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

doi:10.1021/acs.nanolett.6b03958

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^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

113 Scopus citations

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 language	English (US)
Pages (from-to)	7774-7778
Number of pages	5
Journal	Nano letters
Volume	16
Issue number	12
DOIs	https://doi.org/10.1021/acs.nanolett.6b03958
State	Published - Dec 14 2016

Funding

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)

Keywords

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

ASJC Scopus subject areas

Bioengineering
General Chemistry
General Materials Science
Condensed Matter Physics
Mechanical Engineering

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10.1021/acs.nanolett.6b03958

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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

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title = "Conformational Contrast of Surface-Mediated Molecular Switches Yields {\AA}ngstrom-Scale Spatial Resolution in Ultrahigh Vacuum Tip-Enhanced Raman Spectroscopy",

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.",

keywords = "Ultrahigh vacuum, conformational isomers, nanoscale chemical imaging, single molecule spectroscopy, tip-enhanced Raman spectroscopy",

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

note = "Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

year = "2016",

month = dec,

day = "14",

doi = "10.1021/acs.nanolett.6b03958",

language = "English (US)",

volume = "16",

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Chiang, N, Chen, X, Goubert, G, Chulhai, DV, Chen, X, Pozzi, EA, Jiang, N, Hersam, MC , Seideman, T, Jensen, L & Van Duyne, RP 2016, 'Conformational Contrast of Surface-Mediated Molecular Switches Yields Ångstrom-Scale Spatial Resolution in Ultrahigh Vacuum Tip-Enhanced Raman Spectroscopy', Nano letters, vol. 16, no. 12, pp. 7774-7778. https://doi.org/10.1021/acs.nanolett.6b03958

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T1 - Conformational Contrast of Surface-Mediated Molecular Switches Yields Ångstrom-Scale Spatial Resolution in Ultrahigh Vacuum Tip-Enhanced Raman Spectroscopy

AU - Chiang, Naihao

AU - Chen, Xing

AU - Goubert, Guillaume

AU - Chulhai, Dhabih V.

AU - Chen, Xu

AU - Pozzi, Eric A.

AU - Jiang, Nan

AU - Hersam, Mark C.

AU - Seideman, Tamar

AU - Jensen, Lasse

AU - Van Duyne, Richard P.

PY - 2016/12/14

Y1 - 2016/12/14

N2 - 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.

AB - 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.

KW - Ultrahigh vacuum

KW - conformational isomers

KW - nanoscale chemical imaging

KW - single molecule spectroscopy

KW - tip-enhanced Raman spectroscopy

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ER -

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

Abstract

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Keywords

ASJC Scopus subject areas

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