across the 1-14 pH range. And, as a preliminary investigation of the template-tecton hypothesis, the BETI- [bis(pentafluoroethanesulfonyl)imide] salt of a representative cation was prepared. Significantly, the crystals of the latter were determined by X-ray crystallography to feature continuous, fluorine-rich veins.