当前位置：
X-MOL 学术
›
Chem. Eur. J.
›
论文详情
Our official English website, www.x-mol.net, welcomes your
feedback! (Note: you will need to create a separate account there.)
Boron-Nitrogen-Doped Nanographenes: A Synthetic Tale from Borazine Precursors.
Chemistry - A European Journal ( IF 3.9 ) Pub Date : 2020-03-24 , DOI: 10.1002/chem.201905794 Jacopo Dosso 1 , Tommaso Battisti 1 , Benjamin D Ward 1 , Nicola Demitri 2 , Colan E Hughes 1 , P Andrew Williams 1 , Kenneth D M Harris 1 , Davide Bonifazi 1
Chemistry - A European Journal ( IF 3.9 ) Pub Date : 2020-03-24 , DOI: 10.1002/chem.201905794 Jacopo Dosso 1 , Tommaso Battisti 1 , Benjamin D Ward 1 , Nicola Demitri 2 , Colan E Hughes 1 , P Andrew Williams 1 , Kenneth D M Harris 1 , Davide Bonifazi 1
Affiliation
|
In this work, a comprehensive account of the authors' synthetic efforts to prepare borazino-doped hexabenzocoronenes by using the Friedel-Crafts-type electrophilic aromatic substitution is reported. Hexafluoro-functionalized aryl borazines, bearing an ortho fluoride leaving group on each of the N- and B-aryl rings, was shown to lead to cascade-type electrophilic aromatic substitution events in the stepwise C-C bond formation, giving higher yields of borazinocoronenes than those obtained with borazine precursors bearing fluoride leaving groups at the ortho positions of the B-aryl substituents. By using this pathway, an unprecedented boroxadizine-doped PAH featuring a gulf-type periphery could be isolated, and its structure proven by single-crystal X-ray diffraction analysis. Mechanistic studies on the stepwise Friedel-Crafts-type cyclization suggest that the mechanism of the planarization reaction proceeds through extension of the π system. To appraise the doping effect of the boroxadizine unit on the optoelectronic properties of topology-equivalent molecular graphenes, the all-carbon and pyrylium PAH analogues, all featuring a gulf-type periphery, were also prepared. As already shown for the borazino-doped hexabenzocoronene, the replacement of the central benzene ring by its B3 N2 O congener widens the HOMO-LUMO gap and dramatically enhances the fluorescence quantum yield.
中文翻译：
硼氮掺杂纳米石墨烯：硼嗪前体的合成物。
在这项工作中，报告了作者通过使用Friedel-Crafts型亲电芳香族取代基制备硼氮杂掺杂的六苯并甲酮的综合努力。已显示在N-和B-芳基环的每个环上均带有邻氟离去基团的六氟官能化芳基硼嗪在逐步CC键形成中导致级联型亲电子芳族取代事件，从而使硼氮杂ino酮的收率更高。用在B-芳基取代基的邻位带有氟离去基团的硼嗪前驱体制得。通过这种途径，可以分离出具有海湾型外围特征的空前的掺有硼环二嗪的PAH，并通过单晶X射线衍射分析证明了其结构。对逐步Friedel-Crafts型环化的机理研究表明，平面化反应的机理是通过π系统的延伸进行的。为了评估硼环二嗪单元对拓扑等效分子石墨烯的光电性能的掺杂效果，还制备了均具有海湾型外围的全碳和吡啶鎓PAH类似物。如已经针对掺有硼氮杂硅的六苯并二苯所显示的那样，用其B3 N2 O同系物取代中心苯环会扩大HOMO-LUMO间隙，并显着提高荧光量子产率。还制备了均具有海湾型外围的全碳和吡啶鎓PAH类似物。如已经针对掺有硼氮杂硅的六苯并二苯所显示的那样，用其B3 N2 O同系物取代中心苯环会扩大HOMO-LUMO间隙，并显着提高荧光量子产率。还制备了全碳和吡咯PAH类似物，均具有海湾型外围。如已经针对掺有硼氮杂硅的六苯并二苯所显示的那样，用其B3 N2 O同系物取代中心苯环会扩大HOMO-LUMO间隙，并显着提高荧光量子产率。
更新日期：2020-02-05
中文翻译：
硼氮掺杂纳米石墨烯：硼嗪前体的合成物。
在这项工作中，报告了作者通过使用Friedel-Crafts型亲电芳香族取代基制备硼氮杂掺杂的六苯并甲酮的综合努力。已显示在N-和B-芳基环的每个环上均带有邻氟离去基团的六氟官能化芳基硼嗪在逐步CC键形成中导致级联型亲电子芳族取代事件，从而使硼氮杂ino酮的收率更高。用在B-芳基取代基的邻位带有氟离去基团的硼嗪前驱体制得。通过这种途径，可以分离出具有海湾型外围特征的空前的掺有硼环二嗪的PAH，并通过单晶X射线衍射分析证明了其结构。对逐步Friedel-Crafts型环化的机理研究表明，平面化反应的机理是通过π系统的延伸进行的。为了评估硼环二嗪单元对拓扑等效分子石墨烯的光电性能的掺杂效果，还制备了均具有海湾型外围的全碳和吡啶鎓PAH类似物。如已经针对掺有硼氮杂硅的六苯并二苯所显示的那样，用其B3 N2 O同系物取代中心苯环会扩大HOMO-LUMO间隙，并显着提高荧光量子产率。还制备了均具有海湾型外围的全碳和吡啶鎓PAH类似物。如已经针对掺有硼氮杂硅的六苯并二苯所显示的那样，用其B3 N2 O同系物取代中心苯环会扩大HOMO-LUMO间隙，并显着提高荧光量子产率。还制备了全碳和吡咯PAH类似物，均具有海湾型外围。如已经针对掺有硼氮杂硅的六苯并二苯所显示的那样，用其B3 N2 O同系物取代中心苯环会扩大HOMO-LUMO间隙，并显着提高荧光量子产率。
京公网安备 11010802027423号