The immobilization of homogeneous catalysts onto 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 few strategies to append catalysts to support materials. Here,
we introduce a modular heterogenous catalysis platform that addresses
these challenges. Our approach leverages the well-defined interiors
of self-assembled Pd12L24 metal–organic
cages/polyhedra (MOCs): simple mixing of a catalyst-ligand of choice
with a polymeric ligand, spacer ligands, and a Pd salt induces self-assembly
of Pd12L24-cross-linked polymer gels featuring
endohedrally catalyst-functionalized junctions. Semi-empirical calculations
show that catalyst incorporation into the MOC junctions of these materials
has minimal affect on the MOC geometry, giving rise to well-defined
nanoconfined catalyst domains as confirmed experimentally using several
techniques. Given the unique network topology of these freestanding
gels, they are mechanically robust regardless of their endohedral
catalyst composition, allowing them to be physically manipulated and
transferred from one reaction to another to achieve multiple rounds
of catalysis. Moreover, by decoupling the catalyst environment (interior
of MOC junctions) from the physical properties of the support (the
polymer matrix), this strategy enables catalysis in environments where
homogeneous catalyst analogues are not viable, as demonstrated for
the Au(I)-catalyzed cyclization of 4-pentynoic acid in aqueous media.