A supramolecular C60S8 adduct: dynamic and interaction energy considerations of an orbiting S8 motif from MD + EDA calculations

Abstract

Dynamics of supramolecular complexes serve to rationalize the constant motion inherent to the formation of non-covalent adducts. Here, the C₆₀S₈ adduct is evaluated through the combined molecular dynamics energy decomposition analysis approach (MD + EDA), unraveling the constant orbit-like motion of S₈ around the C₆₀ fullerene globe, showing comparable supramolecular interaction energies for the entire dynamic process, arising from a balance between stabilizing (electrostatic, London dispersion, orbital) and destabilizing (Pauli repulsion) forces. Thus, molecular dynamics simulations reveal the dynamic flexibility, with the S₈ ring freely reorienting in relation to the C₆₀ surface, remaining at a similar distance with similar interaction energy. The charge transfer analysis indicates negligible net electron transfer, but interestingly, the calculated electronic coupling and charge hopping rates suggest efficient charge transport. These findings highlight the delicate interplay of weak non-covalent interactions governing the formation of the C₆₀–S₈ system and its potential for supramolecular charge transport applications, combining dynamic adaptability with specific binding properties for applications in supramolecular chemistry and related fields.