On the Auxetic Potential of Synthesizable Calix[4]arene Polymers

Materials exhibiting auxetic behavior have garnered significant interest due to their potential applications across various fields, with synthetic auxetic materials being one such group. Theoretical studies have demonstrated the potential for various organic polymeric systems to exhibit auxetic behavior. However, to date, only a few synthesized molecular systems have shown some degree of auxetic behavior. Among the theoretical classes of molecular systems that have attracted attention are calix[4]arene systems in the “egg‐rack” conformation. While the theoretical systems proposed in the literature have been deemed difficult to synthesize, calix[4]arene chemistry has advanced tremendously in recent years. In fact, a number of molecular systems with configurations similar to those predicted to exhibit a negative Poisson's ratio have been synthesized, albeit with different chemical moieties. Consequently, it is deemed valuable to study the potential of these synthesized systems to exhibit a negative Poisson's ratio through force‐field‐based simulations. This study is extended to include theoretical calix[4]arene systems linked by acetylene moieties, which are also potentially synthesizable through known methods. It is suggested that these materials can exhibit auxetic behavior when subjected to on‐axis loading in the [001] direction. A detailed mechanistic study of these systems is also conducted.