CBe2 H5 - : Unprecedented 2σ/2π Double Aromaticity and Dynamic Structural Fluxionality in a Planar Tetracoordinate Carbon Cluster.

A 14-electron ternary anionic CBe2 H5 - cluster containing a planar tetracoordinate carbon (ptC) atom is designed herein. Remarkably, it can be stabilized by only two beryllium atoms with both π-acceptor/σ-donor properties and two hydrogen atoms, which means that the conversion from planar methane (transition state) to ptC species (global minimum) requires the substitution of only two hydrogen atoms. Moreover, two ligand H atoms exhibit alternate rotation, giving rise to interesting dynamic fluxionality in this cluster. The electronic structure analysis reveals the flexible bonding positions of ligand H atoms due to C-H localized bonds, highlighting the rotational fluxionality in the cluster, and two CBe2 3c-2e delocalized bonds endow its rare 2σ/2π double aromaticity. Unprecedentedly, the fluxional process exhibits a conversion in the type of bonding (σ bond↔π bond), which is an uncommon fluxional mechanism. The cluster can be seen as an attempt to apply planar hypercoordinate carbon species to molecular motors.

Dynamic Structural Fluxionality in a Planar Tetracoordinate Carbon Cluster Stabilized by Boron Ligands.

The design of boron-based molecular rotors stems from boron-carbon binary clusters containing multiple planar hypercoordinate carbons (phCs, such as C2B8). However, the design of boron-coordinated phCs is challenging due to boron's tendency to occupy hypercoordinate centers more than carbon. Although this challenge has been addressed, the designed clusters of interest have not exhibited dynamic fluxionality similar to that of the initial C2B8. To address this issue, we report a σ/π doubly aromatic CB2H5+ cluster, the first global minimum containing a boron-coordinated planar tetracoordinate carbon atom with dynamic fluxionality. Dynamics simulations show that two ligand H atoms exhibit alternate rotation, resulting in an intriguing dynamic fluxionality in this cluster. Electronic structure analysis reveals the flexible bonding positions of the ligand H atoms because they do not participate in π delocalized bonding nor bond to any other non-carbon atom, highlighting this rotational fluxionality. Unprecedentedly, the fluxional process involves not only the usual conversion of the number of bonding atoms, but also the type of bonding (3c π bonds ↔ 4c σ bonds), which is an uncommon fluxional mechanism. The cluster represents an effort to apply phC species to molecular machines.

Planar Hexacoordinate Beryllium: Covalent Bonding Between s-block Metals.

Achieving a planar hypercoordinate arrangement of s-block metals through covalent bonding with ligands is challenging due to the strong ionicity involved. Herein, we report the first case of a neutral binary global minimum containing a planar hexacoordinate beryllium atom. The central Be atom is coordinated by six active Be atoms, the latter in turn are enclosed by an equal number of more electronegative chlorine atoms in the periphery, forming a star-like phBe cluster (Be©Be6 Cl6 ). Importantly, the cluster exhibits dynamically stabilized stemming geometrically from the appropriate matching of metal-ligand size and electronically from adherence to the octet rule as well as possessing a 6σ/2π double aromaticity. Remarkably, energy decomposition analysis-natural orbitals for chemical valence (EDA-NOCV) analysis reveals a significant covalent interaction between the ligand and the central metal beryllium atoms, a fact further supported by a large Wiberg bond index. This cluster is a promising synthetic as its excellent electronic, dynamic and thermodynamic stability.

Be3B11- cluster: a dynamically fluxional beryllo-borospherene.

The beryllium-doped Be3B11- cluster has two nearly isoenergetic isomers, adopting the smallest trihedral spherical geometries with a boron single-chain skeleton. The B11 skeleton in the global minimum (C2v, 1A1) comprises three conjoined boron rings (one B8/two B7) on the waist, sharing two B3 equilateral triangles at the top and bottom, respectively. However, the local minimum (Cs, 1A') has one deformed B4 pyramid at the top. The drastic structural transformation of B11 skeletons from perfectly planar B11 clusters mainly profited from robust electrostatic interaction between Be atoms and B11 skeletons. The dynamic simulations suggest that two species can interconvert via a novel mechanism, that is "triangle-pyramid-triangle", which facilitates the free migration of boron atoms in the B11 skeleton, thereby showing the fascinating dynamic fluxionality. The chemical bonding analyses reveal that the B11 skeleton is covered by two types of delocalized π bonds in an orthogonal direction, which leads to its spherical aromaticity.

