Helicene-Based Chiral Macrocycles and Molecular Cages: Synthetic Strategies, Chiroptical Modulation, and Emerging
Zewei Qi1, Jianjian Zhao1, Leyong Zhou1
1State Key Laboratory of Petroleum Molecular & Process Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Shanghai Frontiers Science Center of Molecule Intelligent Syntheses, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, China.
Helicene-based macrocycles and molecular cages offer tunable, enzyme-like cavities for advanced applications. This review details their synthesis, chiroptical properties, and potential in chiral functional materials.
Area of Science:
- Supramolecular Chemistry
- Organic Chemistry
- Materials Science
Background:
- Macrocycles and molecular cages mimic enzyme active sites with engineered cavities.
- Helicenes, with rigid, chiral structures, are ideal scaffolds for complex supramolecular architectures.
- These structures exhibit unique properties like circularly polarized luminescence (CPL) and enantioselective recognition.
Purpose of the Study:
- To provide a comprehensive overview of recent advances in helicene-based macrocycle and cage construction.
- To highlight synthetic strategies, chiroptical property modulation, and applications.
- To critically discuss challenges and future opportunities in the field.
Main Methods:
- Review of coordination and covalent synthesis strategies for helicene-based architectures.
- Analysis of methods for tuning chiroptical properties, including CPL.
- Discussion of applications in enantioselective recognition and guest adsorption.
Main Results:
- Helicene scaffolds enable the creation of highly distorted chiral macrocycles and cages.
- These architectures show enhanced CPL, enantioselective recognition, and guest adsorption capabilities.
- Recent advances in synthetic methodologies and applications have been detailed.
Conclusions:
- Helicene-derived macrocycles and cages offer a promising framework for advanced chiral functional materials.
- Addressing challenges like fluorescence quenching and synthetic complexity is crucial for future development.
- Opportunities lie in stimuli-responsive designs and dynamic covalent strategies for novel applications.
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