Dodecameric Anion-Sealed Capsules based on Pyrogallol[5]arenes and Resorcin[5]arenes

The paper reports formation of exceptionally large capsular species (diameter of c. a. 30 Å) by interactions of polyphenolic macrocycles with 5-fold symmetry with anions. Pyrogallol[5]arenes and resorcin[5]arenes interact with anions via hydrogen bonds involving phenolic OH groups or aromatic CH groups. Based on NMR titration experiments, diffusion coefficients, and geometric requirements, it is postulated that the capsules have (P5H)₁₂ (X^- )₆₀ or (R5H)₁₂ (X^- )₆₀ stoichiometry and a unique geometry of one of the Platonic solids-a dodecahedron. The capsules exist in THF and in benzene, but not in chloroform, reflecting competitive effects in the solvation of anions. It is also demonstrated that mechanochemical pre-treatment (dry-milling) of solid samples is indispensable to initialize self-assembly in benzene.