Force-induced tautomerization in a single molecule

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...

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Bibliographic Details
Published in:Nature chemistry 2016-10, Vol.8 (10), p.935-940
Main Authors: Ladenthin, Janina N., Frederiksen, Thomas, Persson, Mats, Sharp, John C., Gawinkowski, Sylwester, Waluk, Jacek, Kumagai, Takashi
Format: Article
Language:English
Subjects:
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147/138
147/3
639/638/542
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639/925
Analytical Chemistry
Biochemistry
Chemical bonds
Chemical reactions
Chemistry
Chemistry/Food Science
Electrons
Heat transfer
Hydrogen
Inorganic Chemistry
Microscopy
Organic Chemistry
Physical Chemistry
Science
Xenon
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Summary: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. Force-induced tautomerization in a single porphycene molecule is investigated on a Cu(110) surface at 5 K by using non-contact atomic force microscopy. The force needed to trigger the tautomerization process is quantified by force spectroscopy and theoretical calculations reveal the atomistic mechanism behind the reaction.
ISSN:1755-4330
1755-4349
DOI:10.1038/nchem.2552