A Lead Carboxylate‐Azolate Metal‐Organic Framework Based on Hexanuclear Clusters: Luminescence and Accelerating the Thermal Decomposition of Ammonium Perchlorate

: A lead carboxylate-azolate framework, [Pb3 (μ4 -O)(L)2 (H2 O)] ⋅ 2H2 O (1), has been constructed from the reaction of 2-methyl-4-(1H-tetrazol-5-yl) benzoic acid (H2 L) and Pb(NO3 )2 under solvothermal conditions. Compound 1 contains an unprecedented hexanuclear cluster [Pb6 (μ4 -O)2 (COO)4 (CN4 )2 ], which as an 8-connected node is connected by 3-connected L linkers to give rise to a three-dimensional framework with an uncommon (3,8)-connected tfz-d; UO3 topology. Framework 1 possesses strong solid-state yellow luminescence (563 nm), which stems from ligand-to-metal charge transfer (LMCT), however, the removal of water molecules in 1 lead to the significant luminescent decrease of the sample. Importantly, in the presence of 1, the thermal decomposition of ammonium perchlorate is significantly accelerated.