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

Abstract 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.