Complete charge separation provoked by full cation encapsulation in the radical mono- and di-anions of 5,6:11,12-di-o-phenylene-tetracene.
Complete charge separation provoked by full cation encapsulation in the radical mono- and di-anions of 5,6:11,12-di-o-phenylene-tetracene.
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5,6:11,12-二邻亚苯基并四苯的自由基单阴离子和双阴离子中的完全阳离子封装引发了完全电荷分离。
DOI：
10.1039/c8dt01285g
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发表时间：
2018
影响因子：
4
通讯作者：
J. J. Schneider
中科院分区：
文献类型：
--
作者：
T. Wombacher;R. Goddard;C. Lehmann;J. J. Schneider
本文报道了以5，6：11，12-二邻苯并三烯(DOPT)为母体，通过可控的单、双电子化学还原反应合成的单、双阴离子芳香族分子[(B15C5-κ5O)2K+](LDOPT.-)(1)和[(B15C5-κ5O)2K+]2(LDOPT2-)THFsolv(2)的合成和分子结构。证明了单电子和双电子电荷转移对聚合芳烃(PAH)的影响，而不受缔合金属阳离子的干扰。这是通过将阳离子K+反离子完全夹在两个苯并-15-冠-5-醚(B15C5)配体之间实现的，从而形成了完全包覆的(κ10O)几何构型，确保了K+反离子与裸露的阴离子多环芳烃物种[LDOPT.-]和[LDOPT2-]的完全分离。讨论了伴随着从LDOPT到[LDOPT·-]到[LDOPT2-]的逐步还原的结构变化，并与以前基于密度泛函理论(DFT)的预测以及DOPT的碱金属阳离子多环芳烃阴离子相互作用的研究结果进行了比较，这些结果到目前为止只实现了部分金属阳离子的包裹。
Herein, we report the synthesis and molecular structure of the mono- and dianionic aromatic molecules [(B15C5-κ5O)2K+](LDOPT˙-) (1) and [(B15C5-κ5O)2K+]2(LDOPT2-)THFsolv (2) derived from the parent aromatic polyhydrocarbon 5,6:11,12-di-o-phenylenetetracene (DOPT, LDOPT) by a controlled stepwise one and two electron chemical reduction. The effect of single and double electron charge transfer to a polycondensed aromatic hydrocarbon (PAH) without any disturbing influence of an associated metal cation has been demonstrated. This was achieved by fully sandwiching the cationic K+ counterions between two benzo-15-crown-5-ether (B15C5) ligands resulting in a fully encapsulating (κ10O) geometry which ensures a complete separation of the K+ counterions and the bare anionic PAH species [LDOPT˙-] and [LDOPT2-]. The structural changes accompanied by the stepwise reduction from LDOPT to [LDOPT˙-] to [LDOPT2-] are discussed and compared to earlier predictions based on density functional theory (DFT) as well as the results of previous studies of alkaline metal cationic PAH anion interactions of DOPT in which only a partial metal cation encapsulation has been achieved so far.