Dynamic Metal Nanoclusters: History
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Contributor:
Xiang Liu
,
Fan Peng
,
Gao Li
,
Kai Diao

Dynamic metal nanoclusters refer to a class of nanoscale metallic assemblies that exhibit dynamic behavior or undergo structural transformations under certain conditions. Unlike conventional static nanoclusters, dynamic metal nanoclusters can exhibit changes in their size, shape, composition, or ligand environment, leading to altered properties and functionalities. These dynamic characteristics arise from the inherent flexibility and adaptability of the metal nanocluster structures, allowing them to respond to external stimuli or undergo reversible transformations. The study of dynamic metal nanoclusters has gained significant attention due to their unique properties and potential applications in various fields, including catalysis, optics, electronics, and energy storage.

  • metal nanoclusters
  • dynamic structures
  • catalysis
  • synthesis

1. Introduction

In recent years, many fundamental properties of dynamic metal nanoclusters have been gradually revealed. Due to their unique optical and electronic properties, these materials have found wide-ranging applications in assembly, biological labeling and sensing, drug delivery and therapy, molecular recognition and molecular electronics, photoluminescence, and catalysis. Their applications have been extensively demonstrated [1][2][3][4][5][6][7]. Under ligand protection, nanostructured metal materials composed of Au and Ag with precise structures have become typical prototypes. The correlation between structural properties at the atomic level and their assembly mechanisms has been extensively investigated and understood [8][9][10][11][12].
In addition to well-established size-focused methods, single-atom substitution and size/structure conversion have also been considered successful approaches for preparing atomically precise clusters [13][14][15][16][17][18][19][20]. The single exchange of metal atoms in and out of metal clusters is of significant importance for establishing structure–property relationships based on the single-variant principle. Wang et al. [21] proposed a highly controlled method to shuttle single Ag or Cu atoms into the central void of Au24 nanoclusters, resulting in Ag1Au24 and Cu1Au24 nanoclusters. The ligand exchange-induced size/structure transformation (LEIST) [16][17][18][19], structure transformation induced by heteroatom doping, and oxygen-induced size/structure transformation [20][22][23][24] are considered successful methods for the preparation of atomically precise nanoclusters with precise structures. The LEIST method is widely used to transform a stable atomically precise nanocluster into another atomically precise cluster with a different size and structure through ligand exchange. Konishi et al. [25] reported the reaction of cyclic [Au9(PPh3)8](NO3)3 with excess dppp (dppp = Ph2P(CH2)3PPh2) at room temperature, resulting in the formation of an edge-sharing triangular bipyramid [Au8(dppp)4](NO3)2 with a different size and structure. Metallic nanoclusters with multidimensional self-assembled structures have been formed by connecting organic ligands and halide atoms as linkers. They have recently been used to tailor the physicochemical properties [26]. Zhu et al. [27] synthesized three-dimensional metal nanoclusters using [Au1Ag22(SAdm)12](SbF6)2Cl and [Au1Ag22(SAdm)12](SbF6)3 as building blocks.
In addition, the irreversible structural isomerization of atomically precise nanoclusters has been reported in a few cases, while the reversible conformational isomerization of metal nanoclusters has been rarely explored [27]. Teo et al. [28][29][30] reported the thermal transformation of metastable Au38(Sc2H4PH)24 to the thermodynamically stable icosahedral Au38(Sc2H4PH)24 under elevated temperature conditions. However, it is unfortunate that the reverse transformation does not occur. Chen et al. [31] achieved reversible conversion between Au28(Sc6H11)2 and Au28(SpHC4H9)20 nanoclusters. However, this case involves different surface-protecting ligands (-SC6H11 and -SC4H9), which does not meet the definition of isomeric transformation.

2. Advances in the Synthesis and Properties of Dynamic Metal Nanoclusters

The synthesis and properties of dynamic metal nanoclusters have seen significant progress in recent years. Researchers have developed various methods to synthesize these nanoclusters with precise control over their size, composition, and surface properties. These synthesis techniques include ligand exchange, surface modification, templated growth, and size conversion strategies [32][33][34][35][36][37][38]. Researchers have discovered that the band structure of ultrafine metal nanocrystals may differ from that of bulk metals and larger metal nanoparticles. This leads to changes in the surface thermodynamics of metal particles, resulting in different catalytic activity and physical properties. The synthesis of gold nanoparticles protected by a monolayer of thiol ligands using the two-phase and single-phase methods has provided a convenient and effective approach for size-controlled preparation of metal nanoclusters, greatly facilitating their subsequent development.
Overall, the synthesis and properties of dynamic metal nanoclusters continue to be an active area of research, offering great potential for the development of novel materials with tailored functionalities. Further investigations into their synthesis methodologies, characterization techniques, and applications are expected to advance our understanding and utilization of these fascinating nanoscale systems.

