Self‐Assembly of Adaptive Chiral [1]Rotaxane for Thermo‐Rulable Circularly Polarized Luminescence

Abstract It remains a formidable challenge to realize thermo‐rulable circularly polarized luminescence (CPL). Herein, we propose a new strategy by covalently “potting” the emitter into a flexible chiral macrocycle as an adaptive chiral [1]rotaxane to address this issue. Different from its included analogue, the potted emitter [DS] showed adaptive conformers with tunable CPL in varied solvents. Significantly, upon controlled self‐assembly, [DS] formed a channel‐type nanoarchitecture ( [DS] A ), which exhibited an extraordinary thermo‐rulable CPL between 25–100 °C. Impressively, the g lum was large as 0.024 at 25 °C, which was amplified to 0.040 at 90 °C with a decrease of QY (from 92 % to 80 %). By comparison, the assemblies of cage‐type [DS] B and the unpotted emitter showed irreversible or unanswered thermal behaviors. The work demonstrated the thermo‐rulable and durable CPL for the first time and provided an insightful understanding of thermal effect on high‐temperature and switchable CPL materials.