Reversible anion-templated self-assembly of [2 + 2] and [3 + 3] metallomacrocycles containing a new dicopper(I) motif

摘要

A new dicopper(Ⅰ) complex is reported that can be incorporated into extended architectures through multitopic carboxylate linkers; reversible carboxylate templation under pH control led to the formation of [2 + 2] and [3 + 3] metallomacrocycles. Recent years have seen major advances in the creation of complex self-assembled architectures from simple building blocks.' Subtle alterations in components' geometries2 or the identities of metal ions3 can result in major changes in a product's structure. The use of multiple 'chemically orthogonal' linkages has been exploited to generate structures in which each different kind of linkage contributes to the overall structure.4 We have recently shown how subcomponent self-assembly,5 the simultaneous formation of both dynamic covalent (C=N) and dative (ligand→M) bonds under thermodynamic control, can yield complex and functional dynamic systems.6 Here we describe a new self-assembled dicopper(Ⅰ) complex for use as a building block in the formation of extended multinuclear architectures including the anion templated assembly7 of both a 52-membered [2 + 2] and a 78-membered [3 + 3] metallomacrocycle.