Dye-based metal–organic frameworks(MOFs)have received great attention due to their excellent photochemical stability in photocatalysis.However,the control of photoinduced electron transfer(PET)from dye to substrates ...Dye-based metal–organic frameworks(MOFs)have received great attention due to their excellent photochemical stability in photocatalysis.However,the control of photoinduced electron transfer(PET)from dye to substrates rather than to metal nodes is still a challenging task for modern chemistry and organic synthesis,limiting the application of dye-based MOFs in photocatalytic transformations.Herein,we report a new method by introducing a carbonyl group into triphenylamine to form a planar conjugate acridone to compulsively generate a greater degree of conjugation torsion between the dye-based ligands and the metal–carboxylate nodes for controlling the direction of electron flow in the MOF.A new heterogeneous three-dimensional(3D)acridone-based Co-MOF was fabricated by the solvothermal reaction.In comparison with the similar triphenylamine-based Co-MOF,extensive control experiments in combination with density functional theory(DFT)calculations demonstrated that the acridone-based Co-MOF successfully inhibits the intramolecular PET process between the acridone-based ligands and the metal nodes for efficient photocatalytic organic transformations.This new heterogeneous platform exhibits a promising approach to modulating the direction of PET in MOFs by fine modifications of the ligands,thus providing a new avenue to develop multipurpose and flexible catalytic systems.展开更多
基金supported by the National Natural Science Foundation of China(Grant No.22171034,21890381 and 21820102001)the Natural Science Foundation of Jiangsu Province(Grant No.BK20220033)+1 种基金the Natural Science Foundation of Liaoning Province(Grant No.2023MS116)the Fundamental Research Funds for the Central Universities(Grant No.DUT22LAB606).
文摘Dye-based metal–organic frameworks(MOFs)have received great attention due to their excellent photochemical stability in photocatalysis.However,the control of photoinduced electron transfer(PET)from dye to substrates rather than to metal nodes is still a challenging task for modern chemistry and organic synthesis,limiting the application of dye-based MOFs in photocatalytic transformations.Herein,we report a new method by introducing a carbonyl group into triphenylamine to form a planar conjugate acridone to compulsively generate a greater degree of conjugation torsion between the dye-based ligands and the metal–carboxylate nodes for controlling the direction of electron flow in the MOF.A new heterogeneous three-dimensional(3D)acridone-based Co-MOF was fabricated by the solvothermal reaction.In comparison with the similar triphenylamine-based Co-MOF,extensive control experiments in combination with density functional theory(DFT)calculations demonstrated that the acridone-based Co-MOF successfully inhibits the intramolecular PET process between the acridone-based ligands and the metal nodes for efficient photocatalytic organic transformations.This new heterogeneous platform exhibits a promising approach to modulating the direction of PET in MOFs by fine modifications of the ligands,thus providing a new avenue to develop multipurpose and flexible catalytic systems.
