Control of Heterometallic Three‐Dimensional Macrocycles with Aromatic Stacks in Tunable Host Cavities

Using coinage metal (Cu(II), Ag(I)) hinges, two sets of heterometallic molecular capsules with analogous open-ended cavities were prepared based on the half-sandwich rhodium fragments. In the case of [Rh4Cu4] cages, up to six-fold-stacked host-guest structures were formed by varying the cavity’s dimensions. Moreover, the series of capsules were demonstrated to self-fine-tune to form multi-heteroguest arrays via favourable donor-acceptor π interactions and Ag-π interactions, as evidenced from single-crystal X-ray analysis.

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