Spin-polarized nitroxide radicals in organic glasses.
Nonequilibrium spin polarization formed in a stable nitroxide radical, 2,2,6,6-tetramethyl-1-piperidinyloxy (Tempo) due to the occurrence of Chemically Induced Dynamic Electron Polarization (CIDEP) in photoexcited molecular complexes of this radical with 1,4-benzoquinone, 1,4-naphthaquinone, 9,10-anthraquinone, and their derivatives is observed. These complexes occur spontaneously in low-temperature organic glasses (20-70 K) upon freezing the concentrated liquid solutions. The emissive net polarization in the nitroxide radical is observed 0.1-10 {mu}s after the photoexcitation of the p-quinone moiety. No degradation of the polarized magnetic resonance signal from Tempo after >104 excitation cycles was observed. This spin polarization is shown to be mainly due to a polarization transfer from the lowest triplet state of the p-quinone. This transfer is driven by the electron spin exchange interaction between the nitroxide radical and the triplet p-quinone; it occurs simultaneously with a spin-selective electronic relaxation of the photoexcited complex. The resulting mechanism combines the features of the electron spin polarization transfer (ESPT) and radical-triplet pair mechanisms (RTPM) in liquid. A theoretical model of such a mechanism is suggested.
- Research Organization:
- Argonne National Laboratory (ANL)
- Sponsoring Organization:
- SC
- DOE Contract Number:
- AC02-06CH11357
- OSTI ID:
- 949487
- Report Number(s):
- ANL/CHM/JA-41417
- Journal Information:
- J. Phys. Chem. A, Journal Name: J. Phys. Chem. A Journal Issue: 19 ; 2002 Vol. 106; ISSN 1089-5639; ISSN JPCAFH
- Country of Publication:
- United States
- Language:
- ENGLISH
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