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Supramolecular Architecture of Chiral Macrocycles: Hierarchical Assembly and Confinement Effect for Enhanced Circularly Polarized Luminescence
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DOI：10.1021/accountsmr.6c00071.png)
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Abstract
En 中文
ConspectusCircularly polarized luminescence has emerged as a cutting-edge research field owing to its dual significance in advancing the fundamental understanding of chiral excited states and enabling the design of novel functional materials. A central challenge in realizing efficient CPL lies in the effective integration of chirality with the luminescent moieties. Conventional strategies, often based on covalent bonding between chiral and luminescent units in small molecules, frequently lead to systems that show either no or only weak CPL. Meaningfully, supramolecular assembly offers a transformative alternative by facilitating chiral transfer and amplifying the CPL signals. In a broader context, supramolecular assembly serves as a foundational methodology for constructing macroscopic functional supramolecular architectures from molecular-scale building blocks. More importantly, by regulating noncovalent interactions, supramolecular approaches enable efficient chirality transfer from chiral sites to assembled luminescent architecture, even allowing achiral luminophores to display stronger CPL activity through simple mixing or doping. Moreover, such an assembled architecture can significantly enhance CPL intensity, greatly broadening the scope of high-performance CPL-active materials.Macrocycles are fundamental to supramolecular chemistry owing to their critical roles in molecular recognition. However, most macrocycles are intrinsically achiral or exhibit poor chirality in their isolated molecular state, posing a significant challenge for effective integration of chirality with luminophores and subsequent amplification of CPL. This Account presents an innovative strategy to address this issue through a hierarchical confinement effect at both molecular and supramolecular assembly levels. We demonstrate how chirality can be introduced or transferred within a macrocycle-based hierarchical assembled architecture to generate and enhance CPL signals. Key advances discussed include the successful induction and propagation of chirality via hierarchical assembly of the macrocyclic supramolecular architecture under a multiple confinement effect, leading to efficient activation and substantial amplification of CPL within the supramolecular system. Specific approaches encompass (1) steering CPL by organizing macrocycles into helical architecture for supramolecular chirality induction, transfer, and signal amplification; (2) tuning CPL through spatial confinement of achiral luminophores within chiral inner cavities of the hierarchical macrocyclic assembled architecture; and (3) modulating CPL via macrocycle outward surface-mediated coassembly of guests for precise control of the morphology and CPL. Collectively, these multiple confinement effects establish a systematic framework for manipulating the chiroptical properties of the hierarchically assembled nanoarchitectures. Beyond advancing the fundamental understanding of chiral luminescence, these methodologies enable the rational design of high-performance CPL-active materials.
Keywords:
Chirality
Luminescence
Macrocycles
Materials
Supramolecular structures and assemblies
Journal
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14.7
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Citations:
5.2K
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