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In one fell swoop eleven building blocks— five ligands and six metal ions—self-assemble to give the discrete Cu1 complex 1 shown schematically on the right (phenyl substituents at the two central ligands and the methyl substituents at the three outer ligands have been omitted). The formation of 1 demonstrates how molecular self-organization can be controlled by the design and selection of the individual components to provide unusual structures. In the case of 1 the bridging ligands define a cylindrical cavity. • = copper(I) atom.