Superatomic Electron Research Articles

Enhanced stability of the Nb3O6- and Nb4O6+ clusters: the nxcπ rule versus superatomic nature.

This study examines the chemical reactivity of niobium clusters with carbon dioxide (CO2), with an emphasis on the analysis of the ensuing products Nb4O6+ and Nb3O6-, which show up in the cationic and anionic mass spectra, respectively. Using density functional theory (DFT) calculations, we demonstrate the reactivity of the Nbn± clusters with CO2 and reveal distinct stabilization mechanisms for the two prominent products. The stability of Nb3O6- is determined by the existence of ten π bonds pertaining to π-electron delocalization, which conforms to the nxcπ electron configuration model. Despite having only a one-atom distinction, Nb4O6+ exhibits superatomic electron shells embodying superatom stability. The divergent stabilizing mechanisms found in Nb4O6+ and Nb3O6- illustrate the intricate nature of cluster chemistry and the significance of electronic structure in governing cluster stability and reactivity.

Collision-Induced Fission of Oblate Gold Superatom in [Au9(PPh3)8]3+: Deformation-Mediated Mechanism.

Collision-induced dissociation (CID) patterns of the phosphine-protected Au-based clusters [PdAu8(PPh3)8]2+ (PdAu8) and [Au9(PPh3)8]3+ (Au9), featuring crown-shaped M@Au8 (M = Pd, Au) cores, were investigated. For PdAu8, ordinary sequential PPh3 losses (PdAu8 → [PdAu8(PPh3)m]2+ + (8 - m)PPh3 (m = 7, 6, 5)) were observed. In contrast, Au9 underwent cluster-core fission (Au9 → [Au6(PPh3)6]2+ (Au6) + [Au3(PPh3)2]+ (Au3)) upon sufficiently high energy collision, associated with splitting the number of valence electrons in the superatomic orbitals from 6e (Au9) into 4e (Au6) and 2e (Au3). Density functional theory calculations revealed oblate and prolate cores of Au9 and Au6 with semiclosed superatomic electron configurations of (1S)2(1Px)2(1Py)2 and (1S)2(1Pz)2, respectively. This result indicated a significant deformation of the cluster-core motif during the CID process. We attribute the clear difference between PdAu8 and Au9 to the softer Au-Au bond in Au9 and propose that the collision-induced structural deformation plays a critical role in the fission.

Controlled Shell and Kernel Modifications of Atomically Precise Pd/Ag Superatomic Nanoclusters.

The first 8-electron Pd/Ag superatomic alloys with an interstitial hydride [PdHAg19(dtp)12] (dtp = S2P(O i Pr)2-) 1 and [PdHAg20(dtp)12]+2 are reported. The targeted addition of a single Ag atom to 1 is achieved by the reaction of one equivalent of trifluoroacetic acid, resulting in the formation of 2 in 55% yield. Further modification of the shell results in the formation of [PdAg21(dtp)12]+3 via an internal redox reaction, with the system retaining an 8-electron superatomic configuration. The interstitial hydride in 1 and 2, contributes its 1s1 electron to the superatomic electron count, and occupies a PdAg3 tetrahedron. The distributions of isomers corresponding to different dispositions of the outer capping Ag atoms are investigated by multinuclear VT-NMR spectroscopy. The emissive state of 3 has a lifetime of 200 μs (λex =448; λem =842), while 1 and 2 are non-emissive. The catalytic reduction of 4-nitrophenol is demonstrated with 1-3 at room temperature.

