Controlling intramolecular hydrogen transfer in a porphycene molecule with single atoms or molecules located nearby
Journal article, 2014

Although the local environment of a molecule can play an important role in its chemistry, rarely has it been examined experimentally at the level of individual molecules. Here we report the precise control of intramolecular hydrogen-transfer (tautomerization) reactions in single molecules using scanning tunnelling microscopy. By placing, with atomic precision, a copper adatom close to a porphycene molecule, we found that the tautomerization rates could be tuned up and down in a controlled fashion, surprisingly also at rather large separations. Furthermore, we extended our study to molecular assemblies in which even the arrangement of the pyrrolic hydrogen atoms in the neighbouring molecule influences the tautomerization reaction in a given porphycene, with positive and negative cooperativity effects. Our results highlight the importance of controlling the environment of molecules with atomic precision and demonstrate the potential to regulate processes that occur in a single molecule.

derivatives

tautomerism

manipulation

phthalocyanine

dynamics

electronics

conductance

surface

Author

T. Kumagai

Max Planck Society

F. Hanke

University of Liverpool

Accelrys Limited, UK

S. Gawinkowski

Polish Academy of Sciences

J. Sharp

University of Liverpool

K. Kotsis

University of Liverpool

J. Waluk

Polish Academy of Sciences

Mats Persson

Chalmers, Applied Physics, Materials and Surface Theory

L. Grill

University of Graz

Max Planck Society

Nature Chemistry

1755-4330 (ISSN) 1755-4349 (eISSN)

Vol. 6 1 41-46

Subject Categories

Chemical Engineering

DOI

10.1038/NCHEM.1804

More information

Latest update

10/30/2018