A Diastereodynamic Probe Transducing Molecular Length into Chiroptical Readout

Area of Science:

• Supramolecular Chemistry
• Chiral Materials
• Molecular Recognition

Background:

• Nature utilizes molecular conformational changes for functions like signaling and allosteric activation.
• Synthetic systems employ molecular recognition to induce conformational changes for catalysis and sensing.
• Transduction of stereochemical information, particularly chiral information, is a key strategy in synthetic chemistry.

Purpose of the Study:

• To design and synthesize a chiral supramolecular cage with stereodynamic units.
• To investigate the cage's ability to invert helicity based on guest molecular length.
• To demonstrate the transduction of achiral information into chiroptical signals.

Main Methods:

• Construction of a chiral supramolecular cage incorporating two stereodynamic units.
• Encapsulation of molecular guests of varying lengths within the supramolecular cage.
• Analysis of chiroptical properties (e.g., circular dichroism) in response to guest inclusion.

Main Results:

• The supramolecular cage exhibits stereodynamic units that invert helicity depending on the confined guest's length.
• Achiral molecular dimension information is transduced into distinct diastereomeric states with opposite chiroptical absorptions.
• Continuous modulation of chiroptical output is achieved by varying the physical dimension of achiral guests.

Conclusions:

• This work presents the first example of a supramolecular system capable of continuous chiroptical modulation based on achiral guest dimension.
• The developed system offers potential for programming conformational control and developing novel sensors.
• It enables the transduction of molecular properties into measurable chiroptical information.