A Solid Zn-Ion Conductor from an All-Zinc Metal-Organic Framework Replete with Mobile Zn 2+ Cations.

We describe the synthesis and properties of Zn 3 [(Zn 4 Cl) 3 (BTT) 8 ] 2 (ZnZnBTT, BTT 3- = 1,3,5-benzenetristetrazolate), a heretofore unknown member of a well-known, extensive family of metal-organic frameworks (MOFs) with the general formula M II 3 [(M II 4 Cl) 3 (BTT) 8 ] 2 , which adopts an anionic, sodalite-like structure. As with previous members in this family, ZnZnBTT presents two crystallographically distinct metal cations: a skeletal Zn 2+ site, fixed within Zn 4 Cl(tetrazole) 8 secondary building units (SBUs), and a charge-balancing Zn 2+ site. Self-assembly of ZnZnBTT from its building blocks has remained elusive; instead, we show that ZnZnBTT is readily accessed by quantitative postsynthetic exchange of all Mn 2+ ions in MnMnBTT with zinc. We further demonstrate that ZnZnBTT is a promising Zn-ion conductor owing to the mobile charge-balancing extra-framework Zn 2+ cations. The new material displays a Zn-ion conductivity of σ = 1.15 × 10 -4 S/cm at room temperature and a relatively low activation energy of E a = 0.317 eV, enabling potential applications in the emerging field of quasi-solid-state zinc-ion batteries.