Thiolate-protected Gold Nanoclusters Research Articles

Pursuing Extreme Descriptive Power and Generality in Chemical Bond Theories: A Method to Decipher "Interatomic Genomes" from Interatomic Electron Structures.

The description and analysis of chemical bonds have been difficult following the popularization of electronic structure calculations. Although many attempts have been made from the perspective of electronic structure, the sheer volume of information in the electronic structure has left contemporary chemical bond analysis methods grappling with an inescapable "Trilemma" where the model briefness, generality, and descriptiveness (descriptive power) cannot be obtained simultaneously. To push the generality and descriptiveness to their extremes, herein a general machine learning-based framework is introduced to compact chemical bonds into a detailed residue-by-residue "genome" with matched encoding/decoding tools. The framework fuses the quantum mechanical aspects, auto feature extraction, nanostructures and/or simulations, and generative models. The encoded genomes are information-dense and decodable, where 100% generality is guaranteed. The descriptiveness of genomes appears to be broader than most known models. As a proof of concept, the realization presented in this work compacts the complete information regarding two critical chemical bonds in thiolate-protected gold nanoclusters, the S-Au and Au-Au bonds, from a Bosonic-Fermionic character perspective into 8-valued genomes. The machine learning component is trained based on 26,528 density functional theory simulated electron localization function images. With an exploration of the space span for the genome, bond polarization, hybridization, intrusion of other atoms, alignments, crystal orientation, atomic motions, and more details are observed. Furthermore, it has emerged from extensive generation tests that molecules and solids can be integrated in such a concise manner than is typically achieved with purely geometric representations. To showcase the intraclass complexity of S-Au and Au-Au bonds visually, a roadmap is plotted by summarizing and correlating the similarities of 8-value-genomes. Furthermore, genomes can be associated with realistic indices easily with a simple multilayer perception architecture as a simple calculating tool. Besides, there are 3 sets of applications, including a set of chemisorption, a set of molecular dynamical analysis, and a set of ultrafast processes, showcasing the interpretability potentials of interatomic genomes in the geometric structures, kinetic properties, and vibration characteristics of molecular systems. As the framework rose to the challenge of nanoclusters from a complicated mesoscopic family of material, the displayed generality and comprehensiveness indicate that the model may "understand" chemical bonds in a machine's way.

Regioselective Ligand Substitution of Thiolate-Protected Gold Nanoclusters with Porphyrins

