From the synthesis of small biomolecules to complex macromolecular structures, click chemistry is one of the most promising and straightforward methodologies owing to its easy accessibility and high efficiency. A dual-heterogeneous photocatalyst with the capability of engendering light emission in upconversion materials combined with graphitic carbon nitride (g-CN) could present a powerful tool in electron transfer reactions, specifically in copper-catalyzed azide-alkyne cycloaddition (CuAAC) click reactions. We herein describe a “geared photochemistry” approach for producing an electron from g-CN by in-source lightening in the near-infrared region using upconversion glass that produces copper(i) to initiate the click reaction. Using this approach, the photocatalytic activation of g-CN has been achieved by using Tm3+ and Yb3+ ion-doped zinc-tellurite glass which absorbs laser irradiation at 975 nm and is capable of emitting blue light at 475 nm. The efficiency of this system has been investigated for various CuAAC reactions ranging from small molecule synthesis to the macromolecular scale including modification strategies of polymers.@en

Two-dimensional (2D) materials have great potential in macromolecular synthesis, yet there are some areas that still need to be explored, such as anionic polymerization. In this study, we present the first example of photoinduced anionic polymerization of ethyl-2-cyanoacrylate (ECA) using 2D graphitic carbon nitride (g-C3N4) as an active photocatalyst responsive to visible light. Our results demonstrate that particularly the mesoporous structure of g-C3N4 can initiate polymerization through the generation of electron-hole pairs upon exposure to visible light. To have a better insight into mechanistic pathways, several experiments, including control experiments, are conducted. The obtained polymers and the synthesized g-C3N4 materials are characterized comprehensively by chromatographic, thermal, and spectroscopic techniques. Accordingly, this study demonstrates an innovative process that can offer several advantages over traditional polymerization methods, including the ability to initiate polymerization at ambient temperatures and achieve high polymerization rates.@en