From 8- to 18-Cluster Electrons Superatoms: Evaluation via DFT Calculations of the Ligand-Protected W@Au12(dppm)6 Cluster Displaying Distinctive Electronic and Optical Properties

The iconic W@Au12 icosahedral bare cluster reaches the favorable closed-shell superatomic electron configuration 1S2 1P6 1D10, making it an 18-cluster electron (18-ce) superatom. Here, we pursue the evaluation of a ligand-protected counterpart based on the construction of a fully phosphine-protected [W@Au12(dppm)6] cluster strongly related to the characterized [Au13(dppm)6]5+ homometallic counterpart. The later cluster has the same total number of valence electrons as the former but is considered an 8-ce superatom with 1S2 1P6 configuration. The fundamental differences between 8- and 18-ce species are investigated. The character of the frontier orbitals varies from 1P/1D in the 8-ce case to a 1D/ligand for 18-ce species, enabling an efficient charge transfer toward the ligands upon irradiation, being interesting for electron injection in optoelectronic devices and black absorbers applications. Excited-state properties are also revisited, showing different geometrical and electronic structure variations between 8- and 18-ce species. Moreover, the continuum between the 8- and 18-ce limits has been explored by varying the nature of the encapsulated dopant between group 6 and group 11. The transition between the 8- and 18-ce counts can be formally situated between Pt (8-ce) and Ir (18-ce). Thus, 18-ce derivatives obtained as doped counterparts of homometallic gold clusters can introduce useful alternatives to achieve different properties in related structural motifs, which can be further explored owing to their extension of the well-established versatility of current gold nanoclusters.

Robust Gold Nanocluster Protected with Amidinates for Electrocatalytic CO2 Reduction.

The first all-amidinate-protected gold nanocluster [Au28 (Ph-form)12 ](OTf)2 (Ph-form=N,N'-diphenylformamidinate) (Au28 ) has been synthesized and structurally resolved. Single crystal X-ray diffraction reveals that Au28 has a compact Au4 @Au24 tetrahedral core-shell structure of T symmetry, which is fully protected by 12 bridging formamidinate ligands. This cluster is quite robust as indicated by the fact that it can stay intact in solution at 80 °C for 6 d. It exhibits excellent catalytic performance for the electroreduction of CO2 with 96.5 % Faradaic efficiency (FE) at -0.57 V and a maximum TOF of 1731 h-1 at -0.87 V. Its superior stability is also manifested in the fact that the supported catalyst Au28 /CNTs maintains stable potentials at ca. -0.69 V for 40 h with FE(CO)s>91 %. A superatomic electron configuration of 1S2 1P6 2S2 1D4 has been clarified by DFT computations, and the strong gold-ligand binding and geometric shell closure account for the superior stability of Au28 .

Robust Gold Nanocluster Protected with Amidinates for Electrocatalytic CO2 Reduction

AbstractThe first all‐amidinate‐protected gold nanocluster [Au28(Ph−form)12](OTf)2 (Ph‐form=N,N′‐diphenylformamidinate) (Au28) has been synthesized and structurally resolved. Single crystal X‐ray diffraction reveals that Au28 has a compact Au4@Au24 tetrahedral core–shell structure of T symmetry, which is fully protected by 12 bridging formamidinate ligands. This cluster is quite robust as indicated by the fact that it can stay intact in solution at 80 °C for 6 d. It exhibits excellent catalytic performance for the electroreduction of CO2 with 96.5 % Faradaic efficiency (FE) at −0.57 V and a maximum TOF of 1731 h−1 at −0.87 V. Its superior stability is also manifested in the fact that the supported catalyst Au28/CNTs maintains stable potentials at ca. −0.69 V for 40 h with FE(CO)s>91 %. A superatomic electron configuration of 1S21P62S21D4 has been clarified by DFT computations, and the strong gold–ligand binding and geometric shell closure account for the superior stability of Au28.

Atomically Precise Alkynyl- and Halide-Protected AuAg Nanoclusters Au78Ag66(C≡CPh)48Cl8 and Au74Ag60(C≡CPh)40Br12: The Ligation Effects of Halides.

Reported herein are the synthesis and structures of two high-nuclearity AuAg nanoclusters, namely, [Au78Ag66(C≡CPh)48Cl8]q- and [Au74Ag60(C≡CPh)40Br12]2-. Both clusters possess a three-concentric-shell Au12@Au42@Ag60 structure. However, the dispositions of the metal atoms, and the ligand coordination modes, of the outermost shells of these clusters are distinctly different. These structural differences reflect the bonding characteristics of the halide ligands. As revealed by density functional theory analysis, these clusters exhibit superatomic electron shell closings at magic numbers of 92 (for q = 4) and 84, respectively, consistent with their spherical shapes. Both clusters exhibit unusual multivalent redox properties.

