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J Phys Chem A. 2012 Oct 4;116(39):9662-73. doi: 10.1021/jp3071037. Epub 2012 Sep 24.

Time-resolved electron paramagnetic resonance and phosphorescence studies of the lowest excited triplet states of Rh(III) corrole complexes.

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Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Sendai 980-8577, Japan.


The lowest excited triplet (T(1)) ππ* states of gallium (Ga) and various rhodium (Rh) 5,10,15-trispentafluorophenyl corroles (Cors) were studied in the liquid crystal (LC) E-7 and in rigid glasses by time-resolved electron paramagnetic resonance (TR-EPR) spectroscopy. The triplet sublevel energies were experimentally determined by the alignment of the molecules in the LC and by magnetophotoselection in the glass. The sublevel scheme of GaCor was determined by calculating the zero field splitting (ZFS) parameters. Axial ligand effects and quantum chemical calculations were used for the sublevel assignment of RhCors. The anisotropic EPR parameters were used to determine the important higher excited states and the magnitudes of their spin-orbit coupling (SOC) contributions were evaluated. On the basis of these results and analyses, the EPR parameters and triplet lifetime were discussed for each RhCor complex.

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