Cationic Pb₂ Dumbbells Stabilized in the Highly Covalent Lead Nitridosilicate Pb₂ Si₅ N₈

Due to the weak oxidative force of N₂ , nitrides are only typically formed with the less electronegative metals. Meeting this challenge, we here present Pb₂ Si₅ N₈ , the first nitridosilicate containing highly electron-affine cations of a metal from the right side of the Zintl border. By using advanced synchrotron X-ray diffraction, the crystal structure was determined from a tiny single crystal of 1×3×3 μm³ in size, revealing a significantly different bonding situation compared to all other nitridosilicates known so far. Indeed, DFT calculations confirm distinct amounts of covalency not only between Pb and N but also between formal Pb²⁺ cations. Thus, unprecedented cationic Pb₂ dumbbells with a stretching vibration at 117 cm^-1 were found in Pb₂ Si₅ N₈ , the first representative of a crystallographically elucidated lead nitride, stabilized by high amounts of covalency.