Switchable Dynamics and Flexibility in Gas-absorptive Porous Materials

Our approach is to design porosity in combination with switchable dynamics and flexibility in porous materials for gaining control over gas capture and selectivity. This approach was made possible by fabricating rotor-on-axel molecular struts and tetrahedral building blocks. Ultra-fast molecular rotors as fast as 1011 Hz were engineered in porous crystalline frameworks (molecular crystals, MOFs and mesoporous organosilicas) containing rod-like linkers as amphidynamic elements. The porous frameworks promise access to the control of rotary motion by chemical and physical stimuli. If a gas or a vapor is diffused to the cavities, such as CO 2, iodine and hydrocarbon vapors, rotor dynamics is hampered. In turn, on/off switching produces modulated physical responses. When C-F dipoles were mounted on the rotors, they induced fast oscillating dipoles that interact with an applied electric field. Direct evidence of hostguest interactions at the molecular level were established by 2D solid-state NMR. We achieved the fabrication of swellable porous adamantoid frameworks by the use of highly symmetrical tetrahedral elements and the co-operation of 8 surrounding hydrogen bonds mounted on conformationally flexible groups. The flexibility of the porous crystals manifests itself in response to stimuli of selected gases: CO2, Xe and hexane triggers the enlargement of channel cross-section. The accomodation of CO2 and Xe in the channel chambers was revealed by synchrotron-light XRD, combined with modelling. Xenon dynamics was gathered by 129Xe NMR chemical shift anisotropy profiles, which encode the shape and orientation of each visited cavity. Jump rate and activation energy experienced by exploring Xe atoms were uniquely established. Covalent connection of tetrahedral nodes results in expandable frameworks, especially if 3 instead of all 4 branches are cross-linked: the forth branch can be dedicated to bearing a functional group to catch the gas molecules (CO 2 is retained by –NH2 group by an energy as high as 54 kJ/mol). Moreover, photo-responsive molecular crystals were fabricated by tetrahedral azobenzene tetramers that form porous molecular crystals in their trans configuration. The efficient trans-to-cis photoisomerization converts the crystals into a non-porous phase but crystallinity and porosity are restored upon reverse isomerization promoted by heat. We demonstrated that the photo-isomerization enables reversible on/off switching of optical properties as well as CO2 capture from the gas phase. We thank Cariplo Foundation, Lombardy Region/INSTM Consortium and PRIN 2016. References 1. Acc.Chem.Res.2016,49,1701; 2. Chem.Eur.J. 2017,23,11210; 3. J.Am.Chem.Soc.2014,136,618; 4. Angew.Chem.Int.Ed. 2014,53,1043. 5. Chem.Comm.2017,53,7776; 6. J.Mater.Chem.A2018,6,14231; 7. Chem.Comm. DOI:10.1039/C8CC03951H; 8. NatureChem. 2015,7,634.