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-I and/or Cu-II cations that show a remarkable range of framework topologies and structures. Complex [(Cu4Cu1.5II)-Cu-I(L1)(3)(CN)(6)]center dot CN center dot n(DMF) 1 features a novel 3,4-connected framework of cyano-linked hexagonal metallo-cages. In complexes [Cu-3(L2)(4)(H2O)(3)]center dot 6(OTf)center dot n(DMSO) 2 and [Cu-2(L3)(2)Br-2(H2O)(DMSO)]center dot 2Br center dot 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)(H2O)(2)]center dot 2(OTf)center dot 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)]center dot BF4 center dot 2(CH3CN)center dot H2O 5 features a 2D network of 6(3) topology while the Cu-II analogue [Cu-2(L1)(2)(NMP)(H2O)]center dot 4BF(4)center dot 12NMP center dot 1.5H(2)O 6 has an interpenetrating (10,3)-b type structure and complex [Cu-2(L2)(2)Br-3(DMSO)]center dot Br center dot 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.