Hybridization of photofunctional organic molecules like porphyrins with inorganic nanomaterials provides interesting photophysical properties like photo-induced electron transfer, energy transfer, or photoemission from charge transfer states. For fine tuning of these photo-functionalities, precise control over organic-inorganic interfaces, including spatial distances and orientations of organic molecules against inorganic nanomaterial, should be crucial. However, control and evaluation of the interfaces are quite difficult, mainly due to heterogeneous and unclear environments on the surface of inorganic nanomaterials like metal nanoparticles and metal nanosheet, which basically have size and/or composition distributions.Among the inorganic nanomaterials, atomically-precise metal nanoclusters (MNCs) are one of the homogeneous materials with uniform composition and distinct surface structure at an atomic level. Thus, MNCs can be an appropriate model to evaluate the effects of organic-inorganic interfaces on photophysical properties of the hybridized materials. Nevertheless, even in one of the most common and simplest MNCs like thiolate-protected Au25 cluster ([Au25(SR)18]–, SR = thiolate), two kinds of inequivalent ligands (S1, S2 in Figure 1) are present on surface. Thus, control over the regioselectivity should be required to archive precise substitution of photo-functional molecules, which has yet to be reported. In this work, we have controlled regioselectivity in the modification of [Au25(SC2Ph)18]– (SC2Ph = phenylethanethiolate) with porphyrinthiol ligands (Por) through ligand-exchange reactions. An advantage of Por as a photofunctional ligand for Au25 cluster is more bulkiness than that of original ligands (SC2Ph), which aids the isolation of mono-porphyrin-coordinated Au25 cluster ([Au25(SC2Ph)17(Por)1]–, Au25-Por1 ). Moreover, synthetic flexibility of porphyrins enabled us to control the regioselectivity in Au25-Por1 systematically.We sythesized a series of Por with a thiol moiety at different positions to evaluate the steric effect on the regioselectivity in ligand-exchange reactions (Figure 1). Porphyrin thiol with different substituents at meso-phenyl groups were also synthesized to evaluate the electronic effect. Substitution of porphyrins onto Au25 clusters was conducted by ligand-exchange reactions of [Au25(SC2Ph)18]– with 1 equivalent of Por in tetrahydrofuran. After the careful purification of the reaction mixture through size-exclusion column chromatography, we have successfully isolated Au25-Por1 in ca. 20% yield. The characterizations of Au25-Por1 were performed by MALDI-TOF-MS and 1H NMR spectroscopy, which confirmed the high purities of a series of Au25-Por1 .The regioselectivity in Au25-Por1 was evaluated through 1H NMR measurements. When using para-substituted porphyrin (PorSH) as an incoming ligand, 1H NMR spectrum of Au25-SPor1 in acetone-d 6 indicated the presence two kinds of regioisomers with the ratio of 2.5:1. Interestingly, the regioselectivity increased up to 80% (4:1) in Au25 cluster with more steric meta-substituted porphyrin (Au25-S m Por1 ), whereas the ratio reached to almost 1:1 in the case of Au25 cluster with less steric phenyl-spacer introduced porphyrin (Au25-SPhPor1 ). Because S2 position in the Au25 clusters was less steric than S1 position, we concluded that more steric ligands like m PorSH tend to be introduced at S2 position favorably. On the other hand, we hardly observed the electronic effect of Por on the regioselectivity in Au25-Por1 , indicating the importance of steric factor of an incoming ligand for precise control over the exchanged position (Figure 1). This is the first report to control over ligand-exchange position of MNCs, which could be achieved through ligand design.Finally, we briefly evaluated the photophysical properties of Au25-Por1 in toluene solution. When the Soret band of coordinated-porphyrins was photoexcited, the fluorescence quenching was clearly observed in each Au25-Por1 . Judging from the energy diagram of Au25-Por1 , electron transfer from Au25 to singlet excited state of porphyrin ligand would occur to form charge separated state. It should be noted that the quenching efficiency depended on not only the distance between electron donor and acceptor, but also the position of the coordinated chromophore. These results suggest the importance of precise modification of organic-inorganic interfaces to tune photodynamics of chromophore-nanocluster systems.In conclusion, we have successfully controlled the regioselectivity in the ligand-exchange reactions of thiolate-protected gold nanoclusters with porphyrinthiol derivatives through the steric effect. The essential roles of the ligand-introduced position on altering photodynamics of porphyrin-coordinated MNCs were also clarified, which provides an interesting insight into fine-tuning of photofunctional materials.Figure 1.Reaction scheme of ligand-exchange reaction of [Au25(SC2Ph)18]– with Por. The R groups of SR ligands were omitted for clarity. Figure 1

Unveiling Complex Structural Features of Thiolate-Protected Gold Nanoclusters: From Internal Core to External “Staple” Motifs and Overall Charge States

Unveiling Complex Structural Features of Thiolate-Protected Gold Nanoclusters: From Internal Core to External “Staple” Motifs and Overall Charge States

Gold-Thiolate Nanocluster Dynamics and Intercluster Reactions Enabled by a Machine Learned Interatomic Potential.

Monolayer protected metal clusters comprise a rich class of molecular systems and are promising candidate materials for a variety of applications. While a growing number of protected nanoclusters have been synthesized and characterized in crystalline forms, their dynamical behavior in solution, including prenucleation cluster formation, is not well understood due to limitations both in characterization and first-principles modeling techniques. Recent advancements in machine-learned interatomic potentials are rapidly enabling the study of complex interactions such as dynamical behavior and reactivity on the nanoscale. Here, we develop an Au-S-C-H atomic cluster expansion (ACE) interatomic potential for efficient and accurate molecular dynamics simulations of thiolate-protected gold nanoclusters (Aun(SCH3)m). Trained on more than 30,000 density functional theory calculations of gold nanoclusters, the interatomic potential exhibits ab initio level accuracy in energies and forces and replicates nanocluster dynamics including thermal vibration and chiral inversion. Long dynamics simulations (up to 0.1 μs time scale) reveal a mechanism explaining the thermal instability of neutral Au25(SR)18 clusters. Specifically, we observe multiple stages of isomerization of the Au25(SR)18 cluster, including a chiral isomer. Additionally, we simulate coalescence of two Au25(SR)18 clusters and observe series of clusters where the formation mechanisms are critically mediated by ligand exchange in the form of [Au-S]n rings.

