Photochemistry of 1,1-diazenes. Direct and sensitized photolyses of N-(2,2,5,5-tetramethylpyrrolidyl)nitrene, dl-N-(2,5-diethyl-2,5-dimethylpyrrolidyl)nitrene, and N-(2,2,6,6-tetramethylpiperidyl)nitrene
作者:Peter G. Schultz、Peter B. Dervan
DOI:10.1021/ja00388a031
日期:1982.12
infrared spectrum of 2. The fluorescence quantum yield Φ_F = 9 X 10^(-3) (MTHF, -196 °C). The direct and sensitized irradiation of 2 in the visible affords hydrocarbon products 14-19 and tetrazene 20 in different ratios. The retention of stereochemistry in the cyclobutane products in the direct and sensitized photodecomposition was 98 and 68%, respectively, similar to the spin correlation effect seen
l, 1-diazenes N-(2,2,5,5-tetramethylpyrrolidyl)nitrene (1), d/-N-(2,5-diethyl-2,5-methylpyrrolidyl)nitrene (2) 的光化学,报道了 N-(2,2,6,6-四甲基哌啶基)氮 (3)。1,1-二氮烯 1 的荧光光谱在 607 nm 处有一个 0-0 谱带,这是最大值。607 和 672 nm 处的峰间距对应于 S0 的 N=N 拉伸,与从 1 的红外光谱获得的 1638-cm^(-1) 拉伸一致。荧光量子产率为 Φ_F = 2 X 10^ (-3) (MTHF, -78 °C)、7 x 10^(-3) (MTHF, -196 °C) 和 l X 10^(-3) (EPA, -196 °C)。1 的荧光寿命为 T_F = 2.3 x 10^(-8) s (CFCl_3, -196 °C)。1