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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Magnetic Field Effects on the Photodissociation Reaction of Triarylphosphine in Nonviscous Homogeneous Solutions
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Magnetic Field Effects on the Photodissociation Reaction of Triarylphosphine in Nonviscous Homogeneous Solutions

机译：磁场对非粘均相溶液中三芳基膦光解离反应的影响

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摘要

The magnetic field effects (MFEs) on the photodecomposition reactions of triphenylphosphine and its halogen and methyl derivatives are investigated in fluid solutions. The yield of diarylphosphinyl radicals decreased with increasing magnetic field from 0.1 to 5 T but was stationary below 0.1 T and above 5 T. The MFE becomes larger by the substitution of halogen atoms and the 3- or 4-methyl group. In cyclohexane, the yields of the escaped diarylphosphinyl radicals at 1 T are reduced to 0.69, 0.55, 0.59, and 0.56 of those at 0 T for triphenylphosphine and its tris(4-chloro), tris(3-methyl), and tris(4-methyl) derivatives, respectively. This magnetic field dependence was ascribed to originate from the deactivation process of the excited triplet state, which is a variant of the d-type triplet mechanism originally proposed by Steiner. The interaction between the closely lying nπ~* and ππ~* states makes their solvent dependence complicated.
机译：在流体溶液中研究了磁场对三苯膦及其卤素和甲基衍生物的光分解反应的影响。随着磁场的增加，二芳基次膦基的收率从0.1 T降低到5 T，但在0.1 T以下和5 T以上保持稳定。MFE因卤素原子和3-或4-甲基的取代而变大。在环己烷中，三苯膦及其三（4-氯），三（3-甲基）和三（三）膦在1 T时逸出的二芳基次膦基的收率分别降至0 T时的0.69、0.55、0.59和0.56。 4-甲基）衍生物。这种磁场依赖性归因于激发三重态的失活过程，该过程是Steiner最初提出的d型三重态机制的变体。紧密位于nπ〜*和ππ〜*状态之间的相互作用使它们的溶剂依赖性变得复杂。

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