On the Reaction of Naphthalene Diimides with Fluoride Ions: Acid/Base versus Redox Reactions

The characterization of a naphthalene diimide (NDI) radical anion is presented. Its properties allow a reliable comparison point for other systems involving the NDI radical anion, such as systems claimed to perform the oxidation of the fluoride anion. In addition to reiterating the obvious thermodynamic objections to such an unlikely oxidation, we present several observations that show that the fluoride anion does not act as a one‐electron reducing agent toward the NDI investigated in this work.     

Synthesis,Structure, and Anion Binding Properties of Electron‐Deficient Tetrahomocorona[4]arenes: Shape Selectivity in Anion–π Interactions

Tetrahomocorona[2]arene[2]tetrazines were constructed by means of a fragment coupling strategy based on nucleophilic aromatic substitution reaction starting from 3,6‐dichlorotetrazine and o‐, m‐, and p‐bis(hydroxymethyl)benzenes. The unprecedented macrocycles gave rectangular box‐like cavities with tunable cavity sizes and deficient electronic properties depending on the substitution pattern of phenylene. Due to anion–π interactions, they formed complexes selectively with azide and thiocyanate owing to complementary shapes between host and guest.