Search

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. [ABSTRACT FROM AUTHOR]

[Display omitted] • A supramolecular catalytic strategy for the alkene hydrosilylation is presented by using DFT calculations. • Anti-Markovnikov mechanism is confirmed with and without cucurbiturils. • The hydrosilylation can be well catalyzed by cucurbit[6]uril as a reaction container with thermodynamic and kinetic advantages. • The cavity size of a molecular container and the host–guest interactions are critical to the catalytic properties. Transition metal catalysts have been widely used in hydrosilylation reactions. However, these catalysts result in many adverse consequences for precise control of reactions and sustainable development of valuable resources. In this work, a transition metal-free catalytic strategy is proposed, which is a supramolecular catalysis based on cucurbituril (CB[ n ]) as a reaction container. To shed new insight into the alkene hydrosilylation, DFT calculations are carried out at the ωB97XD/6-311G(d,p) level of theory. The geometrical structures, frontier molecular orbitals, non-covalent interactions, thermodynamics, and kinetics of the reaction systems are discussed systematically. It is found that CB6 can catalyze the title hydrosilylation by activating the reactants, reducing the reaction barriers, and increasing the reaction rate constants. This finding will bring a new opportunity for the development of hydrosilylation reactions. [ABSTRACT FROM AUTHOR]