Synthesis of Molecular Precursors to Carbon−Nitrogen−Phosphorus Polymeric Systems

Abstract

The synthesis, single-crystal X-ray structure, and decomposition reactions of new molecular precursors to amorphous C3N3P, a material analogous to C3N4, are described. These precursors, F2(C3N3)P(SiMe3)2 and Cl2(C3N3)P(SiMe3)2, are prepared via reactions of C3N3X3 (X = F, Cl) with P(SiMe3)3 and decompose at 200−400 °C via complete elimination of stable SiMe3X (X = F, Cl) byproducts to produce thin films and bulk material of composition C3N3P. This material reacts with oxygen to form a novel C3N3PO polymer. C3N3P and C3N3PO represent promising precursors for high-pressure synthesis of three-dimensionally bonded structures that are expected to be hard, strong, and refractory.