2.1. Synthesis and Characterization of Au13Ag12(PPh3)10Cl8 Nanoclusters (Single-Atom Exchange)

The synthesis and characterization of Au13Ag12(PPh3)10Cl8 nanoclusters through single-atom exchange have been investigated. These nanoclusters are composed of a combination of gold (Au) and silver (Ag) atoms, with a ligand shell consisting of PPh3 (triphenylphosphine) and chloride (Cl) ions. With regard to the synthesis of Au13Ag12(PPh3)10Cl8 nanoclusters, Qin et al. [39] reported the formation of Au13Ag12·Au12Ag13 “pigeon pair” clusters through single-atom exchange between Au13Ag12 and AgCl. TGA (thermogravimetric analysis), ESI-MS (electrospray ionization mass spectrometry), and SCXRD (single-crystal X-ray diffraction) confirmed the successful replacement of individual Au atoms in Au13Ag12 with single Ag atoms to form Au12Ag13 clusters. However, the location of the thirteenth Ag atom is still unknown. SCXRD revealed the crystallization of the clusters in the space group of pbca.

2.2. Synthesis and Characterization of [Au25−yAgy(PPh3)10Cl8]+ Nanoclusters (Photoinduced)

The ligand exchange-induced size/structure transformation (LEIST) method has been widely used to transform a stable, atomically precise nanocluster (precursor) into another atomically precise nanocluster through ligand exchange. Photoinduced methods, on the other hand, utilize light as an energy source to excite metal ions, leading to the formation of cores and nanoclusters. Qin et al. [40] reported the synthesis of [Au37−xAgx(PPh3)13Cl10]3+ (M37) nanoclusters through the reduction of Ph3PAuCl with Ph3PAgCl using NaBH4 in anhydrous ethanol. M37 nanoclusters undergo size/structure transformation under light irradiation. The irreversible size/structure transformation from M37 to M25 clusters was observed in situ using time-dependent UV-vis, ESI-MS, and femtosecond transient absorption spectroscopy. The M25 cluster was expected to exhibit a rod-like framework with a dodecahedral M25 metal core.

2.3. Synthesis and Characterization of [Au13Ag12(PPh3)10Cl8]SbBF6 Nanoclusters (Reduction Method)

The Au13Ag12 nanoclusters were synthesized by reducing a mixture of Ph3PAuCl and AgSbF6 using NaBH4 in an ice bath [41]. The synthesized nanoclusters were analyzed using electrospray ionization mass spectrometry (ESI-MS) in positive mode, and their molecular formula was determined to be [Au13Ag12(PPh3)10Cl8]+, indicating the high purity of the product. Thin-layer chromatography (TLC) identified the presence of two isomers in the Au13Ag12 product. Fresh solutions containing both isomers of Au13Ag12 nanoclusters were found to exclusively contain S-Au13Ag12 when kept at 25 °C for 4 weeks, and E-Au13Ag12 when kept at −10 °C for 6 weeks.

2.4. Synthesis and Characterization of Multidimensional Silver Cluster-Based Polymers (Ag-CBPs) via Self-Assembly

In the study [42], scholars describe the synthesis and characterization of one-dimensional {[Ag22(L1)8(CF3CO2)14](CH3OH)2}n chains and two-dimensional {[Ag12(L2)2(CO2CF3)14(H2O)4(AgCO2CF3)4](HNEt3)2}n sheets, which were constructed through the bottom-up assembly of Ag22-CBPs and Ag16-CBPs. Alkanoic acids and thiolate salts were selected as ligands due to their strong interactions with Ag atoms and flexible coordination capabilities, resulting in highly stable Ag-CBPs. The composition and atomic structures of the Ag-CBPs were determined using single-crystal X-ray diffraction. The Ag22-CBPs consist of asymmetric units of Ag22-CBP, which rotate 180° around the c2 axis to form Ag22-CBP monomers. These monomers are connected head-to-tail via Ag-Ag bonds, Ag-O-C (CF3) -O-Ag and Ag-trifluoroacetate-Ag sequences, as well as Ag-alkanoic acid bonds, forming one-dimensional silver chains along the c-axis. The Ag16-CBPs are formed by the interconnection of two Ag6 units, resulting in the formation of zigzag Ag12 clusters along the z-axis. The Ag12 clusters are connected head-to-tail along the b-axis via (Ag12)-trifluoroacetate-(Ag12) sequences, and each Ag12 cluster interacts with four neighboring Ag12 clusters through four Ag2 units via (Ag12)-trifluoroacetate-(Ag2) sequences, forming a two-dimensional sheet structure.

