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

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 and/or Cu cations that show a remarkable range of framework topologies and structures. Complex [CuCu(L1)(CN)]·CN·(DMF) features a novel 3,4-connected framework of cyano-linked hexagonal metallo-cages. In complexes [Cu(L2)(HO)]·6(OTf)·(DMSO) and [Cu(L3)Br(HO)(DMSO)]·2Br·(DMSO) capsule-like metallo-cryptophane motifs are formed which linked through their metal vertices into a hexagonal 2D network of (4.12)(4.12) topology or a coordination chain. Complex [Cu(L1)(OTf)(NMP)(HO)]·2(OTf)·2NMP has an interpenetrating 2D 3,4-connected framework of (4.6.8)(6.8)(4.6.8) topology with tubular channels. Complex [Cu(L1)(NCMe)]·BF·2(CHCN)·HO features a 2D network of 6 topology while the Cu analogue [Cu(L1)(NMP)(HO)]·4BF·12NMP·1.5HO has an interpenetrating (10,3)- type structure and complex [Cu(L2)Br(DMSO)]·Br·(DMSO) has a 2D network of 4.8 topology. Strategies for formation of coordination polymers with hierarchical spaces emerge in this work and complex is shown to absorb fullerene-C through soaking the crystals in a toluene solution.