Noncovalent Bonding Interactions in Supramolecular Chemistry

Supramolecular chemistry centres on the assembly and function of systems held together by noncovalent forces. Rather than forming or breaking covalent bonds, these interactions rely on electrostatic attraction, dispersion, induction and specific directional effects. Hydrogen bonding remains the most renowned example, underpinning the structure of biological macromolecules and advanced materials. Beyond hydrogen bonds, the classification has expanded to include halogen, chalcogen and tetrel bonding, each arising from anisotropic regions of positive electrostatic potential—so-called σ- and π-holes—on atoms of the p-block. These interactions exhibit remarkable directionality and tunable strength, allowing precise control over self-assembly, molecular recognition and catalysis. Cooperative effects and multivalent arrangements can amplify binding affinities, enabling responsive nanostructures, selective receptors and stimuli-responsive frameworks. Recent advances have extended the scope of noncovalent bonding to areas such as gas capture, drug design and materials engineering, presenting a versatile toolkit for constructing functional supramolecular architectures with applications spanning energy storage, sensing and molecular machines.

Research from Nature Portfolio

Recent work has illustrated the design of a polycyclic frustrated Lewis pair on a nanographene scaffold capable of sequential and simultaneous capture of multiple carbon dioxide molecules. By positioning boron and phosphorus centres within a conjugated framework, researchers observed a cooperativity effect driven by π-delocalisation: initial CO₂ fixation alters the acid–base character of neighbouring sites, enhancing subsequent capture events. Detailed computational studies of activation barriers and thermodynamic stability revealed how multivalent arrangements on an extended surface can optimise greenhouse-gas sequestration. This approach demonstrates the potential of noncovalent multicomponent assemblies in gas capture and environmental applications.

Noncovalent Bonding Interactions in Supramolecular Chemistry publication trend

The graph below shows the total number of articles in noncovalent bonding interactions in supramolecular chemistry across all publications each year (not limited to Nature Index journals).

Technical terms

Hydrogen bond: An attractive interaction between a hydrogen atom bonded to an electronegative donor and a neighbouring acceptor with lone pairs.

Halogen bond: A noncovalent interaction where an electron-rich site binds to a region of positive electrostatic potential on a halogen atom.

Chalcogen bond: A directional attraction between a lone pair donor and an electrophilic region (σ- or π-hole) on a chalcogen atom (group 16).

Tetrel bond: A noncovalent interaction involving group 14 elements acting as Lewis acids towards electron donors.

σ-hole interaction: An attraction occurring along the extension of a covalent bond where positive electrostatic potential is concentrated.

π-hole interaction: A noncovalent bond formed at a region of positive potential above or below the plane of a molecule’s π system.

Frustrated Lewis pair (FLP): A combination of Lewis acid and base sites prevented from forming a stable adduct, enabling activation of small molecules.

References

1. Reactivity of a model of B3P3-doped nanographene with up to three CO2 molecules. Scientific Reports (2023).
2. Computational Study of Driving Forces in ATSP, PDIQ, and P53 Peptide Binding: CO···CO Tetrel Bonding Interactions at Work. Journal of Chemical Information and Modeling (2023).
3. Computational Insight into the Nature and Strength of the π-Hole Type Chalcogen∙∙∙Chalcogen Interactions in the XO2∙∙∙CH3YCH3 Complexes (X = S, Se, Te; Y = O, S, Se, Te). International Journal of Molecular Sciences (2023).
4. Relation between Halogen Bond Strength and IR and NMR Spectroscopic Markers. Molecules (2023).