Shape-persistent phthalocyanine cages

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 chal-lenge related to geometric requirements and poor solubility (strong aggregation), discrete shape-persistent cages consisting of site -iso-lated, 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 sta-bility, superior to the non-caged control molecules in electrocata-lytic CO2RR.

Automated summary

We successfully synthesized novel zinc and nickel-based Phthalocyanine cages via one-step synthesis with high yields. The structure of the zinc-based cage was determined by single-crystal X-ray diffraction. Due to the site-isolated redox-active metal centers, easily accessible intrinsic cavity, and shape-persistent backbone, these nickel-based cages exhibited high catalytic efficiency, selectivity, and stability in electrocatalytic CO2 reduction reaction, surpassing the non-caged control molecules.