Kharlamova Alisa D, Ermakova Elizaveta V, Abel Anton S, Gontcharenko Victoria E, Cheprakov Andrei V, Averin Alexei D, Beletskaya Irina P, Andraud Chantal, Bretonnière Yann, Bessmertnykh-Lemeune Alla
Lomonosov Moscow State University, Department of Chemistry, Leninskie Gory, 1-3, Moscow 119991, Russia.
Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Leninsky Pr. 31, Moscow 119071, Russia.
Org Biomol Chem. 2024 Jun 26;22(25):5181-5192. doi: 10.1039/d4ob00558a.
The development of luminescent molecular materials has advanced rapidly in recent decades, primarily driven by the synthesis of novel emissive compounds and a deeper understanding of excited-state mechanisms. Herein, we report a streamlined synthetic approach to light-emitting diazapolyoxa- and polyazamacrocycles NCOQ and NCQ ( = 3-10; = 2, 3; = 2-5), incorporating a 2,3-diphenylquinoxaline residue (DPQ). This synthetic strategy based on macrocyclization through Pd-catalyzed amination reaction yields the target macrocycles in good or high yields (46-92%), enabling precise control over their structural parameters. A key role of the PhPF-Bu ligand belonging to the JosiPhos series in this macrocyclization was elucidated through DFT computation. This macrocyclization reaction eliminates the need for complex protecting-deprotecting procedures of secondary amine groups, offering a convenient and scalable method for the preparation of target compounds. Moreover, it boasts a potentially broad substrate scope, making it promising for structure-properties studies within photophysics, sensor development, and material synthesis. Photophysical properties of representative macrocycles were investigated, employing spectroscopic techniques and DFT computation. It was demonstrated that DPQ-containing macrocycles display aggregation-induced emission in a DCM-hexane solvent mixture despite the presence of flexible tethers within their structures. Single-crystal X-ray diffraction analysis of a representative compound NCOQ allowed us to gain deeper insight into its molecular structure and AIE behaviour. The emissive aggregates of the NCOQ macrocycle were immobilized on filter paper yielding AIE-exhibiting test strips for measuring acidity in vapors and in aqueous media.
近几十年来，发光分子材料的发展迅速，这主要得益于新型发光化合物的合成以及对激发态机制的更深入理解。在此，我们报道了一种简化的合成方法，用于制备含2,3-二苯基喹喔啉残基（DPQ）的发光二氮杂聚氧化和聚氮杂大环化合物NCOQ和NCQ（ = 3 - 10； = 2, 3； = 2 - 5）。这种基于钯催化胺化反应进行大环化的合成策略能够以良好或较高的产率（46 - 92%）得到目标大环化合物，从而能够精确控制其结构参数。通过密度泛函理论（DFT）计算阐明了JosiPhos系列的PhPF - Bu配体在该大环化反应中的关键作用。这种大环化反应无需对仲胺基团进行复杂的保护 - 脱保护步骤，为制备目标化合物提供了一种便捷且可扩展的方法。此外，它具有潜在广泛的底物范围（适用范围），在光物理、传感器开发和材料合成的结构 - 性质研究方面具有广阔前景。利用光谱技术和DFT计算研究了代表性大环化合物的光物理性质。结果表明，尽管其结构中存在柔性连接链，但含DPQ的大环化合物在二氯甲烷 - 己烷混合溶剂中表现出聚集诱导发光现象。对代表性化合物NCOQ进行单晶X射线衍射分析，使我们能够更深入地了解其分子结构和聚集诱导发光行为。将NCOQ大环化合物的发光聚集体固定在滤纸上，得到用于测量蒸汽和水性介质中酸度的具有聚集诱导发光性能的测试条。
