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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Intramolecular transport of charge carriers in trimeric aniline upon a three-step acid doping process
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Intramolecular transport of charge carriers in trimeric aniline upon a three-step acid doping process

机译：三步酸掺杂过程中电荷载体在三聚苯胺中的分子内运输

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摘要

The "acid doping" of a methyl-capped aniline trimer, N-[4-(dimethylamino)phenyl]-N-(4-{[4-(dimethylamino)phenyl]imino}-2,5- cyclohexadien-1-ylidene)-amine (TANI), was performed stoichiometrically to study the nature of charge carriers induced by the acid protonation process. The redox centers in TANI were found to undergo a reversible three-step protonation with 1 equiv, 2 equiv and a large molar excess of dodecylbenzenesulfonic acid (DBSA) in chloroform, as evidenced by three different chromophores (doping levels I, II and III) observed using UV-vis-NIR. Acidity of the dopants and solvent polarity were controlling factors. As revealed by electron paramagnetic resonance spectroscopy (EPR), the doping levels I, II, and III achieved by doping 0.1 mM TANI/chloroform solutions with different amounts of DBSA exhibited relative spin densities of 1:1.2:2.2. Since the expected maximum spin population of TANI through acid doping is two spins per molecule, the reduced paramagnetism given by the doubly protonated TANI (doping level II) indicated partially coupled unpaired spins. The third protonation step (doping level III) produced almost double the unpaired spin concentration compared to the lower doping levels and a multiline EPR spectrum likely comprising two overlapping signals of similar overall line width. The hyperfine couplings contributing to the splittings in this signal were estimated by simulation incorporating 6-H and 1-N nuclei most likely from one highly localized unpaired spin on a terminal dimethylamino group, with an underlying apparent singlet arising from a delocalized unpaired spin; the diradical proposed as the species exhibiting the multiplet EPR signal is isolated by the bridging ammonium cation created by the third doping step. The phenomena suggested the stepwise evolution of partly formed diamagnetic bipolarons from polaron interactions at doping level II and the transformation to the more isolated unsymmetrical system we label "two polarons on a chain" in a triplet state at doping level III. The results provide the characterization of novel doping behaviors for a trimeric aniline molecule in organic solution.
机译：甲基封端的苯胺三聚体N- [4-（二甲基氨基）苯基] -N-（4-{[4-（二甲基氨基）苯基]亚氨基} -2,5-环己二-1-基的“酸掺杂”以化学计量的方式对1-胺（TANI）进行研究，以研究由酸质子化过程诱导的电荷载体的性质。发现TANI中的氧化还原中心经历了可逆的三步质子化反应，氯仿中的当量浓度为1当量，2当量且摩尔摩尔过量的十二烷基苯磺酸（DBSA），这由三种不同的生色团（掺杂水平I，II和III）证明使用UV-vis-NIR观察。掺杂剂的酸度和溶剂极性是控制因素。如电子顺磁共振波谱（EPR）所揭示的，通过用不同量的DBSA掺杂0.1 mM TANI /氯仿溶液达到的掺杂水平I，II和III的相对自旋密度为1：1.2：2.2。由于预期通过酸掺杂产生的TANI的最大自旋种群为每个分子两个自旋，因此由双质子化的TANI（II级掺杂）产生的顺磁性降低表示部分耦合的不成对自旋。与较低的掺杂水平相比，第三质子化步骤（掺杂水平III）产生的未成对自旋浓度几乎翻了一番，并且多线EPR光谱可能包括两个相似总线宽的重叠信号。通过模拟结合了6-H和1-N核，最有可能来自末端二甲基氨基上的一个高度局部化的不成对自旋，而潜在的表观单峰则由离域化的不成对自旋产生;超精细偶合是通过模拟合并6-H和1-N核而估计的。提出的双自由基是因为表现出多重EPR信号的物质被第三掺杂步骤产生的桥联铵阳离子隔离。这种现象表明部分形成的反磁性双极化子从掺杂水平II的极化子相互作用逐步演化，并转变为更掺杂的不对称系统，我们在掺杂水平III处以三重态标记为“链上的两个极化子”。结果提供了三聚苯胺分子在有机溶液中的新型掺杂行为的表征。

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