Metal‐Organic Cages with Missing Linker Defects

We present here the controlled synthesis of defective coordination cages by employing steric hindrance of organic linkers to manipulate coordination modes of the assembled metal ions. Three chiral 1,1'-bi-2-naphthol (BINOL) derived bis-tridentate ligands L¹ -L³ with pyridine-2,6-dicarboxamides (pcam) chelating moieties are therefore designed and synthesized, among which L³ has a smaller steric hindrance on the coordinating sites relative to the other two linkers. Complexes of L¹ and L² with lanthanides afford the irregular Ln₈ (L¹ )₁₀ hexahedra with two missing edges and Ln₄ (L² )₅ tetrahedra with one missing edge, respectively, both of which contain a 1:1 mixture of Ln(pcam)₂ and Ln(pcam)₃ . In contrast, complex of L³ produces the regular twisted Ln₆ (L³ )₉ trigonal prisms without missing edges that contain only Ln(pcam)₃ vertices. The defective cage has more freedom to adjust its structural conformation, affording adaptable cavity to accommodate a range of guest molecules with sizes comparable or much larger than the cavity portals.