skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Pressure-induced polymerization of acetylene: Structure-directed stereoselectivity and a possible route to graphane

Abstract

Geometric isomerism in polyacetylene is a basic concept in chemistry textbooks. Polymerization to cis-isomer is kinetically preferred at low temperature, not only in the classic catalytic reaction in solution but also, unexpectedly, in the crystalline phase when it is driven by external pressure without a catalyst. Until now, no perfect reaction route has been proposed for this pressure-induced polymerization. Using in situ neutron diffraction and meta-dynamic simulation, we discovered that under high pressure, acetylene molecules react along a specific crystallographic direction that is perpendicular to those previously proposed. Moreover, following this route produces a pure cis-isomer and more surprisingly, predicts that graphane is the final product. Experimentally, polycyclic polymers with a layered structure were identified in the recovered product by solid-state nuclear magnetic resonance and neutron pair distribution functions, which indicates the possibility of synthesizing graphane under high pressure.

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [2];  [3];  [3];  [1];  [1];  [4];  [5];  [6];  [1];  [4];  [4]
  1. Center for High Pressure Science and Technology Advanced Research, Beijing (People's Republic of China)
  2. Carnegie Institution of Washington, Washington D.C. (United States)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  4. (United States)
  5. Chinese Academy of Sciences, Beijing (China)
  6. (China)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1361379
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 56; Journal Issue: 23; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; acetylene; graphane; neutron diffraction; pressure-induced polymerization; solid-state reactions

Citation Formats

Sun, Jiangman, Dong, Xiao, Wang, Yajie, Li, Kuo, Zheng, Haiyan, Wang, Lijuan, Cody, George D., Tulk, Christopher A., Molaison, Jamie J., Lin, Xiaohuan, Meng, Yufei, Carnegie Institution of Washington, Washington, D.C., Jin, Changqing, Collaborative Innovation Center of Quantum Matter, Beijing, Mao, Ho-kwang, Carnegie Institution of Washington, Washington, D.C., and Carnegie Institution of Washington, Argonne, IL. Pressure-induced polymerization of acetylene: Structure-directed stereoselectivity and a possible route to graphane. United States: N. p., 2017. Web. doi:10.1002/anie.201702685.
Sun, Jiangman, Dong, Xiao, Wang, Yajie, Li, Kuo, Zheng, Haiyan, Wang, Lijuan, Cody, George D., Tulk, Christopher A., Molaison, Jamie J., Lin, Xiaohuan, Meng, Yufei, Carnegie Institution of Washington, Washington, D.C., Jin, Changqing, Collaborative Innovation Center of Quantum Matter, Beijing, Mao, Ho-kwang, Carnegie Institution of Washington, Washington, D.C., & Carnegie Institution of Washington, Argonne, IL. Pressure-induced polymerization of acetylene: Structure-directed stereoselectivity and a possible route to graphane. United States. doi:10.1002/anie.201702685.
Sun, Jiangman, Dong, Xiao, Wang, Yajie, Li, Kuo, Zheng, Haiyan, Wang, Lijuan, Cody, George D., Tulk, Christopher A., Molaison, Jamie J., Lin, Xiaohuan, Meng, Yufei, Carnegie Institution of Washington, Washington, D.C., Jin, Changqing, Collaborative Innovation Center of Quantum Matter, Beijing, Mao, Ho-kwang, Carnegie Institution of Washington, Washington, D.C., and Carnegie Institution of Washington, Argonne, IL. Tue . "Pressure-induced polymerization of acetylene: Structure-directed stereoselectivity and a possible route to graphane". United States. doi:10.1002/anie.201702685. https://www.osti.gov/servlets/purl/1361379.
@article{osti_1361379,
title = {Pressure-induced polymerization of acetylene: Structure-directed stereoselectivity and a possible route to graphane},
author = {Sun, Jiangman and Dong, Xiao and Wang, Yajie and Li, Kuo and Zheng, Haiyan and Wang, Lijuan and Cody, George D. and Tulk, Christopher A. and Molaison, Jamie J. and Lin, Xiaohuan and Meng, Yufei and Carnegie Institution of Washington, Washington, D.C. and Jin, Changqing and Collaborative Innovation Center of Quantum Matter, Beijing and Mao, Ho-kwang and Carnegie Institution of Washington, Washington, D.C. and Carnegie Institution of Washington, Argonne, IL},
abstractNote = {Geometric isomerism in polyacetylene is a basic concept in chemistry textbooks. Polymerization to cis-isomer is kinetically preferred at low temperature, not only in the classic catalytic reaction in solution but also, unexpectedly, in the crystalline phase when it is driven by external pressure without a catalyst. Until now, no perfect reaction route has been proposed for this pressure-induced polymerization. Using in situ neutron diffraction and meta-dynamic simulation, we discovered that under high pressure, acetylene molecules react along a specific crystallographic direction that is perpendicular to those previously proposed. Moreover, following this route produces a pure cis-isomer and more surprisingly, predicts that graphane is the final product. Experimentally, polycyclic polymers with a layered structure were identified in the recovered product by solid-state nuclear magnetic resonance and neutron pair distribution functions, which indicates the possibility of synthesizing graphane under high pressure.},
doi = {10.1002/anie.201702685},
journal = {Angewandte Chemie (International Edition)},
number = 23,
volume = 56,
place = {United States},
year = {2017},
month = {5}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 4 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Raman study of the solid‐state polymerization of acetylene at high pressure
journal, July 1988

