Computation of Aromatic C₃N₄ Networks and Synthesis of the Molecular Precursor N(C₃N₃)₃Cl₆

Abstract The successful synthesis and structural characterization of molecules that represent segments of extended solids is a valuable strategy for learning metric and stereochemical characteristics of those solids. This approach has been useful in cases in which the solids are particularly difficult to crystallize and thus their atomic connectivity and overall structures become difficult to deduce with X‐ray diffraction techniques. One such class of materials is the covalently linked C x N y extended solids, where molecular analogues remain largely absent. In particular, structures of C 3 N 4 solids are controversial. This report illustrates the utility of a simple molecule, N(C 3 N 3 ) 3 Cl 6 , in answering the question of whether triazine based C 3 N 4 phases are layered or instead they adopt 3D structures. Here, we present density functional calculations that clearly demonstrate the lower stability of graphitic C 3 N 4 relative to 3D analogues.