3. Properties and Applications of Dynamic Metal Nanoclusters

3.1. Catalytic Applications

The electronic structure of Au12Ag13 clusters is significantly perturbed by the exchange of Ag atoms, resulting in differences in catalytic performance. Both Au13Ag12 and Au13Ag12·Au12Ag13 clusters were loaded on TiO2 for the photocatalytic conversion of ethanol [39]. Under UV irradiation (λ = 365 nm) at 30 °C, the conversion rate of ethanol by Au13Ag12·Au12Ag13 clusters was 1.5 times higher than that of Au13Ag12 clusters. The selectivity of Au13Ag12·Au12Ag13 clusters towards ethanol was slightly higher compared to Au13Ag12 clusters. The single-atom exchange (Ag) in M25 clusters with different electronic properties indeed has a significant impact on catalytic activity.
Li et al. [43] conducted a study on the catalytic performance of water-soluble Aun(SR)m nanocluster catalysts [Au15(SG)13, Au18(SG)14, Au25(SG)18, Au38(SG)24, and Au25(Capt)18] in the homogeneous chemical selective hydrogenation reaction in water. They observed significant size dependence and spatial effects of ligands in the hydrogenation reactions catalyzed by gold nanoclusters. The catalytic activity of the gold nanoclusters (based on the conversion of 4-nitrobenzaldehyde) increased with increasing core size: Au15(SG)13 < Au18(SG)14 < Au25(SG)18 < Au38(SG)24. On the other hand, gold nanoclusters with smaller ligand volumes exhibited better catalytic performance [Au25(Capt)18 > Au25(SG)18]. The DFT calculations were performed using the Perdew–Burke–Ernzerhof (PBE) functional [44] based on the generalized gradient approximation, the def2-SVP basis set, and empirical dispersion correction. The surface area of the clusters in the solvent was calculated using the default values of ri and rsolv in Turbomole 6.5 [45]. 

3.2. Optical Applications

The electronic structure of metal nanoclusters greatly influences their fluorescence properties. The maximum excitation wavelength of Au13Ag12·Au12Ag13 clusters is increased compared to Au13Ag12, and a redshift phenomenon is observed in the fluorescence spectrum. The quantum yield (QY) is significantly enhanced. Metal nanoclusters find wide applications in areas such as lighting, biotechnology, and medicine [39]. Pniakowska et al. [46] conducted experimental research and time-dependent density functional theory (TD-DFT) simulations to investigate the influence of gold atom doping on the single-photon and two-photon absorption and emission properties of connected silver nanoclusters.

3.3. Electronics Applications

Due to the discovery that the two enantiomers of metal nanoclusters (S-Au13Ag12 and E-Au13Ag12) can undergo reversible conversion by controlling the temperature [41], it has been found that the metal configuration with higher symmetry (D5h) is favored for the formation of the E-Au13Ag12 isomer at low temperatures (−10 °C). As the temperature increases to 25 °C, the S-Au13Ag12 isomer (lower symmetry) is exclusively formed. Alloying and ligand engineering (such as Ag–halogen bonding) provide a rational strategy to make the framework of metal nanoclusters more flexible, enabling conformational isomerism with the potential for designing smart molecular engines driven by Gibbs free energy. These temperature-driven, interconvertible nanocluster isomers open up avenues for the design of thermal sensors and intelligent catalysts utilizing ultra-small nanoclusters.

4. Trends and Challenges in Dynamic Nanometal Clusters

4.1. Size and Composition Control

One of the major trends in the field is the precise control over the size and composition of nanometal clusters. In terms of size control, the complex structure and atomic-scale variations of dynamic nanoclusters make it difficult to precisely manipulate their sizes. Conditions during the synthesis process, reaction kinetics, and aggregation states can all influence the cluster sizes. Additionally, controlling the composition of dynamic nanoclusters also presents challenges. In the synthesis process, precise control over the selection, ratio, and doping of different metal atoms is required to achieve the desired composition.

