Solvent Cage Effects: A Comparison of Geminate and Nongeminate Radical Cage Pair Combination Efficiencies

被引：6

作者：

Barry, Justin T. ^{[1
]}

Tyler, David R. ^{[1
]}

机构：

[1] Dept Chem & Biochem, 1253 Univ Oregon, Eugene, OR 97403 USA

来源：

INORGANIC CHEMISTRY | 2020年 / 59卷 / 19期

关键词：

RECOMBINATION EFFICIENCY; PHOTOCHEMISTRY; MECHANISM; MASS; MICROVISCOSITY; REACTIVITY; PHOTOLYSIS; DIFFUSION; SIZE; CP;

D O I：

10.1021/acs.inorgchem.0c01441

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

This study measured and compared the combination efficiencies (FcP) of geminate radical cage pairs to non-geminate (collisional) radical cage pairs (F-c'). For the [Cp'(CO)(3)Mo center dot, center dot Mo(CO)(3)Cp'] radical cage pair, Fc' was found to be smaller than FcP in solutions having the same viscosity. It is proposed that the difference in FcP and Fc' arises because the radicals in the collisional cage pair are less likely to have the correct orbital orientation for radical-radical combination to occur, whereas photochemically generated geminate cage pairs are more likely to have the correct orbital orientation. As predicted, F-cP and F-c' both increase when the microviscosity of a solution increases.

引用

页码：13875 / 13879

页数：5

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