Metallo‐supramolecular cages have garnered tremendous attention for their diverse yet molecular‐level precision structures. However, physical properties of these supramolecular ensembles, which are of potential significance in molecular electronics, remain largely unexplored. We herein constructed a series of octahedral metallo‐cages and cage‐fullerene complexes with notably enhanced structural stability. As such, we could systematically evaluate the electrical conductivity of these ensembles at both single‐molecule level and aggregated bulk state (as well‐defined films). Our findings reveal that counteranions and fullerene guests play a pivotal role in determining the electrical conductivity of aggregated state, while such effects are less significant for single‐molecule conductance. Both counteranions and fullerenes effectively tune the electronic structures and packing density of metallo‐supramolecular assemblies, and facilitate efficient charge transfer between the cage hosts and fullerenes, resulting in a notable one order of magnitude increase in electrical conductivity of the aggregated state.

中文翻译：

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富勒烯客体和抗衡离子对八面体金属超分子笼的结构稳定性和导电性的增强作用


金属超分子笼因其多样化的分子级精密结构而引起了极大的关注。然而，这些超分子系综的物理性质在分子电子学中具有潜在的重要意义，但在很大程度上仍未得到探索。我们在此构建了一系列八面体金属笼和笼富勒烯配合物，其结构稳定性显着增强。因此，我们可以系统地评估这些系综在单分子水平和聚集体状态（以及明确定义的薄膜）的电导率。我们的研究结果表明，抗衡阴离子和富勒烯客体在决定聚集态电导率方面发挥着关键作用，而这种影响对于单分子电导率来说不太重要。抗衡阴离子和富勒烯都能有效地调节金属超分子组装体的电子结构和堆积密度，并促进笼主体和富勒烯之间的有效电荷转移，从而导致聚集态的电导率显着增加一个数量级。