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<p>Metal-organic frameworks offer a convenient means for capturing, transporting, and
releasing small molecules. Rational design of such systems requires an in-depth understanding of the
underlying non-covalent interactions, and the ability to easily and rapidly pre-screen candidate
architectures in silico. In this work, we devised a recipe for computing the strength and analysing the
nature of the host-guest interactions in MOFs. Using experimentally characterised complexes of
calcium-adipate framework with 4,4’-bipyridine and 1,2-bis(4-pyridyl)ethane guests as test systems,
we have assessed a range of density functional theory methods, energy decomposition schemes, and
non-covalent interactions indicators across realistic periodic and finite supramolecular cluster scales.
We find that appropriately constructed clusters readily reproduce the key interactions occurring in
periodic models at a fraction of the computational cost and with an added benefit of diverse density
partitioning schemes. Host-guest interaction energies can be reliably computed with dispersion-
corrected density functional theory methods; however, decoding their precise nature demands insights
from energy decomposition schemes and quantum-chemical tools beyond local bonding indices (e.g.,
the quantum theory of atoms in molecules), such as the non-covalent interactions index and the
density overlap regions indicator.
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Heterogenisation of polyoxometalates and other metal-based complexes in metal–organic frameworks: from synthesis to characterisation and applications in catalysis
