Predicting Nitrogen‐Based Families of Compounds: Transition‐Metal Guanidinates TCN3 (T=V,Nb, Ta) and Ortho‐Nitrido Carbonates T′2CN4 (T′=Ti,Zr, Hf)

Due to its unsurpassed capability to engage in various sp hybridizations or orbital mixings, carbon may contribute in expanding solid‐state nitrogen chemistry by allowing for different complex anions, such as the known NCN^2? carbodiimide unit, the so far unknown CN₃^5? guanidinate anion, and the likewise unknown CN₄^8? ortho‐nitrido carbonate (onc) entity. Because the latter two complex anions have never been observed before, we have chemically designed them using first‐principles structural searches, and we here predict the first hydrogen‐free guanidinates TCN₃ (T=V, Nb, Ta) and ortho‐nitrido carbonates T′₂CN₄ (T′=Ti, Zr, Hf) being mechanically stable at normal pressure; the latter should coexist as solid solutions with the stoichiometrically identical nitride carbodiimides and nitride guanidinates. We also suggest favorable exothermic reactions as useful signposts for eventual synthesis, and we trust that the decay of the novel compounds is unlikely due to presumably large kinetic activation barriers (C?N bond breaking) and quite substantial Madelung energies stabilizing the highly charged complex anions. While chemical‐bonding analysis reveals the novel CN₄^8? to be more covalent compared to NCN^2? and CN₃^5? within related compounds, further electronic‐structure data of onc phases hint at their physicochemical potential in terms of photoelectrochemical water splitting and nonlinear optics.