Impact of electron-electron spin interaction on electron spin relaxation of nitroxide diradicals and tetraradical in glassy solvents between 10 and 300 K

Hideo Sato, Velavan Kathirvelu, Gaëlle Spagnol, Suchada Rajca, Andrzej Rajca, Sandra S. Eaton, Gareth R. Eaton

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To determine the impact of electron-electron spin-spin interactions on electron spin relaxation rates, 1/T1 and 1/Tm were measured for nitroxide monoradical, diradical, and tetraradical derivatives of 1,3-alternate calix[4]arenes, for two pegylated high-spin nitroxide diradicals, and for an azine-linked nitroxide diradical. The synthesis and characterization by SQUID (superconducting quantum interference device) magnetometry of one of the high-spin diradicals, in which nitroxides are conformationally constrained to be coplanar with the m-phenylene unit, is reported. The interspin distances ranged from about 5-9 Å, and the magnitude of the exchange interaction ranged from > 150 to >0.1 K. 1/T1 and 1/Tm were measured by long-pulse saturation recovery, three-pulse inversion recovery, and two-pulse echo decay at X-band (9.5 GHz) and Q-band (35 GHz). For a diradical with interspin distance about 9 Å, relaxation rates were only slightly faster than for a monoradical with analogous structure. For interspin distances of about 5-6 Å, relaxation rates in glassy solvents up to 300 K increased in the order monoradical < diradical < tetraradical. Modulation of electron-electron interaction enhanced relaxation via the direct, Raman, and local mode processes. The largest differences in 1/T1 were observed below 10 K, where the direct process dominates. For the three diradicals with comparable magnitude of dipolar interaction, 1/Tm and 1/T1 were faster for the molecules with more flexible structures. Relaxation rates were faster in the less rigid low-polarity sucrose octaacetate glass than in the more rigid 4:1 toluene/chloroform or in hydrogen-bonded glycerol glasses, which highlights the impact of motion on relaxation.

Original languageEnglish (US)
Pages (from-to)2818-2828
Number of pages11
JournalJournal of Physical Chemistry B
Issue number10
StatePublished - Mar 13 2008


ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

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