Li Hui, Chang Jianhong, Li Shanshan, Guan Xinyu, Li Daohao, Li Cuiyan, Tang Lingxue, Xue Ming, Yan Yushan, Valtchev Valentin, Qiu Shilun, Fang Qianrong
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University , Changchun 130012 , People's Republic of China.
Department of Chemical and Biomolecular Engineering , Center for Catalytic Science and Technology, University of Delaware , Newark , Delaware 19716 , United States.
J Am Chem Soc. 2019 Aug 28;141(34):13324-13329. doi: 10.1021/jacs.9b06908. Epub 2019 Aug 15.
The functionalization of three-dimensional (3D) covalent organic frameworks (COFs) is essential to broaden their applications. However, the introduction of organic groups with electroactive abilities into 3D COFs is still very limited. Herein we report the first case of 3D tetrathiafulvalene-based COFs (3D-TTF-COFs) with non- or 2-fold interpenetrated topology and tunable electrochemical activity. The obtained COFs show high crystallinity, permanent porosity, and large specific surface area (up to 3000 m/g). Furthermore, these TTF-based COFs are redox active to form organic salts that exhibit tunable electric conductivity (as high as 1.4 × 10 S cm at 120 °C) by iodine doping These results open a way toward designing 3D electroactive COF materials and promote their applications in molecular electronics and energy storage.
三维（3D）共价有机框架（COF）的功能化对于拓宽其应用至关重要。然而，将具有电活性的有机基团引入3D COF的情况仍然非常有限。在此，我们报道了首例具有非互穿或二重互穿拓扑结构以及可调电化学活性的基于三维四硫富瓦烯的COF（3D-TTF-COF）。所获得的COF表现出高结晶度、永久孔隙率和大比表面积（高达3000 m²/g）。此外，这些基于TTF的COF具有氧化还原活性，通过碘掺杂形成具有可调电导率（在120°C时高达1.4×10⁻³ S/cm）的有机盐。这些结果为设计3D电活性COF材料开辟了一条道路，并促进了它们在分子电子学和能量存储中的应用。
