Computational investigation of the structures, properties, and host‐guest chemistry of prism[n]arenes

Abstract The discovery of new and functional macrocyclic host compounds is an important part of supramolecular chemistry. Since the experimental synthesis, prism[ n ]arenes (Pr[ n ]As), a class of naphthol‐based macrocyclic arenes, have attracted much attention. In this work, from the perspective of theoretical calculation and research, Pr[ n ]As ( n = 4 ~ 7) were studied by density functional theory (DFT) calculations and molecular dynamics (MD) simulations. The prismatic configuration isomers, electronic structures, absorption spectra, and host‐guest chemistry were discussed thoroughly. DFT calculation results showed that 1,5‐, 3,7‐, and “hybrid” 15,37‐Pr[ n ]As were the most representative configurations with the rigid prismatic molecular skeleton. Based on time‐dependent density functional theory (TD‐DFT), the absorption spectra of Pr[ n ]As were all in the range of ultraviolet light which were mainly attributed to π‐π * transitions. The molecular cavities of Pr[ n ]As were electron‐rich and capable of accommodating a variety of cations or electron‐conjugated molecules. MD simulation results showed that a Pr[ n ]A molecule was able to capture the guest molecule into its molecular cavity and maintain in the state of equilibrium in solvents.