Themed collection Metal nanoclusters
Luminescent metal nanoclusters and their application in bioimaging
This review focuses on the structure–property correlation and bioimaging application of luminescent metal nanoclusters, which feature atomically precise structures, diverse optical properties and excellent biocompatibility.
Nanoscale, 2024,16, 19589-19605
https://doi.org/10.1039/D4NR03111C
Hydrogen production catalysed by atomically precise metal clusters
Atomically precise metal clusters for electrocatalytic and photocatalytic H2 production are systematically summarized, which is expected to provide new insights into the design of high-performance H2 production catalysts.
Nanoscale, 2024,16, 13834-13846
https://doi.org/10.1039/D4NR01835D
Recent advances in synthesis and properties of silver nanoclusters
This minireview outlines recent progress in synthetic strategies, photophysical, surface reactivity, and catalytic properties of Ag(0)-containing ligand-protected atomically precise silver nanoclusters.
Nanoscale, 2024,16, 12329-12344
https://doi.org/10.1039/D4NR01788A
Synergism between copper and silver nanoclusters induces fascinating structural modifications, properties, and applications
Development of intriguing structures, physiochemical properties, and applications due to CuAgCN synergism.
Nanoscale, 2024,16, 18666-18683
https://doi.org/10.1039/D4NR03114H
Atomic-level design of biomimetic iron–sulfur clusters for biocatalysis
Schematic representation of the structural regulation strategy and progress of Fe–S clusters.
Nanoscale, 2024,16, 18644-18665
https://doi.org/10.1039/D4NR02883J
Circular dichroism and circularly polarized luminescence of ligand-protected molecular metal clusters: insights into structure–chiroptical property relationships
The potential of circular dichroism and circularly polarized luminescence spectroscopies to unravel the structure–chiroptical properties of ligand-protected, atomically precise noble metal clusters is discussed.
Nanoscale, 2024,16, 11914-11927
https://doi.org/10.1039/D4NR01232A
An organophosphate 3d–4f heterometallic polyoxoniobate nanowire
Integrate four structural compositions of organophosphate, 3d transition metal, 4f lanthanide and polyoxoniobate at the molecular level, to form a nanowire structure.
Nanoscale, 2024,16, 12420-12423
https://doi.org/10.1039/D4NR01619J
Photoemission spectroscopy and microscopy for Ta@Si16 superatoms and their assembled layers
An alkaline-like Ta-encapsulating Si16 superatom film was fabricated on a C60 substrate. Charge transfer between Ta@Si16 and C60 lowers the work function. In the multilayer film, the central Ta atom's positive charge is compensated by the Si16 cage.
Nanoscale, 2024, Advance Article
https://doi.org/10.1039/D4NR02778G
Modulating the photodynamic modality of Au22 nanoclusters through surface conjugation of arginine for promoted healing of bacteria-infected wounds
An Au nanocluster (NC)-based photodynamic antibacterial is designed by conjugating arginine on the surface of Au22 NCs, achieving healing of bacteria-infected wounds via producing reactive oxygen species (ROS) and reactive nitrogen species (RNS).
Nanoscale, 2024,16, 20089-20099
https://doi.org/10.1039/D4NR03278K
Effective enrichment of glycated proteome using ultrasmall gold nanoclusters functionalized with boronic acid
A novel approach was developed for the first time by combining ultrasmall Au22 nanoclusters with boronic acid (BA) affinity chemistry, achieving highly efficient enrichment of early-stage glycated peptides.
Nanoscale, 2024,16, 20147-20154
https://doi.org/10.1039/D4NR03283G
Chemical activation of atom-precise Pd3 nanoclusters on γ-Al2O3 supports for transfer hydrogenation reactions
Pd3 nanoclusters on Al2O3 supports were activated by reducing agents. The activity and selectivity of the catalysts for the transfer hydrogenation of cinnamaldehyde was a function of both the identity and loading of the reducing agent used.
Nanoscale, 2024,16, 19763-19774
https://doi.org/10.1039/D4NR03364G
Coalescence-induced shape transformations in Pd and AuPd clusters
The final structures after the collision of icosahedral nanoparticles with fcc ones depend on composition. Icosahedral final structures are obtained when colliding AuPd clusters, while collisions of pure Pd clusters leads to fcc structures.
Nanoscale, 2024,16, 19775-19785
https://doi.org/10.1039/D4NR03201B
High-throughput screening of bifunctional catalysts for oxygen evolution/reduction reaction at the subnanometer regime
OER/ORR activity for transition metal subnano clusters catalysts (TMn, n = 7–15), reshaping the bifunctional activity at the subnanometer regime, replacing the Pt(111) surface and IrO2/RuO2 with Au11 clusters from the peak of the activity volcano.
