2D covalent organic frameworks (COFs) are receiving ongoing attention in semiconductor photocatalysis. Herein, we present ap hotocatalytic selective chemical transformation by combining sp 2 carbon-conjugated porphyrinbased covalent organic framework (Por-sp 2 c-COF) photocatalysis with TEMPO catalysis illuminated by 623 nm red light-emitting diodes (LEDs). Highly selective conversion of amines into imines was swiftly afforded in minutes.S pecifically,t he p-conjugation of porphyrin linker leads to extensive absorption of red light;t he sp 2 ÀC=CÀ double bonds linkage ensures the stability of Por-sp 2 c-COF under high concentrations of amine.M ost importantly,w ef ound that crystalline framework of Por-sp 2 c-COF is pivotal for cooperative photocatalysis with (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEM-PO). This work foreshadows that the outstanding hallmarks of COFs,p articularly crystallinity,c ould be exploited to address energy and environmental challenges by cooperative photocatalysis.

metal sulfides belong to an important subgroup of semiconductor photocatalysts that could promote a variety of valuable redox reactions under mild conditions. One notable merit of metal sulfides is their relatively smaller bandgaps than metal oxides, which in turn make sure that many of them can directly utilize visible light. Historically, the deployment of metal sulfides for visible-light-induced organic transformations took place shortly after the genesis of the research field of heterogeneous photocatalysis. In this review, we primarily focus on recent state-of-the-art advancements of metal sulfide photocatalysis aimed at visible-light-induced selective organic transformations. Interests in this specific branch of photocatalysis have been rekindled due to the new methods for materials synthesis; the pursuit of new mechanisms; or the integration of metal sulfides with metal oxides, metal nanoparticles or other emerging materials. Thus we categorize them into four sections according to the different strategies in developing novel or more efficient organic processes. Binary and ternary metal sulfides, usually associated with new materials synthesis and mechanistic insights, can be used directly for visible-lightinduced organic transformations. This is the basis of other further developments and will be introduced firstly. Next, the cooperation between metal sulfides and metal oxides or metal nanoparticles can be conducive to many photocatalytic systems. These developments will be discussed in the next two ensuing sections. Furthermore, the integration of metal sulfides with recent developed emerging materials such as metalorganic frameworks (MOFs), graphene and graphitic carbon nitride (g-C 3 N 4 ) will be discussed in another section to highlight the importance of merging metal sulfides with these materials. We attempt to keep an impartial panorama of these four distinctive sections even though the phases of development are quite different among sections, leaving plenty of room for the future expansion of this burgeoning area.

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This work reports the cooperative photocatalysis of a two-dimensional covalent organic framework with an electron transfer mediator in a selective organic transformation.