Modeling Coordination-Directed Self-Assembly of M₂L₄ Nanocapsule Featuring Competitive Guest Encapsulation

Exploring the mechanism of self-assembly and guest encapsulation of nanocapsules is highly imperative for the design of sophisticated molecular containers and multistimuli-responsive functional materials. Here we present a molecular dynamics simulation protocol with implicit solvent and simulated annealing techniques to investigate the self-assembly and competitive guest (C₆₀ and C₇₀ fullerenes) encapsulation of a M₂L₄ nanocapsule that is self-assembled by the coordination of mercury cations and bent bidentate ligands. Stepwise formation of the nanocapsule and competitive fullerene encapsulation during dynamic structural changes in the self-assembly were detected successfully. Such processes were driven by coordination bonding and π–π stacking and obey the minimum total potential energy principle. Potential of mean force calculations for guest binding to the M₂L₄ nanocapsule explained the mechanism underlying the competitive encapsulations of C₆₀ and C₇₀. This work helps design new functional nanomaterials capable of guest encapsulation and release