aWe report a robust and modular synthetic route to heterometallic rare earth-transition metal complexes.We have used the redox-active bridging ligand 1,10-phenathroline-5,6-dione ( pd), which has selective N,N' or O,O' binding sites as the template for this synthetic route. The coordination complexes [Ln(hfac)

The highest nitrogen-containing binary C-N anion, 5-azido-tetrazolate (CN 7 − ), has attracted significant attention owing to its high-energy content. Due to its relative instability and high sensitivity, it is an ongoing challenge to develop more stable and less sensitive novel materials based on CN 7 − . Towards this goal, we have stabilized the CN 7 − anion without compromising its energetic performance by formation of its NH 3 OH + salt containing an additional NH 2 OH molecule, [NH 3 OH][CN 7 ][NH 2 OH] (2). It possesses the best detonation performance and the lowest mechanical sensitivity among all known CN 7 − -based materials. The structure-property relationship was elucidated through a careful investigation of the noncovalent interactions in the crystal lattice and the important role of the NH 2 OH moiety. In addition, the structurally related compound [NH 3 OH][CN 7 ] (1) was also studied.