In Situ Regulation of Microphase Separation-Recognized Circularly Polarized Luminescence via Photoexcitation-Induced Molecular Aggregation

Circularly polarized luminescence (CPL) has attracted great interest owing to its extensive optical information and chiral structural dependence. However, rationally regulating solid-phase CPL signals remains difficult because of the close packing of molecules in solid-state materials and the lack of structural visualization. In this work, we proposed a microphase-separation-recognized CPL regulation strategy via coassembly of a hexathiobenzene-based luminophore and chiral block copolymer (cBCP) with in situ photocontrollability. As a consequence to the continuous increase in the luminophore-to-cBCP ratio, the CPL signal of the supramolecular system exhibited an increasing trend until a critical point. Then, further increasing the ratio stretched the helical pitch of cBCP, which led to CPL reduction. With the photoexcitation-induced molecular aggregation of the luminophore, which was implemented using in situ photoirradiation, the helical pitch was retracted along with the restoration of the CPL signal. These processes were fully recognized and monitored by the microphase-separated nanomorphological change of the coassembled system, which indicated that such a structural contrast could be an effective method for rationally regulating the supramolecular chiropticity of solid-state materials.