Structural and Chemical Bonding Properties of AuS2H0/-: A Photoelectron Velocity-Map Imaging Spectroscopic and Theoretical Study.

Mass-selected photoelectron velocity-map imaging spectroscopy was employed to investigate the geometrical and electronic properties of AuS2H-/0. The comprehensive comparison between the experiment and theoretical calculations establishes that the ground-state AuS2H- anion has a mixed-ligand structure [SAuSH]- with an unsymmetrical S-Au-S unit. Further chemical bonding analyses on AuS2H and comparison with the isoelectronic AuS2- suggest that the unique S-Au-S unit in these species features two three-center, three-electron π-bonding, and one three-center, two-electron σ-bonding. The isoelectronic replacement of the extra electron in AuS2- by the H atom can lead to σ bonding evolution from the electron-sharing bond to the dative bond. These findings are conducive to the fundamental understanding of the intrinsic stability of thiolate-protected gold nanoclusters and their delicate ligand design to achieve desirable properties.

Proposed Structural Model for Chiral Au40(SC2H4Ph)24 Nanoclusters.

The structural configuration of thiolate-protected gold nanoclusters plays a pivotal role in elucidating the correlation between their structure and properties, comprehending their stability, and guiding experimental synthesis. In this study, utilizing the grand unified model and the ring model, we employed an innovative strategy of fusing triangular Au3 and tetrahedral Au4 elementary blocks by sharing a gold atom to design the gold core, predicting the structure of the Au40(SR)24 nanoclusters. Density functional theory calculations indicate that with the protective ligands simplified to methyl groups the energy of the predicted Au40(SR)24 is 0.45 eV lower than that of the experimentally reported Au40(o-MBT)24 nanoclusters, implying its substantial stability. Furthermore, the calculated UV absorption spectrum and circular dichroism spectrum of predicted Au40(SR)24 are consistent with the experimental results of Au40(SC2H4Ph)24 nanoclusters, suggesting that the predicted structure is a likely candidate for the structure of Au40(SC2H4Ph)24 nanoclusters.

Quantitative analysis of air-oxidation reactions of thiolate-protected gold nanoclusters.

The interaction of dioxygen (O2) with inorganic nanomaterials is one of the most essential steps to understanding the reaction mechanism of O2-related reactions. However, quantitative analyses for O2-binding processes and subsequent oxidation reactions on the surface are still elusive, whereas the reaction of O2 with molecules such as transition metal complexes has been widely explored. Herein, we have quantitatively evaluated reaction processes of air-oxidation reactions of atomically precise thiolate-protected Au25 nanoclusters ([Au25(SR)18]-) as a model of O2 activation by inorganic nanomaterials. Kinetic analyses on the air-oxidation reaction of [Au25(SR)18]- revealed a controlling factor for O2-activation processes, which could be finely tunable by the protecting thiolate ligands.

Core-Packing-Related Vibrational Properties of Thiol-Protected Gold Nanoclusters and Their Excited-State Behavior.

Thiolate-protected gold nanoclusters, with unique nuclearity- and structure-dependent properties, have been extensively used in energy conversion and catalysis; however, the mystery between kernel structures and properties remains to be revealed. Here, the influence of core packing on the electronic structure, vibrational properties, and excited-state dynamics of four gold nanoclusters with various kernel structures is explored using density functional theory combined with time-domain nonadiabatic molecular dynamics simulations. We elucidate the correlation between the geometrical structure and excited-state dynamics of gold nanoclusters. The distinct carrier lifetimes of the four nanoclusters are attributed to various electron-phonon couplings arising from the different vibrational properties caused by core packing. We have identified specific phonon modes that participate in the electron-hole recombination dynamics, which are related to the gold core of nanoclusters. This study paints a physical picture from the geometric configuration, electronic structure, vibrational properties, and carrier lifetime of these nanoclusters, thereby facilitating their potential application in optoelectronic materials.