  • Aoki, K.; Usuba, S.; Yoshida, M.
  • The Journal of Chemical Physics, Vol. 89, Issue 1
  • DOI: 10.1063/1.455441

Graphane sheets and crystals under pressure
journal, April 2011

  • Wen, X. -D.; Hand, L.; Labet, V.
  • Proceedings of the National Academy of Sciences, Vol. 108, Issue 17
  • DOI: 10.1073/pnas.1103145108

Calculated high‐pressure properties of solid acetylene and possible polymerization paths
journal, February 1987

  • LeSar, R.
  • The Journal of Chemical Physics, Vol. 86, Issue 3
  • DOI: 10.1063/1.452238

High‐pressure Raman study of liquid and crystalline C 2 H 2
journal, April 1988

  • Aoki, K.; Kakudate, Y.; Usuba, S.
  • The Journal of Chemical Physics, Vol. 88, Issue 8
  • DOI: 10.1063/1.453768

Derivation of charge distribution from infrared intensities: The case of polyacetylene
journal, January 1985

  • Gussoni, M.; Castiglioni, C.; Miragoli, M.
  • Spectrochimica Acta Part A: Molecular Spectroscopy, Vol. 41, Issue 1-2
  • DOI: 10.1016/0584-8539(85)80118-5

Solid-state polymerization of acetylene under pressure
journal, February 1989


FT-IR Study of the Solid State Polymerization of Acetylene under Pressure
journal, January 1996

  • Sakashita, Mami; Yamawaki, Hiroshi; Aoki, Katsutoshi
  • The Journal of Physical Chemistry, Vol. 100, Issue 23
  • DOI: 10.1021/jp960306l

A new type of compact large-capacity press for neutron and x-ray scattering
journal, January 2004


Infrared Spectra of Poly(acetylene)
journal, March 1971


Carbon-13 magic angle NMR study of the isomerization of cis- to trans-polyacetylene
journal, July 1981

  • Gibson, Harry W.; Pochan, John M.; Kaplan, Samuel
  • Journal of the American Chemical Society, Vol. 103, Issue 15
  • DOI: 10.1021/ja00405a072

Fourier transform infrared study of the pressure and laser induced polymerization of solid acetylene
journal, October 2000

  • Ceppatelli, Matteo; Santoro, Mario; Bini, Roberto
  • The Journal of Chemical Physics, Vol. 113, Issue 14
  • DOI: 10.1063/1.1288800

    Works referencing / citing this record:

    Chemistry through cocrystals: pressure-induced polymerization of C 2 H 2 ·C 6 H 6 to an extended crystalline hydrocarbon
    journal, January 2018

    • Ward, Matthew D.; Huang, Haw-Tyng; Zhu, Li
    • Physical Chemistry Chemical Physics, Vol. 20, Issue 10
    • DOI: 10.1039/c7cp07852h

    Pressure-Induced Polymorphism of Caprolactam: A Neutron Diffraction Study
    journal, June 2019


    Chemistry through cocrystals: pressure-induced polymerization of C 2 H 2 ·C 6 H 6 to an extended crystalline hydrocarbon
    journal, January 2018

    • Ward, Matthew D.; Huang, Haw-Tyng; Zhu, Li
    • Physical Chemistry Chemical Physics, Vol. 20, Issue 10
    • DOI: 10.1039/c7cp07852h

    Pressure-Induced Polymorphism of Caprolactam: A Neutron Diffraction Study
    journal, June 2019