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

Matthew L. Schneider, Adrian W. Markwell-Heys, Oliver M. Linder-Patton, Witold M. Bloch

Research output: Contribution to journalArticlepeer-review

6 Citations (Scopus)
2 Downloads (Pure)


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.

Original languageEnglish
Article number696081
Number of pages9
JournalFrontiers in Chemistry
Publication statusPublished - 25 May 2021
Externally publishedYes


  • amine-functionality
  • cage compound
  • coordination
  • cross-linking
  • porosity
  • self-assembly


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