Ratiometric fluorescence sensing of hazardous ciprofloxacin based on aggregation induced emission enhancement of thiolate-protected gold nanoclusters induced by La3+ ion

In this research work, ultrasensitive and reliable ratiometric sensor was designed for assay of ciprofloxacin (CIPRO). The platform consists of thiolate-protected gold nanoclusters (GSH@AuNCs) with high fluorescence quantum yield and long-term stability. In the existence of lanthanum (La3+) ion, the GSH@AuNCs emission was sharply raised owing to the formation of La3+/GSH@AuNCs system accompanied with aggregation-induced emission enhancement (AIEE). Addition of CIPRO, a good La3+ ion coordinator, decreased the fluorescence emission of La3+/GSH@AuNCs system at 610 nm significantly as a result of disaggregation caused by the removal of La3+ ion from GSH@AuNCs surface. Furthermore, the blue emission of La3+-CIPRO coordination complex appears at 440 nm. Under optimized conditions, the fluorescence ratios (F440/F610) were linearly increased with increasing the CIPRO amount within the range of 0.003–200 µM with a limit of detection equal to 0.2 nM (S/N = 3). The as-fabricated La3+/GSH@AuNCs system possesses outstanding reliability and sensitivity for the detection of CIPRO. The system was effectively used to assay CIPRO in human urine and milk specimens with recoveries % of 97.6–102.3 % and 96.7–105.7 % for urine and milk samples, respectively and RSD % did not exceed 2.5 %, suggesting the accuracy of the method.

Theoretical predictions and electronic properties of thiolate-protected gold nanocluster: Au44(SR)32

Thiolate-protected gold nanoclusters have received extensive attention both experimentally and theoretically due to their excellent physical and chemical properties. However, comprehending the geometric structure of thiolate-protected gold nanoclusters remains a challenging task. Predicting the structural configuration of these ligand-protected gold nanoclusters can enhance our understanding of this class of materials. Due to the current lack of knowledge regarding the structure of Au44(SR)32, we employed the grand unified model (GUM) for gold core stacking and the ring model to describe interfacial interactions between gold cores and the protection motifs. Based on these models, we successfully predicted the geometric structure of Au44(SR)32 clusters and demonstrated partial reproducibility between the calculated absorption spectra and experimental results. Furthermore, by analyzing the energy levels and molecular orbitals, we have identified that the absorption spectra of Au44(SR)32 arise from d→d and d→sp transitions, with the low-energy state primarily resulting from Au44-to-core transitions and the high-energy state from Au44-to-ligand transitions. These findings not only enhance our understanding of Au44(SR)32 clusters but also validate the effectiveness and applicability of GUM and ring model in predicting stable structures of thiolate-protected gold nanoclusters.

Ligand impact on reactive oxygen species generation of Au10 and Au25 nanoclusters upon one- and two-photon excitation

In photodynamic therapy (PDT), light-sensitive photosensitizers produce reactive oxygen species (ROS) after irradiation in the presence of oxygen. Atomically-precise thiolate-protected gold nanoclusters are molecule-like nanostructures with discrete energy levels presenting long lifetimes, surface biofunctionality, and strong near-infrared excitation ideal for ROS generation in PDT. We directly compare thiolate-gold macromolecular complexes (Au10) and atomically-precise gold nanoclusters (Au25), and investigate the influence of ligands on their photoexcitation. With the ability of atomically-precise nanochemistry, we produce Au10SG10, Au10AcCys10, Au25SG18, and Au25AcCys18 (SG: glutathione; AcCys: N-acetyl-cysteine) fully characterized by high-resolution mass spectrometry. Our theoretical investigation reveals key factors (energetics of excited states and structural influence of surface ligands) and their relative importance in singlet oxygen formation upon one- and two-photon excitation. Finally, we explore ROS generation by gold nanoclusters in living cells with one- and two-photon excitation. Our study presents in-depth analyses of events within gold nanoclusters when photo-excited both in the linear and nonlinear optical regimes, and possible biological consequences in cells.

