Axially Modified Square-Pyramidal CoN4-F1 Sites Enabling High-Performance Zn-Air Batteries.

Cobalt-nitrogen-carbon (Co-N-C) catalysts with a CoN4 structure exhibit great potential for oxygen reduction reaction (ORR), but the imperfect adsorption energy toward oxygen species greatly limits their reduction efficiency and practical application potential. Here, F-coordinated Co-N-C catalysts with square-pyramidal CoN4-F1 configuration are successfully synthesized using F atoms to regulate the axial coordination of Co centers via hydrothermal and chemical vapor deposition methods. During the synthesis process, the geometry structure of the Co atom converts from six-coordinated Co-F6 to square-pyramidal CoN4-F1 in the coordinatively unsaturated state, which provides an open binding site for the O2. The introduction of axial F atoms into the CoN4 plane alters the local atomic environment around Co, significantly improving the ORR activity and Zn-air batteries performance. In situ spectroscopy proves that CoN4-F1 sites strongly combine with the OOH* intermediate and facilitate the splitting of O-O bond, making OOH* readily decompose into O* and OH* via a dissociative pathway. Theoretical calculations confirm that the axial F atom effectively reduces the electronic density of the Co centers and facilitates the desorption of the OH* intermediate, efficiently accelerating the overall ORR kinetics. This work advances a feasible synthesis mechanism of axial ligands and provides a route to construct efficient high-coordination catalysts.

In-Plane Topological-Defect-Enriched Graphene as an Efficient Metal-Free Catalyst for pH-Universal H2 O2 Electrosynthesis.

Developing efficient metal-free catalysts to directly synthesize hydrogen peroxide (H2 O2 ) through a 2-electron (2e) oxygen reduction reaction (ORR) is crucial for substituting the traditional energy-intensive anthraquinone process. Here, in-plane topological defects enriched graphene with pentagon-S and pyrrolic-N coordination (SNC) is synthesized via the process of hydrothermal and nitridation. In SNC, pentagon-S and pyrrolic-N originating from thiourea precursor are covalently grafted onto the basal plane of the graphene framework, building unsymmetrical dumbbell-like S─C─N motifs, which effectively modulates atomic and electronic structures of graphene. The SNC catalyst delivers ultrahigh H2 O2 productivity of 8.1, 7.3, and 3.9 mol gcatalyst -1  h-1 in alkaline, neutral, and acidic electrolytes, respectively, together with long-term operational stability in pH-universal electrolytes, outperforming most reported carbon catalysts. Theoretical calculations further unveil that defective S─C─N motifs efficiently optimize the binding strength to OOH* intermediate and substantially diminish the kinetic barrier for reducing O2 to H2 O2 , thereby promoting the intrinsic activity of 2e-ORR.

Self-Termination of Borophene Edges.

Due to boron's unique bonding nature, planar boron materials, including borophenes, boron nanoclusters, and nanoribbons, show very puzzling features, especially the superior stability of the free-standing planar boron edges. Here, we present a systematic investigation of the bonding configurations of various edges of borophene. Because of the flexibility of forming either three-center two-electron (3c-2e) or two-center two-electron bonds (2c-2e), an edge of borophene tends to be self-terminated by adopting a different bonding configuration at the edge from that in bulk. Among various borophene edge types, the double-chain-terminated flat edge is found to be significantly stable. As a consequence, we found that the double- and triple-chain borophene nanoribbons with a triangular lattice and wider ribbons with hexagonal holes in the central area are more stable than the quadruple-chain borophene nanoribbon. This study greatly deepens our understanding of the bonding configurations, electronic properties, and stabilities of planar boron nanostructures and paves the way for the rational design and synthesis of various boron materials.

Bifunctional diatomic site catalysts supported by ß12-borophene for efficient oxygen evolution and reduction reactions.

