Stabilization of the Pentazolate Anion in a Zeolitic Architecture with Na20N60 and Na24N60 Nanocages

Abstract The experimental detection and synthesis of pentazole (HN 5 ) and its anion (cyclo‐N 5 − ) have been actively pursued for the past hundred years. The synthesis of an aesthetic three‐dimensional metal–pentazolate framework (denoted as MPF‐1) is presented. It consists of sodium ions and cyclo‐N 5 − anions in which the isolated cyclo‐N 5 − anions are preternaturally stabilized in this inorganic open framework featuring two types of nanocages (Na 20 N 60 and Na 24 N 60 ) through strong metal coordination bonds. The compound MPF‐1 is indefinitely stable at room temperature and exhibits high thermal stability relative to the reported cyclo‐N 5 − salts. This finding offers a new approach to create metal–pentazolate frameworks (MPFs) and enables the future exploration of interesting pentazole chemistry and also related functional materials.