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_xN_y extended solids, where molecular analogues remain largely absent. In particular, structures of C₃N₄ solids are controversial. This report illustrates the utility of a simple molecule, N(C₃N₃)₃Cl₆, in answering the question of whether triazine based C₃N₄ phases are layered or instead they adopt 3D structures. Here, we present density functional calculations that clearly demonstrate the lower stability of graphitic C₃N₄ relative to 3D analogues.