Boron-based Pd3B26 alloy cluster as a nanoscale antifriction bearing system: tubular core-shell structure, double π/σ aromaticity, and dynamic structural fluxionality.

Boron-based nanoclusters show unique geometric structures, nonclassical chemical bonding, and dynamic structural fluxionality. We report here on the theoretical prediction of a binary Pd3B26 cluster, which is composed of a triangular Pd3 core and a tubular double-ring B26 unit in a coaxial fashion, as identified through global structural searches and electronic structure calculations. Molecular dynamics simulations indicate that in the core-shell alloy cluster, the B26 double-ring unit can rotate freely around its Pd3 core at room temperature and beyond. The intramolecular rotation is virtually barrier free, thus giving rise to an antifriction bearing system (or ball bearing) at the nanoscale. The dimension of the dynamic system is only 0.66 nm. Chemical bonding analysis reveals that Pd3B26 cluster possesses double 14π/14σ aromaticity, following the (4n + 2) Hückel rule. Among 54 pairs of valence electrons in the cluster, the overwhelming majority are spatially isolated from each other and situated on either the B26 tube or the Pd3 core. Only one pair of electrons are primarily responsible for chemical bonding between the tube and the core, which greatly weaken the bonding within the Pd3 core and offers structural flexibility. This is a key mechanism that effectively diminishes the intramolecular rotation barrier and facilitates dynamic structural fluxionality of the system. The current work enriches the field of nanorotors and nanomachines.

Chemical Bonding and Dynamic Structural Fluxionality of a Boron-Based Na5B7 Sandwich Cluster.

Doping alkali metals into boron clusters can effectively compensate for the intrinsic electron deficiency of boron and lead to interesting boron-based binary clusters, owing to the small electronegativity of the former elements. We report on the computational design of a three-layered sandwich cluster, Na5B7, on the basis of global-minimum (GM) searches and electronic structure calculations. It is shown that the Na5B7 cluster can be described as a charge-transfer complex: [Na4]2+[B7]3-[Na]+. In this sandwich cluster, the [B7]3- core assumes a molecular wheel in shape and features in-plane hexagonal coordination. The magic 6π/6σ double aromaticity underlies the stability of the [B7]3- molecular wheel, following the (4n + 2) Hückel rule. The tetrahedral Na4 ligand in the sandwich has a [Na4]2+ charge-state, which is the simplest example of three-dimensional aromaticity, spherical aromaticity, or superatom. Its 2σ electron counting renders σ aromaticity for the ligand. Overall, the sandwich cluster has three-fold 6π/6σ/2σ aromaticity. Molecular dynamics simulation shows that the sandwich cluster is dynamically fluxional even at room temperature, with a negligible energy barrier for intramolecular twisting between the B7 wheel and the Na4 ligand. The Na5B7 cluster offers a new example for dynamic structural fluxionality in molecular systems.

Y©B8C4 cluster: a boron-carbon molecular wheel with dodeca-coordination number in plane.

Computational evidence is reported for the largest planar molecular wheel of the Y©B8C4 cluster, featuring an yttrium atom enclosed by a highly symmetric B8C4 ring. The B8C4 ring is viable in the -(BCB)4- form with double 9π/10σ aromaticity. The centered yttrium atom is dodeca-coordinated with the peripheral B8C4 ring, which sets a record coordination number for a planar structure in chemistry heretofore.

The structure and chemical bonding in inverse sandwich B6Ca2 and B8Ca2 clusters: conflicting aromaticity vs. double aromaticity.

The typical electron-deficiency of the boron element renders fascinating architectures and chemical bonding to boron-based nanoclusters. We theoretically predict two di-Ca-doped boron clusters, B6Ca2 (D2h, 1Ag) and B8Ca2 (D8h, 1A1g), and both adopt interesting inverse sandwich geometries, showing an elongated D2h B6 or perfectly planar D8h B8 ring being sandwiched by two Ca atoms only, respectively. Natural atomic charge analyses indicate that the Ca atoms donate nearly all the 4s electrons to the B6 (or B8) ring, forming [Ca]2+[B6]4-[Ca]2+ and [Ca]2+[B8]4-[Ca]2+ charge transfer complexes. The interaction between the two Ca atoms and the boron rings is governed by robust electrostatics albeit by weaker B-Ca covalent interaction. Chemical bonding analyses show that B6Ca2 has 4σ and 6π delocalized electrons on the elongated B6 ring, leading to a conflicting aromatic system. B8Ca2, possessing 6σ and 6π delocalized electrons on the B8 ring, is doubly aromatic. Additionally, the B6Ca2 and B8Ca2 clusters show noticeable structural and electronic transmutation relative to their equivalent electronic B6Be2 and B8Mg2 clusters, respectively. The intrinsic reasons behind the transmutations are elucidated via in-depth bonding analyses.

