Zhang Jie, Wang Zitao, Suo Jinquan, Tuo Chao, Chen Fengqian, Chang Jianhong, Zheng Haorui, Li Hui, Zhang Daliang, Fang Qianrong, Qiu Shilun
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130012, P. R. China.
Zhuhai College of Science and Technology, Zhuhai 519041, P. R. China.
J Am Chem Soc. 2024 Dec 25;146(51):35090-35097. doi: 10.1021/jacs.4c10071. Epub 2024 Dec 13.
The synthesis of high-quality single-crystal covalent organic frameworks (COFs) presents significant challenges, particularly in achieving precise control over their morphologies. Herein, we present a straightforward strategy to fine-tune the morphology of COF single crystals. Using rigid triptycene derivatives as the core building blocks and varying the amounts of aniline modulators, we successfully synthesized a series of high-quality COF single crystals with different aspect ratios and well-defined facets, JUC-663-X (X = 30 to 135, the equivalent of aniline). Their structures were characterized using PXRD, TEM, and N adsorption analyses to confirm the structural consistency. The study of the growth mechanism and DFT calculations elucidated the crucial role of aniline as a modulator in facilitating anisotropic competitive binding throughout the crystal growth process. Furthermore, our findings demonstrate that the aspect ratio of these single crystals significantly influences the adsorption properties of Rh B. This research not only paves new paths in the synthesis and morphological control of COF single-crystal materials but also provides profound insights into the relationship between COF morphology and functional performance.
高质量单晶共价有机框架（COF）的合成面临重大挑战，尤其是在精确控制其形态方面。在此，我们提出了一种直接的策略来微调COF单晶的形态。使用刚性三蝶烯衍生物作为核心构建单元，并改变苯胺调节剂的用量，我们成功合成了一系列具有不同纵横比和清晰晶面的高质量COF单晶，即JUC-663-X（X = 30至135，相当于苯胺的量）。使用粉末X射线衍射（PXRD）、透射电子显微镜（TEM）和N吸附分析对其结构进行了表征，以确认结构的一致性。对生长机制的研究和密度泛函理论（DFT）计算阐明了苯胺作为调节剂在整个晶体生长过程中促进各向异性竞争结合的关键作用。此外，我们的研究结果表明，这些单晶的纵横比对罗丹明B（Rh B）的吸附性能有显著影响。这项研究不仅为COF单晶材料的合成和形态控制开辟了新途径，还为COF形态与功能性能之间的关系提供了深刻见解。
