jp0c02966_si_001.pdf (3.15 MB)
London Dispersion Governs the Interaction Mechanism of Small Polar and Nonpolar Molecules in Metal–Organic Frameworks
journal contribution
posted on 2020-05-21, 19:37 authored by Patrick Melix, Thomas HeineIn
this work, we investigate the adsorption of chlorinated methanes
(CHxCl4–x, x = 0–4) in a representative layer-pillar
metal–organic framework, the flexible MOF Ni2(ndc)2(dabco) (ndc = 2,6-naphthalene-dicarboxylate, dabco = 1,4-diazabicyclo-[2.2.2]-octane),
also known as DUT-8(Ni). The guest molecules show a systematic increase
of polarizability with increasing number of chlorine atoms, whereas
the dipole moment exceeds 2 debye for x = 2 and 3.
Our ligand field molecular mechanics simulations show that, at first,
counter-intuitively, the host–guest interactions are mainly
characterized by London dispersion despite the molecular dipole moments
reaching magnitudes as large as water. This highlights the importance
of London dispersion interactions in the description of host–guest
interactions.