Boron-based ternary Rb6Be2B6 cluster featuring unique sandwich geometry and a naked hexagonal boron ring.

Computational evidence is reported on a boron-based ternary Rb6Be2B6 cluster as the "Big Mac" sandwich on a subnanoscale with thickness of 0.58 nm. The core hexagonal B6 ring, occurring in the naked form due to double 6π/6σ aromaticity, is capped by two tetrahedral BeRb3 ligands. Such a B6 motif is scarce in boron clusters. The sandwich cluster has four-fold 2σ/6π/6σ/2σ aromaticity and its tetrahedral BeRb3 ligand is the simplest case of three-dimensional aromaticity (or spherical aromaticity). The sandwich can be formulated as a charge-transfer complex, [Rb3Be]3+[B6]6-[BeRb3]3+, whose components are held together by robust electrostatics, facilitating dual-mode dynamic fluxionality.

Sandwich-type Na6B7- and Na8B7+ clusters: charge-transfer complexes, four-fold π/σ aromaticity, and dynamic fluxionality.

Boron-based clusters possess unusual structural and bonding properties owing to boron's electron-deficiency. We report on the theoretical prediction of two binary B-Na clusters, Na6B7- and Na8B7+, which assume unique sandwich geometries, featuring a perfectly planar B7 wheel and two triangular Na3 or quasi-tetrahedral Na4 ligands. Despite distinct electronegativities of B/Na, the B-Na clusters do not form typical salts. Both sandwich species are dynamically fluxional at 300 K and beyond. Two dynamic modes are observed: an in-plane rotation of the B7 wheel versus twisting of the two Na3/Na4 ligands. Their energy barriers are negligibly small. Natural bond orbital calculations show that the clusters are charge-transfer complexes [Na3]+[B7]3-[Na3]+ and [Na4]2+[B7]3-[Na4]2+, respectively. Chemical bonding analyses indicate that the B7 wheel in the clusters has 6π/6σ double aromaticity and the Na3/Na4 ligands are 2σ aromatic, collectively leading to four-fold π/σ aromaticity. The quasi-tetrahedral Na4 ligand is the simplest example of spherical aromaticity and can also be considered a superatom. Interlayer bonding in the sandwiches is greater than 20 eV, due to electrostatics, which should not be confused with weakly bound species. Four-fold π/σ aromaticity and robust interlayer ionic bonding offer uniform and dilute electron clouds over the sandwiches, facilitating their dual-mode dynamic fluxionality. The Na8B7+ cluster is also a superalkali cation.

Predictive Value of Quantitative Uterine Fibroid Perfusion Parameters From Contrast-Enhanced Ultrasound for the Therapeutic Effect of High-Intensity Focused Ultrasound Ablation.

OBJECTIVES: To assess the predictive significance of quantitative perfusion parameters from contrast-enhanced ultrasound (CEUS) for the therapeutic response to high-intensity focused ultrasound (HIFU) ablation in patients with uterine fibroids. METHODS: A total of 263 patients with single uterine fibroids were treated with HIFU ablation under ultrasound guidance. The arrival time, peak time, enhancement time, enhancement intensity, and enhancement rate were evaluated with pretreatment CEUS. According to a nonperfused volume ratio evaluation by posttreatment magnetic resonance imaging, all patients were assigned to groups with volume ratios of 70% or higher and lower than 70%. Then the predictive performances of different parameters for ablation efficacy were studied. RESULTS: The arrival time, peak time, and enhancement time in the group with a nonperfused volume ratio of 70% or higher were longer than those in the group with a volume ratio lower than 70% (mean ± SD, 16.7 ± 3.5, 26.5 ± 4.9, and 10.2 ± 2.6 seconds, respectively, versus 13.3 ± 4.2, 20.8 ± 5.4, and 7.6 ± 2.3 seconds), whereas patients with a volume ratio of 70% or higher had a lower mean enhancement intensity and enhancement rate than those with a volume ratio lower than 70% (29.7 ± 16.7 dB and 3.2 ± 1.5 dB/s versus 63.2 ± 26.3 dB and 8.6 ± 4.3 dB/s; P < .05). The nonperfused volume ratio was negatively correlated with the enhancement intensity and enhancement rate (r = -0.631 and -0.712) but positively correlated with the arrival time, peak time, and enhancement time (r = 0.322, 0.456, and 0.477; P < .05). The areas under the receiver operating characteristic curve for the enhancement time, enhancement intensity, and enhancement rate were 0.73, 0.79, and 0.81 (P < .05). CONCLUSIONS: Quantitative parameters from CEUS are potentially useful for evaluating the therapeutic effect of HIFU ablation for uterine fibroids.

