Charging OBO‐Fused Double [5]Helicene with Electrons
Charging OBO‐Fused Double [5]Helicene with Electrons
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DOI：
10.1002/anie.201908658
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发表时间：
2019-09
期刊：
影响因子：
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通讯作者：
Zheng Zhou;Xiao-Ye Wang;Zheng Wei;K. Müllen;M. Petrukhina
中科院分区：
文献类型：
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作者：
Zheng Zhou;Xiao-Ye Wang;Zheng Wei;K. Müllen;M. Petrukhina
本文首次研究了OBO稠合双[5]螺烯与第1族金属(Na和K)的化学还原反应。分离出了两个双还原产物，并用单晶X射线衍射仪对其结构进行了表征，发现了与Na+离子的溶剂分离离子三重态(SSIT)和与K+离子的接触离子对(CIP)。作为关键的结构结果，X射线结晶学分析揭示了在没有金属结合的情况下向SSIT中的双螺烯核添加两个电子的后果，并揭示了CIP中K+反离子的优先结合位置。在这两种产品中，都观察到充电时双螺烯核心的扭曲增加。通过理论计算确定了中心核的负电荷局域化，这与X射线结晶学和核磁共振谱的结果完全一致。值得注意的是，证实了OBO稠合双[5]螺烯的两电子还原是可逆的。
Abstract Chemical reduction of OBO‐fused double[5]helicene with Group 1 metals (Na and K) has been investigated for the first time. Two doubly‐reduced products have been isolated and structurally characterized by single‐crystal X‐ray diffraction, revealing a solvent‐separated ion triplet (SSIT) with Na+ ions and a contact‐ion pair (CIP) with K+ ion. As the key structural outcome, the X‐ray crystallographic analysis discloses the consequences of adding two electrons to the double helicene core in the SSIT without metal binding and reveals the preferential binding site in the CIP with K+ counterions. In both products, an increase in the twisting of the double helicene core upon charging was observed. The negative charge localization at the central core has been identified by theoretical calculations, which are in full agreement with X‐ray crystallographic and NMR spectroscopic results. Notably, it was confirmed that the two‐electron reduction of OBO‐fused double[5]helicene is reversible.