Twofold C-H Activation Enables Synthesis of a Diazacoronene-Type Fluorophore with Near Infrared Emission Through Isosteric Replacement
Twofold C-H Activation Enables Synthesis of a Diazacoronene-Type Fluorophore with Near Infrared Emission Through Isosteric Replacement
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DOI：
10.1002/chem.202004080
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发表时间：
2021-01-19
影响因子：
4.3
通讯作者：
Glorius, Frank
中科院分区：
文献类型：
--
作者：
Gressies, Steffen;Ito, Masato;Glorius, Frank
报道了一种可溶性酰胺嵌苯并苯的合成及其物理性质。在该合成中的关键步骤是通过铑（III）Cp* 催化剂的二重C-H活化。这种前所未有的结构基序在近红外区域显示出强烈的荧光，具有小的斯托克斯位移和独特的电子振动结构，其表现出轻微程度的负溶剂化变色。该化合物与一些相关化合物的比较揭示了在包括角位置的外围凹区域中的酰胺掺入的重要性，以保留反映母体晕苯的高芳香性。用刘易斯酸B（C6 F5）（3）处理该化合物，形成双加合物，由于酰胺C-N键的双键特征增加，其表现出增强的芳香性。
The synthesis and photophysical properties of a soluble amide-embedded coronene is reported. The key step in this synthesis is the twofold C-H activation of diazaperylene by a rhodium(III)Cp* catalyst. This unprecedented structural motif shows intense fluorescence in the near infrared region with a small Stokes shift and a distinct vibronic structure, which exhibits a slight extent of negative solvatochromism. Comparison of this compound with some relevant compounds revealed the importance of the amide incorporation in the peripheral concave region including an angular position to retain high aromaticity reflecting that of parent coronene. Treatment of this compound with Lewis acid B(C6F5)(3) formed a bis-adduct, which exhibited enhanced aromaticity as a consequence of the increased double bond character of the amide C-N bonds.