Amides Do Not Always Work: Observation of Guest Binding in an Amide-Functionalized Porous Metal–Organic Framework

An amide-functionalized
metal organic framework (MOF) material,
MFM-136, shows a high CO2 uptake of 12.6 mmol g–1 at 20 bar and 298 K. MFM-136 is the first example of an acylamide
pyrimidyl isophthalate MOF without open metal sites and, thus, provides
a unique platform to study guest binding, particularly the role of
free amides. Neutron diffraction reveals that, surprisingly, there
is no direct binding between the adsorbed CO2/CH4 molecules and the pendant amide group in the pore. This observation
has been confirmed unambiguously by inelastic neutron spectroscopy.
This suggests that introduction of functional groups solely may not
necessarily induce specific guest–host binding in porous materials,
but it is a combination of pore size, geometry, and functional group
that leads to enhanced gas adsorption properties.