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π-Extended and Curved Antiaromatic Polycyclic Hydrocarbons
Journal of the American Chemical Society ( IF 15.0 ) Pub Date : 2017-05-16 00:00:00 , DOI: 10.1021/jacs.7b01619
Junzhi Liu , Ji Ma , Ke Zhang 1 , Prince Ravat 1 , Peter Machata 2 , Stanislav Avdoshenko 2 , Felix Hennersdorf , Hartmut Komber 3 , Wojciech Pisula 1, 4 , Jan J. Weigand , Alexey A. Popov 2 , Reinhard Berger , Klaus Müllen 1 , Xinliang Feng
Affiliation  

Synthesis of antiaromatic polycyclic hydrocarbons (PHs) is challenging because the high energy of their highest occupied molecular orbital and low energy of their lowest unoccupied molecular orbital cause them to be reactive and unstable. In this work, two large antiaromatic acene analogues, namely, cyclopenta[pqr]indeno[2,1,7-ijk]tetraphene (CIT, 1a) and cyclopenta[pqr]indeno[7,1,2-cde]picene (CIP, 1b), as well as a curved antiaromatic molecule with 48 π-electrons, dibenzo[a,c]diindeno[7,1,2-fgh:7′,1′,2′-mno]phenanthro[9,10-k]tetraphene (DPT, 1c), are synthesized on the basis of the corona of indeno[1,2-b]fluorene. These three antiaromatic PHs possess a narrow energy gap down to 1.55 eV and exhibit high kinetic stability under ambient conditions. Moreover, these compounds display reversible electron transfer processes in both the cathodic and anodic regimes. Their cation and anion radicals are characterized by in situ vis–NIR absorption and electron paramagnetic resonance spectroelectrochemistry. The X-ray crystallographic analysis confirms that while CIP and CIT manifest planar structures, DPT shows a curved π-conjugated carbon skeleton. The synthetic strategy starting from ortho-substituted benzene units to construct five-membered rings in this work provides a unique entry to novel pentagon-embedding or curved antiaromatic polycyclic hydrocarbons. In addition, besides the detailed chemical and physical investigations, microscale single-crystal fiber field-effect transistors were also fabricated.

中文翻译:

π扩展和弯曲的抗芳族多环烃

抗芳族多环烃(PHs)的合成具有挑战性,因为其最高占据分子轨道的高能和其最低未占据分子轨道的低能使它们具有反应性和不稳定性。在这项工作中,两个大的抗芳烃并苯类似物,即环戊[ pqr ]茚并[2,1,7- ijk ]四苯(CIT,1a)和环戊[ pqr ]茚并[7,1,2- cde ]庚烯(CIP ,1b),以及具有48个π电子的弯曲抗芳族分子,dibenzo [ ac ] diindeno [7,1,2- fgh:7',1',2'- mno ] phenthro [9,10- k ]四苯(DPT,1c)是在茚并[1,2- b ]芴的电晕的基础上合成的。这三种抗芳香族PH均具有低至1.55 eV的窄能隙,并在环境条件下表现出高动力学稳定性。此外,这些化合物在阴极和阳极体系中均显示出可逆的电子转移过程。它们的阳离子和阴离子自由基的特征是原位对近红外光谱吸收和电子顺磁共振光谱电化学。X射线晶体学分析证实,尽管CIP和CIT表现出平面结构,但DPT显示出弯曲的π共轭碳骨架。从邻里出发的综合策略这项工作中构建五元环的取代苯单元为新型五边形嵌入或弯曲的抗芳族多环烃提供了独特的入口。此外,除了进行详细的化学和物理研究外,还制造了微型单晶纤维场效应晶体管。
更新日期:2017-05-25
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