Catalytically active supramolecular porphyrin boxes: acceleration of the methanolysis of phosphate triesters via a combination of increased local nucleophilicity and reactant encapsulation

Instantaneous Hydrolysis of Nerve‐Agent Simulants with a Six‐Connected Zirconium‐Based Metal–Organic Framework

“…[4] Although phosphate esters can be hydrolyzed directly with water, [4a] the reaction rate is too slow for realworld applications which often require an early immediate response.T hus,w eh ave been investigating catalysts for the rapid detoxification of nerve-agent stimulants by both hydrolysis and methanolysis.H omogeneous dimers and tetramers of aluminum-porphyrin-based catalysts showed enhanced hydrolysis by catalytic acid activation of the phosphate.Ahalf-life (t 1/2 )o f1 0h for the methanolysis reaction was attributed to the favorable positioning of pairs of acidic Al III sites. [5] Porous organic polymers (POPs) containing Al-porphyrins or La-catecholates moieties demonstrated an early seven-fold greater methanolysis rates (t 1/2 = 90 min). Furthermore,the heterogeneous nature of the POPs allowed for facile separation, and thus recyclability,o ft he catalyst from solution.…”

Simple and Compelling Biomimetic Metal–Organic Framework Catalyst for the Degradation of Nerve Agent Simulants

“…There have been several reports regarding the catalytic degradation of organophosphates using bimetallic Zn II systems in which the active sites commonly comprise alkoxide-bridged Zn II centers surrounded by 2-3 nitrogen-based donors. [7][8][9][10] Additionally, complexes containing highly Lewis-acidic cations such as, but not limited to, Ln III , [11][12][13][14] Al III , [15,16] and Ce IV have been explored. [3,17] While these studies have provided valuable mechanistic information, in the context of chemical-threat protection (i.e.…”

Simple and Compelling Biomimetic Metal–Organic Framework Catalyst for the Degradation of Nerve Agent Simulants

“…There have been several reports regarding the catalytic degradation of organophosphates using bimetallic Zn II systems in which the active sites commonly comprise alkoxide‐bridged Zn II centers surrounded by 2–3 nitrogen‐based donors 7–10. Additionally, complexes containing highly Lewis‐acidic cations such as, but not limited to, Ln III ,11–14 Al III ,15, 16 and Ce IV have been explored 3. 17 While these studies have provided valuable mechanistic information, in the context of chemical‐threat protection (i.e.…”