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

• Published in: Chemical science (Cambridge) 2015-10, Vol.6 (10), p.5779-5792
• Main Authors: Thorp-Greenwood, Flora L, Ronson, Tanya K, Hardie, Michaele J
• Format: Article
• Language: English
• Subjects: Channels; Chemistry; Coordination polymers; Interpenetrating networks; Ligands; Strategy; Toluene; Topology; Two dimensional
• ISSN: 2041-6520; 2041-6539
• DOI: 10.1039/c5sc01801c

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 [Cu Cu (L1) (CN) ]·CN· (DMF) features a novel 3,4-connected framework of cyano-linked hexagonal metallo-cages. In complexes [Cu (L2) (H O) ]·6(OTf)· (DMSO) and [Cu (L3) Br (H O)(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) (H O) ]·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(CH CN)·H O features a 2D network of 6 topology while the Cu analogue [Cu (L1) (NMP)(H O)]·4BF ·12NMP·1.5H O 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.