The photoexcited triplet state of a 4-4'-disubstituted dithiophene has been investigated by time-resolved electron paramagnetic resonance in two different solid matrixes-glassy toluene which acts as an amorphous isotropic medium and a spirocyclophosphazene inclusion compound-which provides an ordered confining structure to the guest molecules. Different spectral line shapes with different temperature dependence have been obtained using continuous-wave or spin-echo detection. This behavior was attributed to spin relaxation due to modulation of the zero-field splitting tensor induced by fast librational motion of the dithiophene triplet. Moreover, differences between line shapes in the two matrixes were reproduced considering a librational motion occurring preferentially around different molecular axes.
Dynamics of the triplet state of a dithiophene in different solid matrixes studied by transient and pulse EPR techniques / A., Barbon; M., Bortolus; M., Brustolon; A., Comotti; Al, Maniero; Segre, Ulderico; P., Sozzani. - In: JOURNAL OF PHYSICAL CHEMISTRY. B, CONDENSED MATTER, MATERIALS, SURFACES, INTERFACES & BIOPHYSICAL. - ISSN 1520-6106. - 107:14(2003), pp. 3325-3331. [10.1021/jp026214f]
Dynamics of the triplet state of a dithiophene in different solid matrixes studied by transient and pulse EPR techniques
SEGRE, Ulderico;
2003
Abstract
The photoexcited triplet state of a 4-4'-disubstituted dithiophene has been investigated by time-resolved electron paramagnetic resonance in two different solid matrixes-glassy toluene which acts as an amorphous isotropic medium and a spirocyclophosphazene inclusion compound-which provides an ordered confining structure to the guest molecules. Different spectral line shapes with different temperature dependence have been obtained using continuous-wave or spin-echo detection. This behavior was attributed to spin relaxation due to modulation of the zero-field splitting tensor induced by fast librational motion of the dithiophene triplet. Moreover, differences between line shapes in the two matrixes were reproduced considering a librational motion occurring preferentially around different molecular axes.
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