Understanding Superatomic Ag Nanohydrides.

Bulk Ag hydrides are extremely challenging to make even at very high pressures, but they may become stable as the particle size shrinks to the nanometer regime. Here, the formation and electronic structure of Ag nanohydrides are investigated from a superatomic perspective by density functional theory. It is found that as the coverage increases, adsorption energy of hydrogen atoms on Ag38 cluster to form Ag38 H2 n nanohydride (n is from 1 to 15) can be energetically favorable with respect to bare Ag38 and H2 . Furthermore, the adsorbed hydrogen atoms contribute their 1s electrons to the superatom electron count and behave as a metal instead of a ligand. The electronic structure of the silver nanohydrides follows the superatomic complex model, leading to magic or relatively more stable compositions such as Ag38 H2 , Ag38 H20 , and Ag38 H30 , which correspond to 40-electron, 58-electron, and 68-electron shell closings, respectively. Angular momentum analyses of the superatomic orbitals suggest a convoluted interaction of geometry, symmetry, and orbital splitting.

Observable but Not Isolable: The RhAu24 (PET)181+ Nanocluster.

The synthesis and characterization of RhAu24 (PET)18 (PET = 2-phenylethanethiol) is described. The cluster is cosynthesized with Au25 (PET)18 and rhodium thiolates in a coreduction of RhCl3 , HAuCl4 , and PET. Rapid decomposition of RhAu24 (PET)18 occurs when purified from the other reaction products, precluding the study of isolated cluster. Mixtures containing RhAu24 (PET)18 , Au25 (PET)18 , and rhodium thiolates are therefore characterized. Mass spectrometry, X-ray photoelectron spectroscopy, and chromatography methods suggest a combination of charge-charge and metallophilic interactions among Au25 (PET)181- , rhodium thiolates and RhAu24 (PET)18 resulting in stabilization of RhAu24 (PET)18 . The charge of RhAu24 (PET)18 is assigned as 1+ on the basis of its stoichiometric 1:1 presence with anionic Au25 (PET)18 , and its stability is contextualized within the superatom electron counting rules. This analysis concludes that the Rh atom absorbs one superatomic electron to close its d-shell, giving RhAu24 (PET)181+ a superatomic electron configuration of 1S2 1P4 . Overall, an updated framework for rationalizing open d-shell heterometal dopant electronics in thiolated gold nanoclusters emerges.

Tuneable magnetic moments in superatomic CuXNi8−X clusters

The geometries and electronic structures for CuXNi8−X (X = 1–8) clusters have been elucidated using density functional theory methods. These clusters have been demonstrated to be eight superatomic electron species, with a substantial HOMO-LUMO gap and closed 1S and 1P subshells. Through sequential replacement of copper atoms for nickel in these clusters it has been shown that the magnetic moment of bimetallic clusters can be controllably altered, with the nickel atoms localising spin density in their 3d orbitals.

Insights into Interfaces, Stability, Electronic Properties, and Catalytic Activities of Atomically Precise Metal Nanoclusters from First Principles.

