Journal of Physical Chemistry A, Vol.106, No.19, 4838-4845, 2002
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 mus after the photoexcitation of the p-quinone moiety. No degradation of the polarized magnetic resonance signal from Tempo after > 10(4) 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.