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

The discovery of new and functional macrocyclic host compounds is an important part of supramolecular chemistry. Since the experimental synthesis, prismn]arenes (Prn]As), a class of naphthol-based macrocyclic arenes, have attracted much attention. In this work, from the perspective of theoretical calculation and research, Prn]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-Prn]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 Prn]As were all in the range of ultraviolet light which were mainly attributed to π-π* transitions. The molecular cavities of Prn]As were electron-rich and capable of accommodating a variety of cations or electron-conjugated molecules. MD simulation results showed that a Prn]A molecule was able to capture the guest molecule into its molecular cavity and maintain in the state of equilibrium in solvents.