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

Marco S. Messina, Jonathan C. Axtell, Yiqun Wang, Paul Chong, Alex I. Wixtrom, Kent O. Kirlikovali, Brianna M. Upton, Bryan M. Hunter, Oliver S. Shafaat, Saeed I. Khan, Jay R. Winkler, Harry B. Gray, Anastassia N. Alexandrova, Heather D. Maynard, Alexander M. Spokoyny*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

81 Scopus citations


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.

Original languageEnglish (US)
Pages (from-to)6952-6955
Number of pages4
JournalJournal of the American Chemical Society
Issue number22
StatePublished - Jun 8 2016

ASJC Scopus subject areas

  • Chemistry(all)
  • Biochemistry
  • Catalysis
  • Colloid and Surface Chemistry


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