Coaxial Triple-Layered versus Helical Be6 B11- Clusters: Dual Structural Fluxionality and Multifold Aromaticity.

Two low-lying structures are unveiled for the Be6 B11- nanocluster system that are virtually isoenergetic. The first, triple-layered cluster has a peripheral B11 ring as central layer, being sandwiched by two Be3 rings in a coaxial fashion, albeit with no discernible interlayer Be-Be bonding. The B11 ring revolves like a flexible chain even at room temperature, gliding freely around the Be6 prism. At elevated temperatures (1000 K), the Be6 core itself also rotates; that is, two Be3 rings undergo relative rotation or twisting with respect to each other. Bonding analyses suggest four-fold (π and σ) aromaticity, offering a dilute and fluxional electron cloud that lubricates the dynamics. The second, helix-type cluster contains a B11 helical skeleton encompassing a distorted Be6 prism. It is chiral and is the first nanosystem with a boron helix. Molecular dynamics also shows that at high temperature the helix cluster readily converts into the triple-layered one.

On the nature of bonding in binary Be2O2 and Si2O2 clusters: rhombic four-center four-electron π and σ bonds.

The structural and electronic properties and chemical bonding of binary Be2O2 and Si2O2 clusters have been studied using quantum chemical calculations at the B3LYP level. For the Be2O2 cluster, the potential energy surface is probed by unbiased structural searches and the global-minimum structure was established using the B3LYP calculations, complemented by PBE0 and single-point CCSD(T) calculations for top isomers. The perfectly planar D2h Be2O2 ((1)Ag) global minimum is well defined, being at least 3.64 eV lower in energy than alternative structures at the CCSD(T)//B3LYP/aug-cc-pVTZ level. Chemical bonding analyses show that D2h Be2O2 and Si2O2 clusters possess the rhombic four-center four-electron (4c-4e) π bond, that is, the o-bond, a conception derived from electron-deficient boron oxide clusters lately. Furthermore, the Be2O2 and Si2O2 clusters also exhibit rhombic 4c-4e σ bonds, both for the radial and tangential σ frameworks (σr and σt). The σt framework is classified as an o-bond only formally, due to the secondary contribution from the Be/Si s component. The three-fold (π, σr, and σt) o-bonds in Be2O2 and Si2O2 are considered to resemble the three-fold aromaticity in all-metal Al4(2-) dianions. A 4c-4e o-bond makes use of four O 2p electrons, which would otherwise be two lone-pairs, for a delocalized and completely bonding orbital, as well as a residual nonbonding orbital. Three-fold o-bonds thus greatly stabilize the binary Be2O2 and Si2O2 clusters. We anticipate that the bonding concept should be applicable to additional molecular systems, including those with larger heterocyclic rings.

Concentric dual π aromaticity in bowl-like B30 cluster: an all-boron analogue of corannulene.

A chemical bonding model is presented for the bowl-like C5v B30 global-minimum cluster with a central pentagonal hole. The B30 cluster is composed of three concentric boron rings: first B5, second B10, and third B15. The first and second B rings constitute an inner double-chain ribbon and support a delocalized π sextet. The second and third rings form an outer double-chain ribbon, where 14π delocalized electrons are situated. The unique π systems lead to concentric dual π aromaticity for B30, a concept established from concerted computational data on the bases of canonical molecular orbital (CMO) analysis, adaptive natural density partitioning (AdNDP), nucleus-independent chemical shifts (NICS), and natural charge calculations. A proposal is put forward that the bowl-like B30 cluster is an exact all-boron analogue of corannulene (C20H10), a fragment of C60 fullerene. The bonding nature of corannulene is revisited and fully elucidated herein. A comparison of the bonding patterns in bowl-like C5v B30 cluster and two other structural isomers (Cs and C1) unravels the mechanism as to why the defective hole prefers to be positioned at the center.

