Boron-Containing Organic Diradicaloids: Dynamically Modulating Singlet Diradical Character by Lewis Acid–Base Coordination,Journal of the American Chemical Society

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Boron-Containing Organic Diradicaloids: Dynamically Modulating Singlet Diradical Character by Lewis Acid–Base Coordination
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2021-10-19 , DOI: 10.1021/jacs.1c08486
Jiaxiang Guo ₁ , Yue Yang ₁ , Chuandong Dou ₁ , Yue Wang ₁

Affiliation

Organic diradicaloids have unique open-shell structures and properties and promising applications in organic electronics and spintronics. Incorporation of heteroatoms is an effective strategy to alter the electronic structures of organic diradicaloids. However, B-containing organic diradicaloids are very challenging due to their high reactivities, which are caused by not only diradical nature but also the B atom. In this article, we report a new kind of organic diradicaloids containing boron atoms. Our strategy is to incorporate planarized triarylboranes to antiaromatic polycyclic hydrocarbons (PHs). We synthesized two isomeric B-containing PHs composed of indenofluorene π-skeletons and two dioxa-bridged triphenylborane moieties. As proved by theoretical and experimental results, both of them have excellent ambient stability and open-shell singlet diradical structures, as well as intriguing magnetic and optoelectronic properties, such as thermally accessible triplet species, reversible multiredox ability, and narrow energy gaps. Notably, they possess sufficient Lewis acidity, which has never been observed for organic diradicaloids. In addition, they can coordinate with Lewis bases to form Lewis adducts, achieving unprecedented dynamic modulations of (anti)aromaticity and thus diradical character of organic diradicaloids.

中文翻译：

含硼有机双自由基：通过路易斯酸碱配位动态调节单线态双自由基

有机双自由基具有独特的开壳结构和性质，在有机电子学和自旋电子学中有广阔的应用前景。杂原子的掺入是改变有机双自由基电子结构的有效策略。然而，含 B 的有机双自由基由于它们的高反应性而非常具有挑战性，这不仅是由双自由基性质引起的，而且是由 B 原子引起的。在本文中，我们报告了一种新型的含有硼原子的有机双自由基。我们的策略是将平面化的三芳基硼烷与反芳香族多环烃 (PH) 结合。我们合成了由茚并芴π-骨架和两个二氧杂环丙烷桥连的三苯基硼烷部分组成的两种异构体B PH。理论和实验结果证明，它们都具有出色的环境稳定性和开壳单线态双自由基结构，以及引人入胜的磁和光电特性，例如热可及的三线态物质、可逆的多氧化还原能力和窄能隙。值得注意的是，它们具有足够的路易斯酸度，这是有机双自由基从未观察到的。此外，它们可以与路易斯碱协调形成路易斯加合物，实现前所未有的（反）芳香性动态调制，从而实现有机双自由基的双自由基特性。

更新日期：2021-11-03

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