4.2. Structural Characterization

(a) There are challenges in measuring the dynamic phenomena in dynamic metal nanoclusters. The dynamic processes of metal nanoclusters typically occur on the femtosecond or picosecond timescale. Accurate measurement and observation of these processes require experimental equipment and techniques with high temporal resolution, such as femtosecond laser systems and fast detectors. However, due to the short timescale of the dynamic processes in metal nanoclusters, conventional experimental techniques often cannot directly observe these processes. Therefore, the key to explaining and understanding the observed phenomena is to combine experimental results with theoretical models.

(b) Dynamic metal nanoclusters exhibit complex structural features, including variations in atomic composition, crystal structure, and surface ligands. Due to their small size and structural diversity, conventional structural characterization techniques may not directly observe their precise structures. Therefore, a combination of multiple characterization methods is required for comprehensive analysis.
(c) Dynamic metal nanoclusters undergo reversible isomerization, where their structures and properties can change with varying environmental conditions. This dynamic nature makes it challenging to accurately understand their structures, necessitating the use of time-resolved experiments and theoretical simulations to reveal their dynamic behavior.
(d) Size effects are significant in dynamic metal nanoclusters [47][48][49][50], where their structures and properties can be influenced by their sizes. However, precise control over the size of nanoclusters remains a challenge, especially for synthesizing and characterizing large-sized clusters.
(e) Surface modification is commonly employed in dynamic metal nanoclusters through ligand attachments, which can impact their structures and properties. However, the ligand environment on the cluster’s surface is often difficult to directly observe and determine, requiring the utilization of surface analysis techniques and theoretical simulations to uncover their structures and properties.
(f) In practical applications, dynamic metal nanoclusters may exhibit clustering phenomena, where multiple clusters aggregate together [51][52][53]. Cluster aggregation can affect the structures and properties of the individual clusters, posing challenges in characterizing and analyzing the structure of clustered systems.

4.3. Functional Applications

Despite the promising prospects, several challenges exist in the field of dynamic nanometal clusters. In the field of catalysis, the challenge lies in the design and synthesis of clusters with ideal catalytic performance, including controlling their sizes, compositions, and structures, as well as improving their stability and regenerability. In optical applications, precise control over the morphologies, sizes, and compositions of clusters is needed to achieve specific optical responses and improve photostability and quantum yield. 

4.4. Stability and Scalability

There are many challenges in stability and scalability. Dynamic metal nanoclusters have the characteristics of reversible isomerization and structural rearrangement, which make the stability of clusters difficult to predict and control. Under different environmental conditions, the structures and properties of clusters may change, resulting in their stability being affected. The surfaces of clusters are usually covered by ligands or modified molecules, and these surface modifications play a key role in the stability of clusters. However, the selection and control of surface modification is a challenge because different ligands or modified molecules have different effects on the stability and activity of clusters. Large-scale preparation of dynamic metal nanoclusters with consistency and controllability is a challenge. The synthesis method needs to be reproducible to ensure that different batches of clusters have similar properties. 

4.5. Understanding the Structure–Property Relationship

Establishing a comprehensive understanding of the relationship between the atomic structures and the properties of dynamic nanometal clusters is crucial for their rational design [54]. This requires further theoretical and experimental investigations to elucidate the underlying principles governing their behavior. The understanding of the structure–property relationship in dynamic metal nanoclusters can provide valuable insights into their functionality and potential applications. However, there are challenges in unraveling this relationship. Firstly, for complex structures, it is sometimes difficult to directly observe and determine their precise structure using traditional characterization techniques. This challenge is particularly pronounced for larger clusters or those present in solutions. Secondly, the dynamic nature of metal nanoclusters, which undergo reversible isomerization, leads to variations in their structures and properties under different environmental conditions, such as temperature, solvent, and atmosphere. This dynamic behavior adds complexity to the understanding of the structure–property relationship and requires a combination of experimental and theoretical studies to reveal their dynamic behavior. Lastly, the selection of different metal elements, ligands, and synthesis methods significantly influences the structures and properties of dynamic metal nanoclusters.

4.6. Integration and Compatibility

Integrating dynamic nanometal clusters into practical devices and systems while maintaining their dynamic behavior poses challenges. Compatibility with different matrices and substrates, as well as long-term stability, need to be addressed for successful integration into functional devices. In general, dynamic metal nanoclusters have vast application prospects, but they also require overcoming various challenges encountered during their preparation and application processes. These challenges include improving preparation efficiency and simplifying synthesis steps, optimizing assembly materials, studying the relationship between the structure and properties of dynamic metal nanoclusters, and enhancing their evaluation in environmental and biological contexts.

This entry is adapted from the peer-reviewed paper 10.3390/molecules28145306

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