Presence versus Proximity: The Role of Pendant Amines in the Catalytic Hydrolysis of a Nerve Agent Simulant |
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| Authors: | Dr. Timur Islamoglu Dr. Manuel A. Ortuño Emmanuel Proussaloglou Dr. Ashlee J. Howarth Dr. Nicolaas A. Vermeulen Ahmet Atilgan Prof. Abdullah M. Asiri Prof. Christopher J. Cramer Prof. Omar K. Farha |
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| Affiliation: | 1. Department of Chemistry, Northwestern University, Evanston, IL, USA;2. Department of Chemistry, Supercomputing Institute, and Chemical Theory Center, University of Minnesota, Minneapolis, MN, USA;3. Department of Chemistry, Faculty of Science King Abdulaziz, University Jeddah, Jeddah, Saudi Arabia |
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| Abstract: | 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‐NH2, where the amino groups reside near the node, compared to UiO‐67‐m‐NH2, 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 Zr6‐node active site and therefore increase the overall catalytic rates. |
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| Keywords: | amino groups heterogeneous catalysis hydrolysis metal– organic frameworks nerve agents |
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