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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Formation and Behavior of Fluorescent Lewis Acid-Base Exciplexes and Triplexes between 3-Aminostilbenes and Aliphatic Amines
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Formation and Behavior of Fluorescent Lewis Acid-Base Exciplexes and Triplexes between 3-Aminostilbenes and Aliphatic Amines

机译：荧光路易斯酸基激进分子和3-氨基芪和脂肪胺之间的三元体的形成和行为

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摘要

The excited singlet states of trans-3-aminostilbene and its N-methyl derivatives are strongly fluorescent in cyclohexane solution and have large singlet state dipole moments. Addition of low concentrations of alkylamines results in a continuous red shift of the emission maximum and decreasing fluorescence intensity. Analysis of the fluorescence behavior using a combination of singular value decomposition with self-modeling and kinetic analysis provides evidence for the sequential formation of a 1:1 complex (exciplex) and 1:2 complex (triplex) between the excited stilbene and ground state alkylamine, both of which are strongly fluorescent. Both the formation and decay of the exciplex and triplex are dependent upon the extent of amine N-alkylation, primary amines forming the most stable exciplex and triplex. Similarly, N-aminoalkyl derivatives of the aminostilbenes form intramolecular exciplexes that in turn form 1:1 complexes with added amines. Addition of diaminoalkanes to the aminostilbenes results in sequential formation of 1:1 and 1:2 complexes rather than the formation of a triplex with a single molecule of the diaminoalkanes. Excited state complex formation is attributed to a Lewis acid-base interaction between the excited stilbene (lone pair acceptor) and ground state amine (lone pair donor). An alternative explanation for the red-shifted emission based on Suppan's theory of solvent dielectric enrichment is found to be incompatible with the experimental results.
机译：反式-3-氨基苯乙烯及其N-甲基衍生物的激发单重态在环己烷溶液中强烈发出荧光，并具有较大的单重态偶极矩。添加低浓度的烷基胺会导致发射最大值的连续红移并降低荧光强度。结合使用奇异值分解，自建模和动力学分析对荧光行为进行分析，为激发的二苯乙烯与基态烷基胺之间依次形成1：1配合物（exciplex）和1：2配合物（triplex）提供了证据。 ，两者都是强荧光的。激基复合物和三链体的形成和衰变均取决于胺N-烷基化的程度，伯胺形成最稳定的激基复合物和三链体。类似地，氨基磺基苯的N-氨基烷基衍生物形成分子内激基复合物，其继而与添加的胺形成1：1的复合物。将二氨基链烷烃加到氨基苯乙烯中，导致依次形成1：1和1：2的配合物，而不是与单分子的二氨基链烷烃形成三链体。激发态复合物的形成归因于激发的二苯乙烯（孤对受体）和基态胺（孤对供体）之间的路易斯酸碱相互作用。发现基于Suppan溶剂介电富集理论的红移发射的另一种解释与实验结果不兼容。

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