Efficient bifunctional catalysts for oxygen evolution and reduction reactions (OERs/ORRs) are of great importance for sustainable and renewable clean energy, especially for metal-air batteries. Herein, we investigated ß12-borophene with double-hole sites capped with 3d transition metal atoms to explore its catalyst performance for hydrogen evolution reactions (HERs), OERs and ORRs. It was found that the borophene is a good platform for diatomic site catalysts (DASCs) due to their advantage of stability over the corresponding single-atom catalysts (SACs) or clusters. The HER performance of DASCs on ß12-BM was further improved compared to the SAC case. Furthermore, the supported FeNi DASC exhibited good catalytic performance for both OERs and ORRs, the overpotentials for which were 0.43 and 0.55 V, respectively, better than those of the corresponding supported Ni or Fe SAC due to synergistic effects. We herein propose a novel descriptor involving the Bader charges of coordinated atoms explicitly, behaving much better than the d-band center and integrated crystal orbital Hamilton population (-ICOHP) for DASCs. The synergistic effect of Fe-Ni pairs balanced the too strong binding of OH and further activated OH to achieve better catalytic performance. The results of this study can provide theoretical guidance for the design of efficient bifunctional electrocatalysts.

Perfect cubic metallo-borospherenes TM8B6 (TM = Ni, Pd, Pt) as superatoms following the 18-electron rule.

Transition-metal (TM)-doped metallo-borospherenes exhibit unique structures and bonding in chemistry which have received considerable attention in recent years. Based on extensive global minimum searches and first-principles theory calculations, we predict herein the first and smallest perfect cubic metallo-borospherenes Oh TM8B6 (TM = Ni (1), Pd (2), Pt (3)) and Oh Ni8B6- (1-) which contain eight equivalent TM atoms at the vertexes of a cube and six quasi-planar tetra-coordinate face-capping boron atoms on the surface. Detailed canonical molecular orbital and adaptive natural density partitioning bonding analyses indicate that Oh TM8B6 (1/2/3) as superatoms possess nine completely delocalized 14c-2e bonds following the 18-electron principle (1S21P61D10), rendering spherical aromaticity and extra stability to the complex systems. Furthermore, Ni8B6 (1) can be used as building blocks to form the three-dimensional metallic binary crystal NiB (4) (Pm3̄m) in a bottom-up approach which possesses a typical CsCl-type structure with an octa-coordinate B atom located exactly at the center of the cubic unit cell. The IR, Raman, UV-vis and photoelectron spectra of the concerned clusters are computationally simulated to facilitate their experimental characterization.

[Sc©[3]CPP]+: A Viable Metal-Centered [3]Cycloparaphenylene.

[n]Cycloparaphenylenes ([n]CPPs, n denotes the number of phenyl groups) are difficult to synthesize because of the strain related to their bent phenyl rings. In particular, the strain in [3]CPP is high enough to destroy the π electron delocalization, leading to the spontaneous structural transition to an energetically more stable "bond-shift" (BS) isomer ([3]BS). In this contribution, we propose to achieve [3]CPP by enhancing the π electron delocalization through hosting a guest metal atom. Our computations revealed that Sc could stabilize [3]CPP by forming the [Sc©[3]CPP]+ complex through the favorable π-Sc donation-backdonation interactions. Thermodynamically, the binding energy between the Sc atom and [3]CPP was -205.7 kcal/mol, which could well compensate not only the energy difference of 44.2 kcal/mol between [3]CPP and [3]BS but also the extremely high strain energy of 170.3 kcal/mol in [3]CPP. Simultaneously, the [Sc©[3]CPP]+ complex is stable up to 1500 K in dynamic simulations, suggesting its high viability in the synthesis.

Heptacoordinate transition-metal-decorated metallo-borospherenes and multiple-helix metallo-boronanotubes.

