Visible-Light-Mediated Diels-Alder Reactions Under Single-Chain Polymer Confinement: Investigating the Role of the Crosslinking Moiety on Catalyst Activity DOI Creative Commons
Michael J. Spicuzza,

Shweta Gaikwad,

S. HUSS

et al.

Published: Sept. 14, 2023

Macromolecular scaffolds are rapidly emerging in catalysis owing to the ability control catalyst placement at precise locations framework. This often allows for cooperation multi-catalytic reactions that may not be observed using small molecules, enabling high levels of reactivity. Herein, we describe a triphenylpyrylium (TPT)-based visible-light active single-chain polymer nanoparticle (SCNP) scaffold facilitates radical cation [4+2]-cycloaddition. In our studies, find catalytic activity is highly dependent on identity crosslinking group – incorporated 5-10% overall its act as redox mediator Diels-Alder reaction. Mechanistic studies indicate vast majority TPT excited states quenched by acene, with resultant formed from either naphthalene- or phenanthrene-based SCNPs able proceed oxidizing dienophile elementary step reaction, leading near quantitative yields cycloadduct. The TPT-SCNP demonstrates enhanced reactivity low loadings when compared molecule TPT, and also recycled reused three iterations reaction prior substantial drops yield photobleaching. Our results suggest feature multiple subtle design elements can use catalysts diffusion-limited reactions.

Language: Английский

Visible-Light-Mediated Diels-Alder Reactions Under Single-Chain Polymer Confinement: Investigating the Role of the Crosslinking Moiety on Catalyst Activity DOI Creative Commons
Michael J. Spicuzza,

Shweta Gaikwad,

S. HUSS

et al.

Published: Sept. 14, 2023

Macromolecular scaffolds are rapidly emerging in catalysis owing to the ability control catalyst placement at precise locations framework. This often allows for cooperation multi-catalytic reactions that may not be observed using small molecules, enabling high levels of reactivity. Herein, we describe a triphenylpyrylium (TPT)-based visible-light active single-chain polymer nanoparticle (SCNP) scaffold facilitates radical cation [4+2]-cycloaddition. In our studies, find catalytic activity is highly dependent on identity crosslinking group – incorporated 5-10% overall its act as redox mediator Diels-Alder reaction. Mechanistic studies indicate vast majority TPT excited states quenched by acene, with resultant formed from either naphthalene- or phenanthrene-based SCNPs able proceed oxidizing dienophile elementary step reaction, leading near quantitative yields cycloadduct. The TPT-SCNP demonstrates enhanced reactivity low loadings when compared molecule TPT, and also recycled reused three iterations reaction prior substantial drops yield photobleaching. Our results suggest feature multiple subtle design elements can use catalysts diffusion-limited reactions.

Language: Английский

Citations

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