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首页> 外文期刊>Chemistry: A European journal >Multistep π Dimerization of Tetrakis(n-decyl)heptathienoacene Radical Cations: A Combined Experimental and Theoretical Study
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Multistep π Dimerization of Tetrakis(n-decyl)heptathienoacene Radical Cations: A Combined Experimental and Theoretical Study

机译：四（正癸基）庚炔并茂自由基阳离子的多步π二聚：组合的实验和理论研究。

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Radical cations of a heptathienoacene α,β-substituted with four n-decyl side groups (D4T7~(?+)) form exceptionally stable π-dimer dications already at ambient temperature (Chem. Comm. 2011, 47, 12622). This extraordinary p-dimerization process is investigated here with a focus on the ultimate [D4T7~(?+)]_2 π-dimer dication and yet-unreported transitory species formed during and after the oxidation. To this end, we use a joint experimental and theoretical approach that combines cyclic voltammetry, in situ spectrochemistry and spectroelectrochemistry, EPR spectroscopy, and DFT calculations. The impact of temperature, thienoacene concentration, and the nature and concentration of counteranions on the p-dimerization process is also investigated in detail. Two different transitory species were detected in the course of the one-electron oxidation: 1) a different transient conformation of the ultimate [D4T7~(?+)]_2 π-dimer dications, the stability of which is strongly affected by the applied experimental conditions, and 2) intermediate [D4T7]_2~(?+) π-dimer radical cations formed prior to the fully oxidized [D4T7]_2~(?+) π-dimer dications. Thus, this comprehensive work demonstrates the formation of peculiar supramolecular species of heptathienoacene radical cations, the stability, nature, and structure of which have been successfully analyzed. We therefore believe that this study leads to a deeper fundamental understanding of the mechanism of dimer formation between conjugated aromatic systems.
机译：被四个正癸基侧基（D4T7〜（α+））取代的庚炔并苯α，β的自由基阳离子已经在环境温度下形成格外稳定的π二聚体（Chem。Comm。2011，47，12622）。本文研究了这种非同寻常的p-二聚过程，重点研究了最终[D4T7〜（α+）] _ 2π-二聚体和氧化过程中和氧化后尚未形成的过渡物种。为此，我们使用联合的实验和理论方法，将循环伏安法，原位光谱化学和光谱电化学，EPR光谱和DFT计算相结合。还详细研究了温度，硫杂并苯浓度以及抗衡阴离子的性质和浓度对对二聚过程的影响。在单电子氧化过程中检测到两种不同的瞬态物种：1）最终[D4T7〜（？+）] _ 2π-二聚体药物的不同瞬态构象，其稳定性受到应用实验的强烈影响。条件，以及2）在完全氧化[D4T7] _2〜（α+）π-二聚体指示之前形成的中间[D4T7] _2〜（α+）π-二聚体自由基阳离子。因此，这项全面的工作证明了庚二炔并苯自由基阳离子特有的超分子物种的形成，其稳定性，性质和结构已得到成功分析。因此，我们认为，该研究导致对共轭芳族体系之间二聚体形成机理的更深刻的基本理解。

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