The recent discovery of lanthanide-metal-decorated metallo-borospherenes LM3B18- (LM = La, Tb) marks the onset of a new class of boron-metal binary nanomaterials. Using the experimentally observed or theoretically predicted borospherenes as ligands and based on extensive first-principles theory calculations, we predict herein a series of novel chiral metallo-borospherenes C2 Ni6 ∈ B39- (1), C1 Ni6 ∈ B41+ (3), C2 Ni6 ∈ B422+ (4), C2 Ni6 ∈ B42 (5), and C2 Ni8 ∈ B56 (6) as the global minima of the systems decorated with quasi-planar heptacoordinate Ni (phNi) centers in η7-B7 heptagons on the cage surfaces, which are found to be obviously better favoured in coordination energies than hexacoordinate Ni centers in previously reported D2d Ni6 ∈ B40 (2). Detailed bonding analyses indicate that these phNi-decorated metallo-borospherenes follow the σ + π double delocalization bonding pattern, with two effective (d-p)σ coordination bonds formed between each phNi and its η7-B7 ligand, rendering spherical aromaticity and extra stability to the systems. The structural motif in elongated axially chiral Ni6 ∈ B422+ (4), Ni6 ∈ B42 (5), and Ni8 ∈ B56 (6) can be extended to form the metallic phNi-decorated boron double chain (BDC) double-helix Ni4 ∈ B28 (2, 0) (P4̄m2) (8), triple-helix Ni6 ∈ B42 (3, 0) (P3̄m1) (9), and quadruple-helix Ni8 ∈ B56 (4, 0) (P4mm) (10) metallo-boronanotubes, which can be viewed as quasi-multiple-helix DNAs composed of interconnected BDCs decorated with phNi centers in η7-B7 heptagons on the tube surfaces in the atomic ratio of Ni : B = 1 : 7.

Lanthanide/actinide boride nanoclusters and nanomaterials based on boron frameworks consisting of conjoined Bn rings (n = 7-9).

Extensive global minimum searches augmented with first-principles theory calculations performed in this work indicate that the experimentally observed perfect inverse sandwich lanthanide boride complexes D7h La2B7- (1), D8h La2B8 (3), D9h La2B9- (7) can be extended to their actinide counterparts C2v Ac2B7- (1'), D8h Ac2B8 (3'), D9h Ac2B9- (7') with a Bn monocyclic ring (n = 7-9) sandwiched by two Ac dopants. Such M2Bn-/0 inverse sandwiches (1/1', 3/3', 7/7') can be used as building blocks to generate the ground-state C2 La4B13- (2)/Ac4B13- (2'), D2 La4B15- (4)/Ac4B15- (4'), C3v/C3 La4B18 (5)/Ac4B18 (5'), Oh Ac7B24+ (6'), Oh Ac7B24, Td Ac4B24 (8'), C1 La5B24+ (9)/Ac5B24+ (9'), and Td Ac4B29- (10') which are based on boron frameworks consisting of multiple conjoined Bn rings (n = 7-9). Detailed bonding analyses show that effective (d-p)σ, (d-p)π and (d-p)δ coordination bonds are formed between the Bn rings and metal doping centers, conferring three-dimensional aromaticity and extra stability to the systems. In particular, the perfect body-centered cubic Oh Ac7B24+ (6') and Oh Ac7B24 with six conjoined B8 rings can be extended in x, y, and z dimensions to form one-dimensional Ac10B32 (11'), two-dimensional Ac3B10 (12'), and three-dimensional AcB6 (13') nanomaterials, presenting a B8-based bottom-up approach from metal boride nanoclusters to their low-dimensional nanomaterials.

A bottom-up approach from medium-sized bilayer boron nanoclusters to bilayer borophene nanomaterials.

