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

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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 {Cu 3 (L1) 2 (X) 6 } cages (X=anion) are mechanically interlocked, and link to each other and to another {Cu 3 (L1) 2 (X) 6 } 2 cage‐catenane through a planar, linear tetranuclear {Cu 4 ( μ‐ Cl) 6 Cl 2 } cluster. The complex of discrete tetrameric {Cu 3 (L1) 2 (X) 6 } 4 assemblies (dimers of cage‐catenanes) transforms through solvent‐exchange processes to 1D coordination chain structures through additional {Cu 2 ( μ‐ Cl) 2 } bridges between the tetrameric {Cu 3 (L1) 2 (X) 6 } 4 assemblies. Complex [Cu 6 (L1) 4 Cl 12 (H 2 O) 3 ] ⋅ (H 2 O) ⋅ 15(DMF) C2 features a 2D coordination network of 6 3 topology linked through three different Cu(II) clusters, namely {Cu 4 ( μ‐ Cl) 6 }, {Cu 2 ( μ‐ Cl) 2 } and a rare linear {Cu 2 ( μ ‐Cl)} linkage. Break‐down of C2 in water likely proceeds through hydrolysis of this unusual linear Cu‐Cl‐Cl bond.