Supramolecular Exchange Reaction in the Cavity of Naphthalene Diimides Extended‐Pillar[6]arene

Abstract A new naphthalene diimides extended‐pillar[6]arene 1 with a large cavity and rich host‐guest complexation properties was synthesized in high yield. It can not only form 1 : 2 complexes with large size polycyclic aromatic hydrocarbons but also form 1 : 1 : 1 ternary complex with perylene and 2,7‐diazapyrenium. Moreover, the supramolecular exchange reaction from a 1 : 2 host‐guest complex 1 ⋅ (G3) 2 formed by 1 and perylene to a 1 : 1 : 1 ternary complex 1 ⋅ G3 ⋅ G5 formed by 1 with perylene and 2,7‐diazapyrenium salt was also investigated by 1 H NMR experiments as well as theoretically calculations.