Inspired by the experimentally observed bilayer B48-/0 and theoretically predicted bilayer B50-B72 and based on extensive density functional theory calculations, we report herein a series of novel medium-sized bilayer boron nanoclusters C1 B84 (I), C2v B86 (II), C1 B88 (III), C1 B90 (IV), C1 B92 (V), C1 B94 (VI), C2v B96 (VII), and C1 B98 (VIII) which are the most stable isomers of the systems reported to date effectively stabilized by optimum numbers of interlayer B-B σ bonds between the inward-buckled atoms on top and bottom layers. Detailed bonding analyses indicate that these bilayer species follow the universal bonding pattern of σ + π double delocalization, rendering three-dimensional aromaticity in the systems. More interestingly, the AA-stacked bilayer structural motif in B96 (VII) with a B72 bilayer hexagonal prism at the center can be extended to form bilayer C2 B128 (IX), D2h B214 (X), C2v B260 (XI), D2h B372 (XII), and D2 B828 (XIII) which contain one or multiple conjoined B72 bilayer hexagonal prisms sharing interwoven zig-zag boron triple chains between them. Such bilayer species or their close-lying AB isomers can be viewed as embryos of the newly reported most stable freestanding BL-α+ bilayer borophenes and quasi-freestanding bilayer borophenes on Ag(111) which are composed of interwoven zig-zag boron triple chains shared by conjoined BL B72 hexagonal prisms, presenting a bottom-up approach from medium-sized bilayer boron nanoclusters to two-dimensional bilayer borophene nanomaterials.

Defect-Rich Molybdenum Sulfide Quantum Dots for Amplified Photoluminescence and Photonics-Driven Reactive Oxygen Species Generation.

Transition metal dichalcogenide (TMD) quantum dots (QDs) with defects have attracted interesting chemistry due to the contribution of vacancies to their unique optical, physical, catalytic, and electrical properties. Engineering defined defects into molybdenum sulfide (MoS2 ) QDs is challenging. Herein, by applying a mild biomineralization-assisted bottom-up strategy, blue photoluminescent MoS2 QDs (B-QDs) with a high density of defects are fabricated. The two-stage synthesis begins with a bottom-up synthesis of original MoS2 QDs (O-QDs) through chemical reactions of Mo and sulfide ions, followed by alkaline etching that creates high sulfur-vacancy defects to eventually form B-QDs. Alkaline etching significantly increases the photoluminescence (PL) and photo-oxidation. An increase in defect density is shown to bring about increased active sites and decreased bandgap energy; which is further validated with density functional theory calculations. There is strengthened binding affinity between QDs and O2 due to lower gap energy (∆EST ) between S1 and T1 , accompanied with improved intersystem crossing (ISC) efficiency. Lowered gap energy contributes to assist e- -h+ pair formation and the strengthened binding affinity between QDs and 3 O2 . Defect engineering unravels another dimension of material properties control and can bring fresh new applications to otherwise well characterized TMD nanomaterials.

A family of superconducting boron crystals made of stacked bilayer borophenes.

Monolayer borophenes tend to be easily oxidized, while thicker borophenes have stronger antioxidation properties. Herein, we proposed four novel metallic boron crystals by stacking the experimentally synthesized borophenes, and one of the crystals has been reported in our previous experiments. Bilayer units tend to act as blocks for crystals as determined by bonding analyses. Their kinetic, thermodynamic and mechanical stabilities are confirmed by our calculated phonon spectra, molecular dynamics and elastic constants. Our proposed allotropes are more stable than the boron α-Ga phase below 1000 K at ambient pressure. Some of them become more stable than the α-rh or γ-B28 phases at appropriate external pressure. More importantly, our calculations show that three of the proposed crystals are phonon-mediated superconductors with critical temperatures of about 5-10 K, higher than those of most superconducting elemental solids, in contrast to typical boron crystals with significant band gaps. Our study indicates a novel preparation method for metallic and superconducting boron crystals dispensing with high pressure.

Compression-induced crimping of boron nanotubes from borophenes: a DFT study.

