Novel self-adaptive boat-shaped complexes with a tetraphosphine ligand

Area of Science:

• Supramolecular Chemistry
• Coordination Chemistry
• Host-Guest Chemistry

Background:

• Calixarene-based ligands are versatile scaffolds in supramolecular chemistry.
• Tetraphosphine ligands offer unique coordination properties for metal complexation.
• Host-guest systems are crucial for molecular recognition and encapsulation.

Purpose of the Study:

• To design and synthesize novel boat-shaped host-guest complexes.
• To investigate the self-adaptive encapsulation of various anions.
• To elucidate the role of non-covalent interactions in host-guest complexation.

Main Methods:

• Self-assembly of a calixarene-based tetraphosphine ligand (L) with Group 11 metal salts (Cu(I) and Ag(I)).
• Anion exchange reactions to introduce different guest anions.
• Density Functional Theory (DFT) calculations to analyze host-guest interactions.

Main Results:

• Successful synthesis of novel boat-shaped host-guest complexes.
• Demonstration of self-adaptive encapsulation of anions of varying sizes.
• Identification of M(i)-O coordinations and CHπ interactions as key binding forces.
• DFT calculations confirmed the significant role of CHπ interactions in the self-adaptive phenomenon.

Conclusions:

• The designed boat-shaped host exhibits self-adaptive anion binding capabilities.
• CHπ interactions are crucial for the selective and adaptive encapsulation of guest anions.
• This work expands the scope of calixarene-based supramolecular hosts for anion recognition.