---
_id: '63452'
abstract:
- lang: eng
  text: |-
    <jats:title>ABSTRACT</jats:title>
                      <jats:p>
                        The chemical reactivity of molecules can be controlled by a variety of effects, ranging from chemical reagents to purely physical stimuli. Metal tips employed in scanning probe microscopy are an elegant tool to manipulate reactive centers in single molecules. However, to achieve excellent control over distance and orientation, it is crucial to immobilize the reactive center and align it along the direction of the tip. Here, we aligned a reactive alkyne center via a rigid triphenylmethane‐based tripod for upright adsorption on Au(111) for inducing bond weakening in the alkyne moiety by approaching a silver tip. Single‐molecule ultrahigh vacuum low‐temperature tip‐enhanced Raman scattering was employed for probing tip‐induced bond weakening in the gap distance range from 550 to 250 pm. Both the ≡C–H stretching at ~3330 cm
                        <jats:sup>−1</jats:sup>
                        and the dominant –C≡C– stretching peak at ~2130 cm
                        <jats:sup>−1</jats:sup>
                        exhibit a shift to smaller wavenumbers due to tip‐induced bond weakening and an exponential increase in Raman intensity originating from the increased local electric field in the nanogap. To rationalize the underlying physical contributions and chemical effects of tip‐induced bond weakening, density functional theory calculations for gap distances in the range 800 to 100 pm were performed. The computational results confirmed the presence of different gap distance regimes including the onset of Pauli repulsion for short distances; for the latter, the calculations additionally predict structural distortions of the terminal alkyne induced by the nearby metal tip. These findings allow us to set a lower limit for the tip–tripod gap distance in studies requiring an intact upright configuration of the alkyne‐tripod, for example, electric field‐induced chemistry.
                      </jats:p>
article_number: jrs.70084
author:
- first_name: Gang
  full_name: Li, Gang
  last_name: Li
- first_name: Simon
  full_name: Mennicken, Simon
  last_name: Mennicken
- first_name: Lu‐Yao
  full_name: Zhu, Lu‐Yao
  last_name: Zhu
- first_name: Sadaf
  full_name: Ehtesabi, Sadaf
  last_name: Ehtesabi
- first_name: Till
  full_name: Reichenauer, Till
  last_name: Reichenauer
- first_name: Stephan
  full_name: Kupfer, Stephan
  last_name: Kupfer
- first_name: Daniel
  full_name: Schäfer, Daniel
  last_name: Schäfer
- first_name: Saber
  full_name: Mehrparvar, Saber
  last_name: Mehrparvar
- first_name: Gebhard
  full_name: Haberhauer, Gebhard
  last_name: Haberhauer
- first_name: Yao
  full_name: Zhang, Yao
  last_name: Zhang
- first_name: Stefanie
  full_name: Gräfe, Stefanie
  last_name: Gräfe
- first_name: Sebastian
  full_name: Schlücker, Sebastian
  last_name: Schlücker
- first_name: Zhen‐Chao
  full_name: Dong, Zhen‐Chao
  last_name: Dong
citation:
  ama: Li G, Mennicken S, Zhu L, et al. Probing Metal Tip‐Induced Bond Weakening of
    a Reactive Alkyne Center Aligned via a Rigid Triphenylmethane‐Based Tripod on
    Au(111) by TERS and DFT. <i>Journal of Raman Spectroscopy</i>. Published online
    2025. doi:<a href="https://doi.org/10.1002/jrs.70084">10.1002/jrs.70084</a>
  apa: Li, G., Mennicken, S., Zhu, L., Ehtesabi, S., Reichenauer, T., Kupfer, S.,
    Schäfer, D., Mehrparvar, S., Haberhauer, G., Zhang, Y., Gräfe, S., Schlücker,
    S., &#38; Dong, Z. (2025). Probing Metal Tip‐Induced Bond Weakening of a Reactive
    Alkyne Center Aligned via a Rigid Triphenylmethane‐Based Tripod on Au(111) by
    TERS and DFT. <i>Journal of Raman Spectroscopy</i>, Article jrs. 70084. <a href="https://doi.org/10.1002/jrs.70084">https://doi.org/10.1002/jrs.70084</a>
  bibtex: '@article{Li_Mennicken_Zhu_Ehtesabi_Reichenauer_Kupfer_Schäfer_Mehrparvar_Haberhauer_Zhang_et
    al._2025, title={Probing Metal Tip‐Induced Bond Weakening of a Reactive Alkyne
    Center Aligned via a Rigid Triphenylmethane‐Based Tripod on Au(111) by TERS and
    DFT}, DOI={<a href="https://doi.org/10.1002/jrs.70084">10.1002/jrs.70084</a>},
    number={jrs. 70084}, journal={Journal of Raman Spectroscopy}, publisher={Wiley},
    author={Li, Gang and Mennicken, Simon and Zhu, Lu‐Yao and Ehtesabi, Sadaf and
    Reichenauer, Till and Kupfer, Stephan and Schäfer, Daniel and Mehrparvar, Saber
    and Haberhauer, Gebhard and Zhang, Yao and et al.}, year={2025} }'
  chicago: Li, Gang, Simon Mennicken, Lu‐Yao Zhu, Sadaf Ehtesabi, Till Reichenauer,
    Stephan Kupfer, Daniel Schäfer, et al. “Probing Metal Tip‐Induced Bond Weakening
    of a Reactive Alkyne Center Aligned via a Rigid Triphenylmethane‐Based Tripod
    on Au(111) by TERS and DFT.” <i>Journal of Raman Spectroscopy</i>, 2025. <a href="https://doi.org/10.1002/jrs.70084">https://doi.org/10.1002/jrs.70084</a>.
