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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Formation and Reaction Kinetics of Biradicals and Triplet States in a Series of Carboxylated 1,4,5,8-Naphthalene Diimides
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Formation and Reaction Kinetics of Biradicals and Triplet States in a Series of Carboxylated 1,4,5,8-Naphthalene Diimides

机译：一系列羧化1,4,5,8-萘二酰亚胺的抗体和三联态的形成和反应动力学

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摘要

The singlet-state deactivation products in a series of alkyl carboxylate substituted 1,4,5,8-naphthalene diimide (NDI) compounds were characterized using fluorescence and phosphorescence spectroscopies, as well as nanosecond laser flash photolysis. The reactive intermediates were quantified as a function of the number of methylenes in the alkyl linker. Rate constants for photoinduced electron transfer (PET) to the singlet excited state of the NDIs varied from 1.2 x 10(10) to 4.9 x 10(10) s(-1) The yield of the long-lived amino ketyl radical ranged from 15% to 60% in compounds having 4 to 1 intervening methylenes between the NDI chromophore and the covalently attached carboxylic acid. A predominantly triplet state was observed upon direct excitation of the compound having the slowest PET. This T-1 state of the NDIs was reductively quenched by DABCO electron donor. The amino ketyl radical was unreactive toward electron donors but was found to react with the hydrogen atom donor beta-mercaptoethanol. The compounds comprise a novel class of long-wavelength and strongly absorbing UV-activated chromophores that generate carbon-centered biradicals via direct 355 nm excitation in the absence of a cosensitizer.
机译：所述单线态失活产品中的一系列烷基羧酸的取代的1,4,5,8-萘使用荧光和磷光光谱酰亚胺（NDI）的化合物进行了表征，以及纳秒激光闪光光解。活性中间体量化为在烷基连接基的亚甲基的数目的函数。对于光诱导电子转移（PET）的NDIS的单重激发态的速率常数变化从1.2×10（10）4.9×10（10）S（-1）的产率长寿命从15不等氨基羰自由基％至60％具有NDI发色团和共价连接的羧酸之间4〜1中间亚甲基化合物中。在具有最慢的PET的化合物的直接激发，观察到主要的三线态。此T-1的NDIS的状态被还原由DABCO电子供体猝灭。氨基羰自由基是朝向电子供体反应性的，但发现与氢原子供体的β-巯基乙醇反应。所述化合物包括一类新的长波长的和强烈吸收UV活化的发色团产生经由直接355 nm激发在不存在共增感剂的碳为中心的双自由基。

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