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dc.contributor.authorHamzah, Harina Amer
dc.contributor.authorGee, William J
dc.contributor.authorRaithby, Paul R
dc.contributor.authorTeat, Simon J
dc.contributor.authorMahon, Mary F
dc.contributor.authorBurrows, Andrew D
dc.date.accessioned2020-02-19T04:11:52Z
dc.date.available2020-02-19T04:11:52Z
dc.date.issued2018
dc.identifier.issn0947-6539
dc.identifier.doi10.1002/chem.201801419
dc.identifier.urihttp://hdl.handle.net/10072/391684
dc.description.abstractThe 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)]⋅2 C7H8 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)(bdc‐NH2)0.41(bdc‐NHCH2OCH3)0.30(bdc‐N=CH2)0.29], with addition of the heterocycle prevented by steric interactions.
dc.description.peerreviewedYes
dc.languageEnglish
dc.language.isoeng
dc.publisherWiley Blackwell
dc.relation.ispartofpagefrom11094
dc.relation.ispartofpageto11102
dc.relation.ispartofissue43
dc.relation.ispartofjournalChemistry: A European Journal
dc.relation.ispartofvolume24
dc.subject.fieldofresearchChemical sciences
dc.subject.fieldofresearchcode34
dc.subject.keywordsScience & Technology
dc.subject.keywordsPhysical Sciences
dc.subject.keywordsChemistry, Multidisciplinary
dc.subject.keywordsMannich reactions
dc.titlePost-Synthetic Mannich Chemistry on Metal-Organic Frameworks: System-Specific Reactivity and Functionality-Triggered Dissolution
dc.typeJournal article
dc.type.descriptionC1 - Articles
dcterms.bibliographicCitationHamzah, HA; Gee, WJ; Raithby, PR; Teat, SJ; Mahon, MF; Burrows, AD, Post-Synthetic Mannich Chemistry on Metal-Organic Frameworks: System-Specific Reactivity and Functionality-Triggered Dissolution, Chemistry: A European Journal, 2018, 24 (43), pp. 11094-11102
dcterms.licensehttp://creativecommons.org/licenses/by/4.0/
dc.date.updated2020-02-19T04:07:47Z
dc.description.versionVersion of Record (VoR)
gro.rights.copyright© 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
gro.hasfulltextFull Text
gro.griffith.authorGee, William J.


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