Charged nitrogen dimers are ubiquitous in high-pressure binary metal-nitrogen systems. They are known to possess integer formal charges x varying from one through four. Here, we present the investigation of the binary alkali- and alkaline earth metal-nitrogen systems, Na-N, Ca-N, Sr-N, Ba-N to 70 GPa. We report on compounds-Na3(N2)4, Ca3(N2)4, Sr3(N2)4, and Ba(N2)3-featuring charged nitrogen dimers with paradigm-breaking non-integer charges, x = 0.67, 0.75 and 1.5. The metallic nature of all four compounds is deduced from ab initio calculations. The conduction electrons occupy the pi* antibonding orbitals of the charged nitrogen dimers that results in anion-driven metallicity. Delocalization of these electrons over the pi* antibonding states enables the non-integer electron count of the dinitrogen species. Anion-driven metallicity is expected to be found among a variety of compounds with homoatomic anions (e.g., polynitrides, carbides, and oxides), with the conduction electrons playing a decisive role in their properties.
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