Inside Front Cover: Atomically precise thiolate‐protected gold nanoclusters: Current status of designability of the structure and physicochemical properties

Negishi et al. summarized representative examples of previous studies concerning the geometry, electronic structure, luminescence properties, catalysis, magnetism and optical activity of thiolate-protected gold nanoclusters, and discusses the current status of the designability of those nanoclusters to impart specific structural and physicochemical characteristics. This information is expected to accelerate the fabrication of highly functional materials based on metal nanoclusters (e255).

Structural predictions of three medium-sized thiolate-protected gold nanoclusters Au44(SR)30, Au56(SR)32, and Au60(SR)34.

The knowledge of structural evolution among thiolate-protected gold nanoclusters is not only helpful for understanding their structure-property relationship but also provides scientific evidence to rule-guided structure predictions of gold nanoclusters. In this paper, three new atomic structures of medium-sized thiolate-protected gold nanoclusters, i.e. Au44(SR)30, Au56(SR)32, and Au60(SR)34, are predicted based on the grand unified model and ring model. Two structural evolution rules, i.e., Au44(SR)28 + [Au12(SR)4] → Au56(SR)32 + [Au12(SR)4] → Au68(SR)36 and Au44(SR)30 + [Au8(SR)2] → Au52(SR)32 + [Au8(SR)2] → Au60(SR)34 + [Au8(SR)2] → Au68(SR)36, are explored. The generic growth patterns underlying both sequences of nanoclusters can be viewed as sequential addition of four and three highly stable tetrahedral Au4 units on the cores, respectively. In addition, density functional theory calculations show that these three newly predicted gold nanoclusters have very close formation energies with their adjacent structures, large highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gaps, and all-positive harmonic vibration frequencies, indicating their high stabilities.

Control over product formation and thermodynamic stability of thiolate-protected gold nanoclusters through tuning of surface protecting ligands.

Surface-protecting ligands can regulate the structure of a cluster's core either through electronic or steric effects. However, the influence of the steric effect along with the electronic effect over controlling the structure during ligand exchange reactions remains elusive. To understand this, we have carried out ligand exchange on [Au23(CHT)16]- (CHT: cyclohexane thiol) using aromatic thiolates where we have tuned the bulkiness at the para position of the thiolate group on the incoming ligands. The outcome of the experiments reveals that each of the ligands in the chosen series is precisely selective towards the parent cluster transformation through specific intermediates. The ligand with more steric crowding directed the reaction pathway to have Au28 nanocluster as the major product while Au36 was the final product obtained with the gradual decrease of bulkiness over the ligand. The combined experimental and theoretical results elucidated the mechanism of the reaction pathways, product formation, and their stability. Indeed, this study with the series of ligands will add up to the ligand library, where we can decide on the ligand to obtain our desired cluster for specific applications through the ligand exchange reaction.

Elucidation of the electronic structures of thiolate-protected gold nanoclusters by electrochemical measurements.

Metal nanoclusters (NCs) with sizes of approximately 2 nm or less have different physical/chemical properties from those of the bulk metals owing to quantum size effects. Metal NCs, which can be size-controlled and heterometal doped at atomic accuracy, are expected to be the next generation of important materials, and new metal NCs are reported regularly. However, compared with conventional materials such as metal complexes and relatively large metal nanoparticles (>2 nm), these metal NCs are still underdeveloped in terms of evaluation and establishment of application methods. Electrochemical measurements are one of the most widely used methods for synthesis, application, and characterisation of metal NCs. This review summarizes the basic knowledge of the electrochemistry and experimental techniques, and provides examples of the reported electronic states of thiolate-protected gold NCs elucidated by electrochemical approaches. It is expected that this review will provide useful information for researchers starting to study metal NCs.

Atomically precise thiolate-protected gold nanoclusters: current advances in solar-powered photoredox catalysis

The latest developments in atomically precise gold nanocluster based photosystems for solar energy conversion are comprehensively summarized and elucidated.

