Arene‐Perfluoroarene Force Driven Sublimation‐Removable Chiral Coassemblies.

Multiple constituent coassembly is an emerging strategy to manipulate supramolecular chirality and chiroptical properties such as circularly polarized luminescence (CPL). However, the second or third constituent could not be removed from pristine self‐assembly. Here we developed a constitute‐removable chiral coassembly using sublimation that could realize coassembly with tunable supramolecular chirality, luminescence and CPL properties. Octafluoronapthalene (OFN) with small sublimation enthalpy formed coassemblies with perylene‐conjugated peptoids via arene‐perfluoroarene (AP) interaction that induced the emergence of macroscopic chirality and hypsochromic luminescence from yellow to green. Coassembly with OFN accelerated one‐dimensional growth and induced the emergence of macroscopic chirality and CPL. Despite the stability at ambient conditions, vacuum‐treatment triggered fast sublimation of OFN, which behaved as a sacrificial template. Physical removal of OFN retained the helical nanoarchitectures as well as the basic features of Cotton effects and CPL activities. X‐ray diffraction suggested the back‐fill consolidation occurred on the molecular voids by OFN removal that slightly varied the templated molecular arrangements. Sublimation of perfluorinated building units is green and efficient and non‐destructive, which is potentially applicable in constructing template‐directed chiroptical materials and devices. [ABSTRACT FROM AUTHOR]