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 D.

doi:10.1002/chem.201801419

Post-Synthetic Mannich Chemistry on Metal-Organic Frameworks: System-Specific Reactivity and Functionality-Triggered Dissolution

Journal Article · Tue Jun 26 00:00:00 EDT 2018 · Chemistry - A European Journal

DOI:https://doi.org/10.1002/chem.201801419· OSTI ID:1623512

Amer Hamzah, Harina ^[1]; Gee, William J. ^[2]; Raithby, Paul R. ^[3]; Teat, Simon J. ^[4]; Mahon, Mary F. ^[3]; ^[3]

Univ. of Bath (United Kingdom). Dept. of Chemistry; DOE/OSTI
Univ. of Bath (United Kingdom). Dept. of Chemistry; Univ. of Kent (United Kingdom). School of Physical Sciences
Univ. of Bath (United Kingdom). Dept. of Chemistry
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)

he 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, imidazole or 2-mercaptoimidazole led to post-synthetic modification (PSM) through C@N bond formation. The reaction with imidazole (Him) goes to completion whereas those with pyrazole (Hpyz) and 2-mercaptoimidazole (HimSH) give up to 41 and 36% conversion, respectively. The BET surface areas for the Mannich products are reduced from that of UiO-66-NH2 , but the compounds show enhanced selectivity for adsorption of CO2 over N2 at 273 K. The thiol-containing MOFs adsorb mercury(II) ions from aqueous solution, removing up to 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 dissolution–recrystallisation 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)(bdcNH2 )0.41(bdc-NHCH2OCH3 )0.30(bdc-N=CH2 )0.29], with addition of the heterocycle prevented by steric interactions.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: Engineering and Physical Sciences Research Council (EPSRC); USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1623512

Alternate ID(s):: OSTI ID: 1630603

Journal Information:: Chemistry - A European Journal, Journal Name: Chemistry - A European Journal Journal Issue: 43 Vol. 24; ISSN 0947-6539

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

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