Atomically precise, ligand-protected metal nanoclusters are of great interest for their well-defined structures, intriguing physicochemical properties, and potential applications in catalysis, biology, and nanotechnology. Their structure precision provides many opportunities to correlate their geometries, stability, electronic properties, and catalytic activities by closely integrating theory and experiment. In this Account, we highlight recent theoretical advances from our efforts to understand the metal-ligand interfaces, the energy landscape, the electronic structure and optical absorption, and the catalytic applications of atomically precise metal nanoclusters. We mainly focus on gold nanoclusters. The bonding motifs and energetics at the gold-ligand interfaces are two main interests from a computational perspective. For the gold-thiolate interface, the -RS-Au-SR- staple motif is not always preferred; in fact, the bridging motif (-SR-) is preferred at the more open facets such as Au(100) and Au(110). This finding helps understand the diversity of the gold-thiolate motifs for different core geometries and sizes. A great similarity is demonstrated between gold-thiolate and gold-alkynyl interfaces, regarding formation of the staple-type motifs with PhC≡C- as an example. In addition, N-heterocyclic carbenes (NHCs) without bulky groups also form the staple-type motif. Alkynyls and bulky NHCs have the strongest binding with the gold surface from comparing 27 ligands of six types, suggesting a potential to synthesize NHC-protected gold clusters. The energy landscape of nanosystems is usually complex, but experimental progress in synthesizing clusters of the same Au-S composition with different R groups and isomers of the same Au n(SR) m formula have made detailed theoretical analyses of energetic contributions possible. Ligand-ligand interactions turn out to play an important role in the cluster stability, while metastable isomers can be obtained via kinetic control. Although the superatom-complex theory is the starting point to understand the electronic structure of atomically precise gold clusters, other factors also greatly affect the orbital levels that manifest themselves in the experimental optical absorption spectra. For example, spin-orbit coupling needs to be included to reproduce the splitting of the HOMO-LUMO transition observed experimentally for Au25(SR)18-, the poster child of the family. In addition, doping can lead to structural changes and charge states that do not follow the superatomic electron count. Atomically precise metal nanoclusters are an ideal system for understanding nanocatalysis due to their well-defined structures. Active sites and catalytic mechanisms are explored for selective hydrogenation and hydrogen evolution on thiolate-protected gold nanoclusters with and without dopants. The behavior of H in nanogold is analyzed in detail, and the most promising site to attract H is found to be coordinately unsaturated Au atoms. Many insights have been gained from first-principles studies of atomically precise, ligand-protected gold nanoclusters. Interesting and important questions remaining to be addressed are pointed out in the end.

Hydride Induced Formation and Optical Properties of Tetrahedral [Cu4(μ4-H)(μ2-X)2(PPh2Py)4]+ Clusters (X = Cl, Br; Py = pyridyl)

Three standalone tetrahedral copper hydride clusters, [Cu4(μ4-H)(μ2-X)2(PPh2Py)4]+ (X = Cl, Br; Py = pyridyl), containing a tetrahedral [Cu4(μ4-H)] unit have been synthesized and structurally characterized. The six Cu–Cu distances of the [Cu4(μ4-H)] unit can be divided into three groups (2.65, 2.85, and 2.95 A), lowering the idealized point group of the Cu4 core to D2 symmetry, thereby resulting in intrinsically chiral metal clusters which exist as racemic pairs of enantiomers in the centrosymmetric crystal structures. Strong photoluminescence (attributable to the existence of the two short Cu–Cu distances of 2.65 A) was observed in solution and in the solid state upon near-UV irradiation. According to the Jellium model, the title clusters can be considered as two-shell Jelliumatic systems with superatomic electron counts of 2e@0e corresponding to the two shells of H−@[Cu4X2(PPh2Py)4]2+. The four-coordinated hydride in the tetrahedral Cu4 cavity adopts the superatomic electronic configuration of 1S2.

Practical Stability of Au25(SR)18-1/0/+1.

Superatom electron shell and/or geometric shell filling underlies the thermodynamic stability of coinage and alkali metal clusters in both theoretical and experimental results. Factors beyond simple shell filling contribute substantially to the lifetime of ligated clusters in solution. Such factors include the nature of the solvent, the atmosphere and the steric size of the ligand shell. Here we systematically lay out a 'practical' stability model for ligated metal clusters, which includes both shell-closing aspects and colloidal stability aspects. Cluster decomposition may follow either fusion or fission pathways. Solvent polarity can be determinative of the decomposition pathway.

