Realization of an Ideal Cairo Tessellation in Nickel Diazenide NiN2: High-Pressure Route to Pentagonal 2D Materials

Most of the studied two-dimensional (2D) materials are based on highly symmetric hexagonal structural motifs. In contrast, lower-symmetry structures may have exciting anisotropic properties leading to various applications in nanoelectronics. In this work we report the synthesis of nickel diazenide NiN 2 which possesses atomic-thick layers comprised of Ni 2 N 3 pentagons forming Cairo-type tessellation. The layers of NiN 2 are weakly bonded with the calculated exfoliation energy of 0.72 J/m 2 , which is just slightly larger than that of graphene. The compound crystallizes in the space group of the ideal Cairo tiling ( P 4/ mbm ) and possesses significant anisotropy of elastic properties. The single-layer NiN 2 is a direct-band-gap semiconductor, while the bulk material is metallic. This indicates the promise of NiN 2 o be a precursor of a pentagonal 2D material with a tunable direct band gap.