Imparting gas selective and pressure dependent porosity into a non-porous solid: Via coordination flexibility
De Luna, P
MetadataShow full item record
Nandi, S., De Luna, P., Maity, R., Chakraborty, D., Daff, T., Burns, T., Woo, T., & et al. (2019). Imparting gas selective and pressure dependent porosity into a non-porous solid: Via coordination flexibility. Materials Horizons, 6 (9), 1883-1891. https://doi.org/10.1039/c9mh00133f
Using a simple hard-soft acid-base concept we have deliberately designed gas-specific and pressure dependent porosity into a non-porous solid via coordination flexibility. This creates distinct gate-openings wherein the CO2 molecule opens-up the framework pores by rotating the ligand about the weaker hard-soft bonds (hard-soft gate control). For this, we have studied the CO2 gating behaviour of M(4-PyC)2 (M = Mg, Mn and Cu), which represent metals of varying hardness. A combination of quantum chemical calculations, molecular dynamics and Grand canonical Monte Carlo simulations were performed to examine the gate opening of the isonicotinate ligands in Mg(4-PyC)2. The simulations show that interaction of the CO2 molecules with the isonicotinate ligands at different CO2 loadings can result in pressure-dependent gate opening. Furthermore, the simulated CO2 uptake values calculated using the partially gate-opened structures at different loadings showed good agreement with the experimental uptake values. This provides an effective strategy for designing highly-stable dynamic porous solids employing rigid frameworks.
External DOI: https://doi.org/10.1039/c9mh00133f
This record's URL: https://www.repository.cam.ac.uk/handle/1810/294197
All rights reserved