TEMPERATURE-DEPENDENCE OF PHOTOPHYSICAL AND PHOTOCHEMICAL PROPERTIES OF TRIS(2,2'-BIPYRIDYL)RUTHENIUM(II) ION IN AQUEOUS-SOLUTION
TEMPERATURE-DEPENDENCE OF PHOTOPHYSICAL AND PHOTOCHEMICAL PROPERTIES OF TRIS(2,2'-BIPYRIDYL)RUTHENIUM(II) ION IN AQUEOUS-SOLUTION
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DOI：
10.1021/ja00432a028
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发表时间：
1976-01-01
影响因子：
15
通讯作者：
WATTS, RJ
中科院分区：
文献类型：
--
作者：
VANHOUTEN, J;WATTS, RJ
报道了Ru(Bipy)32+在0~100℃水溶液中的发光寿命和量子产率。这项研究包括H20和D20中的Perprotio和Perdeurio复合体。虽然发光寿命和量子产率与溶剂和温度有关，但辐射寿命对这些参数不敏感。寿命和量子产额数据的温度依赖关系与一个模型相关联，该模型假设较低的一组发光能级经历弱耦合无辐射失活，而较高的一组非发光能级经历强耦合无辐射失活。虽然在0.1MHCl中，络合离子在25℃时基本上是光惰性的，但在95℃，436 nm的光照下，2，2‘-联吡啶的光解是不稳定的。光物理和光化学数据表明，在我们的模型中，较低的一组能级是电荷转移到配位态，这是通过与电荷转移到溶剂的组态混合来修改的。这些能级是光惰性的，而较高的能级比较低的能级高出约3600厘米-1，产生了配体取代光化学。上面的一组能级被分配给dd轨道亲代。
Luminescence lifetimes and quantum yields of Ru (bipy) 32+ in aqueous solution between 0 and 100 C are reported. The study includes both the perprotio and perdeuterio complex in H20 and D20. Although the luminescence lifetimes and quantum yields are found to be solvent and temperature dependent, the radiativelifetime is insensitive to these parameters. The temperature dependence of the lifetime and quantum yield data is correlated with a model which assumes a lower set of luminescent levels which undergo weak-coupled radiationless deactivation and a higher set of nonluminescent levels which un-dergo strong-coupled radiationless deactivation. Although the complex ion is essentially photoinert at 25 C in 0.1 M HC1, photolysis at 95 C with 436-nm irradiation results inlabilization of 2, 2'-bipyridine. Photophysicaland photochemical data suggest that the lower set of levels in our model are charge-transfer-to-ligand states, which are modified by mixing with charge-transfer-to-solvent configurations. These levels are photoinert, whereas the upper set of levels, which are~ 3600 cm-1 above the lower set, give rise to ligand substitution photochemistry. The upper set of levels is assigned to dd orbital parent-age.