Chen Yong-Jun, Liu Ming, Chen Jie, Huang Xin, Li Qiao-Hong, Ye Xiao-Liang, Wang Guan-E, Xu Gang
State Key Laboratory of Structural Chemistry, Fujian Provincial Key Laboratory of Materials and Techniques Toward Techniques Toward Hydrogen Energy, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences (CAS) Fuzhou Fujian 350002 P. R. China
University of Chinese Academy of Sciences (UCAS) Beijing 100049 P. R. China.
Chem Sci. 2023 Apr 6;14(18):4824-4831. doi: 10.1039/d3sc00562c. eCollection 2023 May 10.
Dangling bond formation for COF materials in a rational manner is an enormous challenge, especially through post-treatment which is a facile strategy while has not been reported yet. In this work, a "chemical scissor" strategy is proposed for the first time to rationally design dangling bonds in COF materials. It is found that Zn coordination in post-metallization of TDCOF can act as an "inducer" which elongates the target bond and facilitates its fracture in hydrolyzation reactions to create dangling bonds. The number of dangling bonds is well-modulated by controlling the post-metallization time. Zn-TDCOF-12 shows one of the highest sensitivities to NO in all reported chemiresistive gas sensing materials operating under visible light and room temperature. This work opens an avenue to rationally design a dangling bond in COF materials, which could increase the active sites and improve the mass transport in COFs to remarkably promote their various chemical applications.
以合理的方式为共价有机框架(COF)材料形成悬键是一项巨大的挑战,特别是通过后处理这种简便策略来实现,但目前尚未见报道。在这项工作中,首次提出了一种“化学剪刀”策略,用于合理设计COF材料中的悬键。研究发现,TDCOF后金属化过程中的锌配位可作为“诱导剂”,延长目标键并促进其在水解反应中断裂以产生悬键。通过控制后金属化时间,可以很好地调节悬键的数量。在所有报道的在可见光和室温下工作的化学电阻式气体传感材料中,Zn-TDCOF-12对NO的灵敏度最高。这项工作为合理设计COF材料中的悬键开辟了一条途径,这可以增加活性位点并改善COF中的质量传输,从而显著促进其各种化学应用。