title: In situ EPR spectroscopy of aromatic diyne cyclopolymerization.
abstract: Electron paramagnetic resonance (EPR) spectroscopy was successfully used for the first time to follow the Bergman cyclization of bis-ortho-diynyl arene (BODA) compounds. Five BODA monomers with different spacer (X) and terminal groups (R) were compared. In situ polymerization via EPR spectroscopy yielded first-order rate expressions. Monomers with spacer -O- or -C(CF(3))(2) and terminal group R = Ph exhibited similar kinetic behavior upon thermal polymerization, whereas monomers with pyridine and thiophene terminal groups gave significantly higher rates of polymerization over phenyl-terminated derivatives. A model compound, 1,2-bis(phenylethynyl)benzene, was used to probe the polymerization mechanism, and radical intermediates were found to be stable indefinitely at room temperature.
authors.affiliation: Department of Chemistry and Center for Optical Materials Science and Engineering Technologies (COMSET), Clemson University, Clemson, South Carolina 29634, USA.
authors.forename: Nicolas
authors.initials: N
authors.lastname: Mifsud
authors.forename: Veronique
authors.initials: V
authors.lastname: Mellon
authors.forename: K Prasanna U
authors.initials: KP
authors.lastname: Perera
authors.forename: Dennis W
authors.initials: DW
authors.lastname: Smith
authors.forename: Luis
authors.initials: L
authors.lastname: Echegoyen