Time-resolved EPR investigation of potential model systems for acrylate polymer main chain radicals based on esters of Kemp's tri-acid


Journal Article

Methyl esters of Kemp's tri-acid and cyclohexanetricarboxylic acid are structurally similar to acrylate polymers, having the same functionalities and stereoregularities as poly(methylmethacrylate) and poly(methylacrylate), respectively. The photochemistry and free radicals from these model systems have been studied using time-resolved electron paramagnetic resonance spectroscopy with laser flash photolysis at 248 nm. Chemically induced electron spin polarization from the triplet mechanism (net emission) is observed. Well-resolved spectra are obtained at all temperatures for the model system radicals, which are determined to be in the slow motion condition, that is, there is no interconversion of chair conformations. The temperature dependence of the spectra is minimal; some hyperfine lines shift as the temperature increases, but without much broadening. Density functional theory calculations are presented and discussed in support of the experimental data. © Copyright 2009 by the American Chemical Society.

Full Text

Duke Authors

Cited Authors

  • Lebedeva, NV; Gorelik, EV; Magnus-Aryitey, D; Hill, TE; Forbes, MDE

Published Date

  • May 14, 2009

Published In

Volume / Issue

  • 113 / 19

Start / End Page

  • 6623 - 6629

International Standard Serial Number (ISSN)

  • 1520-6106

Digital Object Identifier (DOI)

  • 10.1021/jp809610t

Citation Source

  • Scopus