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Precise surface engineering of nanoparticles is essential for advancing bioimaging technologies, yet achieving atomically controlled ligand functionalization remains a challenge. Here, the authors develop an interphase-assisted ligand exchange method, which leverages mass transfer resistance between immiscible phases to precisely control the concentration of foreign ligands interacting with gold nanoclusters.

Diverse methods have been developed to tailor the number of metal atoms in metal nanoclusters, but controlling the number of surface ligands is rare. Here, the authors realize reversible addition and elimination of a single thiolate ligand on a gold nanocluster.

Gold nanoclusters are known to grow stepwise from gold-thiolate monomers and oligomers. Here, the authors find that the evolution of silver nanoclusters differs completely from that of gold: rather than following a bottom-up pathway, the clusters evolve from similarly-sized Ag-thiolate cluster intermediates.

Gold nanoparticles typically exhibit hard-sphere-like assembly behaviour, but now the size, morphology and symmetry of crystals of Au₂₅ nanoparticles have been tuned. The presence of excess tetraethylammonium cations has been shown to promote the one-dimensional assembly of the nanoparticles, which in turn form rod-like crystals, by stabilizing dynamically detached ligands from adjacent particles into interparticle linkers through CH⋯π and ion-pairing interactions.

Doping metal nanoclusters at specific sites is a powerful strategy for tuning their properties. Here, the authors precisely control the alloying sites of bimetallic nanoclusters by replacing entire surface motifs with structurally similar heteroatom motifs, tuning the surface composition motif-by-motif rather than atom-by-atom.

Synthetic nanochemistry currently lacks the molecular step-by-step routes afforded to organic chemistry by total synthesis. Here, the authors track the seeded growth of atom-precise gold nanoclusters using mass spectrometry, revealing that the clusters evolve through a series of intermediates in two-electron steps.

The photoluminescence of gold nanoclusters is affected by low-frequency acoustic vibrations. Here, the authors demonstrate that layer-by-layer ligand engineering can suppress such structural vibrations to achieve brighter emissions.

Surface modification using organic molecules is crucial for tailoring the physicochemical properties of electrocatalysts. In this study, we employ atomically precise Au25 nanoclusters with different ligands to identify the ligand effect on switching rate-limiting steps of oxygen evolution reaction.

Boosting the luminescence of atomically precise metal clusters is a main goal in view of applications. Here, the authors describe a strategy to increase the photoluminescence quantum yield of water-soluble gold clusters at the single-cluster level via formation of bis-Schiff base linkages, providing detailed insight into the mechanism.

While Pt is an active fuel cell catalyst, it’s low abundance and high cost spurs research into boosting performances from lesser Pt amounts. Here, authors design atomically precise triphenylphosphine-stabilized Pt nanoclusters with high activities and durabilities for electrocatalytic H₂ oxidation.

How metal nanoclusters evolve in size is poorly understood, particularly at the atomic level. Here, the authors use mass spectrometry to study the size conversion dynamics between two isoelectronic gold nanoclusters with atomic resolution, revealing that the growth reaction proceeds through a distinct balanced equation.

Ligand-protected metal nanoclusters, with their molecule-like structures and properties, represent the molecular state of metal materials. This Review examines what is currently possible in their precise synthesis — from size control at the molecular level to composition and morphology control at the atomic level.

A minute presence of silver nanoclusters in a MoS₂ nanosheet–graphene composite was found to significantly increase the reversibility of Li⁺ storage in the composite through Li⁺ association, pillaring of graphene and the immobilization of S species.

The Guest Editors of Communications Chemistry’s Atomically precise nanochemistry Collection discuss the importance of atomic precision in nanochemistry research, and highlight some of the field’s most pressing challenges.