  ieee: 'G. Li <i>et al.</i>, “Probing Metal Tip‐Induced Bond Weakening of a Reactive
    Alkyne Center Aligned via a Rigid Triphenylmethane‐Based Tripod on Au(111) by
    TERS and DFT,” <i>Journal of Raman Spectroscopy</i>, Art. no. jrs. 70084, 2025,
    doi: <a href="https://doi.org/10.1002/jrs.70084">10.1002/jrs.70084</a>.'
  mla: Li, Gang, et al. “Probing Metal Tip‐Induced Bond Weakening of a Reactive Alkyne
    Center Aligned via a Rigid Triphenylmethane‐Based Tripod on Au(111) by TERS and
    DFT.” <i>Journal of Raman Spectroscopy</i>, jrs. 70084, Wiley, 2025, doi:<a href="https://doi.org/10.1002/jrs.70084">10.1002/jrs.70084</a>.
  short: G. Li, S. Mennicken, L. Zhu, S. Ehtesabi, T. Reichenauer, S. Kupfer, D. Schäfer,
    S. Mehrparvar, G. Haberhauer, Y. Zhang, S. Gräfe, S. Schlücker, Z. Dong, Journal
    of Raman Spectroscopy (2025).
date_created: 2026-01-05T10:21:32Z
date_updated: 2026-01-05T10:22:11Z
doi: 10.1002/jrs.70084
language:
- iso: eng
publication: Journal of Raman Spectroscopy
publication_identifier:
  issn:
  - 0377-0486
  - 1097-4555
publication_status: published
publisher: Wiley
status: public
title: Probing Metal Tip‐Induced Bond Weakening of a Reactive Alkyne Center Aligned
  via a Rigid Triphenylmethane‐Based Tripod on Au(111) by TERS and DFT
type: journal_article
user_id: '116116'
year: '2025'
...
---
_id: '22697'
author:
- first_name: Steffen
  full_name: Knust, Steffen
  last_name: Knust
- first_name: Lukas
  full_name: Ruhm, Lukas
  last_name: Ruhm
- first_name: Andreas
  full_name: Kuhlmann, Andreas
  last_name: Kuhlmann
- first_name: Dennis
  full_name: Meinderink, Dennis
  id: '32378'
  last_name: Meinderink
  orcid: 0000-0002-2755-6514
- first_name: Julius
  full_name: Bürger, Julius
  id: '46952'
  last_name: Bürger
- first_name: Jörg K. N.
  full_name: Lindner, Jörg K. N.
  last_name: Lindner
- first_name: Maria Teresa
  full_name: Arcos de Pedro, Maria Teresa
  last_name: Arcos de Pedro
- first_name: Guido
  full_name: Grundmeier, Guido
  id: '194'
  last_name: Grundmeier
citation:
  ama: Knust S, Ruhm L, Kuhlmann A, et al. In situ backside Raman spectroscopy of
    zinc oxide nanorods in an atmospheric‐pressure dielectric barrier discharge plasma.
    <i>Journal of Raman Spectroscopy</i>. 2021:1237-1245. doi:<a href="https://doi.org/10.1002/jrs.6123">10.1002/jrs.6123</a>
  apa: Knust, S., Ruhm, L., Kuhlmann, A., Meinderink, D., Bürger, J., Lindner, J.
