Supramolecular metallaphenylsilsesquioxanes: non-covalent effects, magnetic and catalytic properties

Phenyl-surrounded silsesquioxane architectures based on transition metal ions including Cu(II), Ni(II) and Mn(II), (III), are reviewed in the context of their supramolecular aggregation. Several noncovalent mechanisms governing the formation of coordination polymers of different dimensionalities (1D, 2D, and 3D) based on cage-like metallasilsesquioxanes used as building blocks are discussed.These mechanisms include the employement of intercage connections via: (i) organic linkers or solvating ligands bridges, (ii) crown ether contacts, (iii) metallocene fragments, and (iv) π–π stacking or C–H…π interactions. Potential applications of supramolecular metallaphenylsilsesquioxanes in catalysis and magnetism are also discussed. For instance, Cu(II)- and Mn(II), (III)-based compounds appear as efficient catalysts in oxidative reactions and carbon dioxide couplings. On the other hand, Cu(II)- and Ni(II)-silsesquioxane-based coordination polymers exhibit intriguing magnetic properties, including observation of a slow relaxation of the magnetization due to spin glass behavior. © 2025 Elsevier B.V.