and Au6 clusters: Superatomic molecules bearing an SP3‐hybrid Au6 core

The octahedral Au₆ core is explored for the formation of novel SP³‐hybrid superatomic molecules by considering and Au₆ clusters (X= F, Cl, Br, I). The bonding between the four capping atoms and the Au₆ core requires a combination of 1S and 1P shells of the core leading to a set of four equivalent hybrid orbitals. Thus, combining the superatom concept with both the Lewis structure model and VSEPR theory contributes to the rationalization of structure and bonding in metal clusters. For example, our results consider the Au₆ clusters as analogues of the simplest perhalogenated hydrocarbon, CX₄.     

Magnesium-Based Clusters as Building Blocks of Electrolytes in Lithium-Ion Batteries

Superhalogens, owing to their large electron affinity (EA, exceeding those of any halogen atom), play an essential role in physical chemistry as well as new material design. They have applications in hydrogen storage and lithium-ion batteries. Owing to the unique geometries and electronic features of magnesium-based clusters, their potential to form a new class of lithium salts has been investigated here theoretically. The idea is assessed by conducting ab initio computations on Li⁺/Mg_nF_2n+1-2mO_m⁻ compounds (n=2, 3; m=0-3) and analyzing their performance as potential Li-ion battery electrolytes. The Mg₃F₇⁻ cluster, with large electron binding energy (EA of 7.93 eV), has been proven to serve as a building block for lithium salts. It is shown that, apart from high electronic stability, the new superhalogen-based electrolytes exhibit a set of desirable properties, including a large band gap, high electrolyte stability window, easy mobility of the Li⁺, and favorable insensitivity to water.     

Perfect Core-Shell Octahedral B@B38+, Be@B38, and Zn@B38 with an Octa-Coordinate Center as Superatoms Following the Octet Rule

Planar, tubular, cage-like, and bilayer boron clusters B_n^+/0/− (n=3∼48) have been observed in joint experimental and theoretical investigations in the past two decades. Based on extensive global searches augmented with first-principles theory calculations, we predict herein the smallest perfect core-shell octahedral borospherene O_h B@B₃₈⁺ ( 1 ) and its endohedral metallo-borospherene analogs O_h Be@B₃₈ ( 2 ), and O_h Zn@B₃₈ ( 3 ) which, with an octa-coordinate B, Be or Zn atom located exactly at the center, turn out to be the well-defined global minima of the systems highly stable both thermodynamically and dynamically. B@B₃₈⁺ ( 1 ) represents the first boron-containing molecule reported to date which contains an octa-coordinate B center covalently coordinated by eight face-capping boron atoms at the corners of a perfect cube in the first coordination sphere. Detailed natural bonding orbital (NBO) and adaptive natural density partitioning (AdNDP) bonding analyses indicate that these high-symmetry core-shell complexes X@B₃₈^+/0/− (X=B, Be, Zn) as super-noble gas atoms follow the octet rule in coordination bonding patterns (1S²1P⁶), with one delocalized 9c-2e S-type coordination bond and three delocalized 39c-2e P-type coordination bonds formed between the octa-coordinate X center and its octahedral O_h B₃₈ ligand to effectively stabilize the systems. Their IR, Raman, and UV-Vis spectra are computationally simulated to facilitate their spectroscopic characterizations.     

Stepwise Assembly of an Electroactive Framework from a Co6S8 Superatomic Metalloligand and Cuprous Iodide Building Units

The design of metal–organic frameworks (MOFs) that incorporate more than one metal cluster constituent is a challenging task. Conventional one-pot reaction protocols require judicious selection of ligand and metal ion precursors, yet remain unpredictable. Stable, preformed nanoclusters, with ligand shells that can undergo additional coordination-driven reactions, provide a platform for assembling multi-cluster solids with precision. Herein, a discrete Co₆S₈(PTA)₆ (PTA=1,3,5-triaza-7-phosphaadamantane) superatomic-metalloligand is assembled into a three-dimensional (3D) coordination polymer comprising Cu₄I₄ secondary building units (SBUs). The resulting heterobimetallic framework ( 1 ) contains two distinct cluster constituents and bifunctional PTA linkers. Solid-state diffuse reflectance studies reveal that 1 is an optical semiconductor with a band-gap of 1.59 eV. Framework-modified electrodes exhibit reversible redox behavior in the solid state arising from the Co₆S₈ superatoms, which remain intact during framework synthesis.     

On the Possibility of Using the Jellium Model as a Guide To Design Bimetallic Superalkali Cations

The potential application of the jellium model as guidance in the rational design of bimetallic superalkali cations is examined under gradient-corrected density functional theory for the first time. By using Li, Mg, and Al as atomic building blocks, a series of bimetallic cationic clusters with 2, 8, 20, and 40 valence electrons are obtained and investigated. As the corresponding neutral clusters tend to lose one valence electron to achieve closed-shell states in the jellium model, these studied cations exhibit much lower vertical electron affinities (EA_vert, 3.42–4.95 eV) than the ionization energies (IEs) of alkali metal atoms, indicating their superalkali identities. The high stability of these cationic clusters is guaranteed by their considerable HOMO–LUMO gaps and binding energies per atom. Moreover, the feasibility of using the designed superalkalis as efficient reductants to activate CO₂ and N₂ molecules and as stable building blocks to assemble ionic superatom compounds is explored. Therefore, this study may provide an effective method for obtaining various metallic superatoms with extensive applications on the basis of the simple jellium rule.     

