Force-induced tautomerization in a single molecule

Ladenthin, Janina N, Frederiksen, Thomas, Persson, MO ORCID: 0000-0002-1443-9490, Sharp, John C, Gawinkowski, Sylwester, Waluk, Jacek and Kumagai, Takashi (2016) Force-induced tautomerization in a single molecule. Nature Chemistry, 8 (10). pp. 935-940.

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Abstract

Heat transfer, electrical potential and light energy are common ways to activate chemical reactions. Applied force is another way, but dedicated studies for such a mechanical activation are limited, and this activation is poorly understood at the single-molecule level. Here, we report force-induced tautomerization in a single porphycene molecule on a Cu(110) surface at 5 K, which is studied by scanning probe microscopy and density functional theory calculations. Force spectroscopy quantifies the force needed to trigger tautomerization with submolecular spatial resolution. The calculations show how the reaction pathway and barrier of tautomerization are modified in the presence of a copper tip and reveal the atomistic origin of the process. Moreover, we demonstrate that a chemically inert tip whose apex is terminated by a xenon atom cannot induce the reaction because of a weak interaction with porphycene and a strong relaxation of xenon on the tip as contact to the molecule is formed.

Item Type:	Article
Uncontrolled Keywords:	Nanoscience and technology, Scanning probe microscopy, Surface chemistry
Depositing User:	Symplectic Admin
Date Deposited:	01 Jun 2016 09:57
Last Modified:	19 Jan 2023 07:36
DOI:	10.1038/nchem.2552
Related URLs:	Author Publisher
URI:	https://livrepository.liverpool.ac.uk/id/eprint/3001468