Molecular cages with arylboronate ester caps at the vertices are described. The cages were obtained by metal-templated polycondensation reactions of a tris(2-formylpyridine oxime) ligand with arylboronic acids. Suited templates are triflate or triflimide salts of Zn II , Fe II , Co II , or Mn II . In the products, the metal ions are coordinated internally to the pyridyl and oximato N atoms adjacent to the boronate ester, resulting in an improved hydrolytic stability of the latter. It is possible to decorate the cages with cyano or aldehyde groups using functionalized arylboronic acids. The aldehyde groups allow for a postsynthetic modification of the cages via an imine bond formation.
Triple‐stranded helicates were obtained by metal‐templated multicomponent reactions of bispyridyloxime ligands with arylboronic acids. The helicates feature two hexa‐coordinated MII ions (M=Fe, Zn, or Mn), which are embedded in a macrobicyclic ligand framework, and two arylboronate ester capping groups. The latter can be used to introduce functional groups such as pyridines, aldehydes, nitriles, and carboxylic acids in apical position. The functionalized helicates have the potential to be used as nanoscale building blocks for more complex assemblies, as evidenced by the synthesis of a 3 nm‐sized trianglimine.
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