Bonding and properties of superatoms. Analogs to atoms and molecules and related concepts from superatomic clusters

Expanding the versatility of well-defined clusters is a fundamental issue in the design of functional nanostructures. In this sense, the concept of super atoms allows us to gain a deeper understanding and rationalization of the different properties of metallic clusters by invoking more familiar aspects. Recently, the super atoms appear to be intimately connected to other relevant tools of great chemical significance which enhance a rational design of superatomic clusters mimicking more complex structures and networks. Here, we expect to account for the research efforts from Latin American groups in the field, highlighting their valuable contribution to superatomic and related clusters.     

Interstitial Hydrides in Nanoclusters can Reduce M(I) (M=Cu,Ag, Au) to M(0) and Form Stable Superatoms

High-nuclearity clusters resemble the closest model between the determination of atomically precise chemical species and the bulk metallic version thereof, and both impacts on a variety of applications, including catalysis, optics, sensors, and new energy sources. Our interest lies with the nanoclusters of the Group 11 (Cu, Ag, Au) metals stabilized by dichalcogenido and hydrido ligands. Herein, we describe superatoms formed by the clusters and their relationship with precursor hydrido clusters. Specifically, our concept seeks to demonstrate a possible correlation that exist between hydrido clusters (and nanoalloys) and the formation of superatoms, with the loss of hydrides and typically with release of H₂ gas. These reactions appear to be internal self-redox reactions and require no additional reducing agent, but does seem to require a similar core structure. Knowledge of such processes could provide insight into how clusters grow and an understanding in bridging the atomically precise cluster – metal nanoparticle mechanism.     

An Atomically Precise Alkynyl‐Protected PtAg42 Superatom Nanocluster and Its Structural Implications

The synthesis and structure determination of an alkynyl‐protected Pt‐doped Ag superatom nanocluster, [PtAg₄₂(C≡CC₆H₄CH₃)₂₈](SbF₆)₆ (1) , are reported. The metallic core of this cluster can be viewed as a concentric three‐shell Russian doll comprising Pt@Ag₁₂@Ag₃₀, in which the missing icosidodecahedral Ag₃₀ shell and a new structural unit, M₄₃, have been observed. On the surface of 1 , 28 alkynyl groups and 4 SbF₆⁻ anions were found co‐protecting it. The protective role of SbF₆⁻ in nanoclusters is unprecedented. Moreover, of the 28 alkynyl ligands, 12 are connected not only with the outermost Ag₃₀ shell, but also the inner Ag₁₂ shell through the twelve pentagonal faces of the outermost icosidodecahedral Ag₃₀ shell. Overall, by determining the crystal structure of 1 , we discovered the missing icosidodecahedral Ag₃₀ shell and the protective effect of SbF₆⁻ anions and demonstrated a novel M₄₃ structural unit and the unique penetrability of pentagonal faces.     

Designing New Materials Using Atomic Clusters

Designing principles for forming stable metallic clusters whose chemistry mimics different atoms of the periodic table are discussed. It is shown that while bulk Al is a metal, the chemistry of an Al₁₃ resembles that of a halogen atom, a CAl₁₂ resembles an inert atom, while a NAl₁₂ resembles an alkali atom. The feasibility of making new materials using clusters as the building blocks is discussed. An ionic solid made out of Al₁₃ (or BAl₁₂) and Cs is shown to be metastable and marked by a large gap at the Fermi energy even though bulk Al and Cs are metals.     

Site Preference in Multimetallic Nanoclusters: Incorporation of Alkali Metal Ions or Copper Atoms into the Alkynyl‐Protected Body‐Centered Cubic Cluster [Au7Ag8(C≡CtBu)12]+

The synthesis, structure, substitution chemistry, and optical properties of the gold‐centered cubic monocationic cluster [Au@Ag₈@Au₆(C≡C^tBu)₁₂]⁺ are reported. The metal framework of this cluster can be described as a fragment of a body‐centered cubic (bcc) lattice with the silver and gold atoms occupying the vertices and the body center of the cube, respectively. The incorporation of alkali metal atoms gave rise to [M_nAg_8?nAu₇(C≡C^tBu)₁₂]⁺ clusters (n=1 for M=Na, K, Rb, Cs and n=2 for M=K, Rb), with the alkali metal ion(s) presumably occupying the vertex site(s), whereas the incorporation of copper atoms produced [Cu_nAg₈Au_7?n(C≡C^tBu)₁₂]⁺ clusters (n=1–6), with the Cu atom(s) presumably occupying the capping site(s). The parent cluster exhibited strong emission in the near‐IR region (λ_max=818 nm) with a quantum yield of 2 % upon excitation at λ=482 nm. Its photoluminescence was quenched upon substitution with a Na⁺ ion. DFT calculations confirmed the superatom characteristics of the title compound and the sodium‐substituted derivatives.