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首页> 外文期刊>Chemistry: A European journal >Twisting the TAPPs: Bay-Substituted Non-planar Tetraazaperopyrenes and their Reduced Anions
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Twisting the TAPPs: Bay-Substituted Non-planar Tetraazaperopyrenes and their Reduced Anions

机译：Tapping Tapps：托架取代的非平面四唑孔及其降低的阴离子

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摘要

A new synthesis of tetraazaperopyrenes (TAPPs) starting from a halogenated perylene derivative 3,4,9,10-tetrabromo-1,6,7,12-tetrachloroperylene (1) gave access to bay-substituted TAPPs for the first time. Selective lithiation of the bromine-positions and subsequent addition of tosyl azide led to the formation of the tetraazidotetrachloroperylene (2), which was subsequently reduced by addition of sodium borohydride to the corresponding tetraaminotetrachloroperylene (3). Oxidation to its semiquinoidal form 4 and subsequent cyclization with acid chlorides gave rise to a series of bay-chlorinated TAPPs. Whereas the aromatic core of the previously studied ortho-substituted TAPPs was found to be planar, the steric pressure of the two chlorine substituents on each side leads to the twist of the peropyrene core of approximately 30 degrees, a structural feature also observed in other bay-substituted perylene derivatives. An experimental and computational analysis reveals that introducing chloride substituents at these positions leads to slightly increased electron affinities (EA) enabling the selective generation and characterization of the reduced mono-anionic radicals and closed shell di-anionic species. These anions were isolated and characterized by UV/Vis spectroscopy and EPR or NMR, respectively. Processing of the bay-chlorinated TAPPs in n-channel organic TFTs revealed electron mobilities of 0.001 to 0.003 cm~2V~(-1) s-1. These reduced electron mobilities compared to the ortho-halogenated TAPPs are thought to be rooted in the less densely packed solid-state structures.
机译：从卤化丙基衍生物3,4,9,10-四溴氟-1,6,7,12-四氯丙烯酸甲烯（1）开始的新合成四唑孔（TAPPS）使得第一次获得湾取代的TAPP。溴 - 位置的选择性锂化合物和随后加入甲酰叠氮化物导致四氮酰氯丙烯酸甲苯（2）的形成，随后通过向相应的四氨基四氯丙烯酸烯烃（3）加入硼氢化钠（3）。氧化于其半环化形式4和随后用酰氯环化，产生了一系列氯化TAPP。虽然发现先前研究的邻替代TAPP的芳香核心是平面的，但是每侧的两氯取代基的空间压力导致大约30℃的聚苯乙烯核的扭曲，在其他海湾也观察到的结构特征 - - 过量的丙烯衍生物。实验和计算分析表明，在这些位置引入氯化物取代基导致略微增加的电子亲和力（EA）能够选择性产生和表征减少的单阴离子自由基和封闭的壳体二阴离子物质。将这些阴离子分离并分别以UV / Vis光谱和EPR或NMR为特征。在N沟道有机TFT中处理湾氯化TAPP，揭示了0.001至0.003cm〜2V〜（-1）S-1的电子迁移率。与卤代TAPP相比，这些降低的电子迁移率被认为是根深蒂固的固态结构。

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