Visible-Light-Induced Olefin Activation Using 3D Aromatic Boron-Rich Cluster Photooxidants

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 bench-top blue LED source, can exhibit excited-state reduction potentials as high as 3 Volts and can participate in electron-transfer processes with a broad range of styrene monomers, initiating their polymerization. Initiation is ob-served in cases of both electron-rich and electron-deficient styrene monomers at cluster loadings as low as 0.05 mol%. Furthermore, photo-excitation of B₁₂(OCH₂C₆F₅)₁₂ in the pres-ence 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 photoredox reagents capable of mediating chemical transformations.