    K. N., … Grundmeier, G. (2021). In situ backside Raman spectroscopy of zinc oxide
    nanorods in an atmospheric‐pressure dielectric barrier discharge plasma. <i>Journal
    of Raman Spectroscopy</i>, 1237–1245. <a href="https://doi.org/10.1002/jrs.6123">https://doi.org/10.1002/jrs.6123</a>
  bibtex: '@article{Knust_Ruhm_Kuhlmann_Meinderink_Bürger_Lindner_Arcos de Pedro_Grundmeier_2021,
    title={In situ backside Raman spectroscopy of zinc oxide nanorods in an atmospheric‐pressure
    dielectric barrier discharge plasma}, DOI={<a href="https://doi.org/10.1002/jrs.6123">10.1002/jrs.6123</a>},
    journal={Journal of Raman Spectroscopy}, author={Knust, Steffen and Ruhm, Lukas
    and Kuhlmann, Andreas and Meinderink, Dennis and Bürger, Julius and Lindner, Jörg
    K. N. and Arcos de Pedro, Maria Teresa and Grundmeier, Guido}, year={2021}, pages={1237–1245}
    }'
  chicago: Knust, Steffen, Lukas Ruhm, Andreas Kuhlmann, Dennis Meinderink, Julius
    Bürger, Jörg K. N. Lindner, Maria Teresa Arcos de Pedro, and Guido Grundmeier.
    “In Situ Backside Raman Spectroscopy of Zinc Oxide Nanorods in an Atmospheric‐pressure
    Dielectric Barrier Discharge Plasma.” <i>Journal of Raman Spectroscopy</i>, 2021,
    1237–45. <a href="https://doi.org/10.1002/jrs.6123">https://doi.org/10.1002/jrs.6123</a>.
  ieee: S. Knust <i>et al.</i>, “In situ backside Raman spectroscopy of zinc oxide
    nanorods in an atmospheric‐pressure dielectric barrier discharge plasma,” <i>Journal
    of Raman Spectroscopy</i>, pp. 1237–1245, 2021.
  mla: Knust, Steffen, et al. “In Situ Backside Raman Spectroscopy of Zinc Oxide Nanorods
    in an Atmospheric‐pressure Dielectric Barrier Discharge Plasma.” <i>Journal of
    Raman Spectroscopy</i>, 2021, pp. 1237–45, doi:<a href="https://doi.org/10.1002/jrs.6123">10.1002/jrs.6123</a>.
  short: S. Knust, L. Ruhm, A. Kuhlmann, D. Meinderink, J. Bürger, J.K.N. Lindner,
    M.T. Arcos de Pedro, G. Grundmeier, Journal of Raman Spectroscopy (2021) 1237–1245.
date_created: 2021-07-09T12:31:06Z
date_updated: 2022-01-06T06:55:38Z
department:
- _id: '302'
doi: 10.1002/jrs.6123
language:
- iso: eng
page: 1237-1245
publication: Journal of Raman Spectroscopy
publication_identifier:
  issn:
  - 0377-0486
  - 1097-4555
publication_status: published
status: public
title: In situ backside Raman spectroscopy of zinc oxide nanorods in an atmospheric‐pressure
  dielectric barrier discharge plasma
type: journal_article
user_id: '32378'
year: '2021'
...
---
_id: '34087'
author:
- first_name: Steffen
  full_name: Knust, Steffen
  last_name: Knust
- first_name: Lukas
  full_name: Ruhm, Lukas
  last_name: Ruhm
- first_name: Andreas
  full_name: Kuhlmann, Andreas
  last_name: Kuhlmann
- first_name: Dennis
  full_name: Meinderink, Dennis
  id: '32378'
  last_name: Meinderink
  orcid: 0000-0002-2755-6514
- first_name: Julius
  full_name: Bürger, Julius
  id: '46952'
  last_name: Bürger
- first_name: Jörg
  full_name: Lindner, Jörg
  id: '20797'
  last_name: Lindner
- first_name: Maria Teresa
  full_name: de los Arcos de Pedro, Maria Teresa
  id: '54556'
  last_name: de los Arcos de Pedro
- first_name: Guido
  full_name: Grundmeier, Guido
  id: '194'
  last_name: Grundmeier
citation:
  ama: Knust S, Ruhm L, Kuhlmann A, et al. In situ backside Raman spectroscopy of
    zinc oxide nanorods in an atmospheric‐pressure dielectric barrier discharge plasma.
