High-Pressure Synthesis of Crystalline Double-Layer Carbon Nitride Networks Stabilized in BiCN(N O ).

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 BiCN(N O ), which features double-layers of poly-N-(1,3,5-triazin-2-yl)-guanidine [CN ] and non-polymerized guanidinate anions CN . 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 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.