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

Research output: Contribution to journalArticle

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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 (US)
Pages (from-to)7774-7778
Number of pages5
JournalNano letters
Volume16
Issue number12
DOIs
StatePublished - Dec 14 2016

Fingerprint

Ultrahigh vacuum
ultrahigh vacuum
Raman spectroscopy
switches
spatial resolution
Switches
Porphyrins
porphyrins
Metals
Scanning probe microscopy
Molecules
room temperature
Adsorbates
Isomers
metal surfaces
Conformations
molecules
isomers
microscopy
Temperature

All Science Journal Classification (ASJC) codes

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

Cite this

Chiang, Naihao ; Chen, Xing ; Goubert, Guillaume ; Chulhai, Dhabih V. ; Chen, Xu ; Pozzi, Eric A. ; Jiang, Nan ; Hersam, Mark C. ; Seideman, Tamar ; Jensen, Lasse ; Van Duyne, Richard P. / Conformational Contrast of Surface-Mediated Molecular Switches Yields Ångstrom-Scale Spatial Resolution in Ultrahigh Vacuum Tip-Enhanced Raman Spectroscopy. In: Nano letters. 2016 ; Vol. 16, No. 12. pp. 7774-7778.
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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 {\AA} 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 {\AA}ngstrom-scale spatial resolution, thereby establishing it as a leading method for the study of metal-adsorbate interactions.",
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Conformational Contrast of Surface-Mediated Molecular Switches Yields Ångstrom-Scale Spatial Resolution in Ultrahigh Vacuum Tip-Enhanced Raman Spectroscopy. / Chiang, Naihao; Chen, Xing; Goubert, Guillaume; Chulhai, Dhabih V.; Chen, Xu; Pozzi, Eric A.; Jiang, Nan; Hersam, Mark C.; Seideman, Tamar; Jensen, Lasse; Van Duyne, Richard P.

In: Nano letters, Vol. 16, No. 12, 14.12.2016, p. 7774-7778.

Research output: Contribution to journalArticle

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AU - Pozzi, Eric A.

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AU - Jensen, Lasse

AU - Van Duyne, Richard P.

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