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Title: Imaging single-molecule reaction intermediates stabilized by surface dissipation and entropy

Abstract

Chemical transformations at the interface between solid/liquid or solid/gaseous phases of matter lie at the heart of key industrial-scale manufacturing processes. A comprehensive study of the molecular energetics and conformational dynamics that underlie these transformations is often limited to ensemble-averaging analytical techniques. In this paper we report the detailed investigation of a surface-catalysed cross-coupling and sequential cyclization cascade of 1,2-bis(2-ethynyl phenyl)ethyne on Ag(100). Using non-contact atomic force microscopy, we imaged the single-bond-resolved chemical structure of transient metastable intermediates. Theoretical simulations indicate that the kinetic stabilization of experimentally observable intermediates is determined not only by the potential-energy landscape, but also by selective energy dissipation to the substrate and entropic changes associated with key transformations along the reaction pathway. Finally, the microscopic insights gained here pave the way for the rational design and control of complex organic reactions at the surface of heterogeneous catalysts.

Authors:
ORCiD logo [1];  [2];  [3];  [4];  [5];  [4];  [6];  [7];  [8];  [9];  [10];  [11]
  1. Univ. of California, Berkeley, CA (United States). Dept. of Physics; Vienna Univ. of Technology (Austria). Inst. of Applied Physics
  2. Univ. of the Basque Country (UPV/EHU), San Sebastián (Spain). Nano-Bio Spectroscopy Group. ETSF
  3. Univ. of California, Berkeley, CA (United States). Dept. of Physics; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
  4. Univ. of California, Berkeley, CA (United States). Dept. of Physics
  5. Donostia International Physics Center, San Sebastián (Spain); Basque Foundation for Science (Ikerbasque), Bilbao (Spain); CSIC/UPV-EHU-Materials Physics Center, San Sebastián (Spain). Center of Physics of Materials
  6. Univ. of California, Berkeley, CA (United States). Dept. of Physics; Basque Foundation for Science (Ikerbasque), Bilbao (Spain); CIC nanoGUNE, San Sebastián (Spain)
  7. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry
  8. Univ. of California, Berkeley, CA (United States). Dept. of Physics. Dept. of Chemistry
  9. Univ. of California, Berkeley, CA (United States). Dept. of Physics; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division. Kavli Energy NanoSciences Inst.
  10. Univ. of the Basque Country (UPV/EHU), San Sebastián (Spain). Nano-Bio Spectroscopy Group. ETSF; Max Planck Inst. for the Structure and Dynamics of Matter, Hamburg (Germany); Center for Free-Electron Laser Science (CFEL), Hamburg (Germany)
  11. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division. Kavli Energy NanoSciences Inst.; Univ. of California, Berkeley, CA (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States); Univ. of the Basque Country (UPV/EHU), San Sebastián (Spain); Donostia International Physics Center, San Sebastián (Spain); Basque Foundation for Science (Ikerbasque), Bilbao (Spain); Vienna Univ. of Technology (Austria)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); Office of Naval Research (ONR) (United States); European Research Council (ERC); Ministry of Economy and Competitiveness (MINECO) (Spain); UPV / EHU Consolidated Groups of the Basque Government; Austrian Science Fund (FWF)
OSTI Identifier:
1461108
Grant/Contract Number:  
AC02-05CH11231; ERC-2010-AdG-267374; FIS2013-46159-C3-1-P; IT-578-13; J3026-N16
Resource Type:
Accepted Manuscript
Journal Name:
Nature Chemistry
Additional Journal Information:
Journal Volume: 8; Journal Issue: 7; Journal ID: ISSN 1755-4330
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; reaction kinetics and dynamics; scanning probe microscopy

Citation Formats

Riss, Alexander, Paz, Alejandro Pérez, Wickenburg, Sebastian, Tsai, Hsin-Zon, De Oteyza, Dimas G., Bradley, Aaron J., Ugeda, Miguel M., Gorman, Patrick, Jung, Han Sae, Crommie, Michael F., Rubio, Angel, and Fischer, Felix R. Imaging single-molecule reaction intermediates stabilized by surface dissipation and entropy. United States: N. p., 2016. Web. doi:10.1038/nchem.2506.
Riss, Alexander, Paz, Alejandro Pérez, Wickenburg, Sebastian, Tsai, Hsin-Zon, De Oteyza, Dimas G., Bradley, Aaron J., Ugeda, Miguel M., Gorman, Patrick, Jung, Han Sae, Crommie, Michael F., Rubio, Angel, & Fischer, Felix R. Imaging single-molecule reaction intermediates stabilized by surface dissipation and entropy. United States. doi:10.1038/nchem.2506.
Riss, Alexander, Paz, Alejandro Pérez, Wickenburg, Sebastian, Tsai, Hsin-Zon, De Oteyza, Dimas G., Bradley, Aaron J., Ugeda, Miguel M., Gorman, Patrick, Jung, Han Sae, Crommie, Michael F., Rubio, Angel, and Fischer, Felix R. Mon . "Imaging single-molecule reaction intermediates stabilized by surface dissipation and entropy". United States. doi:10.1038/nchem.2506. https://www.osti.gov/servlets/purl/1461108.
@article{osti_1461108,
title = {Imaging single-molecule reaction intermediates stabilized by surface dissipation and entropy},
author = {Riss, Alexander and Paz, Alejandro Pérez and Wickenburg, Sebastian and Tsai, Hsin-Zon and De Oteyza, Dimas G. and Bradley, Aaron J. and Ugeda, Miguel M. and Gorman, Patrick and Jung, Han Sae and Crommie, Michael F. and Rubio, Angel and Fischer, Felix R.},
abstractNote = {Chemical transformations at the interface between solid/liquid or solid/gaseous phases of matter lie at the heart of key industrial-scale manufacturing processes. A comprehensive study of the molecular energetics and conformational dynamics that underlie these transformations is often limited to ensemble-averaging analytical techniques. In this paper we report the detailed investigation of a surface-catalysed cross-coupling and sequential cyclization cascade of 1,2-bis(2-ethynyl phenyl)ethyne on Ag(100). Using non-contact atomic force microscopy, we imaged the single-bond-resolved chemical structure of transient metastable intermediates. Theoretical simulations indicate that the kinetic stabilization of experimentally observable intermediates is determined not only by the potential-energy landscape, but also by selective energy dissipation to the substrate and entropic changes associated with key transformations along the reaction pathway. Finally, the microscopic insights gained here pave the way for the rational design and control of complex organic reactions at the surface of heterogeneous catalysts.},
doi = {10.1038/nchem.2506},
journal = {Nature Chemistry},
number = 7,
volume = 8,
place = {United States},
year = {2016},
month = {5}
}

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Works referenced in this record:

Homo-coupling of terminal alkynes on a noble metal surface
journal, January 2012

  • Zhang, Yi-Qi; Kepčija, Nenad; Kleinschrodt, Martin
  • Nature Communications, Vol. 3, Issue 1, Article No. 1286 (2012)
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