Electron spin resonance thermal donors

Electron donor-acceptor complexes, electron transfer in the thermal and photochemical activation of, in organic and organometallic reactions, 29, 185 Electron spin resonance, identification of organic free radicals, 1, 284 Electron spin resonance, studies of short-lived organic radicals, 5, 23 Electron storage and transfer in organic redox systems with multiple electrophores, 28, 1... 

Fully hindered amines are excellent UV stabilizers, but poor thermal antioxidants, for polyolefins. We have found that partially hindered bicyclic amines, such as 3,3-dialkyldecahydroquinoxalin-2-ones, are excellent UV stabilizers and also excellent thermal antioxidants as well. The oxidation of these bicyclic amines with m-chloroperbenzoic acid was studied by electron spin resonance spectroscopy. They form stable, partially hindered nitroxyl radicals (6-line spectra). However, these primary radicals are easily oxidized to a new, fully hindered nitroxyl radical (3-line spectra) which are also very stable. Field desorption mass spectroscopic studies of the oxidation of these amines show that the primary nitroxyl radicals, which form first, lose two hydrogen atoms and add an oxygen. Thus, these bicyclic partially hindered amines are unique in being both stable and at the same time hydrogen atom donors. 

Excitation-transfer processes involving triplet states have been studied by various other methods, such as flash spectroscopy and electron-spin resonance " . With the latter method the important result was obtained that the glassy solvent does not participate in triplet-triplet transfer, as long as the triplet states of the solvent molecules are not accessible from the donor triplet by thermal activation. 

EDMR has allowed several different unusual experiments. For example, neutral arsenic dopants interacting with a 2D electron gas have been studied with continuous-wave EDMR at 9.7 GHz and 94 GHz. The Anderson-Mott transition between conduction by sequential tunneling through isolated dopant atoms, and conduction through thermally activated impurity Hubbard bands has been studied in arrays of a few arsenic dopant atoms in a silicon transistor. Single erbium spins with resolved hyperfine structure have been electrically detected after resonant optical excitation. The use of the valley degree of freedom has been eonsidered with dopants in silicon both experimentally and theoretically. The quantum confinement due to silicon nanowires may inerease the temperatures where silicon donor quantum devices ean operate. ... 

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