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Post-synthetic Mannich chemistry on metal-organic frameworks: system-specific reactivity and functionality-triggered dissolution

Amer Hamzah, Harina, Gee, William J., Raithby, Paul R., Teat, Simon J., Mahon, Mary F., Burrows, Andrew David (2018) Post-synthetic Mannich chemistry on metal-organic frameworks: system-specific reactivity and functionality-triggered dissolution. Chemistry - A European Journal, . ISSN 0947-6539. (doi:10.1002/chem.201801419) (KAR id:67154)

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Abstract

The Mannich reaction of the zirconium MOF [Zr6O4(OH)4(bdc-NH2)6] (UiO-66-NH2, bdc-NH2 = 2-amino-1,4-benzenedicarboxylate) with paraformaldehyde and pyrazole,

99%. The Mannich reaction with pyrazole succeeds on [Zn4O(bdc-NH2)3] (IRMOF-3), but a similar reaction on [Zn2(bdc-NH2)2(dabco)] (dabco = 1,4-diazabicyclo[2.2.2]octane) gave [Zn3(bdc-NH2)1.32(bdc-NHCH2pyz)1.68(dabco)]·2C7H8 5, whereas the reaction with imidazole gave the expected PSM product. Compound 5 forms via a dissolutionrecrystallisation

process that is triggered by the 'free' pyrazolate nitrogen atom competing with dabco for coordination to the zinc(II) centre. In contrast, the 'free' nitrogen atom on the imidazolate is too far away to compete in this way. Mannich reactions on [In(OH)(bdc-NH2)] (MIL-68(In)-NH2) stop after the first step, and the product was identified as [In(OH)(bdc-NH2)0.41(bdc-NHCH2OCH3)0.30(bdc-N=CH2)0.29], with addition of the heterocycle prevented by steric interactions.

Item Type: Article
DOI/Identification number: 10.1002/chem.201801419
Uncontrolled keywords: metal-organic frameworks, post-synthetic modification, mercury sequestration
Divisions: Faculties > Sciences > School of Physical Sciences
Depositing User: William Gee
Date Deposited: 30 May 2018 08:59 UTC
Last Modified: 29 May 2019 23:00 UTC
Resource URI: https://kar.kent.ac.uk/id/eprint/67154 (The current URI for this page, for reference purposes)
Gee, William J.: https://orcid.org/0000-0002-6520-6216
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