Phthalocyanine (Pc), an electro-redox active moiety, has many attractive properties stemming from its large aromatic system and ability to act as a catalyst in electrochemical reactions, such as the CO₂ reduction reaction (CO₂RR). However, due to the synthetic challenge related to geometric requirements and poor solubility (strong aggregation), discrete shape-persistent cages consisting of site-isolated, readily accessible Pc moieties have not been available. Here, we report the synthesis of Zn- and Ni-metallated Pc-based molecular cages via one-step dynamic spiroborate linkage formation in high yields. The ZnPc cage structure is unambiguously elucidated at the atomic level by single-crystal X-ray diffraction. Moreover, owing to the site-isolated redox-active metal centers, readily accessible intrinsic cavity, and shape-persistent backbone, the Ni-metallated Pc (NiPc) cage exhibits high catalytic efficiency, selectivity, and stability, superior to the non-caged control molecules in electrocatalytic CO₂RR.

酞菁 (Pc) 是一种电氧化还原活性基团，具有许多吸引人的特性，这源于其庞大的芳香族体系以及在电化学反应（例如 CO 2 还原反应₍ CO ₂RR）。然而，由于与几何要求和溶解性差（强聚集）相关的合成挑战，由位点隔离、易于接近的 Pc 部分组成的离散形状持久笼尚不可用。在这里，我们报告了通过一步动态螺硼酸盐键形成高产率合成锌和镍金属化 Pc 基分子笼。通过单晶 X 射线衍射在原子水平上明确阐明了 ZnPc 笼结构。此外，由于位点隔离的氧化还原活性金属中心、易于接近的固有腔和形状持久的主链，镍金属化 Pc (NiPc) 笼具有高催化效率、选择性和稳定性，优于非笼状电催化CO ₂ RR中的控制分子。