Reticular Synthesis of Flexible Rare-Earth Metal-Organic Frameworks: Control of Structural Dynamics and Sorption Properties Through Ligand Functionalization

An exciting direction in metal-organic frameworks involves the design and synthesis of flexible structures which can reversibly adapt their structure when triggered by external stimuli. Controlling the extent and nature of response in such solids is critical in order to develop custom dynamic materials for advanced applications. Towards this, it is highly important to expand the diversity of existing flexible MOFs, generating novel materials and gain an in-depth understanding of the associated dynamic phenomena, eventually unlocking key structure-property relationships. In the present work, we successfully utilized reticular chemistry for the construction of two novel series of highly crystalline, flexible rare-earth MOFs, RE-thc-MOF-2 and RE-teb-MOF-1. Extensive single-crystal to single-crystal structural analyses coupled with detailed gas and vapor sorption studies, shed light onto the unique responsive behavior. The development of these series is related to the reported RE-thc-MOF-1 solids which were found to display a unique continuous breathing and gas-trapping property. The synthesis of RE-thc-MOF-2 and RE-teb-MOF-1 materials represents an important milestone as they provide important insights into the key factors that control the responsive properties of this fascinating family of flexible materials and demonstrates that it is possible to control their dynamic behavior and the associated gas and vapor sorption properties. Control of the dynamic effects in flexible metal-organic frameworks (MOFs) is critical towards engineering custom responsive materials. In this work, two novel families of flexible MOFs based on rare-earth metals were developed. The breathing capabilities and the eventual sorption properties change drastically by slight changes in the organic ligand, leading also to the emergence of unique gas and vapor sorption properties, including rare gas trapping phenomena.image