Precision molecular threading/dethreading

Jessica Groppi, Lorenzo Casimiro, Martina Canton, Stefano Corra, Mina Jafari-Nasab, Gloria Tabacchi, Luigi Cavallo, Massimo Baroncini, Serena Silvi, Ettore Fois, Alberto Credi
Angewandte Chemie, (2020)

Keywords

Kinetics, Metadynamics, Molecular machine, Supramolecular Chemistry, Rotaxane

Abstract

​The general principles guiding the design of molecular machines based on interlocked structures are well known. Nonetheless, the identification of suitable molecular components for a precise tuning of the energetic parameters that determine the mechanical link is still challenging. Indeed, what are the reasons of the “all‐or‐nothing” effect, which turns a molecular “speed‐bump” into a stopper in pseudorotaxane‐based architectures? Here we investigate the threading and dethreading processes for a representative class of molecular components, based on symmetric dibenzylammonium axles and dibenzo[24]crown‐8 ether, with a joint experimental‐computational strategy. From the analysis of quantitative data and an atomistic insight, we derive simple rules correlating the kinetic behaviour with the substitution pattern, and provide rational guidelines for the design of modules to be integrated in molecular switches and motors with sophisticated dynamic features.

Code

https://doi.org/10.1002/anie.202003064

Sources

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