一种源自蒂勒烃的晶体自由基阳离子，其氧化还原范围超过1伏特。
A crystalline radical cation derived from Thiele's hydrocarbon with redox range beyond 1 V.
作者信息
Loh Ying Kai, Vasko Petra, McManus Caitilín, Heilmann Andreas, Myers William K, Aldridge Simon
机构信息
Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford, OX1 3QR, UK.
Department of Chemistry, Nanoscience Center, University of Jyväskylä, P. O. Box 35, Jyväskylä, FI-40014, Finland.
出版信息
Nat Commun. 2021 Dec 3;12(1):7052. doi: 10.1038/s41467-021-27104-y.
Thiele's hydrocarbon occupies a central role as an open-shell platform for new organic materials, however little is known about its redox behaviour. While recent synthetic approaches involving symmetrical carbene substitution of the CPh termini yield isolable neutral/dicationic analogues, the intervening radical cations are much more difficult to isolate, due to narrow compatible redox ranges (typically < 0.25 V). Here we show that a hybrid BN/carbene approach allows access to an unsymmetrical analogue of Thiele's hydrocarbon 1, and that this strategy confers markedly enhanced stability on the radical cation. 1 is stable across an exceptionally wide redox range (> 1 V), permitting its isolation in crystalline form. Further single-electron oxidation affords borenium dication 1, thereby establishing an organoboron redox system fully characterized in all three redox states. We perceive that this strategy can be extended to other transient organic radicals to widen their redox stability window and facilitate their isolation.
蒂勒烃作为新型有机材料的开壳层平台发挥着核心作用，然而人们对其氧化还原行为知之甚少。虽然最近涉及CPh端基对称卡宾取代的合成方法可得到可分离的中性/双阳离子类似物，但由于兼容的氧化还原范围狭窄（通常<0.25 V），中间的自由基阳离子要难得多。在这里，我们表明，一种混合的硼氮/卡宾方法可以得到蒂勒烃1的不对称类似物，并且这种策略赋予自由基阳离子显著增强的稳定性。1在异常宽的氧化还原范围内（>1 V）都很稳定，使其能够以晶体形式分离出来。进一步的单电子氧化得到硼正离子双阳离子1，从而建立了一个在所有三种氧化还原状态下都得到充分表征的有机硼氧化还原体系。我们认为，这种策略可以扩展到其他瞬态有机自由基，以拓宽它们的氧化还原稳定性窗口并便于它们的分离。
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