Conformational Contrast of Surface-Mediated Molecular Switches Yields Ångstrom-Scale Spatial Resolution in Ultrahigh Vacuum Tip-Enhanced Raman Spectroscopy

Naihao Chiang, Xing Chen, Guillaume Goubert, Dhabih V. Chulhai, Xu Chen, Eric A. Pozzi, Nan Jiang, Mark C. Hersam, Tamar Seideman, Lasse Jensen, Richard P. Van Duyne

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67 Scopus citations


Tip-enhanced Raman spectroscopy (TERS) combines the ability of scanning probe microscopy (SPM) to resolve atomic-scale surface features with the single-molecule chemical sensitivity of surface-enhanced Raman spectroscopy (SERS). Here, we report additional insights into the nature of the conformational dynamics of a free-base porphyrin at room temperature adsorbed on a metal surface. We have interrogated the conformational switch between two metastable surface-mediated isomers of meso-tetrakis(3,5-ditertiarybutylphenyl)-porphyrin (H2TBPP) on a Cu(111) surface. At room temperature, the barrier between the porphyrin ring buckled up/down conformations of the H2TBPP-Cu(111) system is easily overcome, and a 2.6 Å lateral resolution by simultaneous TERS and STM analysis is achieved under ultrahigh vacuum (UHV) conditions. This work demonstrates the first UHV-TERS on Cu(111) and shows TERS can unambiguously distinguish the conformational differences between neighboring molecules with Ångstrom-scale spatial resolution, thereby establishing it as a leading method for the study of metal-adsorbate interactions.

Original languageEnglish (US)
Pages (from-to)7774-7778
Number of pages5
JournalNano letters
Issue number12
StatePublished - Dec 14 2016

Bibliographical note

Funding Information:
Xing C., D.V.C., L.J., and R.P.V.D. acknowledge support from the National Science Foundation Center for Chemical Innovation dedicated to Chemistry at the Space-Time Limit (CaSTL) Grant CHE-1414466. N.C., E.A.P., N.J., T.S., M.C.H., and R.P.V.D. acknowledge support from the Department of Energy Office of Basic Energy Sciences (SISGR Grant DE-FG02-09ER16109) and the National Science Foundation Materials Research Science and Engineering Center (NSF DMR-1121262). G.G., Xu C., and R.P.V.D acknowledge support from the Air Force Office of Scientific Research MURI (FA9550-14-1-0003)

Publisher Copyright:
© 2016 American Chemical Society.


  • Ultrahigh vacuum
  • conformational isomers
  • nanoscale chemical imaging
  • single molecule spectroscopy
  • tip-enhanced Raman spectroscopy


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