Ce@Au14: A Bimetallic Superatom Cluster with 18-Electron Rule

Doping of gold clusters and nanoparticles has received substantial attention due to their ability to encapsulate atoms and molecules. Here, the geometric and electronic properties of the cerium-encapsulated nanocage Ce@Au14 are reported using density functional theory. Calculated results show that its ground electronic state is a singlet state and conforms to the superatomic 18-electron configuration of 1S21P61D10 jellium state, both primarily involving the bonding interaction between s- and d-shell atomic orbitals of the Ce atom and superatomic orbitals of the hollow polyhedral Au14 cage. In addition, it should be noted that f electrons in rare earth atoms trend to retain their localized state, and their doping in gold clusters could easily lead to clusters with large magnetic moments. However, in the case of superatom clusters, the f-shell electrons will be the preferential arrangement at the unfilled d-shell to satisfy the superatomic electron structure. Further analysis of the electronic structure also proves that the unoccupied 1F superatomic orbitals mainly originate from the contribution of the 4f-shell. As a consequence, this work provides a theoretical basis for the future design and synthesis of f-elements-encapsulated gold nanoclusters.

Electrochemistry of Superatomic M@Au24(SR)18 (M=Pd, Pt) Clusters and Their Application in Electrocatalysis

Atomically precise gold clusters containing from a few to a few hundreds of atoms have been the focus of recent investigations because of their unique electronic structures with high chemical and thermodynamic stability. In particular, the extraordinary stability of these superatom-like gold clusters, for example [Au25(SR)18]- where SR is organothiolate, arises from the closure of superatomic electron shells, leading to a noble-gas-like 8-electron configuration (1S21P6). In this presentation, we report that replacing the core Au atom with Pd or Pt results in stable bimetallic clusters, [MAu24(SR)18]0 (M = Pd, Pt), having a superatomic 6-electron configuration (1S21P4). These clusters exhibit dramatically different optical and electrochemical properties from those of the 8-electron [Au25(SR)18]-. The highest occupied molecular orbital−lowest unoccupied molecular orbital gaps of [PdAu24(SR)18]0 and [PtAu24(SR)18]0 determined by voltammetry were drastically decreased to 0.32 and 0.29 eV from that of [Au25(SR)18]- (1.32 eV), respectively, indicating their electronic structures were significantly altered upon doping of the foreign metal. The unique electrochemical properties observed from the stable bimetallic clusters suggest that doping of a cluster is a powerful means to fine-tune the redox properties of the cluster, offering special advantages in the development of new functional electrocatalysis. Voltammetric investigation shows that the PtAu24(SR)18 cluster exhibits exceptionally high catalytic activity for hydrogen evolution reaction (HER). The origin of the extraordinary catalytic activity of this cluster is discussed along with reaction mechanisms.

Interconversion between Superatomic 6-Electron and 8-Electron Configurations of M@Au₂₄(SR)₁₈ Clusters (M = Pd, Pt).

The exceptional stability of thiolate-protected Au25 clusters, [Au25(SR)18](-), arises from the closure of superatomic electron shells, leading to a noble-gas-like 8-electron configuration (1S(2)1P(6)). Here we present that replacing the core Au atom with Pd or Pt results in stable [MAu24(SR)18](0) clusters (M = Pd, Pt) having a superatomic 6-electron configuration (1S(2)1P(4)). Voltammetric studies of [PdAu24(SR)18](0) and [PtAu24(SR)18](0) reveal that the highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gaps of these clusters are 0.32 and 0.29 eV, respectively, indicating their electronic structures are drastically altered upon doping of the foreign metal. Density functional investigations confirm that the HOMO-LUMO gaps of these clusters are indeed smaller, respectively 0.33 and 0.32 eV, than that of [Au25(SR)18](-) (1.35 eV). Analysis of the optimized geometries for the 6-electron [MAu24(SR)18](0) clusters shows that the MAu12 core is slightly flattened to yield an oblate ellipsoid. The drastically decreased HOMO-LUMO gaps observed are therefore the result of Jahn-Teller-like distortion of the 6-electron [MAu24(SR)18](0) clusters, accompanying splitting of the 1P orbitals. These clusters become 8-electron [MAu24(SR)18](2-) clusters upon electronic charging, demonstrating reversible interconversion between the 6-electron and 8-electron configurations of MAu24(SR)18.

Electronic structure and optical properties of the intrinsically chiral 16-electron superatom complex [Au20(PP3)4](4+).

