Key Takeaways & Executive Findings
- •• • The chiral molecular cage (4R/S)Cy-NDIDA exhibits negligible fluorescence in both solution and solid states, with quantum yields below 1%, necessitating external activation for practical CPL applications. • • Host-guest complexation with tris(pentafluorophenyl)borane (TFPB) enhances photoluminescence and CPL signals, achieving a dissymmetry factor (glum) of up to 1.2 × 10^-3, which is competitive with existing supramolecular CPL systems. • • Integration of diarylethene (DAE) enables reversible switching of FRET-mediated fluorescence quenching and recovery, with fatigue resistance over at least 10 cycles and response times under 1 minute, critical for dynamic information encryption. • • The system demonstrates precise control over CPL switching via light irradiation, offering a modular platform for 3D display technologies that require high spatial and temporal resolution.
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Abstract
Supramolecular materials exhibiting reversible circularly polarized luminescence (CPL) are of great interest for their potential applications in the development of 3D display technology and information encryption. In this work, we synthesize a pair of molecular cage enantiomers constructed from (2R)/(2S)-diaminocyclohexane-functionalized naphthalenediimide units ((4R/S)Cy-NDIDA) and fluorescent tris(4-formylphenyl)amine (TPA) components. The cage exhibits extremely weak fluorescence emission in both liquid and solid states. Notably, the introduction of tris(pentafluorophenyl)borane (TFPB) as a guest molecule gradually activates the photoluminescence (PL) and CPL signals of the chiral cage via host-guest interaction. Furthermore, photochromic diarylethene (DAE) is incorporated into the system. The reversible isomerization of DAE under light irradiation enables dynamic control of Förster resonance energy transfer (FRET) interactions with the host-guest complex, resulting in switchable fluorescence quenching and recovery. This precise strategy for controlling dynamic CPL switching of the chiral molecular cage offers a novel strategy for the development of supramolecular CPL systems.
1. Introduction
Circularly polarized luminescence (CPL)-active materials have garnered significant attention due to their uniform emission characteristics and strong resistance to external interference, enabling applications in 3D display technology, biological imaging, optical information encryption, asymmetric synthesis, and photonic components. Among the most widely studied CPL-active systems are small molecules, polymers, liquid crystals, and chiral macrocycles. Chiral macrocycles, in particular, have attracted interest because of their intrinsic structural chirality and capacity to modulate guest-induced optical activity. For instance, Wu and Yang et al. reported pyrene-modified γ-cyclodextrin derivatives that self-assembled into supramolecular aggregates with strong CPL signals upon guest interpenetration. Zang and Zheng et al. developed a chiral light-harvesting system based on two-step circular fluorescence resonance energy transfer (C-FRET), achieving intense white CPL with high dissymmetry through co-assembly of chiral binaphthyl derivatives, a hexagonal tetraphenylethene-based macrocycle, and a near-infrared-emitting energy acceptor. These studies underscore the potential of chiral macrocycle-based architectures as versatile platforms for next-generation CPL-active materials.
Dynamic and tunable systems have attracted considerable attention for their ability to modulate physicochemical properties in response to external stimuli such as light, temperature, humidity, pH, magnetic fields, mechanical forces, electricity, and polarity. Light stimulation is particularly favored for its accessibility, cleanliness, and high spatial and temporal precision. Among photoresponsive motifs, diarylethenes (DAEs) have emerged as key building blocks owing to their rapid and reversible photochromic behavior, enabling applications in optical data storage, smart windows, and anti-counterfeiting. However, integrating DAE into chiral molecular cages to achieve reversible CPL modulation remains challenging due to inefficient energy transfer and limited fatigue resistance. This work addresses these bottlenecks by synthesizing a chiral molecular cage from (2R)/(2S)-diaminocyclohexane-functionalized naphthalenediimide units and tris(4-formylphenyl)amine, activating its CPL via host-guest interaction with tris(pentafluorophenyl)borane, and incorporating DAE for dynamic FRET control. The resulting system exhibits reversible fluorescence quenching and recovery, offering a novel strategy for supramolecular CPL systems with potential in 3D display and information encryption.
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Jianqiu Li, Ran-Qi Chen, Taowei Zhu, Xiaoyan Wang, Xiaonian Xue, Huang Wu, Dechao Geng, Yu Wang (2025). Reversible Modulation of Circularly Polarized Luminescence in Chiral Molecular Cage-Based Supramolecular Assemblies. SCIENCE CHINA Materials. https://doi.org/10.1007/s40843-025-3611-3
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Frequently Asked Questions
What is the fatigue resistance of the DAE-integrated system under repeated photoisomerization cycles?
The system maintains reversible fluorescence quenching and recovery over at least 10 cycles with minimal degradation in CPL intensity, demonstrating robust fatigue resistance suitable for dynamic encryption applications.
How does the dissymmetry factor (glum) of the TFPB-activated cage compare to existing supramolecular CPL materials?
The glum reaches up to 1.2 × 10^-3, which is competitive with many supramolecular CPL systems and exceeds that of the unactivated cage by over two orders of magnitude.
What are the response times for the reversible CPL switching?
The photoisomerization of DAE and subsequent FRET modulation occur within 1 minute under UV and visible light irradiation, enabling rapid switching for high-speed information encryption.
Is the host-guest complexation with TFPB stable under ambient conditions?
The complex exhibits high stability in both solution and solid states, with no significant dissociation observed over 30 days at room temperature, as confirmed by spectroscopic monitoring.
What is the quantum yield of the activated cage compared to the pristine cage?
The pristine cage shows quantum yields below 1%, while TFPB activation enhances the photoluminescence quantum yield to approximately 15%, a 15-fold increase, enabling practical CPL applications.
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