5 years ago

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

From Linear Molecular Chains to Extended Polycyclic Networks: Polymerization of Dicyanoacetylene
Timothy A. Strobel, Huiyang Gou, Albert Epshteyn, Derek W. Keefer, Duck Young Kim, Liuxiang Yang, Jordan Lerach, Clemens Prescher, Haw-Tyng Huang, Matthew D. Ward, Arani Biswas, John V. Badding, Shengnan Wang, Li Zhu, Artem R. Oganov, Brian L. Chaloux
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.

Publisher URL: http://dx.doi.org/10.1021/acs.chemmater.7b01446

DOI: 10.1021/acs.chemmater.7b01446

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