Introducing Prism[4]arene: A Macrocycle with Enantiomerically Resolvable Inherent Chirality and Intriguing
Paolo Della Sala1, Carmen Talotta1, Margherita De Rosa1
1Laboratory of Supramolecular Chemistry, Dipartimento di Chimica e Biologia "A. Zambelli", Università di Salerno, Via Giovanni Paolo II 132, 84084 Fisciano, Salerno, Italy.
Journal of the American Chemical Society
|June 4, 2025
Summary
Researchers report the first inherently chiral prismarenes with resolved enantiomers. These unique molecules maintain chirality and show potential for enantioselective recognition of guests.
Area of Science:
- Supramolecular Chemistry
- Organic Chemistry
- Chirality Studies
Background:
- Prismarenes are macrocyclic compounds with potential applications in molecular recognition.
- Achieving and resolving enantiomers of complex macrocycles remains a synthetic challenge.
- Understanding the factors that stabilize chirality in strained systems is crucial.
Purpose of the Study:
- To synthesize and resolve enantiomers of an inherently chiral prismarene.
- To investigate the chiroptical properties, including circularly polarized luminescence (CPL).
- To demonstrate the enantioselective recognition capabilities of the resolved prismarenes.
Main Methods:
- Thermodynamic template synthesis using selective cations.
- Chiral high-performance liquid chromatography (HPLC) for enantiomer resolution.
- Time-dependent density functional theory (TDDFT) and ECD/UV-vis spectroscopy for configurational assignment.
Main Results:
- Successful synthesis and resolution of prism[4]arene enantiomers (PrS[4]iPe).
- Solid-state structure revealed racemic crystals forming supramolecular polymeric chains.
- Significant CPL properties with a dissymmetry ratio of 0.008 were observed.
- Demonstrated enantioselective recognition of chiral ammonium guests.
Conclusions:
- The synthesized prismarenes exhibit stable inherent chirality due to strained structures.
- Resolved enantiomers possess distinct chiroptical properties, including CPL.
- These chiral prismarenes are promising candidates for enantioselective host-guest chemistry.
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