Noncovalent Interactions in Coordination Chemistry
Summary
Noncovalent interactions in coordination chemistry encompass a diverse range of directional, yet relatively weak, forces that complement classical metal–ligand bonds and govern the assembly, stability and function of coordination compounds. Beyond hydrogen bonding, modern research highlights the importance of σ-hole and π-hole interactions, halogen and chalcogen bonds, π–π stacking, and metal-centred motifs such as spodium and tetrel bonds. These subtle forces direct supramolecular architectures, influence catalysis, control molecular recognition and enable responsive materials. Advances in single-crystal X-ray diffraction, Hirshfeld surface analysis and quantum-chemical methods now allow detailed mapping of interaction energies and electrostatic potentials at metal centres and within extended lattices. By exploiting these insights, chemists can design coordination networks with tailored porosity, selective ion transport, switchable optical properties and enhanced catalytic activity, forging new frontiers in materials science and bioinorganic applications.
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Noncovalent Interactions in Coordination Chemistry publication trend
The graph below shows the total number of articles in noncovalent interactions in coordination chemistry across all publications each year (not limited to Nature Index journals).
Technical terms
Noncovalent interaction: A reversible, directional attraction between atoms or molecules weaker than a covalent bond.
σ-hole: A region of positive electrostatic potential on an atom, enabling electrophilic interactions with nucleophiles.
π-hole: A positive potential perpendicular to a π‐system that can engage in directional noncovalent bonding.
Halogen bond: An attractive interaction between an electron-deficient halogen atom and a nucleophilic site.
Spodium bond: A noncovalent σ-hole interaction where a Group 12 metal centre acts as electrophilic acceptor.
π–π stacking: A stabilising parallel or offset overlap between aromatic rings driven by dispersion and electrostatic interactions.
References
- From Coordination to π‐Hole Chemistry of Transition Metals: Metalloporphyrins as a Case of Study. Angewandte Chemie International Edition (2024).
- Halogen Bonding Involving Isomeric Isocyanide/Nitrile Groups. International Journal of Molecular Sciences (2023).
- Intramolecular Spodium Bonds in Zn(II) Complexes: Insights from Theory and Experiment. International Journal of Molecular Sciences (2020).
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