Investigating a Seemingly Simple Imine-Linked Covalent Organic Framework Structure,Journal of the American Chemical Society

当前位置： X-MOL 学术 › J. Am. Chem. Soc. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

Investigating a Seemingly Simple Imine-Linked Covalent Organic Framework Structure
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2024-12-12 , DOI: 10.1021/jacs.4c16678
Cailing Chen ₁ , Li Cao ₁ , Yaozu Liu ₂ , Zhihao Li _{3,

4,

5} , Zhen-Hua Li ₂ , Guojun Zhou ₆ , Daliang Zhang ₇ , Xuehai Huang _{3,

4,

5} , Yu Wang _{3,

4,

5} , Guanxing Li ₁ , Lingmei Liu ₇ , You-You Yuan ₈ , Yaping Zhang ₈ , Qingxiao Wang ₈ , Yiqiang Chen ₈ , Zhan Shi ₂ , Qianrong Fang ₂ , Zhehao Huang _{3,

4,

9} , Zhiping Lai ₁ , Yu Han _{3,

4,

9,

10}

Affiliation

Physical Science and Engineering Division (PSE), Advanced Membranes and Porous Materials (AMPM) Center, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia.
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, China.
School of Emergent Soft Matter, South China University of Technology, Guangzhou 510640, China.
Center for Electron Microscopy, South China University of Technology, Guangzhou 510640, China.
Guangdong Provincial Key Laboratory of Functional and Intelligent Hybrid Materials and Devices, South China Advanced Institute for Soft Matter Science and Technology, South China University of Technology, Guangzhou 510640, China.
Department of Materials and Environmental Chemistry, Stockholm University, Stockholm SE-10691, Sweden.
Multi-scale Porous Materials Center, Institute of Advanced Interdisciplinary Studies & School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044, China.
Imaging and Characterization Core Lab, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Saudi Arabia.
Guangdong Basic Research Center of Excellence for Energy & Information Polymer Materials, Guangzhou 510640, China.
State Key Laboratory of Pulp and Paper Engineering, South China University of Technology, Guangzhou 510640, China.

The structures of covalent organic frameworks (COFs) are typically determined through modeling based on powder X-ray diffraction. However, the intrinsically limited crystallinity of COFs often results in structural determinations of low fidelity. Here, we present real-space imaging of an extensively studied two-dimensional imine-based COF. Contrary to the conventional understanding that this COF features uniform hexagonal pores, our observations reveal the presence of two distinct sets of pores with differences in shape and size. Motivated by this finding, we conducted reciprocal-space characterizations, complemented by solid-state nuclear magnetic resonance spectroscopy and density functional theory calculations, to reevaluate this seemingly simple structure. The collective results allow for the establishment of a new structural model for this landmark COF and its derivatives, differing from the conventional model in both intra- and interlayer configurations. Furthermore, we identified various previously unrecognized defective structures through real-space imaging, which have significant implications for COF applications in separation and catalysis. Our study demonstrates the complexity and heterogeneity of COF structures, while also highlighting the imperative for structural reevaluation using advanced characterization techniques.

中文翻译：

研究看似简单的亚胺连接的共价有机框架结构

共价有机框架（COF）的结构通常是通过基于粉末 X 射线衍射的建模来确定的。然而，COF 的固有有限结晶度通常会导致低保真度的结构测定。在这里，我们展示了一种广泛研究的基于二维亚胺的 COF 的真实空间成像。与这种 COF 具有均匀的六边形孔的传统理解相反，我们的观察揭示了存在两组形状和大小不同的不同孔。在这一发现的推动下，我们进行了倒易空间表征，并辅以固态核磁共振波谱和密度泛函理论计算，以重新评估这个看似简单的结构。集体结果允许为这个具有里程碑意义的 COF 及其衍生物建立一个新的结构模型，在层内和层间配置上都与传统模型不同。此外，我们通过实空间成像鉴定了各种以前未被识别的缺陷结构，这对分离和催化中的 COF 应用具有重要意义。我们的研究证明了 COF 结构的复杂性和异质性，同时也强调了使用先进的表征技术进行结构重新评估的必要性。

更新日期：2024-12-12

点击分享查看原文

点击收藏

阅读更多本刊新发论文本刊介绍/投稿指南