Trapping of a Four‐Coordinate Zinc Salphen Complex Inside a Crystal Matrix

A remarkable twosome : Four‐coordinate square‐planar complexes based on [Zn(salen)] derivatives are conveniently captured inside a crystal matrix using a supramolecular protecting strategy (see figure). The four‐coordinate species is accompanied by a five‐coordinate complex that binds an axial ligand able to hydrogen bond to an N‐heterocycle positioned in the axial region of the coordinative unsaturated derivative. The size of the N‐heterocycle is a decisive stabilization parameter.