Tautomerization of single asymmetric oxahemiporphycene molecules on Cu(111)

Jaekel, Simon, Durant, Emile, Schied, Monika, Persson, Mats ORCID: 0000-0002-1443-9490, Ostapko, Jakub, Kijak, Michal, Waluk, Jacek and Grill, Leonhard (2022) Tautomerization of single asymmetric oxahemiporphycene molecules on Cu(111). PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 25 (2). pp. 1096-1104.

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Official URL: http://dx.doi.org/10.1039/d2cp04746b

Abstract

We have studied 22-oxahemiporphycene molecules by a combination of scanning tunneling microscopy at low temperatures and density functional theory calculations. In contrast to other molecular switches with typically two switching states, these molecules can in principle exist in three different tautomers, due to their asymmetry and three inequivalent binding positions of a hydrogen atom in their macrocycle. Different tautomers are identified from the typical appearance on the surface and tunneling electrons can be used to tautomerize single molecules in a controllable way with the highest rates if the STM tip is placed close to the hydrogen binding positions in the cavity. Characteristic switching processes are explained by the different energy pathways upon adsorption on the surface. Upon applying higher bias voltages, deprotonation occurs instead of tautomerization, which becomes evident in the molecular appearance.

Item Type:	Article
Divisions:	Faculty of Science and Engineering > School of Physical Sciences
Depositing User:	Symplectic Admin
Date Deposited:	04 May 2023 09:22
Last Modified:	04 May 2023 09:22
DOI:	10.1039/d2cp04746b
Open Access URL:	https://doi.org/10.1039/D2CP04746B
Related URLs:	Author Publisher
URI:	https://livrepository.liverpool.ac.uk/id/eprint/3170143