Close Packing of Nitroxide Radicals in Stable Organic Radical Polymeric Materials

Thomas Gennett, Wade Braunecker, Ross Larsen, David Bobela, Barbara Hughes, Travis Kemper

Research output: Contribution to journalArticlepeer-review

42 Scopus Citations


The relationship between the polymer network and electronic transport properties for stable radical polymeric materials has come under investigation owing to their potential application in electronic devices. For the radical polymer poly(2,2,6,6-tetramethylpiperidine-4-yl-1-oxyl methacrylate), it is unclear whether the radical packing is optimal for charge transport partially because the relationship between radical packing and molecular structure is not well-understood. Using the paramagnetic nitroxide radical as a probe of the polymer and synthetic techniques to control the radical concentration on the methyl methacrylate backbone, we investigate the dependence of radical concentration on molecular structure. The electron paramagnetic resonance data indicate that radicals in the PTMA assume a closest approach distance to each other when more than 60% of the backbone is populated with radical pendant groups. Below 60% coverage, the polymer rearranges to accommodate larger radical-radical spacing. These findings are consistent with theoretical calculations and help explain some experimentally determined electron-transport properties.

Original languageAmerican English
Pages (from-to)1414-1419
Number of pages6
JournalJournal of Physical Chemistry Letters
Issue number8
StatePublished - 2015

Bibliographical note

Publisher Copyright:
© 2015 American Chemical Society.

NREL Publication Number

  • NREL/JA-5900-63511


  • charge transport
  • electron spin resonance
  • organic radical battery
  • PTMA
  • spin exchange


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