Pentazolate Anion: A Rare and Preferred Five‐Membered Ligand for Constructing Pentasil‐Zeolite Topology Architectures

Abstract As the fourth full‐nitrogen structure, the pentazolate anion ( cyclo ‐N 5 − ) was highly coveted for decades. In 2017, the first air‐stable non‐metal pentazolate salt, (N 5 ) 6 (H 3 O) 3 (NH 4 ) 4 Cl, was obtained, representing a milestone in this field. As the latest member of the azole family, cyclo ‐N 5 − is comprised of five nitrogen atoms. Although significant attention has been paid to the potential of cyclo ‐N 5 − as an energetic material, its poor thermostability hinders any practical application. However, the unique ring structure and multiple coordination capability of cyclo ‐N 5 − provide a platform for the fabrication of various structures, among which pentasil‐zeolite topologies are the most intriguing. In addition, the introduction of structure‐directing auxiliaries enables the self‐assembly of diverse topological architectures, potentially imparting cyclo ‐N 5 − with the potential to impact wide‐ranging areas of coordination chemistry and topology. In this minireview, different pentasil‐zeolite topologies based on metal‐pentazolate frameworks are evaluated. To date, three zeolitic and zeolite‐like topologies have been reported, namely the melanophlogite (MEP), chibaite (MTN), and unj topologies. The MEP topology consists of two nanocages, Na 20 N 60 and Na 24 N 60 , whereas the MTN topology contains Na 20 N 60 and Na 28 N 80 nanocages. Furthermore, the unj topology features multiple homochiral channels consisting of two helical chains. Various possible strategies for obtaining additional pentasil‐zeolite topologies are also discussed.