Azulene–Pyridine-Fused Heteroaromatics
Azulene–Pyridine-Fused Heteroaromatics
复制标题
甘菊环-吡啶稠合杂芳烃
DOI：
10.1021/jacs.0c06299
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发表时间：
2020
影响因子：
15
通讯作者：
Swager, Timothy M.
中科院分区：
文献类型：
--
作者：
Xin, Hanshen;Li, Jing;Lu, Ru-Qiang;Gao, Xike;Swager, Timothy M.
Azulene是一种具有独特电子结构的非苯类双环芳烃，是构建非苯类π共轭体系的重要组成部分。然而，由于合成方法的限制，偶氮烯融合（杂）芳烃仍然很少见。本文报道了用1-硝基噻唑还原环化的方法，意外合成了具有30π电子的七环杂芳香化合物azz - py -1。单晶x射线分析明确了az - py -1的结构，并合成了类似的az - py -2 - az - py -6，表明该方法是构建azulene-和吡啶融合杂芳烃的有效方法。理论计算、光物理和电化学研究表明，az - py -1 - az - py -6具有作为半导体材料的潜力，其单晶带的空穴迁移率高达0.29 cm2V-1s-1。
Azulene, a nonbenzenoid bicyclic aromatic hydrocarbon with unique electronic structure, is a promising building block for constructing nonbenzenoid π-conjugated systems. However, azulene-fused (hetero)aromatics remain rare as a result of limited synthetic methods. We report herein the unexpected synthesis of azulene- and pyridine-fused heteroaromaticsAz-Py-1, a seven fused ring system with 30π electrons, by reductive cyclization of a 1-nitroazulene. The structure ofAz-Py-1was unambiguously confirmed by single-crystal X-ray analysis, and analoguesAz-Py-2–Az-Py-6were also synthesized, demonstrating that this is an effective method for constructing azulene- and pyridine-fused heteroaromatics. Theoretical calculations and photophysical and electrochemical studies ofAz-Py-1–Az-Py-6suggest their potential as semiconductors, and the single-crystal ribbons ofAz-Py-1show high hole mobilities up to 0.29 cm2V–1s–1.