{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,22]],"date-time":"2026-10-22T06:51:56Z","timestamp":1792651916859,"version":"4.5.0"},"reference-count":56,"publisher":"Wiley","issue":"43","license":[{"start":{"date-parts":[[2018,6,26]],"date-time":"2018-06-26T00:00:00Z","timestamp":1529971200000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100000266","name":"Engineering and Physical Sciences Research Council","doi-asserted-by":"publisher","award":["EP\/K004956\/1"],"award-info":[{"award-number":["EP\/K004956\/1"]}],"id":[{"id":"10.13039\/501100000266","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100009233","name":"Majlis Amanah Rakyat","doi-asserted-by":"publisher","id":[{"id":"10.13039\/501100009233","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100000835","name":"University of Bath","doi-asserted-by":"publisher","id":[{"id":"10.13039\/501100000835","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2018,8]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The Mannich reaction of the zirconium MOF [Zr<jats:sub>6<\/jats:sub>O<jats:sub>4<\/jats:sub>(OH)<jats:sub>4<\/jats:sub>(bdc\u2010NH<jats:sub>2<\/jats:sub>)<jats:sub>6<\/jats:sub>] (UiO\u201066\u2010NH<jats:sub>2<\/jats:sub>, bdc\u2010NH<jats:sub>2<\/jats:sub>=2\u2010amino\u20101,4\u2010benzenedicarboxylate) with paraformaldehyde and pyrazole, imidazole or 2\u2010mercaptoimidazole led to post\u2010synthetic modification (PSM) through C\u2212N bond formation. The reaction with imidazole (Him) goes to completion whereas those with pyrazole (Hpyz) and 2\u2010mercaptoimidazole (HimSH) give up to 41 and 36\u2009% conversion, respectively. The BET surface areas for the Mannich products are reduced from that of UiO\u201066\u2010NH<jats:sub>2<\/jats:sub>, but the compounds show enhanced selectivity for adsorption of CO<jats:sub>2<\/jats:sub> over N<jats:sub>2<\/jats:sub> at 273\u2005K. The thiol\u2010containing MOFs adsorb mercury(II) ions from aqueous solution, removing up to 99\u2009%. The Mannich reaction with pyrazole succeeds on [Zn<jats:sub>4<\/jats:sub>O(bdc\u2010NH<jats:sub>2<\/jats:sub>)<jats:sub>3<\/jats:sub>] (IRMOF\u20103), but a similar reaction on [Zn<jats:sub>2<\/jats:sub>(bdc\u2010NH<jats:sub>2<\/jats:sub>)<jats:sub>2<\/jats:sub>(dabco)] (dabco=1,4\u2010diazabicyclo[2.2.2]octane) gave [Zn<jats:sub>3<\/jats:sub>(bdc\u2010NH<jats:sub>2<\/jats:sub>)<jats:sub>1.32<\/jats:sub>(bdc\u2010NHCH<jats:sub>2<\/jats:sub>pyz)<jats:sub>1.68<\/jats:sub>(dabco)]\u22c52\u2009C<jats:sub>7<\/jats:sub>H<jats:sub>8<\/jats:sub> <jats:bold>5<\/jats:bold>, whereas the reaction with imidazole gave the expected PSM product. Compound\u2005<jats:bold>5<\/jats:bold> forms via a dissolution\u2013recrystallisation process that is triggered by the \u201cfree\u201d pyrazolate nitrogen atom competing with dabco for coordination to the zinc(II) centre. In contrast, the \u201cfree\u201d nitrogen atom on the imidazolate is too far away to compete in this way. Mannich reactions on [In(OH)(bdc\u2010NH<jats:sub>2<\/jats:sub>)] (MIL\u201068(In)\u2010NH<jats:sub>2<\/jats:sub>) stop after the first step, and the product was identified as [In(OH)(bdc\u2010NH<jats:sub>2<\/jats:sub>)<jats:sub>0.41<\/jats:sub>(bdc\u2010NHCH<jats:sub>2<\/jats:sub>OCH<jats:sub>3<\/jats:sub>)<jats:sub>0.30<\/jats:sub>(bdc\u2010N=CH<jats:sub>2<\/jats:sub>)<jats:sub>0.29<\/jats:sub>], with addition of the heterocycle prevented by steric interactions.<\/jats:p>","DOI":"10.1002\/chem.201801419","type":"journal-article","created":{"date-parts":[[2018,5,29]],"date-time":"2018-05-29T11:36:28Z","timestamp":1527593788000},"page":"11094-11102","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":18,"title":["Post\u2010Synthetic Mannich Chemistry on Metal\u2010Organic Frameworks: System\u2010Specific Reactivity and Functionality\u2010Triggered Dissolution"],"prefix":"10.1002","volume":"24","author":[{"given":"Harina","family":"Amer\u2005Hamzah","sequence":"first","affiliation":[{"name":"Department of Chemistry University of Bath  Claverton Down Bath BA2 7AY United Kingdom"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"William J.","family":"Gee","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Bath  Claverton Down Bath BA2 7AY United Kingdom"},{"name":"School of Physical Sciences University of Kent  Canterbury Kent CT2 7NZ United Kingdom"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Paul R.","family":"Raithby","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Bath  Claverton Down Bath BA2 7AY United Kingdom"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Simon J.","family":"Teat","sequence":"additional","affiliation":[{"name":"Advanced Light Source Lawrence Berkeley National Laboratory  1 Cyclotron Road Berkeley CA 94720 USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Mary F.","family":"Mahon","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Bath  Claverton Down Bath BA2 7AY United Kingdom"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9268-4408","authenticated-orcid":false,"given":"Andrew D.","family":"Burrows","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Bath  Claverton Down Bath BA2 7AY United Kingdom"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2018,6,26]]},"reference":[{"key":"e_1_2_7_1_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.1230444"},{"key":"e_1_2_7_2_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.6b00626"},{"key":"e_1_2_7_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.7b00091"},{"key":"e_1_2_7_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr200256v"},{"key":"e_1_2_7_5_1","doi-asserted-by":"publisher","DOI":"10.1039\/C7CS00108H"},{"key":"e_1_2_7_6_1","doi-asserted-by":"publisher","DOI":"10.1021\/cm402136z"},{"key":"e_1_2_7_7_1","unstructured":"\u00a0"},{"key":"e_1_2_7_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr200179u"},{"key":"e_1_2_7_9_2","first-page":"195","volume-title":"Metal-Organic Framework Materials","author":"Burrows A. 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