Nanojars are supramolecular assemblies of the formula [anionÌ{Cu(µ-OH)(µ-pz)}n] (n = 27-33) which incarcerate kosmotropic anions, such as carbonate (CO32-), sulfate (SO42-) and hydrogen phosphate (HPO42-). Nanojars consist of three [Cu(µ-OH)(µ-pz)]x (x = 6-14, except 11) rings that are assembled similarly to Matryoshka dolls, where the top and bottom rings act as guests for the central ring. The larger central ring is bound to the two smaller rings by multiple hydrogen bonds and weak oxygen-copper interactions. The three-ring assembly acts as a neutral host for the incarcerated anion. The host binds the anion by a multitude of hydrogen bonds and is capped by tetrabutylammonium countercations. This project investigates: 1) the synthesis of tellurite (TeO32-), selenite (SeO32-), thiosulfate (S2O32-) and sulfite (SO32-) incarcerating nanojars under conditions that reduce the presence of CO32- nanojar impurities, 2) the chemical etching of nanojar mixtures (containing nanojars of different sizes, n = 27-33) using ammonia, leading to a single nanojar size, and 3) the strength of sulfate binding in nanojars by using hydrophobic Ba2+ salts to promote BaSO4 precipitation in organic solvents.

Synthesis and characterization of chalcogen oxyanion-incarcerating nanojars

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

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