Journal
JOURNAL OF PHYSICAL CHEMISTRY A
Volume 116, Issue 39, Pages 9662-9673Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp3071037
Keywords
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Funding
- Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan [22350002, 21655003]
- MEXT, Japan
- FIRST project on Quantum Information Processing, Japan Society for the Promotion of Science
- Center for Absorption in Science, Ministry of Immigration, (KAMEA Foundation)
- Grants-in-Aid for Scientific Research [21102004, 23350011, 23750002, 22350002, 24102701, 21655003] Funding Source: KAKEN
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The lowest excited triplet (T-1) pi pi* states of gallium (Ga) and various rhodium (Rh) 5,10,15-trispenta-fluorophenyl 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 magneto-photoselection 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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