Long‐Distance Rate Acceleration by Bulk Gold

We report on a very unusual case of surface catalysis involving azobenzenes in contact with a Au(111) surface. We observe a rate acceleration (up to 1300‐fold) of cis‐trans isomerization on gold, compared to solution. By using carefully designed molecular frameworks we are able to systematically tune the electronic coupling to the surface. 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. Besides their impact on catalytic processes, these effects could be used to trigger reactions over long distances.

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