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, [Pb 3 (μ 4 ‐O)(L) 2 (H 2 O)] ⋅ 2H 2 O ( 1 ), has been constructed from the reaction of 2‐methyl‐4‐(1H‐tetrazol‐5‐yl) benzoic acid (H 2 L) and Pb(NO 3 ) 2 under solvothermal conditions. Compound 1 contains an unprecedented hexanuclear cluster [Pb 6 (μ 4 ‐O) 2 (COO) 4 (CN 4 ) 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; UO 3 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.