    <i>Journal of Raman Spectroscopy</i>. 2021;52(7):1237-1245. doi:<a href="https://doi.org/10.1002/jrs.6123">10.1002/jrs.6123</a>
  apa: Knust, S., Ruhm, L., Kuhlmann, A., Meinderink, D., Bürger, J., Lindner, J.,
    de los Arcos de Pedro, M. T., &#38; Grundmeier, G. (2021). In situ backside Raman
    spectroscopy of zinc oxide nanorods in an atmospheric‐pressure dielectric barrier
    discharge plasma. <i>Journal of Raman Spectroscopy</i>, <i>52</i>(7), 1237–1245.
    <a href="https://doi.org/10.1002/jrs.6123">https://doi.org/10.1002/jrs.6123</a>
  bibtex: '@article{Knust_Ruhm_Kuhlmann_Meinderink_Bürger_Lindner_de los Arcos de
    Pedro_Grundmeier_2021, title={In situ backside Raman spectroscopy of zinc oxide
    nanorods in an atmospheric‐pressure dielectric barrier discharge plasma}, volume={52},
    DOI={<a href="https://doi.org/10.1002/jrs.6123">10.1002/jrs.6123</a>}, number={7},
    journal={Journal of Raman Spectroscopy}, publisher={Wiley}, author={Knust, Steffen
    and Ruhm, Lukas and Kuhlmann, Andreas and Meinderink, Dennis and Bürger, Julius
    and Lindner, Jörg and de los Arcos de Pedro, Maria Teresa and Grundmeier, Guido},
    year={2021}, pages={1237–1245} }'
  chicago: 'Knust, Steffen, Lukas Ruhm, Andreas Kuhlmann, Dennis Meinderink, Julius
    Bürger, Jörg Lindner, Maria Teresa de los Arcos de Pedro, and Guido Grundmeier.
    “In Situ Backside Raman Spectroscopy of Zinc Oxide Nanorods in an Atmospheric‐pressure
    Dielectric Barrier Discharge Plasma.” <i>Journal of Raman Spectroscopy</i> 52,
    no. 7 (2021): 1237–45. <a href="https://doi.org/10.1002/jrs.6123">https://doi.org/10.1002/jrs.6123</a>.'
  ieee: 'S. Knust <i>et al.</i>, “In situ backside Raman spectroscopy of zinc oxide
    nanorods in an atmospheric‐pressure dielectric barrier discharge plasma,” <i>Journal
    of Raman Spectroscopy</i>, vol. 52, no. 7, pp. 1237–1245, 2021, doi: <a href="https://doi.org/10.1002/jrs.6123">10.1002/jrs.6123</a>.'
  mla: Knust, Steffen, et al. “In Situ Backside Raman Spectroscopy of Zinc Oxide Nanorods
    in an Atmospheric‐pressure Dielectric Barrier Discharge Plasma.” <i>Journal of
    Raman Spectroscopy</i>, vol. 52, no. 7, Wiley, 2021, pp. 1237–45, doi:<a href="https://doi.org/10.1002/jrs.6123">10.1002/jrs.6123</a>.
  short: S. Knust, L. Ruhm, A. Kuhlmann, D. Meinderink, J. Bürger, J. Lindner, M.T.
    de los Arcos de Pedro, G. Grundmeier, Journal of Raman Spectroscopy 52 (2021)
    1237–1245.
date_created: 2022-11-15T14:08:53Z
date_updated: 2023-01-04T14:51:10Z
department:
- _id: '15'
doi: 10.1002/jrs.6123
intvolume: '        52'
issue: '7'
keyword:
- Spectroscopy
- General Materials Science
language:
- iso: eng
page: 1237-1245
publication: Journal of Raman Spectroscopy
publication_identifier:
  issn:
  - 0377-0486
  - 1097-4555
publication_status: published
publisher: Wiley
status: public
title: In situ backside Raman spectroscopy of zinc oxide nanorods in an atmospheric‐pressure
  dielectric barrier discharge plasma
type: journal_article
user_id: '77496'
volume: 52
year: '2021'
...
