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A Stable Trimethylenemethane Triplet Diradical Based on a Trimeric Porphyrin Fused π‐System
Angewandte Chemie International Edition ( IF 16.6 ) Pub Date : 2018-06-21 , DOI: 10.1002/anie.201804644
Kenichi Kato 1 , Ko Furukawa 2 , Atsuhiro Osuka 1
Affiliation  

Trimethylenemethane (TMM) diradical is the simplest non‐Kekulé non‐disjoint molecule with the triplet ground state (ΔEST=+16.1 kcal mol−1) and is extremely reactive. It is a challenge to design and synthesize a stable TMM diradical with key properties, such as actual aliphatic TMM diradical centers and the triplet ground state with a large positive ΔEST value, since such species provide detailed information on the electronic structure of TMM diradical. Herein we report a TMM derivative, in which the TMM segment is fused with three NiII meso‐triarylporphyrins, that satisfies the above criteria. The diradical shows delocalized spin density on the propeller‐like porphyrin π‐network and the triplet ground state owing to the strong ferromagnetic interaction. Despite the apparent TMM structure, the diradical can be handled under ambient conditions and can be stored for months in the solid state, thus allowing its X‐ray diffraction structural analysis.

中文翻译:

基于三聚卟啉融合π系统的稳定的三亚甲基三重自由基

三亚甲基甲烷(TMM)双自由基是具有三重态基态(ΔE ST = + 16.1 kcal mol -1)的最简单的非Kekulé不相交分子,并且具有极强的反应性。设计和合成具有关键特性的稳定TMM双自由基是一个挑战,例如实际的脂肪族TMM双自由基中心和具有大正ΔE ST值的三重态基态,因为此类物质提供了有关TMM双自由基电子结构的详细信息。本文中我们报告了一种TMM衍生物,其中TMM片段与三个Ni II 内消旋体融合满足上述标准的三芳基卟啉。由于强的铁磁相互作用,双基表明在螺旋桨状卟啉π网络上的自旋密度失调,并且三重态基态。尽管TMM具有明显的结构,该双自由基仍可以在环境条件下处理,并且可以固态保存数月,因此可以进行X射线衍射结构分析。
更新日期:2018-06-21
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