High‐Pressure Synthesis of Crystalline Double‐Layer Carbon Nitride Networks Stabilized in Bi ₇ C ₁₀ N ₁₈ (N _3(1‐ <i> _x </i> ₎ O ₃ <i> _x </i> )

Abstract

Abstract Application of high‐pressure conditions in chemical synthesis has proven to access a wide range of novel nitrogen‐rich compounds and to overcome the stability of the dinitrogen molecule. In the present work, we report the high‐pressure high‐temperature (HPHT) synthesis of Bi 7 C 10 N 18 (N 3(1‐ x ) O 3 x ), which features double‐layers of poly‐ N ‐(1,3,5‐triazin‐2‐ yl )‐guanidine [C 4 N 6 x ‐ ] n and non‐polymerized guanidinate anions CN 3 5‐ . The structure model was determined by means of synchrotron single‐crystal X‐ray diffraction and is fully corroborated by theoretical calculations. The poly‐ N ‐(1,3,5‐triazin‐2‐ yl )‐guanidine illustrates an example of a 2D polymerized anionic C─N network and represents the first intermediate between highly charged CN 3 5− anions and fully condensed graphitic carbon nitride networks achieved by HPHT conditions. This opens a pathway to a widely varied family of hydrogen‐free nitridocarbonates, which has the potential to develop into an alternative synthesis route to classical polycondensation reactions.