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

Abstract

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.

Self-Assembly and Circularly Polarized Luminescence from Achiral Pyrene-Adamantane Conjugates by Selective Inclusion with Cyclodextrins

“…In this case, CPL was directly induced from the chiral cavity. Similar to the previous report on induced CPL, 20,29 when β-CD interacted with lumiphores in different types, reversed CPL signals were observed here. In the case of γ-CD, at low concentrations, Pyr was predominantly included into the large cavity at the beginning and an induced CPL with negative sign was obtained.…”

Surfactant-induced chirality transfer, amplification and inversion in a cucurbit[8]uril–viologen host–guest supramolecular system

“…Ionic surfactants have been reported to help chirality transfer from the molecular scale to the macroscopic scale due to their electrostatic and noncovalent interactions that could influence the supramolecular self-assembly. 60,61 These surface species could also enhance the supramolecular chirality as their amphiphilic properties could guide the molecules to assemble towards specific directions. In order to generate sufficient chirality in L4/CB[8] supramolecules, we selected sodium dodecyl sulfate (SDS) as an anionic surfactant in this work.…”

Two‐Dimensional Chiral Polyrotaxane Monolayer with Emergent and Steerable Circularly Polarized Luminescence

“…Since 1 Lb and 1 La were the electronic transitions of the short and long axis of pyrenes, it could be inferred that the long axis of Pyr was parallel to the axis of the βCD cavity according to Harata's rule (Figure 3d) [15] . Moreover, 2D CPR displayed a strong induced negative CPL signal at 450 nm for the chiral βCD wheels (Figure 3e), the sign of which was identical to most cyclodextrin‐based rotaxanes [7f, 15b, 16] . In comparison, neither ECD nor CPL was detected for COF due to the absence of βCD.…”