ENERGY-TRANSFER FROM LUMINESCENT TRANSITION-METAL COMPLEXES TO OXYGEN
ENERGY-TRANSFER FROM LUMINESCENT TRANSITION-METAL COMPLEXES TO OXYGEN
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DOI：
10.1021/ja00453a001
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发表时间：
1977-01-01
影响因子：
15
通讯作者：
MCBRIDE, RP
中科院分区：
文献类型：
--
作者：
DEMAS, JN;HARRIS, EW;MCBRIDE, RP
研究了Ru（II）、Os（II）和Ir（III）的16种发光二亚胺配合物的O2猝灭。衰变时间，双分子猝灭常数，敏化光氧化产率。在Ru（II）和Os（II）物种的电荷转移（CT）激发态下，单态O2（102）的形成效率为0.68-0.85/猝灭剂。O2的形成归因于简单的能量转移，但不能排除通过电子转移过程的化学生成。亚单位产量的可能来源进行了讨论。lr（III）复合物的-* 三重态似乎以高效率产生'02，但复合物的光化学阻止了明确的解释。定量的光氧化研究被证明是一个强大的工具，用于评估光谱和敏化性能的金属络合物敏化剂。溶剂化效应在改变双分子猝灭常数方面显得很重要。其中两种配合物在77 K下的流体溶液寿命（> 5 qs）比广泛使用的发光敏化剂三（2，2 ′-联吡啶）钌（II）离子在刚性玻璃中的流体溶液寿命长。
A study of the 02 quenching of 16 luminescent diimine complexes of Ru (ll), Os (II), and Ir (III) is reported. Decay times, bimolecular quenching constants, and sensitized photooxidation yields are presented. With the charge-transfer (CT) excited states of the Ru (II) and Os (II) species, singlet 02 (102) is formed with efficiencies of 0.68-0.85 per quenching encoun-ter. O2 formation is attributed to simple energy transfer, but a chemical generation by electron transfer processes cannot be ruled out. Possible sources of the subunity yields are discussed. The-* triplet states of the lr (lll) complexes appear to produce'02 with high efficiency, but photochemistry of thecomplexes prevents an unambiguous interpretation. Quantitative photooxygenation studies are shown to be a powerful tool for evaluating the spectroscopic and sensitization properties of metal complex sensitizers. Solvation effects appear important in varying the bimolecular quenching constants. Twoof the complexes have longer fluid solution lifetimes (> 5 qs) than the widely used luminescent sensitizer tris (2, 2'-bipyridine) ruthenium (Il) ion has in a rigid glass at 77 K.