Perylenediimide(PDI)materials have gained considerable interest as photocatalysts owing to their exceptional photophysical properties.However,the development of PDI-based photocatalysts remains constrained by several ...Perylenediimide(PDI)materials have gained considerable interest as photocatalysts owing to their exceptional photophysical properties.However,the development of PDI-based photocatalysts remains constrained by several critical limitations,such as rapid charge recombination and aggregation-induced quenching.Here,we report the design and synthesis of a crystalline porous metal-perylenediimide framework(MPF)through the self-assmebly of PDI-based tetracarboxylate ligand(H_4PDI)with Ce^(3+)ions.The resulting Ce-PDI framework features a distinctive double-walled porous structure,stabilized by robustπ-πstacking interactions between PDI units.This architecture offers abundant active sites and ample space for substrate-catalyst interactions,while mitigating aggregation-induced quenching of PDI units and facilitating efficient photogenerated charge transfer.Compared to the hydrogen-bonded assembly H_(4)PDI with its dense packing,our double-walled porous Ce-PDI framework demonstrated markedly improved photocatalytic activity and recyclability.Specifically,Ce-PDI achieved catalytic yields of up to 95%for the C-3 formylation of indoles and 97%for the condensation of o-phenylenediamine with aromatic aldehydes,significantly outperforming H_(4)PDI,which only achieved yields of 16%-34%.This work provides a simple and effective approach to overcoming the inherent limitations of PDI-based photocatalysts,thereby advancing their catalytic performance.展开更多
基金supported by the National Natural Science Foundation of China(22171002,22301003,22025107)the Natural Science Foundation of Anhui Province(2308085QB38,2408085QB069)+1 种基金the Wanjiang Scholar Programthe Key Scientific Research Foundation of the Education Department of Anhui Province(2023AH051110)。
文摘Perylenediimide(PDI)materials have gained considerable interest as photocatalysts owing to their exceptional photophysical properties.However,the development of PDI-based photocatalysts remains constrained by several critical limitations,such as rapid charge recombination and aggregation-induced quenching.Here,we report the design and synthesis of a crystalline porous metal-perylenediimide framework(MPF)through the self-assmebly of PDI-based tetracarboxylate ligand(H_4PDI)with Ce^(3+)ions.The resulting Ce-PDI framework features a distinctive double-walled porous structure,stabilized by robustπ-πstacking interactions between PDI units.This architecture offers abundant active sites and ample space for substrate-catalyst interactions,while mitigating aggregation-induced quenching of PDI units and facilitating efficient photogenerated charge transfer.Compared to the hydrogen-bonded assembly H_(4)PDI with its dense packing,our double-walled porous Ce-PDI framework demonstrated markedly improved photocatalytic activity and recyclability.Specifically,Ce-PDI achieved catalytic yields of up to 95%for the C-3 formylation of indoles and 97%for the condensation of o-phenylenediamine with aromatic aldehydes,significantly outperforming H_(4)PDI,which only achieved yields of 16%-34%.This work provides a simple and effective approach to overcoming the inherent limitations of PDI-based photocatalysts,thereby advancing their catalytic performance.
