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 [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.