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Dithienyl Acenedithiophenediones as New π-Extended Quinoidal Cores: Synthesis and Properties

机译:作为新的π-延伸奎因芯的二苯基酰基噻吩:合成和性能

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摘要

We have synthesized two isomeric pairs of benzoand naphthodithiophenediones with two flanking thiophenes and characterized them by single-crystal X-ray analysis, cyclic voltammetry, steady-state optical electronic absorption and emission spectroscopies, transient absorption spectroscopy, and vibrational spectroscopies with in situ spectroelectrochemistry techniques, and then compared them with the thieno[3,2-b]thiophene-2,5-dione counterpart that we previously reported. The results show that the central acenedithiophenedione cores have quinoidal conjugation with closed-shell character. The p-extension of the quinoidal core raises (lowers) the HOMO (LUMO) energy levels of the triads, resulting in the drastic reduction of their energy gaps from approximately 2.0 eV to 1.1 eV. Owing to the electron-withdrawing nature of the carbonyl terminal group at the quinoidal core, the triads have low-lying LUMO energy levels ranging from -3.9 eV to -4.3 eV, and can be regarded as strong electron-acceptor building units. Interestingly, the pairs of structural isomers have similar electronic structures in both the neutral and charged states despite the different shapes (linear and angular) and/or symmetry (C_(2h) and C_(2v)) of the acenedithiophenedione cores.
机译:我们已经合成了两种异构对苯并萘二硫噻吩,具有两个侧翼噻吩,通过单晶X射线分析,循环伏安法,稳态光学电子吸收和发射光谱,瞬态吸收光谱和具有原位光谱电化学技术的振动光谱,然后将它们与我们之前报道的Thieno [3,2-B]噻吩-2,5-Dione对手进行比较。结果表明,中央亚苯二硫代芯具有与封闭壳特性的奎胸缀合。 Quinoidal核心的P-延伸升高(降低了三合会的HOMO(LUMO)能级,导致它们的能量间隙从大约2.0 eV到1.1 eV的急剧减少。由于QuinoInal Core的羰基末端组的吸电子性质,三合会具有低于-3.9eV至-4.3 eV的低位Lumo能量水平,并且可以被视为强电子受体构建单元。有趣的是,尽管acEdithiopheIone芯的不同形状(线性和角度)和/或对称(C_(2H)和C_(2V)),所以,所在的结构异构体对中性和带电状态的相似的电子结构。

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