Atomistic Insights into Hydrogen-Bonded Supramolecular Capsule Self-Assembly Dynamics

In this work, we have delved into the intricate assembly dynamics of hydrogen-bonded supramolecular calixarene capsules, particularly focusing on the disparities between resorcinarenes and pyrogallolarenes. Through enhanced sampling simulations, we mapped out the fundamental thermodynamic, structural, and mechanistic details governing the assembly of these capsules in apolar solvents. Notably, our findings highlight the paramount influence of dimer formation, mediated substantially by inter- and intramolecular hydrogen bonding interactions. Furthermore, we observed that water plays an instrumental role in the assembly of resorcinarene, though its kinetic contribution is mitigated by its swift diffusion. Solvent encapsulation analysis suggests that pyrogallolarene capsules can accommodate more solvent molecules relative to their resorcinarene counterparts, an attribute most likely resulting from the absence of water in pyrogallolarene structures. These insights not only offer a detailed understanding of the calixarene assembly dynamics but also showcase the potential adaptability of the methodology to other assembly systems, thereby propelling its implications into broader chemical and biological domains.