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

Momeni, M. R.; Cramer, C. J.
Chem. Mater. 2018, 30, 4432 (doi:10.1021/acs.chemmater.8b01913)

Periodic PBE-D3 and M06-L calculations predict the lowest-energy proton topology of [Zr₆(μ₃-O)₄(μ₃-OH)₄(μ₂-OH)₃]₂ Zr^IV-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 bi-defective Zr₁₂ secondary building units derived from this topology, and built by removing one and two bridging terphenyldicarboxylate linkers and saturating the remaining open Zr^IV 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.