Synthesis of Highly Twisted, Nonplanar Aromatic Macrocycles Enabled by an Axially Chiral 4,5-Diphenylphenanthrene Building Block
Synthesis of Highly Twisted, Nonplanar Aromatic Macrocycles Enabled by an Axially Chiral 4,5-Diphenylphenanthrene Building Block
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DOI：
10.1021/jacs.9b13549
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发表时间：
2020-02-12
影响因子：
15
通讯作者：
Itami, Kenichiro
中科院分区：
文献类型：
--
作者：
Li, Yuanming;Yagi, Akiko;Itami, Kenichiro
介绍了高扭曲、非平面芳香大环化合物的合成、结构和性质。这些大环具有约90度的扭转角，通过一种有效的合成方法，通过四重Suzuki-Miyaura偶联的4，5-二芳基菲，一种新的轴向手性非平面建筑块合成。通过改变作为间隔基的交叉偶联伙伴，合成了一系列扭曲大环，从而系统地研究了间隔基对大环形状和物理性质的影响。例如，一个独特的大环聚集诱导发射（AIE）发射体与双四苯乙烯单元作为间隔很容易合成。此外，由于其构象受限的扭曲结构，3，6-二取代-1，8-萘酰亚胺掺入的大环显示出显着的溶剂化荧光，具有高的荧光量子产率。这些大环化合物优异的构象稳定性进一步使完全的对映体拆分和表征成为可能。实验测定了大环化合物的外消旋反应势垒，并得到了DFT计算的支持。
The synthesis, structures, and properties of highly twisted, nonpianar aromatic macrocycles are described. These macrocycles with an approximately 90 degrees twist angle were synthesized by an effective synthetic approach through a quadruple Suzuki-Miyaura coupling of 4,5-bisarylphenanthrene, a novel axially chiral nonplanar building block. By varying the cross-coupling partner as the spacer, a family of twisted macrocycles was synthesized, allowing for a systematic study of the effect of the spacer on macrocycle shape and photophysical properties. For example, a unique macrocyclic aggregation-induced emission (AIE) emitter with double tetraphenylethylene units as the spacers was readily synthesized. Furthermore, attributed to its conformationally restricted twisted structure, a 3,6-disubstituted-1,8-naphthalimide-incorporated macrocycle showed remarkable solvatofluorochromism with high fluorescence quantum yields. The excellent conformational stability of these macrocycles further enabled complete enantiomeric resolution and characterization. The racemization barrier of macrocycle was determined experimentally and supported by DFT calculations.