Spin-Spin Interaction of TEMPO Molecular Chains Formed in an Organic One-Dimensional Nanochannel as Studied by Electron Spin Resonance (ESR)

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Abstract

The magnitude and dimensionality of spin–spin interactions among 2,2,6,6-tetramethyl-1-piperidinyloxyl radical (TEMPO) molecules in a 1D nanochannel consisting of tris(<I>o</I>-phenylenedioxy)cyclotriphosphazene (TPP) were examined using electron spin resonance (ESR) spectroscopy. Dilution of TEMPO with 2,2,6,6-tetramethyl-1-piperidine (TEMP), a diamagnetic molecule, reduced the dipolar interaction in the TPP/(TEMPO/TEMP) inclusion compound (IC), leading to axially symmetric hyperfine coupling and <I>g</I>-tensors with a molar fraction of 0–0.45: <I>A</I><SUB>⊥</SUB> = 1.93 ± 0.03 mT and <I>A</I><SUB>||</SUB> = 0.7 ± 0.1 mT, and <I>g</I><SUB>⊥</SUB> = 2.0063 ± 0.0003 and <I>g</I><SUB>||</SUB> = 2.0068 ± 0.0005. The resonance line in TPP/(TEMPO/TEMP) IC narrowed when the molar fraction was more than 0.7, implying the existence of exchange narrowing. The ESR lineshape of TPP/TEMPO IC showed pure 1D spin diffusion between 139 and 166 K, while interchain exchange interactions contributed to the line shape in <I>T</I> > 166 K. The magnitude of intra-chain exchange interaction, |<I>J</I><SUB>intra</SUB>|/<I>k</I><SUB>B</SUB>, in TPP/TEMPO IC depended on the temperature from ≈0.05 K in 139–166 K to 0.4 K at 383 K. This aspect implies that molecular motion strongly affects the spin–spin interaction between TEMPO molecules in the TPP crystal. The magnetic susceptibility of TPP/TEMPO IC was also measured, and it was found that the exchange interaction was antiferromagnetic.

Journal

  • Bulletin of the Chemical Society of Japan

    Bulletin of the Chemical Society of Japan 80(4), 711-720, 2007-04-15

    The Chemical Society of Japan

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Codes

  • NII Article ID (NAID)
    10019937935
  • NII NACSIS-CAT ID (NCID)
    AA00580132
  • Text Lang
    ENG
  • Article Type
    ART
  • ISSN
    00092673
  • NDL Article ID
    8703430
  • NDL Source Classification
    ZP1(科学技術--化学・化学工業)
  • NDL Call No.
    Z53-B35
  • Data Source
    CJP  NDL  J-STAGE 
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