Inspired by biology, in which a bimetallic hydroxide-bridged zinc(II)-containing enzyme is utilized to catalytically hydrolyze phosphate ester bonds, the utility of a zirconium(IV)-cluster-containing metal-organic framework as a catalyst for the methanolysis and hydrolysis of phosphate-based nerve agent simulants was examined. The combination of the strong Lewis-acidic Zr(IV) and bridging hydroxide anions led to ultrafast half-lives for these solvolysis reactions. This is especially remarkable considering that the actual catalyst loading was a mere 0.045 % as a result of the surface-only catalysis observed.

An Al(porphyrin) functionalized with a large axial ligand was incorporated into a porous organic polymer (POP) using a cobalt-catalyzed acetylene trimerization strategy. Removal of the axial ligand afforded a microporous POP that is catalytically active in the methanolysis of a nerve agent simulant. Supercritical CO2 processing of the POP dramatically increased the pore size and volume, allowing for significantly higher catalytic activities.

Inspired by biology, in which a bimetallic hydroxide‐bridged zinc(II)‐containing enzyme is utilized to catalytically hydrolyze phosphate ester bonds, the utility of a zirconium(IV)‐cluster‐containing metal–organic framework as a catalyst for the methanolysis and hydrolysis of phosphate‐based nerve agent simulants was examined. The combination of the strong Lewis‐acidic ZrIV and bridging hydroxide anions led to ultrafast half‐lives for these solvolysis reactions. This is especially remarkable considering that the actual catalyst loading was a mere 0.045 % as a result of the surface‐only catalysis observed.

Two robust catechol-functionalized porous organic polymers (catPOPs) with different T d -directing nodes were synthesized using a cobalt-catalyzed acetylene trimerization (CCAT) strategy. Postsynthesis metallation was readily carried out with La(acac) 3 to afford catalytically active Lafunctionalized catPOPs for the solvolytic and hydrolytic degradation of the toxic organophosphate compound methyl paraoxon, a simulant for nerve agents.

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A series of metalloporphyrin dimers were modularly prepared and shown to catalyze the methanolysis of a phosphate triester, yielding rates that are large compared to the rate of the uncatalyzed reaction. Up to 1300-fold rate acceleration can be achieved via a combination of cavity-localized Lewis-acid activation and methoxide-induced methanolysis.

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Covalently linked cyclic metalloporphyrin dimers and tetramers have been demonstrated to be good shape-selective hosts for fullerene guests. The fullerene affinities of these hosts can readily be tuned by modulating the covalent linkage and the metal ions in the porphyrin subunits. A rigid Zn(porphyrin) dimer with conjugated bis(alkynyl) linkers exhibits a high selectivity towards C(70) over C(60) in toluene (K(a,C70)/K(a,C60) = ~28). For the host structures examined, a synergistic combination of rigidity in the linker and electropositive Al ions gives rise to the strongest binding of C(70). In the case of a bisected Zn(porphyrin) tetramer, two well-defined cavities exist; however, due to their comparatively small size, only one C(60) can be accommodated. Studies of fullerene binding as a function of metal ion in a porphyrin divider suggest that the right combination of shape and steric match is essential to exploit both van der Waals and local-charge/induced-dipole interactions.