Tailoring Ultrashort Inter‐Fullerene Spacing in a Continuous Fullerene Stacking Array to Enhance Electron Transport for Boosting Solar‐Driven Hydrogen Production

ABSTRACT The efficiency of organic semiconductor photocatalysts is typically limited by their capability of photogenerated electron transport. Herein, a photocatalyst is proposed initially through the specific axial coordination interaction between imidazole‐C 60 (ImC 60 ) and zinc tetraphenyl porphyrin (ZnTPP) named ImC 60 ‐ZnTPP. Subsequently, detailed structural characterizations along with theoretical calculation reveal that the unique ImC 60 ‐ZnTPP possesses head‐to‐tail stacking supra‐structures, leading to the formation of a continuous array of C 60 –C 60 with ultrashort spacing and ensuring strong π–π interactions and homogeneous electronic coupling, which could tremendously promote electron transport along the (−111) crystal facet of ImC 60 ‐ZnTPP. Consequently, compared to other fullerene‐based photocatalysts, ImC 60 ‐ZnTPP shows exceptional photocatalytic hydrogen production activity, with an efficiency of up to 80.95 mmol g −1 h −1 . This study provides a novel strategy to design highly efficient fullerene‐based photocatalytic systems for solar‐driven energy conversion and extend their artificial photosynthetic use.