Porous Metal–Organic Polyhedra: Morphology, Porosity, and Guest Binding

• DOI: 10.1021/acs.inorgchem.0c01935
• Publication Date: 2020-10-12T16:59:33Z
• Authors: Stephen P. Argent; Ivan da Silva; Alex Greenaway; Mathew Savage; Jack Humby; Andrew J. Davies; Harriott Nowell; William Lewis; Pascal Manuel; Chiu C. Tang; Alexander J. Blake; Michael W. George; Alexander V. Mark...; Elena Besley; Sihai Yang; Neil R. Champness; Martin Schröder
• Keywords: Polyhedron

Designing porous materials which can selectively adsorb CO2 or CH4 is an important environmental and industrial goal requires understanding of the host–guest interactions involved at atomic scale. Metal–organic polyhedra (MOPs) showing permanent porosity upon desolvation are rarely observed. We report a family MOPs (Cu-1a, Cu-1b, Cu-2), derive their from cavities between packed cages rather than within polyhedra. Thus, for Cu-1a, void fraction outside totals 56% with only 2% within. The relative stabilities these MOP structures rationalized by considering weak nondirectional packing using Hirshfeld surface analyses. exceptional stability Cu-1a enables detailed structural investigation into adsorption in situ X-ray neutron diffraction, coupled DFT calculations. primary binding sites adsorbed found to be open metal pockets defined faces phenyl rings. More importantly, analysis hydrated sample reveals strong hydrogen bond molecule Cu(II)-bound water molecule, shedding light on previous empirical theoretical observations that partial hydration metal−organic framework (MOF) containing increases uptake CO2. results crystallographic study MOP–gas have been calculations, yielding individual energies various pore environments Cu-1a.