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- W2397074304 abstract "We report a discovery that perfunctionalized icosahedral dodecaborate clusters of the type B12(OCH2Ar)12 (Ar = Ph or C6F5) can undergo photo-excitation with visible light, leading to a new class of metal-free photooxidants. Excitation in these species occurs as a result of the charge transfer between low-lying orbitals located on the benzyl substituents and an unoccupied orbital delocalized throughout the boron cluster core. Here we show how these species, photo-excited with a benchtop blue LED source, can exhibit excited-state reduction potentials as high as 3 V and can participate in electron-transfer processes with a broad range of styrene monomers, initiating their polymerization. Initiation is observed in cases of both electron-rich and electron-deficient styrene monomers at cluster loadings as low as 0.005 mol%. Furthermore, photo-excitation of B12(OCH2C6F5)12 in the presence of a less activated olefin such as isobutylene results in the production of highly branched poly(isobutylene). This work introduces a new class of air-stable, metal-free photo-redox reagents capable of mediating chemical transformations." @default.
- W2397074304 created "2016-06-24" @default.
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- W2397074304 date "2016-05-26" @default.
- W2397074304 modified "2023-10-17" @default.
- W2397074304 title "Visible-Light-Induced Olefin Activation Using 3D Aromatic Boron-Rich Cluster Photooxidants" @default.
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- W2397074304 doi "https://doi.org/10.1021/jacs.6b03568" @default.
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