Controlling the preferential motion of chiral molecular walkers on a surface

David Abbasi Perez, Hongqian Sang, Lluisa Perez-Garcia, Andrea Floris, David B. Amabilino, Rasmita Raval, J. Manuel Recio, Lev Kantorovitch

Research output: Contribution to journalArticlepeer-review

6 Citations (Scopus)
183 Downloads (Pure)


Molecular walkers standing on two or more “feet” on an anisotropic periodic potential of a crystal surface may perform a one-dimensional Brownian motion at the surface-vacuum interface along a particular direction in which their mobility is the largest. In thermal equilibrium the molecules move with equal probabilities both ways along this direction, as expected from the detailed balance principle, well-known in chemical reactivity and in the theory of molecular motors. For molecules that possess an asymmetric potential energy surface (PES), we propose a generic method based on the application of a time-periodic external stimulus that would enable the molecules to move preferentially in a single direction thereby performing as Brownian ratchets. To illustrate this method, we consider a prototypical synthetic chiral molecular walker, the 1,3-bis(imidazol-1-ylmethyl)-5(1- phenylethyl)benzene, diffusing on the anisotropic Cu(110) surface along the Cu rows. As unveiled by our kinetic Monte Carlo simulations based on the rates calculated using ab initio density functional theory, this molecule moves to the nearest equivalent lattice site via the so-called inchworm mechanism in which it steps first with the rear and then with the front foot. As a result, the molecule diffuses via a two-step mechanism, and due to its inherent asymmetry, the corresponding PES is also spatially asymmetric. Taking advantage of this fact, we show how the external stimulus can be tuned to separate molecules of different chirality, orientation and conformation. The consequences of these findings for molecular machines and the separation of enantiomers are also discussed.
Original languageEnglish
Pages (from-to)5864-5874
Number of pages11
JournalChemical Science
Issue number23
Early online date14 May 2019
Publication statusPublished - 21 Jun 2020


Dive into the research topics of 'Controlling the preferential motion of chiral molecular walkers on a surface'. Together they form a unique fingerprint.

Cite this