Not by Serendipity: Rationally Designed Reversible Temperature-Responsive Circularly Polarized Luminescence Inversion by Coupling Two Scenarios of Harata–Kodaka’s Rule

[Image: see text] Intelligent control over the handedness of circularly polarized luminescence (CPL) is of special significance in smart optoelectronics, information storage, and data encryption; however, it still remains a great challenge to rationally design a CPL material that displays reversible handedness inversion without changing the system composition. Herein, we show this comes true by coupling the two scenarios of Harata–Kodaka’s rule on the same supramolecular platform of crystalline microtubes self-assembled from surfactant–cyclodextrin host–guest complexes. Upon coassembling a linear dye with its electronic transition dipole moment outside of the cavity of β-CyD, the chirality transfer from the induced chirality of SDS in the SDS@2β-CyD microtubes to the dye generates left-handed CPL at room temperature. Upon elevating temperature, the dye forms inclusion complex with β-CyD, so that right-handed CPL is induced because the polar group of the dye is outside of the cavity of β-CyD. This process is completely reversible. We envision that host–guest chemistry would be very promising in creating smart CPL inversion materials for a vast number of applications.