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Presence versus Proximity: The Role of Pendant Amines in the Catalytic Hydrolysis of a Nerve Agent Simulant
Author(s) -
Islamoglu Timur,
Ortuño Manuel A.,
Proussaloglou Emmanuel,
Howarth Ashlee J.,
Vermeulen Nicolaas A.,
Atilgan Ahmet,
Asiri Abdullah M.,
Cramer Christopher J.,
Farha Omar K.
Publication year - 2018
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201712645
Subject(s) - chemistry , catalysis , hydrolysis , amine gas treating , zirconium , nerve agent , amino acid , combinatorial chemistry , metal organic framework , stereochemistry , organic chemistry , enzyme , biochemistry , adsorption , acetylcholinesterase
Amino‐functionalized zirconium‐based metal‐organic frameworks (MOFs) have shown unprecedented catalytic activity compared to non‐functionalized analogues for hydrolysis of organophosphonate‐based toxic chemicals. Importantly, the effect of the amino group on the catalytic activity is significantly higher in the case of UiO‐66‐NH 2 , where the amino groups reside near the node, compared to UiO‐67‐ m ‐NH 2 , where they are directed away from the node. Herein, we show that the proximity of the amino group is crucial for fast catalytic activity towards hydrolysis of organophosphonate‐based nerve agents. The generality of the observed amine‐proximity‐dictated catalytic activity has been tested on two different MOF systems which have different topology. DFT calculations reveal that amino groups on all the MOFs studied are not acting as Brønsted bases; instead they control the microsolvation environment at the Zr 6 ‐node active site and therefore increase the overall catalytic rates.