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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Abstract

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
Pages (from-to)7774-7778
Number of pages5
JournalNano Letters
Volume16
Issue number12
DOIs
Publication statusPublished - Dec 14 2016

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Keywords

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

ASJC Scopus subject areas

  • Bioengineering
  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics
  • Mechanical Engineering

Cite this

Chiang, N., Chen, X., Goubert, G., Chulhai, D. V., Chen, X., Pozzi, E. A., Jiang, N., Hersam, M. C., Seideman, T., Jensen, L., & Van Duyne, R. P. (2016). Conformational Contrast of Surface-Mediated Molecular Switches Yields Ångstrom-Scale Spatial Resolution in Ultrahigh Vacuum Tip-Enhanced Raman Spectroscopy. Nano Letters, 16(12), 7774-7778. https://doi.org/10.1021/acs.nanolett.6b03958