Abstract
Covalent organic frameworks (COFs) are promising materials for applications in photocatalysis, due to their conjugated, porous and chemically stable architectures. Alternating electron donor-acceptor-type structures are known to enhance charge carrier transport mobility and stability in polymers and are therefore also interesting building units for COFs used as photocatalysts but also as photoinitiator. In this work, two donor-acceptor COFs using electron deficient 4,4',4''-(1,3,5-triazine-2,4,6-triyl)trianiline and electron rich thiophene-based thieno[3,2-b]thiophene-2,5-dicarbaldehyde or [2,2'-bithiophene]-5,5'-dicarbaldehyde linkers are presented. The resulting crystalline and porous COFs have been applied as photoinitiator for visible light induced free radical polymerization of methyl methacrylate (MMA) to poly-methyl methacrylate (PMMA). These results pave the way to the development of robust and heterogeneous systems for photochemistry that offers the transfer of radicals induced by visible light.
Highlights
Two donor–acceptor Covalent organic frameworks (COFs) have been prepared using electron deficient 4,4′,4′′-(1,3,5-triazine-2,4,6-triyl)trianiline and electron rich thiophene-based thieno[3,2-b]thiophene-2,5-dicarbaldehyde or [2,2′-bithiophene]-5,5′-dicarbaldehyde linkers
Two donor–acceptor COFs have been prepared using electron deficient 4,4′,4′′-(1,3,5-triazine-2,4,6-triyl)trianiline and electron rich thiophene-based thieno[3,2-b]thiophene-2,5-dicarbaldehyde or [2,2′-bithiophene]-5,5′-dicarbaldehyde linkers. These crystalline and porous COFs have been applied as a photoinitiator for visible light induced free radical polymerization of methyl methacrylate (MMA) to poly-methyl methacrylate (PMMA)
The resulting crystalline and porous COFs have been applied as photoinitiator for visible light induced free radical polymerization of methyl methacrylate (MMA) to polymethyl methacrylate (PMMA)
Summary
To further improve the catalytic activities, strategies such as introduction of heteroatoms (N and S),[10] increasing the catalyst wettability,[24] immobilization of molecular co-catalysts[25] and improving the conjugation have been endeavored.[26] It has further been demonstrated that the precise combination of donor–acceptor moieties in organic materials and COFs can yield enhanced performance in solar cells and optoelectronic applications, respectively.[27,28,29,30,31,32,33,34] two novel COFs are presented, whose structures were designed considering the abovementioned criteria These materials have been successfully applied as photoinitiators for efficient and recyclable radical polymerization, paving the way to the development of robust and heterogeneous systems for photochemistry that offers the transfer of radicals induced by visible light.
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