Synthesis, crystal structure, solid-state optical property and C?H activation of sp3 carbon of highly-stable 1-(2′,6′-dimesitylphenyl)-2,3,4,5-tetraphenylborole
Synthesis, crystal structure, solid-state optical property and C?H activation of sp3 carbon of highly-stable 1-(2′,6′-dimesitylphenyl)-2,3,4,5-tetraphenylborole
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高稳定性1-(2′,6′-二苯基苯基)-2,3,4,5-四苯基硼杂环戊二烯的合成、晶体结构、固态光学性质及sp3碳的C?H活化
DOI：
10.1039/d1nj04666g
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发表时间：
2021
影响因子：
3.3
通讯作者：
Chujo Yoshiki
中科院分区：
文献类型：
--
作者：
Himeno Ryoji;Ito Shunichiro;Tanaka Kazuo;Chujo Yoshiki
以氯代硼杂环戊烯衍生物和三联苯锂为原料，通过亲核取代反应合成了三联苯取代硼杂环戊烯。通过重结晶，得到了两种假多晶型物与苯和正己烷的共晶。由于晶体样品在露天环境中具有极高的耐久性，因此不仅可以进行X射线晶体学测量，还可以进行固态光学测量。从结构分析，提出了强烈的电子分子内相互作用，相比其他硼。事实上，从光学测量，borole有吸收，即使在近红外（NIR）区域，这表明这种较强的相互作用应诱导电子共轭的大程度的稳定，其次是一个显着的红移的吸收带。此外，与固态下的高耐久性相反，在溶液状态下降解迅速进行。从分解化合物的表征来看，获得了意想不到的环稠合分子，表明sp3碳上发生了独特的C-H键活化。这些数据表明，我们的分子应该是通用的设计一个新的C-H活化反应，以及获得先进的光电有机器件的基础上独特的电子性质的borole。
Terphenyl-substituted borole was prepared through the nucleophilic substitution reaction with chloroborole derivative and terphenyl lithium. From recrystallization, two types of pseudo polymorphs as co-crystals with benzene and hexane were obtained. Owing to the extremely high durability of the crystalline sample in open air, not only X-ray crystallography but also optical measurements in the solid state can be executed. From structural analyses, it was proposed that strong electronic intramolecular interaction should be involved, compared to other boroles. Indeed, from the optical measurements, borole has absorption even in the near-infrared (NIR) region, suggesting that this stronger interaction should be inducible to large degree of stabilization of the electronic conjugation, followed by a significant redshift in the absorption band. Moreover, contrary to high durability in the solid state, degradation rapidly proceeds in the solution state. From the characterization of decomposition compounds, an unexpected ring-fused molecule was obtained, indicating that unique C–H bond activation at the sp3 carbon occurs. These data propose that our molecule should be versatile for designing a novel C–H activation reaction as well as obtaining advanced optoelectronic organic devices based on the unique electronic properties of borole.