Synthesis of Sb: Crafting a Homoatomic Antimony Nanotorus.

Pure-element cyclic molecules have garnered extensive attention owing to their intriguing structures and promising applications. Among these, carbon-based cyclic molecules such as []carbon (C, = 10-26) and carbon nanotori have ignited significant interest in both experimental and theoretical investigations. However, systematic investigations of analogous cyclic counterparts of heavier main-group elements are limited, with only a few known by theoretical studies.

Extension and Fusion of Cyclic Polyantimony Units.

The synthesis and characterization of a series of polyantimony anionic clusters are reported. The products [(NbCp)Sb], [MSb] (M = Ru/Fe), and [MSb] (M = Ru/Fe) were isolated as either K(18-crown-6) or K([2.2.

Fe-Fe bonding in the rhombic Fe cores of the Zintl clusters [FeE] (E = Sn and Pb).

We report here the synthesis and characterization of two endohedral Zintl-ion clusters, [FeSn] and [FePb], which contain rhombic Fe cores. The Fe-Fe bond lengths are all below 2.5 Å, distinctly shorter than in the corresponding Cu clusters, indicating the presence of Fe-Fe bonding.

Snap-shots of cluster growth: structure and properties of a Zintl ion with an Fe core, [FeSn].

The endohedral Zintl-ion cluster [FeSn] contains a linear Fe core with short Fe-Fe bond lengths of 2.4300(9) Å. The ground state is a septet, with significant σ and π contributions to the Fe-Fe bonds.

An all-metal fullerene: [K@AuSb].

The C fullerene molecule has attracted tremendous interest for its distinctive nearly spherical structure. By contrast, all-metal counterparts have been elusive: Fullerene-like clusters composed of noncarbon elements typically suffer from instability, resulting in more compact geometries that require multiple embedded atoms or external ligands for stabilization. In this work, we present the synthesis of an all-metal fullerene cluster, [K@AuSb], using a wet-chemistry method.

Spinal TAOK2 contributes to neuropathic pain via cGAS-STING activation in rats.

Thousand and one amino acid kinase 2 (TAOK2) is a member of the mammalian sterile 20 kinase family and is implicated in neurodevelopmental disorders; however, its role in neuropathic pain remains unknown. Here, we found that TAOK2 was enriched and activated after chronic constriction injury (CCI) in the rat spinal dorsal horn. Meanwhile, cyclic guanosine monophosphate-adenosine monophosphate synthase (cGAS)-stimulator of interferon genes (STING) signaling was also activated with hyperalgesia.

[Ga@Bi(NbMes)]: a linear Nb-Ga-Nb filament coordinated by a bismuth cage.

In this work, we report a low-valent Ga(I) complex, [Ga@Bi(NbMes)], with a linear Nb-Ga-Nb fragment, representing the first compound with Nb-Ga and Nb-Bi bonds. Quantum-chemical calculations reveal that the complex is an electron-precise cluster. The possible fragmentation pathway of the title cluster was studied by using electrospray ionization mass spectrometry and theoretical calculations.

Synthesis and Characterization of [Fe (As ) (As )] , a Binary Fe/As Zintl Cluster With an Fe Core.

We report here the synthesis and structural characterization of the first binary iron arsenide cluster anion, [Fe (As ) (As )] , present in both [K([2.2.2]crypt)] [Fe (As ) (As )] (1) and [K(18-crown-6)] [Fe (As ) (As )]⋅en (2).

Single-Metal-Encapsulated Double-Cage [Pt@Sn ] : An Exception from Group 14 Endohedral Clusters.

Group 14 endohedral clusters containing a metal center inside usually possess a single cage topological structure, but here an unexpected single-metal-filled double-cage cluster, [Pt@Sn ] (1 a) is reported. It can be seen as a combination of the more extended Pt-filled [Pt@Sn ] cage and hollow [Sn ] cage sharing a central Sn atom, which is offset from the central position. This double-cage species represents the largest group 14 intermetalloid cluster encapsulating a single transition metal atom.

[Nb@Ge ] : New Family Members of Ge-Based Intermetalloid Clusters.

