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

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.

SUBMITTER: Schneider ML

PROVIDER: S-EPMC8185198 | biostudies-literature | 2021

REPOSITORIES: biostudies-literature

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

Schneider Matthew L ML Markwell-Heys Adrian W AW Linder-Patton Oliver M OM Bloch Witold M WM

Frontiers in chemistry 20210525

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<sub>2</sub> paddlewheel-based MOCs. We demonstrate that tuning the basicity of an aniline-functionalized ligand enables the s ...[more]

PMID: 34113604

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