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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Controlling the Conformation Changes Associated to Electron Transfer Steps through Chemical Substitution: Intriguing Redox Behavior of Substituted Vinylogous TTF
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Controlling the Conformation Changes Associated to Electron Transfer Steps through Chemical Substitution: Intriguing Redox Behavior of Substituted Vinylogous TTF

机译：通过化学取代控制与电子转移步骤相关的构象变化：有趣的取代长胶TTF的氧化还原行为

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摘要

Oxidation of a series of TTF vinylogues has been investigated in acetonitrile and dichloromethane. Depending on the substituent and the solvent, two single-electron transfers or one two-electron process was observed. Density functional modeling calculations and detailed analysis of the electrochemical behavior show that the unusual redox behavior for short-length TTF vinylogues is due to substantial conformation changes concerted with the electron transfers. Flash photolysis and spectroelectrochemistry experiments were also performed to confirm this conclusion. Through fine-tuning of the molecule structure and substituent choice, it is possible to control the relative stabilities of the different redox species. At one end, this leads to situations where the second electron transfer is much easier than the first one. At the other end, opposite situations are observed with a large increase of the separation between the first and second oxidation potentials by comparison to similar TTF without steric hindrance. The inner sphere reorganization energies remain modest (0.35-0.45 eV), allowing a fast passage between the different conformations during the electron transfers.
机译：已经在乙腈和二氯甲烷中研究了一系列TTF乙烯基化合物的氧化。取决于取代基和溶剂，观察到两个单电子转移或一个两个电子过程。密度泛函模型计算和电化学行为的详细分析表明，短型TTF乙烯基化合物的异常氧化还原行为是由于与电子转移一致的构象变化所致。还进行了闪光光解和光谱电化学实验以证实这一结论。通过分子结构的微调和取代基的选择，可以控制不同氧化还原物种的相对稳定性。一方面，这导致第二次电子转移比第一次电子转移容易得多的情况。另一方面，与类似的无空间位阻的TTF相比，观察到相反的情况，第一和第二氧化电位之间的间隔大大增加。内球的重组能量保持适度（0.35-0.45 eV），在电子转移过程中允许不同构象之间快速通过。

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