Liu Huiling, Guo Jimin, Che Tiantian, Ding Changhua, Xu Bin, Tan Qitao
Department of Chemistry, College of Sciences, Shanghai Engineering Research Center of Organ Repair, Joint International Research Laboratory of Biomaterials and Biotechnology in Organ Repair (Ministry of Education), School of Medicine, Shanghai University, Shanghai, 200444, China.
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, 200032, China.
Angew Chem Int Ed Engl. 2025 Aug 11;64(33):e202506862. doi: 10.1002/anie.202506862. Epub 2025 Jun 23.
A nitrogen-containing graphenic buckybowl (3N-HBC) has been synthesized through pentagonal cyclization at the bay positions of hexa-peri-hexabenzocoronene (p-HBC) using a Pd-catalyzed dehydrogenative cycloamination as a key step. The incorporation of three pyrrole rings to the periphery of the bowl endows it with strong electron-rich character, showing three reversible oxidations in cyclic voltammetry (CV), and thus could be progressively oxidized into cationic radical and high-charged species upon gradual addition of the oxidant. Interestingly, the cationic radical was also generated by acids, which could be significantly accelerated by light, whether under an air or inert atmosphere. 3N-HBC exhibits interesting properties that arise from its electron-rich character and the unique curved geometry. 3N-HBC proved to be a superior organic photocatalyst for the conversion of 2-isocyanobiphenyl to phenanthridine derivatives at 1.0 mol% catalytic loading under blue LEDs irradiation. Furthermore, the electron-donating nature and curved π-surface of 3N-HBC enable its association with fullerenes (C and C) in solution and solid states. This work also demonstrates that nanographene sheets can be bent to π-bowls through the introduction of a few pentagons containing small-sized heteroatoms to their bay regions.
通过在六并六苯（p-HBC）的间位进行五边形环化反应，以钯催化的脱氢环胺化反应为关键步骤，合成了一种含氮的石墨烯巴基碗（3N-HBC）。在碗状结构的外围引入三个吡咯环赋予其强富电子特性，在循环伏安法（CV）中显示出三次可逆氧化，因此在逐渐加入氧化剂时可逐步氧化为阳离子自由基和高电荷物种。有趣的是，阳离子自由基也可由酸产生，无论在空气还是惰性气氛下，光照均可显著加速这一过程。3N-HBC因其富电子特性和独特的弯曲几何形状而表现出有趣的性质。在蓝色发光二极管照射下，3N-HBC在1.0 mol%的催化负载量下被证明是将2-异氰基联苯转化为菲啶衍生物的优异有机光催化剂。此外，3N-HBC的供电子性质和弯曲的π表面使其能够在溶液和固态中与富勒烯（C和C）缔合。这项工作还表明，通过在纳米石墨烯片的间位区域引入一些含有小尺寸杂原子的五边形，可以将其弯曲成π碗状。