---
_id: '22535'
author:
- first_name: Steffen
  full_name: Knust, Steffen
  last_name: Knust
- first_name: Lukas
  full_name: Ruhm, Lukas
  last_name: Ruhm
- first_name: Andreas
  full_name: Kuhlmann, Andreas
  last_name: Kuhlmann
- first_name: Dennis
  full_name: Meinderink, Dennis
  last_name: Meinderink
- first_name: Julius
  full_name: Bürger, Julius
  last_name: Bürger
- first_name: Jörg K. N.
  full_name: Lindner, Jörg K. N.
  last_name: Lindner
- first_name: Maria Teresa
  full_name: de los Arcos de Pedro, Maria Teresa
  id: '54556'
  last_name: de los Arcos de Pedro
- first_name: Guido
  full_name: Grundmeier, Guido
  id: '194'
  last_name: Grundmeier
citation:
  ama: Knust S, Ruhm L, Kuhlmann A, et al. In situ backside Raman spectroscopy of
    zinc oxide nanorods in an atmospheric‐pressure dielectric barrier discharge plasma.
    <i>Journal of Raman Spectroscopy</i>. Published online 2021:1237-1245. doi:<a
    href="https://doi.org/10.1002/jrs.6123">10.1002/jrs.6123</a>
  apa: Knust, S., Ruhm, L., Kuhlmann, A., Meinderink, D., Bürger, J., Lindner, J.
    K. N., de los Arcos de Pedro, M. T., &#38; Grundmeier, G. (2021). In situ backside
    Raman spectroscopy of zinc oxide nanorods in an atmospheric‐pressure dielectric
    barrier discharge plasma. <i>Journal of Raman Spectroscopy</i>, 1237–1245. <a
    href="https://doi.org/10.1002/jrs.6123">https://doi.org/10.1002/jrs.6123</a>
  bibtex: '@article{Knust_Ruhm_Kuhlmann_Meinderink_Bürger_Lindner_de los Arcos de
    Pedro_Grundmeier_2021, title={In situ backside Raman spectroscopy of zinc oxide
    nanorods in an atmospheric‐pressure dielectric barrier discharge plasma}, DOI={<a
    href="https://doi.org/10.1002/jrs.6123">10.1002/jrs.6123</a>}, journal={Journal
    of Raman Spectroscopy}, author={Knust, Steffen and Ruhm, Lukas and Kuhlmann, Andreas
    and Meinderink, Dennis and Bürger, Julius and Lindner, Jörg K. N. and de los Arcos
    de Pedro, Maria Teresa and Grundmeier, Guido}, year={2021}, pages={1237–1245}
    }'
  chicago: Knust, Steffen, Lukas Ruhm, Andreas Kuhlmann, Dennis Meinderink, Julius
    Bürger, Jörg K. N. Lindner, Maria Teresa de los Arcos de Pedro, and Guido Grundmeier.
    “In Situ Backside Raman Spectroscopy of Zinc Oxide Nanorods in an Atmospheric‐pressure
    Dielectric Barrier Discharge Plasma.” <i>Journal of Raman Spectroscopy</i>, 2021,
    1237–45. <a href="https://doi.org/10.1002/jrs.6123">https://doi.org/10.1002/jrs.6123</a>.
  ieee: 'S. Knust <i>et al.</i>, “In situ backside Raman spectroscopy of zinc oxide
    nanorods in an atmospheric‐pressure dielectric barrier discharge plasma,” <i>Journal
    of Raman Spectroscopy</i>, pp. 1237–1245, 2021, doi: <a href="https://doi.org/10.1002/jrs.6123">10.1002/jrs.6123</a>.'
  mla: Knust, Steffen, et al. “In Situ Backside Raman Spectroscopy of Zinc Oxide Nanorods
    in an Atmospheric‐pressure Dielectric Barrier Discharge Plasma.” <i>Journal of
    Raman Spectroscopy</i>, 2021, pp. 1237–45, doi:<a href="https://doi.org/10.1002/jrs.6123">10.1002/jrs.6123</a>.
  short: S. Knust, L. Ruhm, A. Kuhlmann, D. Meinderink, J. Bürger, J.K.N. Lindner,
    M.T. de los Arcos de Pedro, G. Grundmeier, Journal of Raman Spectroscopy (2021)
    1237–1245.
date_created: 2021-07-07T08:34:37Z
date_updated: 2023-01-24T08:52:47Z
department:
- _id: '302'
doi: 10.1002/jrs.6123
language:
- iso: eng
page: 1237-1245
publication: Journal of Raman Spectroscopy
publication_identifier:
  issn:
  - 0377-0486
  - 1097-4555
publication_status: published
status: public
title: In situ backside Raman spectroscopy of zinc oxide nanorods in an atmospheric‐pressure
  dielectric barrier discharge plasma
type: journal_article
user_id: '54556'
year: '2021'
...