Tetrahomo corona[4]arene-based spirophanes: synthesis, structure, and properties

Area of Science:

• Supramolecular Chemistry
• Organic Synthesis
• Materials Science

Background:

• Macrocyclic chemistry extensively studies compounds like cyclodextrins and crown ethers.
• Spirocyclic compounds, particularly spirophanes, remain relatively unexplored in supramolecular chemistry.
• There is a need for novel macrocyclic scaffolds with unique structural and functional properties.

Purpose of the Study:

• To synthesize and characterize unprecedented tetrahomo corona[4]arene-based spirocyclic macrocycles.
• To investigate the structural, conformational, and chiroptical properties of these novel compounds.
• To explore their potential for complexation with guest molecules like tetrathiafulvalene (TTF).

Main Methods:

• Efficient nucleophilic aromatic substitution (S_NAr) reactions were employed for synthesis.
• Racemic mixtures of spirophanes were resolved into enantiopure forms.
• Solid-state structural analysis and chiroptical property measurements were performed.

Main Results:

• Novel ditopic and tritopic spirophanes based on tetrahomo corona[4]arene scaffolds were successfully constructed.
• Enantiopure chiral spirophanes and bispirophanes exhibiting interesting chiroptical properties were obtained.
• Electron-deficient macrocycles adopted unique conformations and formed distinct complexes with TTF in the solid state.

Conclusions:

• This study introduces a new class of spirocyclic macrocycles with tunable topologies.
• The developed spirophanes offer unique structural features and chiroptical properties.
• These findings open avenues for developing advanced materials for supramolecular chemistry applications.