Higher Assemblies of Coordination Cage‐Catenanes Linked by Copper(II) Chloride Clusters: Networks and Transformations

Cage-catenanes are chemical constructs where two or more cage-like molecules or assemblies are mechanically interlocked together. We report a new class of cage-catenanes where dimeric metal-organic cage-catenanes are linked into larger assemblies through additional bridging metal chloride links. These crystalline materials are obtained from the reaction of tris(nicotinoyl)cyclotriguaiacylene (L1) with Cu(II) salts, and all feature a tetramer of cages where two {Cu3(L1)2(X)6} cages (X = anion) are mechanically interlocked, and link to each other and to another {Cu3(L1)2(X)6}2 cage-catenane through a planar, linear tetranuclear {Cu4(μ−Cl)6Cl2} cluster. The complex of discrete tetrameric {Cu3(L1)2(X)6}4 assemblies (dimers of cage-catenanes) transforms through solvent-exchange processes to 1D coordination chain structures through additional {Cu2(μ−Cl)2} bridges between the tetrameric {Cu3(L1)2(X)6}4 assemblies. Complex [Cu6(L1)4Cl12(H2O)3]·(H2O)·15(DMF) C2 features a 2D coordination network of 63 topology linked through three different Cu(II) clusters, namely {Cu4(μ−Cl)6}, {Cu2(μ−Cl)2} and a rare linear {Cu2(μ-Cl)} linkage. Break-down of C2 in water likely proceeds through hydrolysis of this unusual linear Cu-Cl-Cl bond.