Isomerism effects in relaxation dynamics of Au24(SR)16 thiolate-protected gold nanoclusters

Understanding the excited state behavior of isomeric structures of thiolate-protected gold nanoclusters is still a challenging task. In this paper, based on grand unified model and ring model for describing thiolate-protected gold nanoclusters, we have predicted four isomers of Au24(SR)16 nanoclusters. Density functional theory calculations show that the total energy of one of the predicted isomers is 0.1 eV lower in energy than previously crystallized isomer. The nonradiative relaxation dynamics simulations of Au24(SH)16 isomers are performed to reveal the effects of structural isomerism on relaxation process of the lowest energy states, in which that most of the low-excited states consist of core states. In addition, crystallized isomer possesses the shorter e–h recombination time, whereas the most stable isomer has the longer recombination time, which may be attributed to the synergistic effect of nonadiabatic coupling and decoherence time. Our results could provide practical guidance to predict new gold nanoclusters for future experimental synthesis, and stimulate the exploration of atomic structures of same sized gold nanoclusters for photovoltaic and optoelectronic devices.

Structural prediction of anion thiolate protected gold clusters of [Au28+7n(SR)17+3n]- (n = 0-4).

Structural prediction of thiolate-protected gold nanoclusters (AuNCs) with diverse charge states can enrich the understanding of this species. Untill now, the number of anion AuNCs is still deficient. In this work, a series of gold nanoclusters with negative total charge, including [Au28(SR)17]-, [Au35(SR)20]-, [Au42(SR)23]-, [Au49(SR)26]-, and [Au56(SR)29]-, are designed. Following a crystallized [Au23(SR)16]- prototype structure, the inner core of the newly predicted clusters is obtained through packing crossed Au7. Next, proper protecting thiolate ligands are arranged to fulfill the duet rule to obtain Au3(2e) and Au4(2e). Extensive analysis indicates that these clusters own high stabilities. Molecular orbital analysis shows that the orbitals for the populations of the valence electron locate at each Au3(2e) and Au4(2e), which demonstrates the reliability of the grand unified model. This work should be helpful for enriching the structural diversity of AuNCs.

Assembling Au4 Tetrahedra to 2D and 3D Superatomic Crystals Based on Superatomic-Network Model.

Thiolate-protected gold nanoclusters (denoted as Aum(SR)n or AunLm) have received extensive attention both experimentally and theoretically. Understanding the growth mode of the Au4 unit in Aum(SR)n is of great significance for experimental synthesis and the search for new gold clusters. In this work, we first build six clusters of Au7(AuCl2)3, Au12(AuCl2)4, Au16(AuCl2)6, Au22(AuCl2)6, and Au30(AuCl2)6 with the Au4 unit as the basic building blocks. Density functional theory (DFT) calculations show that these newly designed clusters have high structural and electronic stabilities. Based on chemical bonding analysis, the electronic structures of these clusters follow the superatom network (SAN) model. Inspired by the cluster structures, we further predicted an Au4 two-dimensional (2D) monolayer and a three-dimensional (3D) crystal using graphene and diamond as templates, respectively. The computational results demonstrate that the two structures have high dynamic, thermal, and mechanical stabilities, and both structures exhibit metallic properties according to the band structures calculated at the HSE06 level. The chemical bonding analysis by the solid-state natural density partitioning (SSAdNDP) method indicates that they are superatomic crystals assembled by two electron Au4– superatoms. With this construction strategy, the new bonding pattern and properties of AunLm are studied and the structure types of gold are enriched.

Doping Effects in the Thiolate-Protected Gold Nanoclusters from the Perspective of Balance Between Ligands and the Core

The atomically precise method has become an important technique for adjusting the core of thiolate-protected gold nanoclusters to improve biological, physical, and chemical properties. But, the doping effect on the structural stability across different elements has not been modeled within the scope of a bigger picture. Therefore, in this work, the H2S–nanoalloy complexes with different doping metal atoms have been investigated to elucidate the effects of the dopant on the structures. Indicated by simplified model complexes and density functional theory (DFT) simulation results, the zinc group atoms as dopants may be influenced by surrounded gold atoms, and binding to the thiolate units is enhanced by the addition of gold atoms. The reactivity of the zinc group atoms may be activated by a gold nanocluster. The simulated zinc group data when combined with the gold group and platinum group data can be summarized in the perspective of balance between the ligand–core binding and core cohesive energies. Most dopants move the modeled nanoclusters away from the balance, especially when the metal atom replaced the gold atom in gold–sulfur bindings. Besides, when cores of the nanoclusters are dominated by gold atoms, the dopants may achieve “saturation” such that the balance in the doped clusters may be corrected. This work provides a simple profile to understand the internal shift of the structure introduced by the atomically precise method.