Formation of a Dimer of Trinuclear Helicates which Encapsulates an Array of Six Hydrogen-Bonded Anions

• Published in: Angewandte Chemie International Edition Vol. 53; no. 49; pp. 13540 - 13543
• Main Authors: Faulkner, Robert A., Harding, Lindsay P., Higginson, Joshua, Rice, Craig R., Slater, Christopher
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01.12.2014; WILEY‐VCH Verlag; Wiley; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Anions; Arrays; Chemistry; Chemistry, Multidisciplinary; Circularity; Clusters; copper; cyclic helicate; Dimers; Encapsulation; Formations; helical structures; Ligands; Phosphates; Physical Sciences; Science & Technology; self-assembly; Unsaturated; X-ray diffraction; self-assembly; LIGANDS; CRYSTAL-STRUCTURE; helical structures; X-ray diffraction; TRIPLE-HELIX; CHEMISTRY; copper; CLUSTER; cyclic helicate
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.201407645

The amine‐containing ligand L, composed of two bidentate pyridyl‐thiazole moieties linked by a 1,3‐diaminophenylene unit, reacts with copper(II) ions to form a dinuclear double helicate [Cu2L2]4+. Reaction of [Cu2L2]4+ with dihydrogen phosphate (0.5 equivalents) gives the unsaturated dinuclear double helicate [Cu2L2(OPO3H2)]3+. [Cu2L2(OPO3H2)]3+ further reacts with another 0.5 equivalents of dihydrogen phosphate to give a trinuclear circular helicate which then self‐assembles into a hexameric cluster [{Cu3L3(OPO3H2)3}]26+. Cu does the twist: Cu2+ ions react with ligand L, containing two bidentate pyridyl‐thiazole units linked by 1,3‐diaminophenylene, to form a dinuclear double helicate [Cu2L2]4+. [Cu2L2]4+ reacts with OPO3H2− ions (0.5 equiv) to give the unsaturated double helicate [Cu2L2(OPO3H2)]3+. Further reaction of [Cu2L2(OPO3H2)]3+ with OPO3H2− yields a trinuclear circular helicate which self‐assembles into a hexameric cluster [{Cu3L3(OPO3H2)3}2]6+ (see structure).