Embracing C(60) with multiarmed geodesic partners

Area of Science:

• Supramolecular Chemistry
• Organic Synthesis
• Materials Science

Background:

• Corannulene, a unique curved polycyclic aromatic hydrocarbon, serves as a versatile platform for constructing host molecules.
• Functionalized corannulenes with thioether linkages offer tailored electronic and steric properties for molecular recognition.

Purpose of the Study:

• To synthesize novel pentakis- and tetrakis-substituted thiophenyl corannulene derivatives.
• To investigate the host-guest complexation behavior of these corannulenes with C(60) fullerenes.

Main Methods:

• Synthesis via chlorination of corannulene followed by nucleophilic aromatic substitution with sodium thiophenolates.
• Characterization using spectroscopic techniques.
• Binding studies employing (1)H NMR titration in toluene-d(8).

Main Results:

• Successful synthesis of 1,3,5,7,9-pentakis(4-methoxyphenylthio)corannulene, 1,3,5,7,9-pentakis(2-naphthylthio)corannulene, and 1,3,6,8-tetrakis(4-methoxyphenylthio)corannulene.
• Demonstration of 1:1 complex formation between the synthesized corannulenes and C(60) fullerenes.
• Quantification of association constants (454, 368, and 280 M(-1)) for the respective complexes.

Conclusions:

• The synthesized corannulene derivatives act as effective hosts for C(60) fullerenes.
• The binding affinity is influenced by the nature and position of the thiophenyl substituents.
• These findings highlight the potential of functionalized corannulenes in fullerene encapsulation and separation.