Copper coordination polymers from cavitand ligands: hierarchical spaces from cage and capsule motifs, and other topologies† †Electronic supplementary information (ESI) available: Further details of crystallographic studies, thermogravimetric analyses, Raman spectroscopy. CCDC 1401250–1401256. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc01801c Click here for additional data file. Click here for additional data file.

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 [Cu4Cu 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 [Cu3(L2)4(H2O)3]$ 6(OTf)$n(DMSO) 2 and [Cu2(L3)2Br2(H2O)(DMSO)]$2Br$n(DMSO) 3 capsule-like metallo-cryptophane motifs are formed which linked through their metal vertices into a hexagonal 2D network of (4.12)(4.12) topology or a coordination chain. Complex [Cu2(L1)2(OTf)2(NMP)2(H2O)2]$2(OTf)$2NMP 4 has an interpenetrating 2D 3,4-connected framework of (4.6.8)(6.8)(4.6.8) topology with tubular channels. Complex [Cu(L1)(NCMe)]$BF4$2(CH3CN)$H2O 5 features a 2D network of 6 3 topology while the Cu analogue [Cu2(L1)2(NMP)(H2O)]$4BF4$12NMP$1.5H2O 6 has an interpenetrating (10,3)-b type structure and complex [Cu2(L2)2Br3(DMSO)]$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-C60 through soaking the crystals in a toluene solution.