Structural Characterization of Pristine and Defective [Zr12(μ3‑O)8(μ3‑OH)8(μ2‑OH)6]18+ Double-Node Metal–Organic Framework and Predicted Applications for Single-Site Catalytic Hydrolysis of Sarin

Periodic PBE-D3 and M06-L calculations predict the lowest-energy proton topology of a [Zr6(μ3-O)4(μ3-OH)4(μ2-OH)3]2 ZrIV–MOF (J. Am. Chem. Soc. 2017, 139, 7004–7011), which has a unique double-node structure, to be 73.4 and 64.2 kcal/mol more stable than that originally proposed. Mono- and bidefective Zr12 secondary building units derived from this topology and built by removing one and two bridging terphenyldicarboxylate linkers and saturating the remaining open ZrIV metal sites with hydroxyl and aqua groups, are predicted to exhibit higher reactivity for the hydrolysis of sarin nerve agent than other coordinatively unsaturated Zr6-based MOFs reported to date.