| Abstract Scope |
Metal-organic frameworks (MOFs) have uniform porosity and large internal surface area to mass ratios, which makes them good adsorbents. By engineering the pore size and chemistry via the choice of metal nodes and ligands, it is possible to create MOFs that selectively adsorb one species over another. For example, azolate-based MOFs such as Co2Cl2(btdd)(H2O)2 strongly adsorb ammonia [Reith et al., J. Am. Chem. Soc. 2016, 138, 9401], while the dipyrazolate-based MOF Zn(azbpz) preferentially adsorbs acetylene over carbon dioxide [Berkbigler et al., Eur. J. Inorg. Chem. 2024, 27, e202300548]. We use density functional theory (DFT) at the GGA + U + nonlocal dispersion level to investigate these systems. Binding sites and binding energies are calculated and compared with available results in the literature. The effects of substitutions for Co and surrounding anions on the charge and spin state of the transmission metal ion in M2Cl2(Bbtdd)(H2O)2 are explored computationally. |