Porous structures based on multi-metallic motifs are
receiving
growing interest, but their general preparation still remains a challenge.
Here, we report the self-assembly and structure of a CuII metal–organic cage (MOC) that is functionalized with free
bis(pyrazolyl)methane sites. The homometallic Cu4L4 cage is isolated as a water-stable crystalline solid, and
its formation is dependent on metal–ligand stoichiometry and
the pre-organization of the Cu2 paddlewheel. We show by
X-ray diffraction and SEM–EDX that PdII chloride
can be quantitatively inserted into the free chelating sites of the
MOC to yield a [Cu4(L(PdCl2))4] structure.
Moreover, the solvent employed in the metalation dictates the solid-state
isomerism of the heterometallic cagea further handle to control
the MOC’s structural diversity and permanent porosity.
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