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The cyclotriveratrylene-type ligands (±)-tris(iso-nicotinoyl)cyclotriguaiacylene L1 (±)-tris(4-pyridylmethyl)cyclotriguaiacylene L2 and (±)-tris{4-(4-pyridyl)benzyl}cyclotriguaiacylene L3 all feature 4-pyridyl donor groups and all form coordination polymers with Cu I and/or Cu II cations that show a remarkable range of framework topologies and structures. Complex [Cu I  4 Cu II  1.5 (L1) 3 (CN) 6 ]·CN· n (DMF) 1 features a novel 3,4-connected framework of cyano-linked hexagonal metallo-cages. In complexes [Cu 3 (L2) 4 (H 2 O) 3 ]·6(OTf)· n (DMSO) 2 and [Cu 2 (L3) 2 Br 2 (H 2 O)(DMSO)]·2Br· n (DMSO) 3 capsule-like metallo-cryptophane motifs are formed which linked through their metal vertices into a hexagonal 2D network of (4 3 .12 3 )(4 2 .12 2 ) topology or a coordination chain. Complex [Cu 2 (L1) 2 (OTf) 2 (NMP) 2 (H 2 O) 2 ]·2(OTf)·2NMP 4 has an interpenetrating 2D 3,4-connected framework of (4.6 2 .8)(6 2 .8)(4.6 2 .8 2 ) topology with tubular channels. Complex [Cu(L1)(NCMe)]·BF 4 ·2(CH 3 CN)·H 2 O 5 features a 2D network of 6 3 topology while the Cu II analogue [Cu 2 (L1) 2 (NMP)(H 2 O)]·4BF 4 ·12NMP·1.5H 2 O 6 has an interpenetrating (10,3)- b type structure and complex [Cu 2 (L2) 2 Br 3 (DMSO)]·Br· n (DMSO) 7 has a 2D network of 4.8 2 topology. Strategies for formation of coordination polymers with hierarchical spaces emerge in this work and complex 2 is shown to absorb fullerene-C 60 through soaking the crystals in a toluene solution.

Copper coordination polymers from cavitand ligands: hierarchical spaces from cage and capsule motifs, and other topologies