화학공학소재연구정보센터
Inorganic Chemistry, Vol.58, No.13, 8622-8632, 2019
How Does the Fluorination of the Linker Affect the Stability of Trimesate-Based Coordination Polymers and Metal-Organic Frameworks?
The syntheses and crystal structures of the monopotassium salts of difluorinated and tri/perfluorinated trimesic acid (1,3,5-benzenetricarboxylic acid H3BTC) are presented, namely, K(H(2)dF-BTC) (Fdd2, Z = 16) and K(H(2)pF-BTC) (Cc, Z = 4). For the first time, together with already known K(H(2)mF-BTC), all fluorination degrees of trimesic acid are accessible and can be used for a systematic study of the influence of fluorination on the stability of the resulting coordination polymers and metal-organic frame- works (MOFs). The monopotassium salts show a decreasing (chemical) stability in water upon heating, as well as a decreasing thermal stability, as evidenced by differential scanning calorimetry/ thermogravimetric analysis (DSC/TGA). A similar decreasing thermal stability is found for two series of isostructural coordination polymers (UHM-33 topology: (2)(infinity)[Cu-2(L)(2)(DMA)(2)]center dot 2DMA with L2-= HmF-BTC2- and HdF-BTC2- and MOFs ((3)(infinity)[Ba(L)-O-2)(2)]center dot 1/2H(2)O with L2- = HBTC2-' HmF-BTC2- and HdF-BTC2-). Remarkably, while the decomposition temperatures decrease with increasing fluorination of the linker, the releasing temperatures for embedded solvent molecules (DMA and H2O, respectively) increase. To identify possible candidates for the synthesis of isostructural coordination polymers and MOFs with BTC3- ligands with different degrees of fluorination, a database-adapted approach was developed, which utilizes the increased torsion angle between the carboxylate groups and the phenyl rings in these materials as a structure-determining parameter.