From Linear Molecular Chains to Extended Polycyclic Networks: Polymerization of Dicyanoacetylene

Huiyang Gou, Li Zhu, Haw Tyng Huang, Arani Biswas, Derek W. Keefer, Brian L. Chaloux, Clemens Prescher, Liuxiang Yang, Duck Young Kim, Matthew D. Ward, Jordan Lerach, Shengnan Wang, Artem R. Oganov, Albert Epshteyn, John V. Badding, Timothy A. Strobel

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4 Scopus citations

Abstract

Dicyanoacetylene (C4N2) is an unusual energetic molecule with alternating triple and single bonds (think miniature, nitrogen-capped carbyne), which represents an interesting starting point for the transformation into extended carbon-nitrogen solids. While pressure-induced polymerization has been documented for a wide variety of related molecular solids, precise mechanistic details of reaction pathways are often poorly understood and the characterization of recovered products is typically incomplete. Here, we study the high-pressure behavior of C4N2 and demonstrate polymerization into a disordered carbon-nitrogen network that is recoverable to ambient conditions. The reaction proceeds via activation of linear molecules into buckled molecular chains, which spontaneously assemble into a polycyclic network that lacks long-range order. The recovered product was characterized using a variety of optical spectroscopies, X-ray methods, and theoretical simulations and is described as a predominately sp2 network comprising "pyrrolic" and "pyridinic" rings with an overall tendency toward a two-dimensional structure. This understanding offers valuable mechanistic insights into design guidelines for next-generation carbon nitride materials with unique structures and compositions.

Original languageEnglish (US)
Pages (from-to)6706-6718
Number of pages13
JournalChemistry of Materials
Volume29
Issue number16
DOIs
StatePublished - Aug 22 2017

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Chemical Engineering(all)
  • Materials Chemistry

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    Gou, H., Zhu, L., Huang, H. T., Biswas, A., Keefer, D. W., Chaloux, B. L., Prescher, C., Yang, L., Kim, D. Y., Ward, M. D., Lerach, J., Wang, S., Oganov, A. R., Epshteyn, A., Badding, J. V., & Strobel, T. A. (2017). From Linear Molecular Chains to Extended Polycyclic Networks: Polymerization of Dicyanoacetylene. Chemistry of Materials, 29(16), 6706-6718. https://doi.org/10.1021/acs.chemmater.7b01446