Plug-and-Play Heterogeneous Catalysis Enabled by Metal–Organic Cage-Crosslinked Polymers

21 December 2021, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


The immobilization of homogeneous catalysts onto solid supports to improve recyclability while maintaining catalytic efficiency is often a trial-and-error process limited by poor control of the local catalyst environment and a lack of modular strategies to append catalysts to support materials. Here, we introduce a “plug-and-play” heterogenous catalysis platform that overcomes these challenges. Our approach leverages the well-defined interiors of self-assembled Pd12L24 metal–organic cages/polyhedra (MOCs): through a simple combination of catalyst-ligands, polymeric ligands, and spacer ligands, we demonstrate facile self-assembly of a diverse range of polymer gels featuring endohedrally-catalyst-functionalized junctions. Through decoupling catalyst incorporation and environment from the physical properties of the support (polymer matrix), this simple strategy is shown to enhance the recyclability of various catalyst systems (e.g., TEMPO-catalyzed oxidation and Au(I)-catalyzed cyclization) and enable catalysis in environments where homogeneous catalyst analogs are not viable.


metal–organic polyhedra
polymer networks
gold catalysis

Supplementary materials

Supplementary Informatio
Methods, materials, spectral data, and additional discussion.


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