Organic Photocatalyst Utilizing Triplet Excited States for Highly Efficient Visible-Light-Driven Polymerizations DOI Creative Commons
Yonghwan Kwon, Woojin Jeon, Johannes Gierschner

et al.

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: May 1, 2025

ConspectusUltraviolet (UV) light has traditionally been used to drive photochemical organic transformations, mainly due the limited visible-light absorption of most molecules. However, high energy associated with UV often causes undesirable side reactions. In late 2000s, MacMillan, Yoon, and Stephenson pioneered use visible in conjunction photocatalysts (PCs) initiate transformations. This innovative approach overcame limitations by utilizing visible-light-absorbing PCs their photoexcited states for electron or transfer, generating reactive radical species promoting photoreactions. Furthermore, while photocatalysis predominantly relied on transition-metal complexes, concerns over potential toxicity, cost, sustainability these metals have driven development PCs. These eliminate need metal removal, offer structural diversity, enable tuning properties, thus paving way creation a tailored library PCs.In recent decades, significant advancements made novel diverse scaffolds, notable example being work Zhang et al. 2016. They demonstrated that cyanoarene analogues, originally developed Adachi thermally activated delayed fluorescence (TADF) light-emitting diodes, could function effectively as Building insights, we PC design platform featuring TADF compounds twisted donor-acceptor structures, which paved new discoveries. We showcased PCs' ability (i) generate long-lived lowest triplet excited (T1) (ii) tune redox potentials independently modifying donor acceptor moieties. Through this platform, discovered varying capability populate T1 states, establishing structure-property relationships within our creating selection criteria targeted Specifically, highly efficient reversible-deactivation polymerizations, including organocatalyzed atom transfer polymerization, photoinduced electron/energy reversible addition-fragmentation chain polymerization dual photoredox/copper catalysis well rapid free polymerizations. also facilitated functionalized, visible-light-cured adhesives advanced display technologies. investigated origins exceptional catalytic performance through comprehensive mechanistic studies, electrochemical photophysical measurements, quantum chemical calculations, kinetics simulations. studied formation degradation key intermediates photocatalytic dehalogenations alkyl aryl halides. Our findings revealed distinctive photodegradation pattern cyanoarene-based PCs, significantly impact efficiency reaction. Additionally, discovery led us introduce concept beneficial first time.Over past based state become central synthesis. Utilizing systems enhance overall various overview contributions visible-light-driven photocatalysis, highlight role broadening applications analysis, enabling more sustainable

Language: Английский

Organic Photocatalyst Utilizing Triplet Excited States for Highly Efficient Visible-Light-Driven Polymerizations DOI Creative Commons
Yonghwan Kwon, Woojin Jeon, Johannes Gierschner

et al.

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: May 1, 2025

ConspectusUltraviolet (UV) light has traditionally been used to drive photochemical organic transformations, mainly due the limited visible-light absorption of most molecules. However, high energy associated with UV often causes undesirable side reactions. In late 2000s, MacMillan, Yoon, and Stephenson pioneered use visible in conjunction photocatalysts (PCs) initiate transformations. This innovative approach overcame limitations by utilizing visible-light-absorbing PCs their photoexcited states for electron or transfer, generating reactive radical species promoting photoreactions. Furthermore, while photocatalysis predominantly relied on transition-metal complexes, concerns over potential toxicity, cost, sustainability these metals have driven development PCs. These eliminate need metal removal, offer structural diversity, enable tuning properties, thus paving way creation a tailored library PCs.In recent decades, significant advancements made novel diverse scaffolds, notable example being work Zhang et al. 2016. They demonstrated that cyanoarene analogues, originally developed Adachi thermally activated delayed fluorescence (TADF) light-emitting diodes, could function effectively as Building insights, we PC design platform featuring TADF compounds twisted donor-acceptor structures, which paved new discoveries. We showcased PCs' ability (i) generate long-lived lowest triplet excited (T1) (ii) tune redox potentials independently modifying donor acceptor moieties. Through this platform, discovered varying capability populate T1 states, establishing structure-property relationships within our creating selection criteria targeted Specifically, highly efficient reversible-deactivation polymerizations, including organocatalyzed atom transfer polymerization, photoinduced electron/energy reversible addition-fragmentation chain polymerization dual photoredox/copper catalysis well rapid free polymerizations. also facilitated functionalized, visible-light-cured adhesives advanced display technologies. investigated origins exceptional catalytic performance through comprehensive mechanistic studies, electrochemical photophysical measurements, quantum chemical calculations, kinetics simulations. studied formation degradation key intermediates photocatalytic dehalogenations alkyl aryl halides. Our findings revealed distinctive photodegradation pattern cyanoarene-based PCs, significantly impact efficiency reaction. Additionally, discovery led us introduce concept beneficial first time.Over past based state become central synthesis. Utilizing systems enhance overall various overview contributions visible-light-driven photocatalysis, highlight role broadening applications analysis, enabling more sustainable

Language: Английский

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