Several borophenes have been prepared successfully, but the synthesis of boron nanotubes is still very difficult. Our results suggest that the high flexibility of borophene in combination with van der Waals interactions makes it possible to coil boron nanotubes from rippled borophenes, which is confirmed by ab initio molecular dynamics simulations. The plane structures transform into rippled structures almost without any barrier under very small compression and weak perturbations like molecular adsorption. The compression energies of the rippled structures increase linearly and slowly with the increase of the compression. This suggests how the geometry of the borophene evolves with compression. Based on the evaluation of the free energy of hydrogen adsorption, a stronger compression suggests the improved hydrogen evolution performance of the borophene and even makes it better than Pt catalysts. Meanwhile, good hydrogen evolution performance is also suggested for boron nanotubes. Our results suggest a novel preparation method for boron nanotubes from borophenes and a possible way to improve their hydrogen evolution performance.

La@[La5&B30]0/-/2-: endohedral trihedral metallo-borospherenes with spherical aromaticity.

It is well-known that transition-metal-doping induces dramatic changes in the structures and bonding of small boron clusters, as demonstrated by the newly observed perfect inverse sandwich D8h [La(η8-B8)La] and D9h [La(η9-B9)La]-. Based on extensive global minimum searches and first-principles theory calculations, we predict herein the possibility of perfect endohedral trihedral metallo-borospherene D3h La@[La5&B30] (1, 3A'1) and its monoanion Cs La@[La5&B30]- (2, 2A') and dianion D3h La@[La5&B30]2- (3, 1A'1). These La-doped boron clusters are composed of three inverse sandwich La(η8-B8)La on the waist and two inverse sandwich La(η9-B9)La on the top and bottom which share one apex La atom at the center and six periphery B2 units between neighboring η8-B8 and η9-B9 rings, with three octo-coordinate La atoms and two nona-coordinate La atoms as integrated parts of the cage surface. Detailed adaptive natural density partitioning (AdNDP) and iso-chemical shielding surface (ICSS) analyses indicate that La@[La5&B30]0/-/2- (1/2/3) are spherically aromatic in nature. The one-dimensional nanowire La4B21 (4, P31m) constructed from D3h La@[La5&B30] (1) along the C3 axis of the system appears to be metallic. The IR and Raman spectra of La@[La5&B30] (1) and photoelectron spectroscopy of the slightly distorted Cs La@[La5&B30]- (2) are theoretically simulated to facilitate their spectroscopic characterizations.

Scalable Production of Freestanding Few-Layer ß12-Borophene Single Crystalline Sheets as Efficient Electrocatalysts for Lithium-Sulfur Batteries.

Two-dimensional (2D) borophene has attracted tremendous interest due to its fascinating properties, which have potential applications in catalysts, energy storage devices, and high-speed transistors. In the past few years, borophene was theoretically predicted as an ideal electrode material for lithium-sulfur (Li-S) batteries because of its low-density, metallic conductivity, high Li-ion surface mobility, and strong interface bonding energy to polysulfide. But until now, borophene-based Li-S batteries have not yet been achieved in experiments due to the absence of a large-scale synthetic method of freestanding borophene nanostructures with a high enough structural stability, conductivity, and uniformity. Herein, we developed a low-temperature liquid exfoliation (LTLE) method to synthesize freestanding few-layer ß12-borophene single-crystalline sheets with a P6¯m2 symmetry in tens of milligrams. The as-synthesized 2D sheets were used as the polysulfide immobilizers and electrocatalysts of Li-S batteries. The resulting borophene-based Li-S battery delivered an extralarge areal capacity of 5.2 mAh cm-2 at a high sulfur loading of 7.8 mg cm-2, an excellent rate performance of 8 C (@721 mAh g-1), and an ultralow capacity fading rate of 0.039% in 1000 cycles, outperforming commercial Li-ion batteries and many other 2D material-based Li-S batteries. Based on the density functional theory model, the excellent electrochemical performances of the borophene-based Li-S batteries should originate from the enormous enhancement of ß12-borophene sheets for both the surface migration of the Li-ions and the adsorption energy of Li2Sn clusters. Our results thus demonstrate a great potential for scalable production of freestanding ß12-borophene single-crystalline sheets in future high-performance Li-S batteries.

