MOFs (metal-organic frameworks) based on fluorinated and perfluorinated aromatic carboxylate ligands: directed synthesis, structures, and properties

基于氟化和全氟化芳香族羧酸酯配体的 MOF（金属有机框架）：定向合成、结构和性能

• 批准号: 397947979
• 负责人: Professor Dr. Uwe Ruschewitz
• 金额: --
• 依托单位: Institut für Anorganische Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2018
• 资助国家: 德国
• 起止时间: 2017-12-31 至 2022-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/397947979?language=en
• 关键词: MOFs; metal; organic; frameworks; based

MOFs (metal-organic frameworks) and coordination polymers (CPs) are an intensely studied research area of modern solid state and materials chemistry. Recently, attempts have been made to optimize the gas storage and separation properties of these compounds by incorporating partial and perfluorinated linker ligands. Also in terms of thermal and chemical stability, these modified materials are expected to have improved properties. However, the references in the literature, whether this is actually successful, are contradictory, since there are only few isostructural MOFs with different degrees of fluorination at which comparative investigations can be carried out.We present a concept based on a simple structural parameter, namely the torsion angle between the carboxylate group and the phenyl ring, which makes it possible to selectively prepare isostructural MOFs with aromatic carboxylate ligands with different degrees of fluorination. Comparative investigations on the chemical and thermal stability as well as the gas adsorption properties for different polar and non-polar gases shall be carried out on these MOFs thus synthesized. In particular, the changed polarity within the MOF pore is important due to the fluorination of the ligand. A simple experiment was developed, which allows the polarity changes to be determined by the incorporation of a solvatochromic dye into the MOF pores. These results shall be correlated with measurements of the contact angle to determine the hydrophobicity of the respective MOFs and theoretical calculations (in cooperation).

金属有机骨架和配位聚合物是现代固体化学和材料化学的研究热点。最近，已经尝试通过引入部分和全氟化的连接体配体来优化这些化合物的气体储存和分离性质。此外，在热稳定性和化学稳定性方面，这些改性材料预计将具有改进的性能。然而，文献中的参考文献，这是否实际上是成功的，是矛盾的，因为只有少数同构的MOFs具有不同程度的可比较的研究，我们提出了一个概念，基于一个简单的结构参数，即扭转角之间的羧酸基团和苯环，这使得可以选择性地制备具有不同取代度的芳族羧酸酯配体的同构MOF。将对由此合成的这些MOFs进行化学和热稳定性以及对不同极性和非极性气体的气体吸附性能的比较研究。特别地，由于配体的极性变化，MOF孔内的极性变化是重要的。开发了一个简单的实验，其允许通过将溶剂化显色染料掺入到MOF孔中来确定极性变化。这些结果应与接触角的测量结果相关联，以确定相应MOF的疏水性和理论计算（合作）。