Nanoscale, 2024, Advance Article
https://doi.org/10.1039/D4NR02787F
Characterization of neutral metal hydride–hydroxide hydrogen-bonded clusters HMOH(H2O)2 (M = Al and Ga)
Characterization of neutral metal hydride–hydroxide hydrogen-bonded clusters HMOH(H2O)2 (M = Al and Ga) using infrared-vacuum ultraviolet spectroscopy combined with quantum chemical calculations.
Nanoscale, 2024, Advance Article
https://doi.org/10.1039/D4NR03440F
Nanoplasmonic sensing to study CO and oxygen adsorption and CO oxidation on size-selected Pt10 clusters
The adsorption of CO and oxygen and CO oxidation on size-selected Pt10 clusters were studied by indirect nanoplasmonic sensing (INPS) in the pressure range of 1–100 Pa at T = 418 K.
Nanoscale, 2024, Advance Article
https://doi.org/10.1039/D4NR02682A
An ionic Cu9Na4-phenylsilsesquioxane/bis(triphenylphosphine)iminium complex: synthesis, unique structure, and catalytic activity
The first example of a metallasilsesquioxane/phosphazene compound, a Cu9Na4-based complex, exhibits high catalytic activity in toluene oxidation.
Nanoscale, 2024,16, 19266-19275
https://doi.org/10.1039/D4NR02298J
Carbon-supported Au25 cluster catalysts partially decorated with dendron thiolates: enhanced loading weight and durability for hydrogen evolution reaction
The loading amount and durability of the carbon-supported Au25 cluster catalyst were successfully enhanced by introducing bulky, dendron thiolates, due to (1) strong non-covalent interactions between ligands and support, and (2) steric repulsion.
Nanoscale, 2024, Advance Article
https://doi.org/10.1039/D4NR03385J
Fragmentation patterns of DNA-stabilized silver nanoclusters under mass spectrometry
Electrospray ionization mass spectrometry and molecular dynamics simulations probe how DNA-stabilized silver nanoclusters fragment.
Nanoscale, 2024, Advance Article
https://doi.org/10.1039/D4NR03533J
Superstructures of copper nanoclusters as NIR TADF emitters: solvent-dependent optical and morphological modulation
Self-assembled thiol-templated CuNCs display NIR-TADF emission which can be modulated by solvent, accompanied by remarkable change in the morphology. The electronic structure of the surface ligands can also be used to tailor the properties of CuNCs.
Nanoscale, 2024, Advance Article
https://doi.org/10.1039/D4NR03074E
Size-dependent catalytic activity for CO oxidation over sub-nano-Au clusters
Gold (Au) nanocatalysts present outstanding activity for many reactions and have long attracted much attention, but the size effect of sub-nano-clusters on catalytic activity lacks systematic research.
Nanoscale, 2024,16, 18871-18881
https://doi.org/10.1039/D4NR02705A
Exploring nitrogen-mediated effects on Fe and Cu cluster development in graphene: a DFT study
The controlled growth and stability of transition metal clusters on N-doped materials have become the subject of intense investigation for unveiling comprehension on the cluster growth evolution.
Nanoscale, 2024, Advance Article
https://doi.org/10.1039/D4NR02713B
Electronic state modulation of Ag30 nanoclusters within a ring-shaped polyoxometalate
This work presents electronic state modulation of Ag30 nanoclusters within a ring-shaped polyoxometalate: oxidation-state modulation by changing the synthetic conditions and charge-distribution modulation by protonation of a polyoxometalate ligand.
Nanoscale, 2024,16, 18383-18388
https://doi.org/10.1039/D4NR02547D
Rational (supra)molecular design and catalytic activity of cage-like Cu4-based phenylsilsesquioxanes
Extended family of cage like Cu4-phenylsilsesquioxanes exhibits unique features of (supra)molecular organization and catalytic activity.
Nanoscale, 2024,16, 18389-18398
https://doi.org/10.1039/D4NR02173H
Nanocluster reaction-driven in situ transformation of colloidal nanoparticles to mesostructures
A one-pot method for creating self-assembled Au–Ag bimetallic mesostructures using a reaction between atomically precise gold nanoclusters and plasmonic silver nanoparticles.
Nanoscale, 2024, Advance Article
https://doi.org/10.1039/D4NR02820A
Click catalysis and DNA conjugation using a nanoscale DNA/silver cluster pair
Silver cluster–DNA conjugates catalyze alkyne–azide cycloadditions. The catalytic activity of the cluster is regulated by the DNA host.