B48-: a bilayer boron cluster.

Size-selected negatively-charged boron clusters (Bn-) have been found to be planar or quasi-planar in a wide size range. Even though cage structures emerged as the global minimum at B39-, the global minimum of B40- was in fact planar. Only in the neutral form did the B40 borospherene become the global minimum. How the structures of larger boron clusters evolve is of immense interest. Here we report the observation of a bilayer B48- cluster using photoelectron spectroscopy and first-principles calculations. The photoelectron spectra of B48- exhibit two well-resolved features at low binding energies, which are used as electronic signatures to compare with theoretical calculations. Global minimum searches and theoretical calculations indicate that both the B48- anion and the B48 neutral possess a bilayer-type structure with D2h symmetry. The simulated spectrum of the D2h B48- agrees well with the experimental spectral features, confirming the bilayer global minimum structure. The bilayer B48-/0 clusters are found to be highly stable with strong interlayer covalent bonding, revealing a new structural type for size-selected boron clusters. The current study shows the structural diversity of boron nanoclusters and provides experimental evidence for the viability of bilayer borophenes.

Novel B-C binary fullerenes following the isolated B4C3 hexagonal pyramid rule.

B-C binary monolayers and fullerenes (borafullerenes) have received considerable attention in recent years. Inspired by the newly reported B4C3 semiconducting boron carbide monolayer isovalent to graphene (Tian et al., Nanoscale, 2019, 11, 11099), we predict herein at density functional theory level a new class of borafullerenes (1-8) following the isolated B4C3 hexagonal pyramid rule. The spherically aromatic borafullerenes C5h B20C35 (1), C5 B20C45 (2), C5h B20C55 (3), and C5 B20C65 (4) isovalent to C50, C60, C70, and C80, respectively, possess five isolated B4C3 hexagonal pyramids evenly distributed on the waist around the C5 molecular axis, while S10 B40C50 (5), C5 B40C60 (6), S10 B40C70 (7), and C5 B40C80 (8) encompass ten isolated B4C3 pyramids symmetrically distributed on the cage surface. Detailed orbital and bonding analyses indicate that these borafullerenes follow similar σ and π-bonding patterns with their fullerene analogues, with three delocalized 7c-2e π bonds forming a local π-aromatic system over each isolated B4C3 hexagonal pyramid. The calculated formation energies of the (B4C3)nC60-6n (n = 1-5) series isovalent to C60 appear to increase almost linearly with the number of isolated B4C3 pyramids in the system. The IR, Raman, and UV-vis spectra of the prototypical B20C45 (2) are theoretically simulated to facilitate its future spectral characterization.

O-coordinated W-Mo dual-atom catalyst for pH-universal electrocatalytic hydrogen evolution.

Single-atom catalysts (SACs) maximize the utility efficiency of metal atoms and offer great potential for hydrogen evolution reaction (HER). Bimetal atom catalysts are an appealing strategy in virtue of the synergistic interaction of neighboring metal atoms, which can further improve the intrinsic HER activity beyond SACs. However, the rational design of these systems remains conceptually challenging and requires in-depth research both experimentally and theoretically. Here, we develop a dual-atom catalyst (DAC) consisting of O-coordinated W-Mo heterodimer embedded in N-doped graphene (W1Mo1-NG), which is synthesized by controllable self-assembly and nitridation processes. In W1Mo1-NG, the O-bridged W-Mo atoms are anchored in NG vacancies through oxygen atoms with W─O─Mo─O─C configuration, resulting in stable and finely distribution. The W1Mo1-NG DAC enables Pt-like activity and ultrahigh stability for HER in pH-universal electrolyte. The electron delocalization of W─O─Mo─O─C configuration provides optimal adsorption strength of H and boosts the HER kinetics, thereby notably promoting the intrinsic activity.

