Theoretical exploration of noncovalent interactions in Sc₂C₂@C₂ (n = 40, 41, and 42)⊂[12]CPP, PF[12]CPP.

Area of Science:

• Supramolecular Chemistry
• Materials Science
• Computational Chemistry

Background:

• Fullerene encapsulation by carbon nanorings creates unique complexes with tunable properties.
• Host-guest interactions significantly impact metal ion orientation and electronic structure within these complexes.

Purpose of the Study:

• To computationally investigate the encapsulation of carbide cluster metallofullerenes by [12]cycloparaphenylene ([12]CPP) and perfluoro[12]cycloparaphenylene (PF[12]CPP).
• To compare the suitability of [12]CPP and PF[12]CPP as hosts for fullerene encapsulation.

Main Methods:

• Dispersion-corrected density functional theory (DFT) calculations were employed.
• Analysis included binding energies, thermodynamic data, charge population, energy decomposition, and real-space functions.

Main Results:

• PF[12]CPP exhibited a significantly lower deformation rate upon complex formation compared to [12]CPP.
• [12]CPP demonstrated greater suitability for fullerene encapsulation based on binding energy and thermodynamic analysis.
• PF[12]CPP facilitated greater electron transfer to the encapsulated metallofullerenes (Sc2C2@Cn, n=40, 41, 42).

Conclusions:

• Perfluoro[12]cycloparaphenylene is a more effective host material for fullerene encapsulation than [12]cycloparaphenylene.
• Detailed analysis of noncovalent interactions provides a fundamental understanding of these supramolecular systems.
• The findings support the development of novel host-guest systems utilizing metallofullerenes.