Gou, HuiyangHuiyangGouZhu, LiLiZhuHAW-TYNG HUANGBiswas, AraniAraniBiswasKeefer, Derek W.Derek W.KeeferChaloux, Brian L.Brian L.ChalouxPrescher, ClemensClemensPrescherYang, LiuxiangLiuxiangYangKim, Duck YoungDuck YoungKimWard, Matthew D.Matthew D.WardLerach, JordanJordanLerachWang, ShengnanShengnanWangOganov, Artem R.Artem R.OganovEpshteyn, AlbertAlbertEpshteynBadding, John V.John V.BaddingStrobel, Timothy A.Timothy A.Strobel2024-09-182024-09-182017https://www.scopus.com/record/display.uri?eid=&origin=resultslisthttps://scholars.lib.ntu.edu.tw/handle/123456789/721236Dicyanoacetylene (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. © 2017 American Chemical Society.journal article10.1021/acs.chemmater.7b014462-s2.0-85027866707