Time-Resolved Electron Paramagnetic Resonance and Phosphorescence Studies of the Lowest Excited Triplet States of Rh(III) Corrole Complexes
Time-Resolved Electron Paramagnetic Resonance and Phosphorescence Studies of the Lowest Excited Triplet States of Rh(III) Corrole Complexes
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Rh(III) Corrole 络合物最低激发三重态的时间分辨电子顺磁共振和磷光研究
DOI：
10.1021/jp3071037
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发表时间：
2012
期刊：
影响因子：
2.9
通讯作者：
M. Tanabe
中科院分区：
文献类型：
--
作者：
H. Kiriyama;T. Shimomura;M. Mori;Y. Nakai;M. Tanoue;S. Kondo;S. Kanazawa;A. S. Pirozhkov;T. Zh. Esirkepov;Y. Hayashi;K. Ogura;H. Kotaki;M. Suzuki;I. Daito;H. Okada;A. Kosuge;Y. Fukuda;M. Nishiuchi;M. Kando;S. V. Bulanov;K. Nagashima;M;M. Tanabe
用时间分辨电子顺磁共振（TR-EPR）谱研究了镓（Ga）和铑（Rh）5，10，15-三氟苯基咯啉（Cors）在液晶（LC）E-7和刚性玻璃中的最低激发三重态（T1）ππ*。三重态次能级的能量通过实验确定的LC中的分子的排列和玻璃中的磁光选择。通过计算零场分裂参数，确定了GaCor的子能级方案。轴向配体效应和量子化学计算被用于RhCors的子能级归属。各向异性EPR参数被用来确定重要的高激发态和自旋轨道耦合（SOC）的贡献的大小进行了评估。在这些结果和分析的基础上，对每个RhCor配合物的EPR参数和三重态寿命进行了讨论。
The lowest excited triplet (T1) 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.