Anthralin-derived transients--II. Formation of the radical by spontaneous fragmentation of both singlet and triplet states of the 10,10'-dehydrodimer: radical pair multiplicity effects.
Anthralin-derived transients--II. Formation of the radical by spontaneous fragmentation of both singlet and triplet states of the 10,10'-dehydrodimer: radical pair multiplicity effects.
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蒽素衍生的瞬变——II。
DOI：
10.1111/j.1751-1097.1990.tb04190.x
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发表时间：
1990
影响因子：
3.3
通讯作者：
McNeeney,SP
中科院分区：
文献类型：
--
作者：
Bruce,JM;Dodd,NJ;Gorman,AA;Hamblett,I;Kerr,CW;Lambert,C;McNeeney,SP
蒽啉（1，8-二羟基-9-蒽酮）脱氢二聚体在苯乙炔激光激发和脉冲辐解中分别产生了单重态和三重态。S的寿命是30 ps，T的寿命很短，但没有具体说明。这两种状态自发地分裂，产生一对蒽自由基。单重态自由基对主要在溶剂笼内进行成对重组。相反，相应的三重态自由基对经历基本上排他性的笼逃逸，得到蒽啉自由基（δ. max 370、490和720 nm），其在正常扩散条件下重新组合。两种重组过程至少部分地导致一种或多种物质，其被指定为原始二聚体的互变异构形式。苯中的蒽啉自由基对维生素E模型6-羟基-2，2，5，7，8-五甲基苯并二氢吡喃不敏感，并且仅与氧气缓慢反应。
The singlet and triplet states of the anthralin (1,8‐dihydroxy‐9‐anthrone) dehydrodimer have been producedselectivelyin benzeneviapulsed laser excitation and pulse radiolysis respectively. The lifetime of S, is 30 ps, that of T, short but unspecified. Both states fragment spontaneously to yield a pair of anthralin radicals. The singlet radical pair predominantly undergoes geminate recombination within the solvent cage. In contrast, the corresponding triplet radical pair undergoes essentially exclusive cage escape to give the anthralin free radical (δ.max370, 490 and 720 nm) which recombines under normal diffusive conditions. Both recombination processes lead, at least in part, to one or more species which have been assigned as tautomeric forms of the original dimer. The anthralin free radical in benzene is insensitive to the vitamin E model 6‐hydroxy‐2,2,5,7,8‐pentamethylchroman and reacts only slowly with oxygen.