Naphth[4]arene: Synthesis, Conformations, and Application in Color‐Tunable Supramolecular Crystalline Assemblies

Although the chemistry of macrocyclic arenes has seen rapid development in recent years, the synthesis of new macrocyclic arenes from aromatic rings with no directing groups remains a challenge. In this work, a new macrocyclic arene, naphth[4]arene (NA[4]A), composed of four naphthalene rings bridged by methylene groups, was synthesized using macrocycle‐to‐macrocycle conversion. NA[4]A shows 1,3‐alternate and 1,2‐alternate conformations in the solid state, which can be selectively obtained. By supramolecular co‐assembly of NA[4]A and 1,2,4,5‐tetracyanobenzene (TCNB) in different concentrations and temperatures, two conformation‐dependent crystalline luminescent co‐assemblies 1,2‐NTC and 1,3‐NTC can be selectively prepared. Interestingly, the two charge‐transfer crystalline assemblies containing NA[4]A with different conformations show bright yellow and green fluorescence, and also display high photoluminescence quantum yields (PLQYs) of 45 % and 43 %. Furthermore, they exhibit color‐tunable two‐photon excited upconversion emission.