Assembly and Covalent Cross-Linking of an Amine-Functionalised Metal-Organic Cage

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...

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Bibliographic Details
Published in:Frontiers in chemistry 2021-05, Vol.9, p.696081-696081
Main Authors: Schneider, Matthew L., Markwell-Heys, Adrian W., Linder-Patton, Oliver M., Bloch, Witold M.
Format: Article
Language:English
Subjects:
amine-functionality
cage compound
Chemistry
coordination
cross-linking
porosity
self-assembly
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Summary: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 Cu 2 paddlewheel-based MOCs. We demonstrate that tuning the basicity of an aniline-functionalized ligand enables the self-assembly of a soluble, amine-functionalized Cu 4 L 4 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.
ISSN:2296-2646
2296-2646
DOI:10.3389/fchem.2021.696081