Theoretical studies on photophysical properties and mechanism of phosphorescence in [fac-Ir(2-phenylpyridine)3]
Theoretical studies on photophysical properties and mechanism of phosphorescence in [fac-Ir(2-phenylpyridine)3]
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DOI：
10.1002/jccs.200600013
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发表时间：
2006-02-01
影响因子：
1.8
通讯作者：
Nozaki, K
中科院分区：
文献类型：
--
作者：
Nozaki, K
[fac-Ir（ppY）（3）]的电子物理性质有。用含时密度泛函理论和单中心自旋-轨道耦合近似研究。[fac-Ir（PPY）（3）]的磷光态的特征在于40%（MLCT）-M-3和58%配体内和配体间（3）pi pi* 的混合物，其中电荷分布部分地局限于单个配体。零场分裂和振子强度计算的最低三重态的子级与观察值一致。利用与[Ru（bpY）（3）]（2+）或[Os（bpY）（3）]（2+）的情况类似的具有C-2 v对称性的假设M-LL单元的定域模型，很好地合理化了次能级中的自旋分量和磷光机制。此外，它表明，激发态的特点是高密度的状态（约'70状态每eV）和相当大的混合之间的单重态和三重态由于强的自旋轨道耦合。
The photophysical properties of [fac-Ir(ppY)(3)] have. been studied using time-dependent density functional theory with one-center spin-orbit coupling approximation. The phosphorescent state of [fac-Ir(PPY)(3)] was characterized by a mixture of 40% (MLCT)-M-3 and 58% intra- and inter-ligand (3)pi pi* with charge distribution being partially localized to a single ligand. Zero-field splittings and oscillator strengths calculated for the sublevels of the lowest triplet state were in agreement with the observed values. The spin components in the sublevels and the mechanism of phosphorescence were well rationalized using a localized model for a hypothetical M-LL unit with C-2v symmetry similarly to the cases for [Ru(bpY)(3)](2+) or [Os(bpY)(3)](2+). Furthermore, it was revealed that the excited states were characterized by both high density-of-state (approximately'70 states per eV) and considerable mixing between singlet and triplet states due to strong spin-orbit coupling.