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


ABSTRACT: 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 CuI and/or CuII cations that show a remarkable range of framework topologies and structures. Complex [CuI4CuII1.5(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 (43.123)(42.122) 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 (4.62.8)(62.8)(4.62.82) topology with tubular channels. Complex [Cu(L1)(NCMe)]·BF4·2(CH3CN)·H2O 5 features a 2D network of 63 topology while the CuII 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 4.82 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.

SUBMITTER: Thorp-Greenwood FL 

PROVIDER: S-EPMC5520774 | biostudies-literature | 2015 Oct

REPOSITORIES: biostudies-literature

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

Thorp-Greenwood Flora L FL   Ronson Tanya K TK   Hardie Michaele J MJ  

Chemical science 20150714 10


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<sup>I</sup> and/or Cu<sup>II</sup> cations that show a remarkable range of framework topologies and structures. Complex [Cu<sup>I</sup><sub>4</sub>Cu<sup>II</sup><sub>1.5</sub>(L1)<sub>3</sub>(CN)<sub>6</sub>]·CN·<i>n</i>(DMF) <b>1</b  ...[more]

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