Novel Synthetic Routes to Carbon Nitride

A novel synthetic route to amorphous C₃N₄ polymeric structures has been developed. This method involves thermal decomposition of novel molecular precursors such as C₃N₃X₂N-(SnMe₃)₂ (X = F, Cl), via elimination of stable XSnMe₃ species, to produce thin films or bulk materials of composition C₃N₄, the highest nitrogen content observed in C-N solids. These materials are primarily sp² hybridized, as indicated by vibrational, solid-state NMR, and electron-energy-loss studies, and they are likely to be excellent precursors for the highpressure synthesis of tetrahedral C₃N₄, the structural analog of β-Si₃N₄. A crystal structure determination of C₃N₃F₂N(SnMe₃)₂ reveals that the N(CN)₃ framework of the molecule is planar, and all C-N bonds have virtually the same length.