Time-Resolved Electron Paramagnetic Resonance and Phosphorescence Studies of the Lowest Excited Triplet States of Rh(III) Corrole Complexes

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• 作者：Mana Tanabe ; Hideto Matsuoka ; Yasunori Ohba ; Seigo Yamauchi ; Kenji Sugisaki ; Kazuo Toyota ; Kazunobu Sato ; Takeji Takui ; Israel Goldberg ; Irena Saltsman ; Zeev Gross
• 刊名：The Journal of Physical Chemistry A
• 出版年：2012
• 出版时间：October 4, 2012
• 年：2012
• 卷：116
• 期：39
• 页码：9662-9673
• 全文大小：623K
• 年卷期：v.116,no.39(October 4, 2012)
• ISSN：1520-5215

文摘

The lowest excited triplet (T₁) 蟺蟺* 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鈥搊rbit 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.