Sano Yuki, Toyoda Ryojun, Chida Koki, Yoshii Takeharu, Nishihara Hirotomo, Nishina Yuta, Asanoma Daisuke, Takaishi Shinya, Sugimoto Kunihisa, Sakamoto Ryota
Department of Chemistry, Graduate School of Science, Tohoku University, 6-3 Aza-Aoba, Aramaki, Sendai 980-8578, Japan.
Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, 2-1-1 Katahira, Aoba, Sendai, Miyagi 980-8577, Japan.
ACS Appl Mater Interfaces. 2024 Aug 14;16(32):42615-42622. doi: 10.1021/acsami.4c06959. Epub 2024 Aug 5.
Porous materials synthesized through bottom-up approaches, such as metal-organic frameworks and covalent organic frameworks, have attracted attention owing to their design flexibility for functional materials. However, achieving the chemical and thermal stability of these materials for various applications is challenging considering the reversible coordination bonds and irreversible covalent bonds in their frameworks. Thus, ordered carbonaceous frameworks (OCFs) emerge as a promising class of bottom-up materials with good periodicity, thermal and chemical stability, and electrical conductivity. However, a few OCFs have been reported owing to the limited range of precursor molecules. Herein, we designed a hexaazatrinaphthylene-based molecule with enediyne groups as a precursor molecule for synthesizing an OCF. The solid-state Bergman cyclization of enediyne groups at a low temperature formed a microporous polymer and an OCF, exhibiting redox activity and demonstrating their potential for electrochemical applications. The microporous polymer was used as an active material in sodium-ion batteries, while the OCF was used as an electrochemical capacitor. These findings illustrate the utility of the Bergman cyclization reaction for synthesizing microporous polymers and OCFs with a customizable functionality for broad applications.
通过自下而上的方法合成的多孔材料，如金属有机框架和共价有机框架，因其对功能材料的设计灵活性而受到关注。然而，考虑到其框架中的可逆配位键和不可逆共价键，要实现这些材料在各种应用中的化学和热稳定性具有挑战性。因此，有序碳质框架（OCF）作为一类有前途的自下而上材料出现，具有良好的周期性、热稳定性和化学稳定性以及导电性。然而，由于前驱体分子范围有限，报道的OCF较少。在此，我们设计了一种带有烯二炔基团的六氮杂三亚萘基分子作为合成OCF的前驱体分子。烯二炔基团在低温下的固态伯格曼环化反应形成了一种微孔聚合物和一种OCF，展现出氧化还原活性并证明了它们在电化学应用中的潜力。该微孔聚合物用作钠离子电池的活性材料，而OCF用作电化学电容器。这些发现说明了伯格曼环化反应在合成具有可定制功能以用于广泛应用的微孔聚合物和OCF方面的实用性。