Nanoscale, 2024,16, 17868-17876
https://doi.org/10.1039/D4NR02938K
Atomically precise rhodium–indium carbonyl nanoclusters: synthesis, characterization, crystal structure and electron-sponge features
The reactivity of [Rh7(CO)16]3− with InCl3 led to the isolation of three new clusters, including [Rh12In(CO)28]3−, which extends the [Rh12E(CO)27]n− series (E = Sn, Ge, Sb, Bi). Its multivalence has been experimentally and theoretically unravelled.
Nanoscale, 2024,16, 17852-17867
https://doi.org/10.1039/D4NR02922D
Assessing the overflowing pile-up effect on the photoluminescence lifetime of nanomaterials
A new insight for accurately interpreting the excited state lifetime has been provided, which is highly misunderstood due to the incomplete decay in heterogeneous luminescent nanomaterials.
Nanoscale, 2024,16, 16958-16966
https://doi.org/10.1039/D4NR01916D
Synthesis of atomically precise Ag16 nanoclusters and investigating solvent-dependent ultrafast relaxation dynamics
Here we demonstrate the synthesis of atomically precise Ag16 NCs and their photophysical properties. The solvent-dependent relaxation dynamics using ultrafast spectroscopy has been investigated.
Nanoscale, 2024,16, 16913-16918
https://doi.org/10.1039/D4NR02392G
Atomically precise alkynyl-protected Ag19Cu2 nanoclusters: synthesis, structure analysis, and electrocatalytic CO2 reduction application
We report the synthesis, structure analysis, and electrocatalytic CO2 reduction application of alkynyl-protected Ag19Cu2 nanoclusters, which exhibited high selectivity of CO formation and robust stability in eCO2RR.
Nanoscale, 2024,16, 16952-16957
https://doi.org/10.1039/D4NR02702G
Modulated assembly and structural diversity of heterometallic Sn–Ti oxo clusters from inorganic tin precursors
A series of heterometallic Sn–Ti oxo clusters was prepared using inorganic tin precursors and polyhydroxyalkane stabilizing ligands, which exhibited record-high nuclearity and different electrocatalytic behaviours.
Nanoscale, 2024,16, 16451-16457
https://doi.org/10.1039/D4NR02644F
Single-atom alloy structure and unique bonding properties of Au104Ag40(PET)60 nanoclusters
X-ray absorption spectroscopy is utilized to study the distribution of Au and Ag within the metal core of the Au104Ag40(PET)60 nanocluster, revealing a Ag single-atom alloy structure associated with unique bonding properties.
Nanoscale, 2024,16, 16140-16147
https://doi.org/10.1039/D4NR02688H
Ditopic ligand effects on solution structure and redox chemistry in discrete [Cu12S6] clusters with labile Cu–S bonds
Ligand coordination modes dictate solution structure of [Cu12S6] clusters.
Nanoscale, 2024,16, 16048-16057
https://doi.org/10.1039/D4NR02615B
A molecular dynamics study on the ion-mediated self-assembly of monolayer-protected nanoclusters
We studied the effects of metal and molecular cations on the aggregation of atomically precise monolayer-protected nanoclusters (MPCs) in an explicit solvent using atomistic molecular dynamics simulations.
Nanoscale, 2024,16, 15141-15147
https://doi.org/10.1039/D4NR02427C
One- and two-photon brightness of proteins interacting with gold. A closer look at gold–insulin conjugates
By combining experimental studies and time-dependent density functional theory simulations, we show the formation of insulin–Au(III) conjugates diplaying charge transfer-like excitation in the visible range.
Nanoscale, 2024,16, 14953-14958
https://doi.org/10.1039/D4NR01697A
Tailoring sensitization properties and improving near-infrared photon upconversion performance through alloying in superatomic molecular Au25 nanoclusters
The alloying of rod-shaped Au25 nanoclusters with Cu atoms significantly enhanced the triplet sensitization and near-infrared photon upconversion properties when paired with 9,10-bis(phenylethynyl)anthracene annihilators.
Nanoscale, 2024,16, 14757-14765
https://doi.org/10.1039/D4NR01948B
The interplay of chromophore–spacer length in light-induced gold nanocluster self-assembly
The chromophore-spacer length controls the cis-trans isomerization of azobenzene ligands in precision nanoclusters and regulates the kinetics of self-assembled superstructure formation.
Nanoscale, 2024,16, 14302-14309
https://doi.org/10.1039/D4NR01954G
Embedding AIE-type Ag28Au1 nanoclusters within ZIF-8 for improved photodynamic wound healing through bacterial eradication
A photodynamic antibacterial agent was created by encapsulating Ag28Au1 NCs in ZIF-8. This agent can eliminate 97.7% of E. coli and 91.6% of S. aureus within 5 minutes under light, promoting effective healing of bacteria-infected wounds.
