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 language | English (US) |
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Pages (from-to) | 6706-6718 |
Number of pages | 13 |
Journal | Chemistry of Materials |
Volume | 29 |
Issue number | 16 |
DOIs | |
State | Published - Aug 22 2017 |
All Science Journal Classification (ASJC) codes
- General Chemistry
- General Chemical Engineering
- Materials Chemistry