[1P01-32] Poster session

[1P03] STM investigation of a plasmon-assisted pericyclic reaction on a metal surface

*Haruki Kiuchi^1,2, Hyungjun Park^1,2, Minhui Lee^1,2, Yousoo Kim^1,2,3,4, Emiko Kazuma^1,2 (1. Graduate School of Engineering, The University of Tokyo (Japan), 2. Institute of Physical and Chemical Research (RIKEN) (Japan), 3. Institute for Basic Science (IBS) (Korea), 4. Gwangju Institute of Science Technology (GIST) (Korea))

Scanning tunneling microscopy (STM) has been employed for mechanistic study on plasmon chemistry, but successful observations are largely limited to homolysis of simple molecules. To bridge the gap toward applicable plasmonic catalysis, we investigated a retro-Diels–Alder reaction at the single-molecule level as a model for pericyclic reactions, which are powerful tools for organic synthesis. This reaction was successfully induced by tunneling electron injection into deposited molecules under both dark and light-illuminated conditions. Notably, the threshold bias voltage required to induce the reaction decreased by light irradiation at the STM nanogap. This result demonstrates a novel plasmon-assisted reaction pathway where the interplay between tunneling electrons and plasmonic hot carriers induces the reaction, which would provide key insights for the rational design of efficient plasmonic catalysts.

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