Spider-like oligothiophenes.
Spider-like oligothiophenes.
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DOI：
10.1002/chem.200701117
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发表时间：
2008-01
期刊：
影响因子：
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通讯作者：
T. Benincori;Marcello Capaccio;F. De Angelis;L. Falciola;M. Muccini;P. Mussini;A. Ponti;S. Toffanin;P. Traldi;F. Sannicolò
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文献类型：
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作者：
T. Benincori;Marcello Capaccio;F. De Angelis;L. Falciola;M. Muccini;P. Mussini;A. Ponti;S. Toffanin;P. Traldi;F. Sannicolò
仔细分析和比较的光学和电化学数据，在最近的文献中多噻吩分子组装提出了一些基本的规则，设计结构简单，易于获得的oligothiophenes赋予的性能不远的那些表现出更复杂和综合要求的架构。根据这些指示定制的一类oligothiophenes（蜘蛛状）的三个例子的合成和计算调查报告连同其详尽的光学和电化学表征。新化合物（T9 5、T14 6、T19 7）的特征在于噻吩、2，2 ′-联噻吩和2，2 ′，5 ′，2 ″-三噻吩单元（蜘蛛体）被5-（2，2 ′-联噻吩）基侧基（蜘蛛腿）完全取代。吸收和电化学数据是在良好的协议，并指向一个高的π共轭水平，相比之下，所显示的更大的组件。在第一氧化峰附近的电极电位循环提供了快速和可再现的导电，高度稳定的[TXn]m膜的形成，主要由二聚体（m=2）。对氘标记的T9 5进行的电氧化动力学实验，再加上对所得二聚体的激光解吸电离质谱，表明偶联过程在共轭程度更高的五噻吩链的α位置具有极强的区域选择性。薄膜的光学和电化学性能的报告和讨论。一个奇特的特征是它们令人印象深刻的电荷捕获能力。蜘蛛型低聚噻吩类化合物是一种很有前途的多功能有机器件活性层材料。
Careful analysis and comparison of optical and electrochemical data available in recent literature for multi-thiophene molecular assemblies suggested a few basic rules for the design of structurally simple and easily accessible oligothiophenes endowed with properties not far from those exhibited by much more complex and synthetically demanding architectures. The synthesis and computational investigation of three examples of a class of oligothiophenes (spider-like) tailored according to these indications are reported together with their exhaustive optical and electrochemical characterization. The new compounds (T9 5, T14 6, T19 7) are characterized by a thiophene, a 2,2'-bithiophene and a 2,2',5',2''-terthiophene unit (the spider body) fully substituted with 5-(2,2'-bithiophen)yl pendants (the spider legs). Absorption and electrochemical data are in good agreement and point to a high pi-conjugation level, comparable to those displayed by much larger assemblies. Electrode potential cycling in proximity of the first oxidation peak affords fast and reproducible formation of conducting, highly stable [TXn]m films, mainly consisting of dimers (m=2). Electrooxidation kinetic experiments on deuterium-labelled T9 5, coupled to laser-desorption-ionization mass spectroscopy on the resulting dimer demonstrated that the coupling process is extremely regioselective in the alpha positions of the more conjugated pentathiophene chain. The optical and the electrochemical properties of the films are reported and discussed. A peculiar feature is their impressive charge-trapping ability. Spider-like oligothiophenes are promising materials for applications as active layers in multifunctional organic devices.