Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 57, Issue 4, Pages 1025-1029Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201710443
Keywords
azobenzene thiols; grain edges; photoisomerization; substrate-mediated charge transfer; tip-enhanced Raman spectroscopy
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Funding
- Chinese Scholarship Council
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An understanding of the photoisomerization mechanism of molecules bound to a metal surface at the molecular scale is required for designing photoswitches at surfaces. It has remained a challenge to correlate the surface structure and isomerization of photoswitches at ambient conditions. Herein, the photoisomerization of a self-assembled monolayer of azobenzene-thiol molecules on a Au surface was investigated using scanning tunneling microscopy and tip-enhanced Raman spectroscopy. The unique signature of the cis isomer at 1525 cm(-1) observed in tip-enhanced Raman spectra was clearly distinct from the trans isomer. Furthermore, tip-enhanced Raman images of azobenzene thiols after ultraviolet and blue light irradiation are shown with nanoscale spatial resolution, demonstrating a reversible conformational change. Interestingly, the cis isomers of azobenzene-thiol molecules were preferentially observed at Au grain edges, which is confirmed by density functional theory.
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