Electron spin polarizations were studied for a system of excited triplet (T1) phthalocyanine (MTNPc; M = H2, Zn) and a nitroxide radical (TEMPO) in toluene solution by means of time-resolved EPR (TREPR) spectroscopy. TREPR spectra of the T1 state and the radical (R) were observed simultaneously. Spin polarizations of both signals were found to consist of two components with different decay rates. From analyses of the polarizations and the decay curves, it was found that the triplet polarizations are generated from anisotropic S1 → T1 intersystem crossings and thermal populations. The initial and late polarizations on TEMPO were interpreted in terms of electron spin polarization transfer (ESPT) from T1 and a radical-triplet pair mechanism (RTPM) with a quartet precursor under J < 0 (J; exchange coupling parameter), respectively. The ESPT rate was determined and found to be dependent on temperature and the central atom(s) of MTNPc. In the H2TNPc system, the ESPT rate is much slower than the diffusion rate and axial ligation of TEMPO remarkably accelerates the ESPT rate in the ZnTNPc system.
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