Covalent Stabilization: A Sturdy Molecular Square from Reversible Metal-Ion-Directed Self-Assembly

Supramolecular self-assembly using weak interactions under quasi-equilibrium conditions has provided easy access to very complex but often quite fragile molecules. We now show how a labile structure obtained from reversible transition-metal-directed self-assembly of rods and connectors serves as a template that can be converted into a sturdy structure of identical topology and similar geometry. The process consists of Cu(I)-catalyzed replacement of all rods or connectors terminated with pyridines for analogues terminated with ethynyls, converting dative N→Pt⁺ bonds into covalent C–Pt bonds. The procedure combines the facility and high yield of reversible self-assembly with the robustness of covalent synthesis.