A Series of Soluble Planar Oligorylenes up to Hexarylene
A Series of Soluble Planar Oligorylenes up to Hexarylene
复制标题
一系列可溶性平面低聚亚萘基直至六亚芳基
DOI：
10.1002/cjoc.202200692
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发表时间：
2023
影响因子：
5.4
通讯作者：
Aratani Naoki
中科院分区：
文献类型：
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作者：
Fujita Ryuichi;Yoshida Shoko;Kano Haruka;Matsuo Kyohei;Hayashi Hironobu;Yamada Hiroko;Aratani Naoki
综述大萘嵌苯的制备通常需要沿萘嵌苯主链沿着使用增溶基团，这导致骨架变形，从而加宽吸收光谱。在本工作中，我们通过氧化熔融反应成功地合成了2，5，8，16，19，22-六[2，6-二（三氟甲基）苯基]亚己基（H），产率为5%。产物可溶于普通有机溶剂，可用柱层析法纯化。单晶X射线衍射分析表明，亚己基核不受取代基的干扰，几乎是平面的。在甲苯中，H的最长吸收在831 nm处显示出尖峰，在875 nm处显示出起始点，半峰全宽（FWHM）较小，为660 cm-1。摩尔消光系数高达131，000 M-1cm-1。取代基不会干扰亚己基的电子性质，因为芳基垂直于亚己基核，并且通过理论计算估计，2，5，16，19-位的碳原子对其HOMO和LUMO的影响可以忽略不计。结果，在可见光区域具有较小吸收的亚己基在溶液中在LED室内光下足够稳定超过1周。该策略为建立在环境条件下表现出稳定性的近红外材料提供了有用的指导。
Comprehensive SummaryPreparation of large rylenes often needs the use of solubilizing groups along the rylene backbone, which results in the distortion of the skeleton and thus broadening of the absorption spectrum. In this work, we successfully synthesized 2,5,8,16,19,22‐hexakis[2,6‐ bis(tri‐fluoromethyl)phenyl]hexarylene (H) by using an oxidative fusion reaction of perylene trimer in 5% yield. The product is soluble in common organic solvents and could be purified with column chromatography. Single‐crystal X‐ray diffraction analysis revealed that the hexarylene core is not disturbed by the substituents very much and is almost planar. The longest absorption ofHexhibits a sharp peak at 831 nm and an on‐set at 875 nm in toluene with a small full‐width‐at‐half‐maximum (FWHM) of 660 cm‐1. The molar extinction coefficient is as large as 131,000 M‐1cm‐1. The substituents could not perturb the electronic properties of the hexarylene because aryl groups are perpendicular to the hexarylene core and the carbon atoms at 2,5,16,19‐positions have negligible coefficients on its HOMO and LUMO, estimated by theoretical calculations. As a result, the hexarylene having less absorption at the visible light region was stable enough in solution under the LED room light for more than 1 week. This strategy gives a useful guideline to establish the near‐infrared materials that exhibit stability under ambient conditions.