Developing heterogeneous photocatalytic platforms to manipulate near-infrared(NIR)light for organic synthesis is challenging.Here,we report vinylene-linked anthraquinone-based conjugated porous polymers(AQ-TVB-CPPs)ca...Developing heterogeneous photocatalytic platforms to manipulate near-infrared(NIR)light for organic synthesis is challenging.Here,we report vinylene-linked anthraquinone-based conjugated porous polymers(AQ-TVB-CPPs)capable of capturing NIR light.As a NIR photon conversion platform,AQ-TVB-CPPs exhibit three functions:photogenerated electron and hole transfer,photothermal conversion,and singlet oxygen(^(1)O_(2))production under 760 nm LED irradiation.This multifunctional material serves as a heterogeneous photocatalyst for NIR light-driven cyanation ofα-amino C(sp^(3))-H bonds.Controlled experiments indicate that ^(1)O_(2)and photothermal effects are crucial for the reaction and its selective regulation.Compared to visible light,this NIR photocatalytic system achieves higher yields and superior selectivity in the cyanation ofα-amino C(sp^(3))-H bonds,particularly for challenging substrates such as molecules with multiple active sites and organic dyes,as well as in gram-scale reactions.Notably,this strategy also enables the cyanation ofα-amino C(sp^(3))-H bonds under natural sunlight.This metal-free,recyclable,and highly stable multifunctional conjugated porous polymer(CPP)offers a new approach to utilizing NIR light and sunlight for organic synthesis.展开更多
基金supported by the Guangxi Science and Technology Major Program(Guike AA24263012)the National Natural Science Foundation of China(22471046,22301048,22201049)the Bagui Outstanding Youth Talent Project。
文摘Developing heterogeneous photocatalytic platforms to manipulate near-infrared(NIR)light for organic synthesis is challenging.Here,we report vinylene-linked anthraquinone-based conjugated porous polymers(AQ-TVB-CPPs)capable of capturing NIR light.As a NIR photon conversion platform,AQ-TVB-CPPs exhibit three functions:photogenerated electron and hole transfer,photothermal conversion,and singlet oxygen(^(1)O_(2))production under 760 nm LED irradiation.This multifunctional material serves as a heterogeneous photocatalyst for NIR light-driven cyanation ofα-amino C(sp^(3))-H bonds.Controlled experiments indicate that ^(1)O_(2)and photothermal effects are crucial for the reaction and its selective regulation.Compared to visible light,this NIR photocatalytic system achieves higher yields and superior selectivity in the cyanation ofα-amino C(sp^(3))-H bonds,particularly for challenging substrates such as molecules with multiple active sites and organic dyes,as well as in gram-scale reactions.Notably,this strategy also enables the cyanation ofα-amino C(sp^(3))-H bonds under natural sunlight.This metal-free,recyclable,and highly stable multifunctional conjugated porous polymer(CPP)offers a new approach to utilizing NIR light and sunlight for organic synthesis.