Nanoscale, 2024,16, 14310-14318
https://doi.org/10.1039/D4NR01769B
Doping-mediated excited state dynamics of diphosphine-protected M@Au12 (M = Au, Ir) superatom nanoclusters
Strong core–shell (Ir–Aun) electronic coupling significantly expands the energy gap, resulting in a weak nonadiabatic coupling matrix element, which in turn increases the carrier lifetime.
Nanoscale, 2024,16, 14081-14088
https://doi.org/10.1039/D4NR02051K
Size onset of metallic behavior in neutral aluminum clusters
The excited state lifetimes of neutral (Al)n clusters up to ∼1 nm in diameter in size, where n ≤ 43, are systematically measured with femtosecond time-resolved mass spectrometry.
Nanoscale, 2024,16, 13516-13524
https://doi.org/10.1039/D4NR02032D
Assembly of anionic silver nanoclusters with controlled packing structures through site-specific ionic bridges
Site-specific linkage of tri-anionic silver nanoclusters with tetrahedrally arranged bridging sites by alkali metal counter cations leads to various network structures.
Nanoscale, 2024,16, 13457-13463
https://doi.org/10.1039/D4NR01691B
Analytical method for the determination of the absorption coefficient of DNA-stabilized silver nanoclusters
A new analytical method to determine the absorption coefficient of DNA-stabilized silver nanoclusters by combining UV-Vis spectroscopy, mass spectrometry, and inductively coupled plasma-optical emission spectrometry.
Nanoscale, 2024,16, 12559-12566
https://doi.org/10.1039/D4NR01765J
[Au9Ag6(CCR)10(DPPM)2Cl2](PPh4): a four-electron cluster with a bi-decahedral twisted metal core
We report a Au9Ag6 cluster characterized by a distinctive bi-decahedral core, formed through two decahedra sharing one vertex. This marks the first occurrence of a cluster of clusters constructed from decahedral units.
Nanoscale, 2024,16, 11090-11095
https://doi.org/10.1039/D4NR01471E
An insight, at the atomic level, into the structure and catalytic properties of the isomers of the Cu22 cluster
The structural isomers of Cu22 exhibit significant differences in the copper-catalyzed [3 + 2] azide-alkyne cycloaddition reaction (CuAAC), which offers a valuable opportunity to investigate the structure-function relationship of copper nanoclusters.
Nanoscale, 2024,16, 10318-10324
https://doi.org/10.1039/D4NR00973H
Construction of novel Ag(0)-containing silver nanoclusters by regulating auxiliary phosphine ligands
Two superatomic silver nanoclusters (Ag17 and Ag32) with similar outer shells were constructed by adjusting phosphine ligands, and their PL intensity and QY varied greatly because of the different surface rigidity.
Nanoscale, 2024,16, 9361-9366
https://doi.org/10.1039/D4NR01152J
Bright near-infrared emission from the Au39(SR)29 nanocluster
A highly luminescent Au39(SR)29 nanocluster is obtained, with its emission at 915 nm and 19% quantum yield in solution and 32% in films at room temperature.
Nanoscale, 2024,16, 7419-7426
https://doi.org/10.1039/D4NR00677A
Doping effect on a two-electron silver nanocluster
The addition of Ag(I) and Cu(I) by doping of a two-electron silver superatom, [Ag10(dtp)8], leads to the formation of [Ag11(dtp)8]+ and [CuxAg11−x(dtp)8]+, exhibiting a notable shift in the absorption spectrum.
Nanoscale, 2024,16, 7011-7018
https://doi.org/10.1039/D4NR00326H
About this collection
Guest edited by Professor Sukhendu Mandal (IISER Thiruvananthapuram, India), Professor Yuichi Negishi (Tokyo University of Science, Japan), Professor Di Sun (Shandong University, China) and Professor Anindita Das (South Methodist University, USA).
Atomically precise metal nanoclusters are novel materials that have the potential to address everyday needs from energy to health. Luminescent metal clusters can be used for effective and efficient energy harvesting and conversion technologies, while water-soluble luminescent metal clusters offer more efficient and personalized biomedical approaches. Furthermore, nanoclusters can be used as building units to form higher-dimensional cluster-assembled materials and can modulate the optoelectronic properties of desired device materials. To create a hierarchy of structures and applications, a fundamental understanding of the structure-property relationship at the atomic level is vital.
This special themed collection aims to look at new structures, photophysical, chemical and electrochemical catalysis reactions, and structure-property correlations within the themes of atomically precise metal nanoclusters. The collection covers new nanocluster structures, transformation reactions, luminescent materials, light-matter interactions, catalysis (photocatalysis and electrocatalysis), bioimaging and sensing, drug delivery, optoelectronic devices and new techniques for characterization.