文献类型：期刊文献

英文题名：Narrow-Pore Engineering of Vinylene-Linked Covalent Organic Frameworks with Weak Interaction-Triggered Multiple Responses

作者：Zhu, Lin[1,2];Zhang, Qian[3];Meng, Fancheng[1];Li, Mengqi[1];Liang, Qifeng[2];Zhang, Fan[1]

机构：[1]Shanghai Jiao Tong Univ, Shanghai Electrochem Energy Devices Res Ctr, Sch Chem & Chem Engn, State Key Lab Met Matrix Composites, 800 Dongchuan Rd, Shanghai 200240, Peoples R China;[2]Shaoxing Univ, Dept Phys, 508 Huanchengxi Rd, Shaoxing 312000, Peoples R China;[3]Shanghai Jiao Tong Univ, Sch Sensing Sci & Engn, Sch Elect Informat & Elect Engn, 800 Dongchuan Rd, Shanghai 200240, Peoples R China

年份：2023

外文期刊名：ANGEWANDTE CHEMIE-INTERNATIONAL EDITION

收录：SCI-EXPANDED(收录号：WOS:001060393600001)、、EI(收录号：20233614697436)、Scopus(收录号：2-s2.0-85169900290)、WOS

基金：We thank the Science and Technology Commission of Shanghai Municipality (20JC1414900), the National Natural Science Foundation of China (22271188, 82272821, 22075178 and 22005189), Natural Science Foundation of Shanghai (No. 22ZR1467600), Zhejiang Provincial Postdoctoral Research program (ZJ2021108).

语种：英文

外文关键词：Colorimetric Detection; Covalent Organic Frameworks; Ultramicropores; Vinylene Linkages; Weak Interactions

外文摘要：Vinylene-linked covalent organic frameworks (COFs) are emerging as promising crystalline materials, but their narrow pore engineering is severely impeded by the weak reversibility of the carbon-carbon double bond formation reaction, which has led to less exploration of their ultramicroporous structures and properties. Herein, we developed a single aromatic ring-based tetratopic monomer, tetramethylpyrazine, which undergoes a smooth Knoevenegal condensation at its four arylmethly carbon atoms with linear aromatic dialdehyde monomers upon the self-catalyzed activation of pyridine nitrogen-containing monomers in the presence of an organic anhydride. This has resulted in the formation of two vinylene-linked COFs, which both crystallized in orthorhombic lattices, and layered in AA stacking fashions along the vertical directions. They exhibit high surface areas and well-tailored ultramicropore sizes up to 0.5 nm. The unique cross-linking mode at two pairs of para-positions of each pyrazine unit through carbon-carbon double bonds afford them with & pi;-extended conjugation over the in-plane backbones and substantial semiconducting characters. The resultant COFs can be well-dispersed in water to form stable sub-microparticles with negative charges (zeta potentials: ca. -30 mV), and exhibiting tunable aggregation behaviors through protonation/deprotonation. As a consequence, they exhibit pore-size-dependent colorimetric responses to various anions with different pKa values in high selectivity. Two vinylene-linked COF with narrow pore sizes of less than 1 nm were constructed by the condensation of tetramethylpyrazine as the smallest tetratopic monomer with linear aromatic dialdehyde monomers. Their aggregates in water feature negative charges and can be tuned through protonation/deprotonation, to give pore-size-dependent colorimetric responses to various anions with different pKa values with high selectivity.+image