CoP/RGO-Pd Hybrids with Heterointerfaces as Highly Active Catalysts for Ethanol Electrooxidation.

The ethanol oxidation reaction is of critical importance to the commercial viability of direct ethanol fuel cell technology. However, owing to the poor C-C bond cleavage capability, almost all ethanol oxidation is incomplete and suffers from low selectivity toward the C1 pathway. Herein, under the support of theoretical calculations that the heterointerfaces between CoP and Pd can reduce the energy barrier of C-C bond cleavage, rich heterointerfaces in CoP/RGO-Pd hybrids were designed to improve ethanol electrooxidation performance through enhancing the selectivity toward the C1 pathway. The experimental results show that the faradaic efficiency of the C1 pathway of CoP/RGO-Pd hybrids is as high as 27.6%, surpassing most reported catalysts in the literature. As a result of this enhancement, CoP/RGO-Pd10 exhibits mass activity as high as 4597 mA·mgPd-1 and specific activity as high as 10 mA·cm-2, which are much higher than those of other Pd-based electrocatalysts.

Perfect cubic La-doped boron clusters La6&[La@B24]+/0 as the embryos of low-dimensional lanthanide boride nanomaterials.

La-doped boron nanoclusters have received considerable attention due to their unique structures and bonding. Inspired by recent experimental observations of the inverse sandwich D 8h La2B8 (1) and triple-decker C 2v La3B14 - (2) and based on extensive global searches and first-principles theory investigations, we present herein the possibility of the perfect cubic La-doped boron clusters O h La6&[La@B24]+ (3, 1A1g) and O h La6&[La@B24] (4, 2A2g) which appear to be the embryos of the metallic one-dimensional La10B32 (5) nanowire, two-dimensional La3B10 (6) nanosheet, and three-dimensional LaB6 (7) nanocrystal, facilitating a bottom-up approach to build cubic lanthanide boride nanostructures from gas-phase clusters. Detailed molecular orbital and bonding analyses indicate that effective (d-p)σ, (d-p)π and (d-p)δ covalent coordination interactions exist in La6&[La@B24]+/0 (3/4) clusters, while the 1D La10B32 (5), 2D La3B10 (6), and 3D LaB6 (7) crystals exhibit mainly electrostatic interactions between the trivalent La centers and cubic B24 frameworks, with weak but discernible coordination contributions from La (5d) ← B (2p) back-donations. The IR and Raman spectra of La6&[La@B24]+/0 (3/4) and band structures of La10B32 (5) and La3B10 (6) are computationally simulated to facilitate their future characterizations.

Sea-shell-like B31 + and B32: two new axially chiral members of the borospherene family.

Since the discovery of the cage-like borospherenes D 2d B40 -/0 and the first axially chiral borospherenes C 3/C 2 B39 -, a series of fullerene-like boron clusters in different charge states have been reported in theory. Based on extensive global minimum searches and first-principles theory calculations, we present herein two new axially chiral members C 2 B31 + (I) and C 2 B32 (VI) to the borospherene family. B31 + (I) features two equivalent heptagons on the top and one octagon at the bottom on the cage surface, while B32 (VI) possesses two equivalent heptagons on top and two equivalent heptagons at the bottom. Detailed bonding analyses show that both sea-shell-like B31 + (I) and B32 (VI) follow the universal σ + π double delocalization bonding pattern of the borospherene family, with ten delocalized π bonds over a σ skeleton, rendering spherical aromaticity to the systems. Extensive molecular dynamics simulations show that these novel borospherenes are kinetically stable below 1000 K. The IR, Raman, and UV-vis spectra of B31 + (I) and B32 (VI) are computationally simulated to facilitate their future experimental characterizations.