The recently solved crystal structure of the [Au20(PP3)4]Cl4 cluster (PP3: tris(2-(diphenylphophino)ethyl)phosphine) is examined using density functional theory (DFT). The Au20 core of the cluster is intrinsically chiral by the arrangement of the Au atoms. This is in contrast to the chirality of thiolate-protected gold clusters, in which the protecting Au-thiolate units are arranged in chiral patterns on achiral cores. We interpret the electronic structure of the [Au20(PP3)4]Cl4 cluster in terms of the superatom complex model. The 16-electron cluster cannot be interpreted as a dimer of 8-electron clusters (which are magic). Instead, a superatomic electron configuration of 1S(2) 1P(6) 1D(6) 2S(2) is found. The 2S band is strongly stabilized, and the 1D states are nondegenerate with a large gap. Ligand protection of the (Au20)(4+) core leads to a significant increase of the HL-gap and thus stabilization. We also tested a charge of +II, which would give rise to an 18-electron superatom complex. Our results indicate that the 16-electron cluster is indeed more stable. We also investigate the optical properties of the cluster. The experimental absorption spectrum is well-reproduced by time-dependent DFT. Prominent transitions are analyzed by time-dependent density-functional perturbation theory. The intrinsic chirality of the cluster is compared to that of Au38(SR)24. We observe that the chiral arrangement of the protecting Au-SR units in Au38(SR)24 has very strong influence on the strength of the CD spectra, whereas phosphine protection in the title compound does not.

Geometric, Electronic, and Optical Properties of Monomer and Assembly of Endohedral Aluminum Superatomic Clusters

Density functional computations are used to evaluate the geometric, electronic, and optical properties of endohedral aluminum clusters X@Al12 (X = B, Al, Si, P) and their assemblies. All X@Al12+/0/– clusters are perfect or slightly distorted icosahedral structures, with the exception of Al13+, which is highly distorted. The projected density of states (PDOS) onto the spherical harmonics of monomers clearly reveals superatom behavior and electron shell closings of F orbitals in a 40-electron species. The electronic absorption spectrum of SiAl12 is analyzed in terms of the superatom orbitals. The optimized structures of X@Al12–Y@Al12 (X–Y = Si–Si, B–P, Al–P) dimers are constructed by facing the sides of the monomers in a staggered fashion. The PDOS of the dimers mostly exhibit five hybridizations: S, P, SD, PF, and SDG. The exceptions are HOMO, which possesses a DFG hybridized character and lies between the PF and SDG regions, and LUMO, which possesses a DG hybridized character. By analyzing the simulated absorption spectra of the B@Al12–P@Al12 and Al13–P@Al12 heterodimers, charge transfers from B/Al@Al12 to P@Al12 are found in the visible region, weakly accompanying the opposite charge transfer. The heterodimers have substantial charge carriers, estimated as the difference in electron counts from the closed-shell Si@Al12, with slight charge depletions (∼0.2). The charge distributions in B@Al12 and P@Al12 are essentially unaltered by the insertion of Si@Al12 into the heterodimer, resulting in that the heterotrimer possesses a larger dipole moment than the heterodimer.

Superatom Electron Configuration Predicts Thermal Stability of Au25(SR)18 Nanoclusters

The exceptional stability of ligand-stabilized gold nanoclusters such as Au(25)(SC(6)H(13))(18)(-), Au(39)(PR(3))(14)X(6)(-), and Au(102)(SR)(44) arises from the total filling of superatomic electron shells, resulting in a "noble-gas superatom" electron configuration. Electrochemical manipulation of the oxidation state can add or remove electrons from superatom orbitals, creating species electronically analogous to atomic radicals. Herein we show that oxidizing the Au(25)(SR)(18)(-) superatom from the noble-gas-like 1S(2)1P(6) electron configuration to the open-shell radical 1S(2)1P(5) and diradical 1S(2)1P(4) configurations results in decreased thermal stability of the compound, as measured by differential scanning calorimetry. Similar experiments probing five oxidation states of the putatively geometrically stabilized Au(144)(SR)(60) cluster suggest a more complex relationship between oxidation state and thermal stability for this compound.