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Atomically precise nanochemistry plays an increasingly important role in nanoscience and nanotechnology. Nanomaterials with well-defined structure–property relationships offer reliable and programmable performances in a diverse range of applications of current interest, such as green catalysis, clean energy, and biomedicine. Furthermore, atomically precise nanochemistry enhances nanomaterial synthesis from an empirical art to science, affording reproducible pathways to nanomaterial synthesis. Recent efforts in wet chemistry have allowed significant advances in the attainment of a range of atomically precise nanomaterials, which among others include:
• Noble metal clusters
• Semi-conductor magic-sized clusters
• Polyoxometalate clusters
• Carbon-based nanostructures
• Metal–organic frameworks
This Collection aims to present the latest progress in the synthesis, characterization, functionalization, self-assembly, and applications of atomically-precise nanomaterials. It is also our intention for the Collection to highlight ongoing challenges and opportunities that such nanomaterials present, allowing us to press forward in nanoscience and nanotechnology. We welcome both experimental and theoretical studies, with topics of interest including but not limited to:
• wet chemistry synthetic approaches
• characterization of structures and physicochemical properties
• applications (such as in catalysis, sensing, and bioimaging)
• self-assembly
The Collection primarily welcomes original research papers, in the form of both full articles and communications. All submissions will be subject to the same review process and editorial standards as regular Communications Chemistry Articles.
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.
Understanding the formation pathways of multimetallic clusters is essential to the progress of cluster research, but remains highly challenging. Here, time-dependent crystallization, mass spectrometry, and quantum chemical calculations are used to gain insight into the formation pathways of bismuth–tungsten carbonyl clusters.
Iron oxide nanoclusters are of interest for a broad range of applications, but limited experimental information on their oxidation mechanism is available outside of the gas phase. Here, the oxidation of graphene-supported size-selected Fen clusters is studied using high-resolution X-ray Photoelectron Spectroscopy.
The atomic structures of metallic nanoparticles dictate their chemical and physical properties, making their structural study under different chemical environments of importance. Here, electron microscopy finds that silver nanoparticles primarily adopt an icosahedron structure under air exposure, while previous reports showed that the face-centred cubic isomer is favoured when the nanoparticles are kept in vacuum.
On-surface synthesis is a useful tool to produce extended macrocyclic structures with atomic precision, with only one type of macrocycle typically formed through on-surface coupling reactions. Here, distinct domains of four-, six- and eight-membered tetraphenylethylene-based macrocycles are synthesized on Ag(111) as segregated large-area mono-component crystals.
Incommensurate double-wall carbon nanotubes give rise to unique stereochemistry originating from twisted stacks of hexagon arrays, but atomic-level studies of molecular analogues are hindered by the challenges in designing and synthesizing pairs of chiral cylindrical molecules. Here, a molecular version of incommensurate double-wall carbon nanotubes is designed by development of a roadmap of synthetically accessible chiral indices.
Atomically precise metal nanoclusters display exciting optical and catalytic properties, but their long-term instability under ambient conditions hinders their practical application. Here, the authors review recent progress in creating nanohybrids from atomically precise nanoclusters and other more stable nanomaterials, forming hybrids with useful properties and improved stabilities.
Controlling the geometric structures of metal clusters through structural isomerization allows for tuning of their optical and catalytic properties. Here, structural isomerization of crown-motif clusters [PdAu8(PPh3)8]2+ and [PtAu8(PPh3)8]2+ to corresponding butterfly-motif clusters is induced using [Mo6O19]2- anions.
Atomically and structurally precise silver nanoclusters hold great potential for catalytic and optoelectronic applications. Here, the authors synthesize and characterize a series of atomically defined dithio- and diselenophosphate-protected eight-electron superatomic palladium-doped silver nanoclusters, including an unprecedented pair of selenolate-protected isomers.
Understanding the relative strengths of metal–ligand and metal–metal interactions in ligated nanoclusters is key to tailoring their properties. Here, collision-induced dissociation of two series of atomically precise metal sulfide nanoclusters provides insight into the modulation of the core–ligand interactions of the atomically precise metal chalcogenide clusters.
Enhancing the hydrophilicity of hydrophobic molecular scaffolds allows to increase their aqueous solubility and therefore their usability for a range of applications. Here, N/O heteroatom doping of polycyclic aromatic hydrocarbons is shown to switch the skeleton from hydrophobic to hydrophilic, enhancing aqueous solubility and facilitating self-assembly in water.
Understanding the atomic dynamics of active catalyst sites is crucial for the precise optimization of catalyst performance. Here, the authors employ operando XAFS and DRIFTS to study the dynamics of the mobility of platinum and copper dopants in bimetallic and trimetallic gold nanoclusters supported on ceria, using the water-gas shift process as a model reaction.
Metal nanoclusters have shown great promise as electrochemiluminescence (ECL) luminophores, but understanding the relationship between ECL and atomic structure is highly challenging. Here, the ECL of nanocluster isomers Au20(SAdm)12(CHT)4 and Au20(TBBT)16 is studied, giving insight into structure–property relationships.
Atomically precise thiolate-protected gold nanoclusters present strong near-infrared excitation, long lifetimes, and surface biofunctionality, making them ideal candidates as photosensitizers in photodynamic therapy. Here, the authors evaluate the influence of the ligands and metal core on the efficiency of photoexcited Au10 and Au25 clusters to produce reactive oxygen species, as well as possible biological consequences in living cells.
Icosahedron-based M13 nanoclusters are common building blocks to produce atomically precise superatomic molecules, but our understanding of the chemistry governing the connection between icosahedral M13 units is limited. Here, the key factors influencing the vertex sharing connection between Ag13−xMx structures are studied, and the effects of different central metal atoms and the type of bridging halogen atom are clarified.
Finding an efficient catalyst to convert CO2 into useful products is a challenging problem. Here, the authors use first-principles calculations to show how the attached donor/acceptor ligands on the Ti6Se8 cluster can be utilized to design effective catalysts for CO2 hydrogenation to formic acid.
Atomically precise gold nanoclusters display useful photoluminescence properties, but limitations in synthetic methods and characterization techniques have hindered their detailed exploration. Here, a Au38(PET)26 nanocluster is found to exhibit fluorescence, phosphorescence, and thermally activated delayed fluorescence emissions, with a significant enhancement in photoluminescence intensity at cryogenic temperatures owing to the suppression of nonradiative pathways.
Copper doping of atomically precise gold nanoclusters is a useful strategy to tune their chemical and physical properties, but Au–Cu nanocluster alloys tend to exhibit poor stability. Here, a [Au12Cu13(Ph3P)10I7](SbF6)2 cluster is prepared and shown to display enhanced stability and fluorescence in comparison to homonuclear cluster [Au25(PPh3)10Br7](SbF6)2, in addition to promising photocatalytic activity for methanol oxidation.
Tuning the metal core and ligand environment of atomically precise nanoclusters enables the correlation of structural and electrocatalytic properties at an atomic level. Here, single-atom doping and ligand tuning of atomically precise copper clusters is shown to be an effective route to tuning CO2 electroreduction activity and selectivity.
Dry reforming of methane into syngas typically requires high temperatures, which can cause aggregation and deterioration of the catalyst. Here, the authors report a lanthanum nickel oxide catalyst prepared by in situ hydrogen reduction of LaNi0.05Co0.05Cr0.9O3 on a LaCrO3 perovskite support that remains stable for over 100 h at 750 °C.