Endohedral Ca@B38: stabilization of a B38(2-) borospherene dianion by metal encapsulation.

Based on extensive global-minimum searches and first-principles electronic structure calculations, we present the viability of an endohedral metalloborospherene Cs Ca@B38 () which contains a Cs B38(2-) () dianion composed of interwoven boron double chains with a σ + π double delocalization bonding pattern, extending the Bn(q) (q = n - 40) borospherene family from n = 39-42 to n = 38. Transition metal endohedral complexes Cs M@B38 (M = Sc, Y, Ti) (, , ) based on Cs B38(2-) () are also predicted.

Chemical bonding and dynamic fluxionality of a B15(+) cluster: a nanoscale double-axle tank tread.

A planar, elongated B15(+) cationic cluster is shown to be structurally fluxional and functions as a nanoscale tank tread on the basis of electronic structure calculations, bonding analyses, and molecular dynamics simulations. The outer B11 peripheral ring behaves like a flexible chain gliding around an inner B4 rhombus core, almost freely at the temperature of 500 K. The rotational energy barrier is only 1.37 kcal mol(-1) (0.06 eV) at the PBE0/6-311+G* level, further refined to 1.66 kcal mol(-1) (0.07 eV) at the single-point CCSD(T)/6-311G*//CCSD/6-311G* level. Two soft vibrational modes of 166.3 and 258.3 cm(-1) are associated with the rotation, serving as double engines for the system. Bonding analysis suggests that the "island" electron clouds, both σ and π, between the peripheral ring and inner core flow and shift continuously during the intramolecular rotation, facilitating the dynamic fluxionality of the system with a small rotational barrier. The B15(+) cluster, roughly 0.6 nm in dimension, is the first double-axle nanoscale tank tread equipped with two engines, which expands the concepts of molecular wheels, Wankel motors, and molecular tanks.

On the nature of chemical bonding in the all-metal aromatic [Sb3Au3Sb3](3-) sandwich complex.

In a recent communication, an all-metal aromatic sandwich [Sb3Au3Sb3](3-) was synthesized and characterized. We report herein a density-functional theory (DFT) study on the chemical bonding of this unique cluster, which makes use of a number of computational tools, including the canonical molecular orbital (CMO), adaptive natural density partitioning (AdNDP), Wiberg bond index, and orbital composition analyses. The 24-electron, triangular prismatic sandwich is intrinsically electron-deficient, being held together via six Sb-Sb, three Au-Au, and six Sb-Au links. A standard, qualitative bonding analysis suggests that all CMOs are primarily located on the three Sb3/Au3/Sb3 layers, three Au 6s based CMOs are fully occupied, and the three extra charges are equally shared by the two cyclo-Sb3 ligands. This bonding picture is referred to as the zeroth order model, in which the cluster can be formally formulated as [Sb3(1.5+)Au3(3-)Sb3(1.5+)](3-) or [Sb3(0)Au3(3-)Sb3(0)]. However, the system is far more complex and covalent than the above picture. Seventeen CMOs out of 33 in total involve remarkable Sb → Au electron donation and Sb ← Au back-donation, which are characteristic of covalent bonding and effectively redistribute electrons from the Sb3 and Au3 layers to the interlayer edges. This effect collectively leads to three Sb-Au-Sb three-center two-electron (3c-2e) σ bonds as revealed in the AdNDP analyses, despite the fact that not a single such bond can be identified from the CMOs. Orbital composition analyses for the 17 CMOs allow a quantitative understanding of how electron donation and back-donation redistribute the charges within the system from the formal Sb3(0)/Au3(3-) charge states in the zeroth order model to the effective Sb3(1.5-)/Au3(0) charge states, the latter being revealed from the natural bond orbital analysis.

Competition between quasi-planar and cage-like structures in the B29- cluster: photoelectron spectroscopy and ab initio calculations.

