Mechanism of the Photodissociation of 4-Diphenyl(trimethylsilyl)methyl-<i>N</i>,<i>N</i>-dimethylaniline
作者:Dimitrios A. Tasis、Michael G. Siskos、Antonios K. Zarkadis、Steen Steenken、Georgios Pistolis
DOI:10.1021/jo000023w
日期:2000.7.1
3-dimethylbuta-1,3-diene, styrene, and methyl methacrylate using nanosecond laser flash photolysis (LFP). The formation of 3(*) is further demonstrated using EPR spectroscopy. The detection of the S(1) state of 2 was achieved using 266-nm picosecond LFP, and its lifetime was found to be 1400 ps, in agreement with the fluorescence lifetime (tau(f) = 1500 ps, Phi(f) = 0.085). The S(1) state is converted almost exclusively
在己烷(248和308 nm激光)下照射4-二苯基(三甲基甲硅烷基)甲基-N,N-二甲基苯胺2时,C-Si键发生光解离,得到4-N,N-二甲基氨基-三苯基甲基基团, 3(*)(在343和403 nm处的λ(max)),具有很高的量子产率(Phi = 0.92)。通过使用纳秒激光闪光光解法(LFP)用2,3-二甲基丁-1,3-二烯,苯乙烯和甲基丙烯酸甲酯的淬灭实验清楚地证明了三重态2的介入(在515 nm处的λmax)。使用EPR光谱进一步证明了3(*)的形成。使用266 nm皮秒LFP实现S(1)状态为2的检测,发现其寿命为1400 ps,与荧光寿命一致(tau(f)= 1500 ps,Phi(f)= 0.085)。S(1)状态几乎完全转换为T(1)状态(Phi(T)= 0.92)。在极性溶剂(例如MeCN)中,2经历(1)离子化成其自由基阳离子2(*)(+),以及(2)C-Si键发生光解