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首页> 外文期刊>Bulletin of the Chemical Society of Japan >Trioxotriangulene: Air- and Thermally Stable Organic Carbon-Centered Neutral pi-Radical without Steric Protection
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Trioxotriangulene: Air- and Thermally Stable Organic Carbon-Centered Neutral pi-Radical without Steric Protection

机译：三氧突：空气和热稳定的有机碳中心中性PI-自由基而无空间保护

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摘要

To stabilize organic neutral radicals, which are usually very unstable chemical species in air atmosphere, "steric protection" is the most general and indispensable method. Based on the design of electronic-spin structure of polycyclic carboncentered p-radicals, we have for the first time realized a peculiarly stable neutral p-radical without bulky substituent groups, 4,8,12-trioxotriangulene (TOT), whose decomposition point is higher than 240 degrees C in the solid state under air. This remarkably high air-stability as a neutral radical is achieved by spin-delocalization originating from the symmetric and expanded p-electronic structure of TOT. The oxo-functionalities also highly contribute to the high stability through electronicspin modulation, where the largest electronic spin density located at the central carbon atom further decreases the spin densities of the peripheral carbon atoms. In the solution state, TOT is in the equilibrium between the monomer and highly symmetric p-dimer, as stabilized by the formation of the strong two-electron-multicenter bonding. Crystal structure analysis revealed that TOT derivatives show strong self-assembling ability forming one-dimensional columns, which further construct three-dimensional networks by multiple intercolumnar non-covalent interactions due to the absence of bulky substituent groups. Substituent groups at the apexes of the triangular carbon-framework of TOT afford variations of the p-stacking mode in the one-dimensional columns, influencing the magnetic properties and photo-absorptions around the near-infrared region. The electronic effect of the substituent groups also affects the redox potentials of TOT. The peculiarly high stability of TOT neutral radicals and their three-dimensional networks by robust intermolecular interactions achieved in our study are very beneficial for the molecular design of new polycyclic air-stable neutral radicals. Furthermore, we believe that the open-shell electronic structures of neutral p-radicals, which are quite different from those of close-shell molecular systems, will also produce milestones for the exploration of peculiar physical properties and catalytic activity for organic transformation originating from their unconventional electronic-spin nature.
机译：为了稳定有机中性自由基，通常在空气气氛中通常是非常不稳定的化学物质，“空间保护”是最通用和最不可或缺的方法。基于多环含有多环碳流体p-自由基的电子旋转结构的设计，我们首次实现了无笨重的取代基的特殊稳定的中性p-自由基，4,8,12-三氧丁烯（Tot），其分解点是在空气下的固态高于240℃。这是通过源自对称和扩展的P-Electronic结构的旋转脱洞来实现作为中性自由基的高空气稳定性。氧官能团也通过电子键调制高度有助于高稳定性，其中位于中央碳原子的最大电子自旋密度进一步降低了外周碳原子的旋转密度。在溶液状态下，TOT在单体和高度对称的p叠层之间的平衡中，通过形成强双电子 - 多电元键合而稳定。晶体结构分析显示，Tot衍生物显示出强烈的自组装能力，形成一维列，其通过不存在庞大的取代基由于不存在而通过多种脑子间非共价相互作用进一步构建三维网络。在Tot的三角形碳框架的顶点处的取代基在一维列中的p堆叠模式的变化，影响近红外区域周围的磁性和光吸收。取代基的电子效果也影响了Tot的氧化还原势。通过我们研究中实现的强大的分子间相互作用，Tot中性自由基及其三维网络的特殊高稳定性对新的多环空气稳定中性自由基的分子设计非常有益。此外，我们认为，与亲密壳分子系统完全不同的中性P自由基的开壳电子结构，也将产生用于探索唯一的有机转化的特殊物理性质和催化活性的里程碑非常规电子旋转性质。

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