Premium
Long‐Distance Rate Acceleration by Bulk Gold
Author(s) -
Schlimm Alexander,
Löw Roland,
Rusch Talina,
Röhricht Fynn,
Strunskus Thomas,
Tellkamp Tobias,
Sönnichsen Frank,
Manthe Uwe,
Magnussen Olaf,
Tuczek Felix,
Herges Rainer
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201814342
Subject(s) - intersystem crossing , isomerization , chemical physics , coupling (piping) , relaxation (psychology) , acceleration , catalysis , photochemistry , chemistry , molecule , kinetics , materials science , atomic physics , physics , excited state , classical mechanics , organic chemistry , psychology , social psychology , singlet state , metallurgy
We report on a very unusual case of surface catalysis involving azobenzenes in contact with a Au(111) surface. A rate acceleration of the cis–trans isomerization on gold up to a factor of 1300 compared to solution is observed. By using carefully designed molecular frameworks, the electronic coupling to the surface can be systematically tuned. The isomerization kinetics of molecules with very weak coupling to the metal is similar to that found in solution. For their counterparts with strong coupling, the relaxation rate is shown to depend on the spin‐density distribution in the triplet states of the molecules. This suggests that an intersystem crossing is involved in the relaxation process. Aside from their impact on catalytic processes, these effects could be used to trigger reactions over long distances.