通过碳硫键活化合成聚合诱导发射分子的一般方法

Aggregate Pub Date : 2024-08-23 DOI:10.1002/agt2.650
Bowei Ma, Xinyu Liang, Gu Xu, Guanghao Zhang, Lutang Zhao, Liangzhuo Ma, Wenbin Xie, Xiang Li, Qinqin Shi, Kaikai Wen, Hui Huang
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摘要

聚取代烯烃是最重要的聚合诱导发光发光剂(AIEgens)之一,由于其在化学和生物传感、生物成像和光电子学方面的各种应用而备受关注。然而,这些烯烃的合成方法仍然有限,阻碍了 AIEgens 的发展。本研究介绍了从天然丰富的硫醚和酮中提取芳基锍三氯酸盐和对甲苯磺酰肼的一种前所未有的交叉偶联反应。这种方法的通用性体现在可以轻松合成 40 多种多取代烯烃。重要的是,这些 AIEgens 的发光特性(如量子产率和发射颜色)可以通过调整亲电子基质和亲核基质的取代基来轻松调节,在生物成像方面表现出卓越的性能。值得注意的是,机理研究揭示了 β-H 消去在双键形成过程中的关键作用。这一贡献为合成多取代烯烃提供了一种有效的方法,推动了 AIEgens 的发展。
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General method to synthesize aggregation‐induced emission molecules via carbon‐sulfur bond activation
Poly‐substituted olefins, one of the most important aggregation‐induced emission luminogens (AIEgens), have garnered significant attention due to their various applications in chemical‐ and bio‐sensing, bio‐imaging, and opto‐electronics. However, the synthetic methods for these olefins remain limited, impeding the progress of AIEgens. This study introduces an unprecedented cross‐coupling reaction between aryl sulfonium triflates and tosylhydrazones from naturally abundant thioethers and ketones. The generality of this method is exemplified by the facile synthesis of over forty poly‐substituted olefins. Importantly, the luminescent properties of these AIEgens (e.g., quantum yield and emission color) can be easily tuned by adjusting the substituents of the electrophile and nucleophile substrates, exhibiting excellent performance in bio‐imaging. Notably, the mechanistic studies reveal the critical role of β‐H elimination in the formation of the double bond. This contribution provides an efficient method to synthesize poly‐substituted olefins, pushing forward the development of AIEgens.
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