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A Postsynthetic Exchange/Deprotection Approach to Append Aliphatic Amines in Defective UiO‐66

Francesco Della Croce, Matthew McPherson Orcid Logo, Elena Pulidori Orcid Logo, Celia Duce Orcid Logo, Marco Taddei Orcid Logo

European Journal of Inorganic Chemistry, Volume: 28, Issue: 19, Start page: e202500110

Swansea University Authors: Matthew McPherson Orcid Logo, Marco Taddei Orcid Logo

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DOI (Published version): 10.1002/ejic.202500110

Abstract

Aliphatic amine-functionalized metal–organic frameworks (MOFs) are receiving increasing attention for their potential as adsorbents for CO2. In this work, a two-step postsynthetic approach is presented, applied to defective ZrIV-based MOF UiO-66, which involves the exchange of N-tert-butyloxycarbony...

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Published in: European Journal of Inorganic Chemistry
ISSN: 1434-1948 1099-0682
Published: Wiley 2025
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URI: https://cronfa.swan.ac.uk/Record/cronfa70040
first_indexed 2025-07-25T10:53:51Z
last_indexed 2025-07-26T10:33:23Z
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spelling 2025-07-25T12:05:20.9635972 v2 70040 2025-07-25 A Postsynthetic Exchange/Deprotection Approach to Append Aliphatic Amines in Defective UiO‐66 69886ed1df27345672e1a52ddee565fe 0000-0002-7529-5355 Matthew McPherson Matthew McPherson true false 5cffd1038508554d8596dee8b4e51052 0000-0003-2805-6375 Marco Taddei Marco Taddei true false 2025-07-25 Aliphatic amine-functionalized metal–organic frameworks (MOFs) are receiving increasing attention for their potential as adsorbents for CO2. In this work, a two-step postsynthetic approach is presented, applied to defective ZrIV-based MOF UiO-66, which involves the exchange of N-tert-butyloxycarbonyl (Boc) protected ω-amino acids for defect-compensating formate groups, followed by thermal deprotection of the Boc groups to yield free amine groups. The chosen amino acids are glycine, 3-aminopropionic acid (β-alanine), γ-aminobutyric acid, and 5-aminovaleric acid. Postsynthetic exchange of the Boc-protected amino acids is carried out in N,N-dimethylformamide, observing no structural damage and a dependence of the loading of functional groups on the length of the aliphatic chain (the longer the chain, the lower the loading). Deprotection is achieved by heating the solids to 160 °C under a N2 stream, accompanied by the release of CO2 and isobutylene, as confirmed by thermogravimetric analysis coupled with infrared spectroscopy and mass spectrometry. The deprotected MOFs are characterized by their gas sorption properties, finding that functionalization of the defects led to a predictable decrease in porosity, without enhancing the affinity for CO2, suggesting that the amine groups might not be accessible. Journal Article European Journal of Inorganic Chemistry 28 19 e202500110 Wiley 1434-1948 1099-0682 amines; defects; metal-organic frameworks; postsynthetic exchange 12 7 2025 2025-07-12 10.1002/ejic.202500110 COLLEGE NANME COLLEGE CODE Swansea University H2020 Marie Skłodowska-Curie Actions. Grant Number: 663830; Engineering and Physical Sciences Research Council. Grant Number: EP/R01910X/1 2025-07-25T12:05:20.9635972 2025-07-25T11:49:11.3863256 Faculty of Science and Engineering School of Engineering and Applied Sciences - Materials Science and Engineering Francesco Della Croce 1 Matthew McPherson 0000-0002-7529-5355 2 Elena Pulidori 0000-0002-8366-5870 3 Celia Duce 0000-0001-9354-7993 4 Marco Taddei 0000-0003-2805-6375 5
title A Postsynthetic Exchange/Deprotection Approach to Append Aliphatic Amines in Defective UiO‐66
spellingShingle A Postsynthetic Exchange/Deprotection Approach to Append Aliphatic Amines in Defective UiO‐66
Matthew McPherson
Marco Taddei
title_short A Postsynthetic Exchange/Deprotection Approach to Append Aliphatic Amines in Defective UiO‐66
title_full A Postsynthetic Exchange/Deprotection Approach to Append Aliphatic Amines in Defective UiO‐66
title_fullStr A Postsynthetic Exchange/Deprotection Approach to Append Aliphatic Amines in Defective UiO‐66
title_full_unstemmed A Postsynthetic Exchange/Deprotection Approach to Append Aliphatic Amines in Defective UiO‐66
title_sort A Postsynthetic Exchange/Deprotection Approach to Append Aliphatic Amines in Defective UiO‐66
author_id_str_mv 69886ed1df27345672e1a52ddee565fe
5cffd1038508554d8596dee8b4e51052
author_id_fullname_str_mv 69886ed1df27345672e1a52ddee565fe_***_Matthew McPherson
5cffd1038508554d8596dee8b4e51052_***_Marco Taddei
author Matthew McPherson
Marco Taddei
author2 Francesco Della Croce
Matthew McPherson
Elena Pulidori
Celia Duce
Marco Taddei
format Journal article
container_title European Journal of Inorganic Chemistry
container_volume 28
container_issue 19
container_start_page e202500110
publishDate 2025
institution Swansea University
issn 1434-1948
1099-0682
doi_str_mv 10.1002/ejic.202500110
publisher Wiley
college_str Faculty of Science and Engineering
hierarchytype
hierarchy_top_id facultyofscienceandengineering
hierarchy_top_title Faculty of Science and Engineering
hierarchy_parent_id facultyofscienceandengineering
hierarchy_parent_title Faculty of Science and Engineering
department_str School of Engineering and Applied Sciences - Materials Science and Engineering{{{_:::_}}}Faculty of Science and Engineering{{{_:::_}}}School of Engineering and Applied Sciences - Materials Science and Engineering
document_store_str 0
active_str 0
description Aliphatic amine-functionalized metal–organic frameworks (MOFs) are receiving increasing attention for their potential as adsorbents for CO2. In this work, a two-step postsynthetic approach is presented, applied to defective ZrIV-based MOF UiO-66, which involves the exchange of N-tert-butyloxycarbonyl (Boc) protected ω-amino acids for defect-compensating formate groups, followed by thermal deprotection of the Boc groups to yield free amine groups. The chosen amino acids are glycine, 3-aminopropionic acid (β-alanine), γ-aminobutyric acid, and 5-aminovaleric acid. Postsynthetic exchange of the Boc-protected amino acids is carried out in N,N-dimethylformamide, observing no structural damage and a dependence of the loading of functional groups on the length of the aliphatic chain (the longer the chain, the lower the loading). Deprotection is achieved by heating the solids to 160 °C under a N2 stream, accompanied by the release of CO2 and isobutylene, as confirmed by thermogravimetric analysis coupled with infrared spectroscopy and mass spectrometry. The deprotected MOFs are characterized by their gas sorption properties, finding that functionalization of the defects led to a predictable decrease in porosity, without enhancing the affinity for CO2, suggesting that the amine groups might not be accessible.
published_date 2025-07-12T18:02:39Z
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score 11.08899

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