Size-selected boron clusters have been found to be predominantly planar or quasi-planar (2D) in the small size regime with the appearance of three-dimensional (3D) borospherene cages of larger sizes. A seashell-like B28- cluster was previously shown to be the smallest borospherene, which competes with a quasi-planar isomer for the global minimum. Here we report a study on the structures and bonding of the B29- and B29 clusters using photoelectron spectroscopy (PES) and first-principles calculations and demonstrate the continued competition between the 2D and borospherene structures. The PES spectrum of B29- displays a complex pattern with evidence of low-lying isomers. Global-minimum searches and extensive theoretical calculations revealed a complicated potential energy surface for B29- with five low-lying isomers, among which the lowest three were shown to contribute to the experimental spectrum. A 3D seashell-like Cs (2, 1A') isomer, featuring two heptagons on the waist and one octagon at the bottom, is the global minimum for B29-, followed by a 2D C1 (3, 1A) isomer with a hexagonal hole and a stingray-shaped 2D Cs (1, 1A') isomer with a pentagonal hole. However, by taking into account the entropic effects, the stingray-shaped isomer 1 was shown to be the lowest in energy at room temperature and was found to dominate the PES spectrum. Isomers 2 and 3, which have lower electron binding energies, were also found to be present in the experiment. Chemical bonding analyses showed that isomer 1 is an all-boron analogue of benzo[ghi]fluoranthene (C18H10), whereas the borospherene isomer 2 possesses 18π electrons, conforming to the 2(N + 1)2 electron counting rule for spherical aromaticity. For the B29 neutral cluster, the seashell-like borospherene isomer is the global minimum, significantly lower in energy than the stingray-shaped quasi-planar structure.

Star-like superalkali cations featuring planar pentacoordinate carbon.

Superalkali cations, known to possess low vertical electron affinities (VEAs), high vertical detachment energies, and large highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) energy gaps, are intriguing chemical species. Thermodynamically, such species need to be the global minima in order to serve as the promising targets for experimental realization. In this work, we propose the strategies of polyhalogenation and polyalkalination for designing the superalkali cations. By applying these strategies, the local-minimum planar pentacoordinate carbon (ppC) cluster CBe5 can be modified to form a series of star-like superalkali ppC or quasi-ppC CBe5X5 (+) (X = F, Cl, Br, Li, Na, K) cations containing a CBe5 moiety. Polyhalogenation and polyalkalination on the CBe5 unit may help eliminate the high reactivity of bare CBe5 molecule by covering the reactive Be atoms with noble halogen anions and alkali cations. Computational exploration of the potential energy surfaces reveals that the star-like ppC or quasi-ppC CBe5X5 (+) (X = F, Cl, Br, Li, Na, K) clusters are the true global minima of the systems. The predicted VEAs for CBe5X5 (+) range from 3.01 to 3.71 eV for X = F, Cl, Br and 2.12-2.51 eV for X = Li, Na, K, being below the lower bound of the atomic ionization potential of 3.89 eV in the periodic table. Large HOMO-LUMO energy gaps are also revealed for the species: 10.76-11.07 eV for X = F, Cl, Br and 4.99-6.91 eV for X = Li, Na, K. These designer clusters represent the first series of superalkali cations with a ppC center. Bonding analyses show five Be-X-Be three-center two-electron (3c-2e) σ bonds for the peripheral bonding, whereas the central C atom is associated with one 6c-2e π bond and three 6c-2e σ bonds, rendering (π and σ) double aromaticity. Born-Oppenheimer molecular dynamics simulations indicate that the CBe5 motif is robust in the clusters. As planar hypercoordination carbon species are often thermodynamically unstable and highly reactive, the superalkali cation characters of these ppC species should be highlighted, which may be suitable for experimental realization.

[Sb4Au4Sb4](2-): A designer all-metal aromatic sandwich.

We report on the computational design of an all-metal aromatic sandwich, [Sb4Au4Sb4](2-). The triple-layered, square-prismatic sandwich complex is the global minimum of the system from Coalescence Kick and Minima Hopping structural searches. Following a standard, qualitative chemical bonding analysis via canonical molecular orbitals, the sandwich complex can be formally described as [Sb4](+)[Au4](4-)[Sb4](+), showing ionic bonding characters with electron transfers in between the Sb4/Au4/Sb4 layers. For an in-depth understanding of the system, one needs to go beyond the above picture. Significant Sb → Au donation and Sb ← Au back-donation occur, redistributing electrons from the Sb4/Au4/Sb4 layers to the interlayer Sb-Au-Sb edges, which effectively lead to four Sb-Au-Sb three-center two-electron bonds. The complex is a system with 30 valence electrons, excluding the Sb 5s and Au 5d lone-pairs. The two [Sb4](+) ligands constitute an unusual three-fold (π and σ) aromatic system with all 22 electrons being delocalized. An energy gap of ∼1.6 eV is predicted for this all-metal sandwich. The complex is a rare example for rational design of cluster compounds and invites forth-coming synthetic efforts.