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Construction of a Three-dimensional Covalent Organic Framework via the linker exchange Strategy

Chemical Research in Chinese Universities 2022年第2期38卷 402-408页

作者： CUI Yumeng MIAO Zhuang LIU Qi JIN Fenchun ZHAI Yufeng ZHANG Lingyan WANG Wenli WANG Ke LIU Guiyan ZENG Yongfei Tianjin Key Laboratory of Structure and Performance for Functional Molecules College of ChemistryTianjin Normal UniversityTianjin 300387P.R.China

Covalent organic framework(COF)is a porous crystalline material with a well-controlled structure and a wide range of potential ***,the construction of new COF faces huge challenges,including the design and synthesis of structural unit monomers,the choice of reaction solvent system,and the study of reaction time and ***,it’s particularly important to widen the application scope of synthetic methods and further promote the development of ***,we performed structural transformations in a three-dimensional(3D)COF(COF-300),and Fourier transform infrared spectroscopy(FTIR),power X-ray diffraction analysis(PXRD)and nitrogen adsorption isotherms confirmed the chemical principles and the successful realization of these *** the same time,we found that the interpenetrating structure in 3D COF can be changed through the conversion of *** structure simulation successfully proved the transformation of COF from five-fold to seven-fold *** addition,in order to prove the versatility of this strategy,we used the same method to convert COF-300 into a high crystallinity 3D COF(TJNU-COF-302)that is also seven-fold interpenetrating and has not been *** simple strategy not only makes it easy to obtain a 3D COF connected with imines,which greatly promotes the development of COF,but also provides a new way to develop 3D COFs with complex interpenetrating structures.

关键词： Covalent organic framework(COF) linker exchange Transformation strategy Porosity

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Functionality proportion and corresponding stability study of multivariate metal-organic frameworks

引用

Chinese Chemical Letters 2018年第6期29卷 837-841页

作者： Jie Li Yecheng Wang Yan Yu Qiaowei Li Department of Chemistry iChEM (Collaborative Innovation Center of Chemistry for Energy Materials) Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials Fudan University State Key Laboratory of Coordination Chemistry School of Chemistry and Chemical Engineering Nanjing University School of Physical Science and Technology Shanghai Tech University

Multivariate metal-organic frameworks（MTV-MOFs） with different ratios of terephthalate（BDC） linker and amino-benzenedicarboxylate（BDC-NH2） linker were synthesized through both direct synthesis from linker mixture and linker exchange of activated single-linker MOFs. Functionality proportion was impacted by the thermodynamics during the one-pot MOF construction, resulting in preference of BDC over BDC-NH2 in the MTV-MOF, in agreement with the quantum mechanics calculations. The functionality difference also affects the thermodynamics in the linker exchange process, as indicated by the more effective linker exchange in BDC-NH2-based IRMOF-3 than in BDC-based MOF-5. Furthermore,the thermal decomposition temperatures and chemical integrity upon ambient air exposure of these MOFs with variate functionalities were investigated, and it reveals that higher proportion of BDC in the MTV-MOF crystals contribute to both higher thermal and higher chemical stabilities.

关键词： Multivariate metal-organic frameworks Direct synthesis linker exchange Functionality proportion

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