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Type: Journal article
Title: Assembly and covalent cross-linking of an amine-functionalised metal-organic cage
Author: Schneider, M.L.
Markwell-Heys, A.W.
Linder-Patton, O.M.
Bloch, W.M.
Citation: Frontiers in Chemistry, 2021; 9:1-9
Publisher: Frontiers Media SA
Issue Date: 2021
ISSN: 2296-2646
Statement of
Matthew L. Schneider, Adrian W. Markwell-Heys, Oliver M. Linder-Patton and Witold M. Bloch
Abstract: The incorporation of reactive functional groups onto the exterior of metal-organic cages (MOCs) opens up new opportunities to link their well-defined scaffolds into functional porous solids. Amine moieties offer access to a rich catalogue of covalent chemistry; however, they also tend to coordinate undesirably and interfere with MOC formation, particular in the case of Cu2 paddlewheel-based MOCs. We demonstrate that tuning the basicity of an aniline-functionalized ligand enables the self-assembly of a soluble, amine-functionalized Cu4L4 lantern cage (1). Importantly, we show control over the coordinative propensity of the exterior amine of the ligand, which enables us to isolate a crystalline, two-dimensional metal-organic framework composed entirely of MOC units (2). Furthermore, we show that the nucleophilicity of the exterior amine of 1 can be accessed in solution to generate a cross-linked cage polymer (3) via imine condensation.
Keywords: Cage compound; self-assembly; coordination; cross-linking; amine-functionality; porosity
Rights: © 2021 Schneider, Markwell-Heys, Linder-Patton and Bloch. This is an open-access article distributed under the terms of the Creative Commons Attribution License (CC BY). The use, distribution or reproduction in other forums is permitted, provided the original author(s) and the copyright owner(s) are credited and that the original publication in this journal is cited, in accordance with accepted academic practice. No use, distribution or reproduction is permitted which does not comply with these terms.
DOI: 10.3389/fchem.2021.696081
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