During the past two decades, single-atom-centered medium-sized germanium clusters [M@Ge ] (M=transition metals, n>12) have been extensively explored, both from theoretical perspectives and experimental gas-phase syntheses. However, the actual structural arrangements of the Ge and Ge endohedral cages are still ambiguous and have long remained an unresolved problem for experimental implementation. In this work, we successfully synthesize 13-/14-vertex Ge clusters [Nb@Ge ] (1) and [Nb@Ge ] (2), which are structurally characterized and exhibit unprecedented topologies, neither classical deltahedra nor 3-connected polyhedral structures.

Synthesis and characterisation of the ternary intermetalloid clusters {M@[As(ZnMes)]} (M = Nb, Ta) from binary [M@As] precursors.

The development of rational synthetic routes to inorganic arsenide compounds is an important goal because these materials are finding applications in many areas of materials science. In this paper, we show that the binary crown clusters [M@As] (M = Nb, Ta) can be used as synthetic precursors which, when combined with ZnMes, generate ternary intermetalloid clusters with 12-vertex cages, {M@[As(ZnMes)]} (M = Nb, Ta). Structural studies are complemented by mass spectrometry and an analysis of the electronic structure using DFT.

Sn: a 2.7 nm naked aromatic tin rod.

In this work, we synthesize naked tin cluster anion Sn, representing the first example of pure Sn nanowire assembled through oxidative coupling reactions of a super atomic cluster Sn. Theoretical analysis confirm the presence of aromaticity for each Sn unit showing four adjacent aromatic subunits bridged by parallel Sn-Sn bonds.

Missing Link in the Growth of Lead-Based Zintl Clusters: Isolation of the Dimeric Plumbaspherene [CuPb].

We report here the structure of an endohedral plumbaspherene, [CuPb], the gold analogue of which was previously postulated to be a "missing link" in the growth of larger clusters containing three and four icosahedral subunits. The cluster contains two [CuPb] subunits linked through a CuPb trigonal antiprism. Density functional theory reveals that the striking ability of mixed Pb/coinage metal Zintl clusters to oligomerize and, in the case of Au, to act as a site of nucleation for additional metal atoms, is a direct consequence of their d( + 1)s configuration, which generates both a low-lying ( + 1)s-based LUMO and also a high-lying Pb-centered HOMO.

Symmetry collapse due to the presence of multiple local aromaticity in Ge.

Understanding the structural changes taking place during the assembly of single atoms leading to the formation of atomic clusters and bulk materials remains challenging. The isolation and theoretical characterization of medium-sized clusters can shed light on the processes that occur during the transition to a solid-state structure. In this work, we synthesize and isolate a continuous 24-atom cluster Ge, which is characterized by X-ray diffraction analysis and Energy-dispersive X-ray spectroscopy, showing an elongated structural characteristic.

Inorganic Ferrocene Analogue [Fe(P)].

Inorganic metallocene derivatives containing only cyclo-P ligands have been targeted for more than 20 years, but their syntheses have never been achieved by pursuing the conventional route of using P phosphorus except for the generation of [Ti(η-P)]. Herein, we report a facile one-step method for the synthesis of the homoleptic iron complex [Fe(P)] by the Zintl-phase-type precursor KP. P NMR analyses indicate that upon dissolving the KP phase in ethylenediamine P was generated only in the presence of 2,2,2-crypt.

Synthesis and Characterization of Ternary Clusters Containing the [As] Anion, [MM'As] (M = Nb or Ta; M' = Cu or Ag).

The [Nb@As] anion was first isolated from solution in 1986, and a number of isostructural [M@Pn] clusters (M = Nb, Cr, or Mo; Pn = As or Sb; = 2 or 3) have since been reported. We show here how anions of this class can be used as synthetic precursors that, in combination with sources of low-valent late transition metals (Cu and Ag), generate ternary polyarsenide cluster anions with unprecedented structural motifs. Chain type [MM'As] (M = Nb or Ta; M' = Cu or Ag) units are found in compounds .

[Co@(GeNi)]: the first edge-sharing double-cage endohedral germanide.

We report here a new double-cage endohedral Ge cluster, [Co@(GeNi)], fused through two [Co@(GeNi)] moieties with a shared Ni-Ge edge. This ternary Co-Ge-Ni species not only represents the first double-cage example of an 18-vertex Zintl cluster, but also fills in the missing link of the edge fusion model in the double-cage systems.

Electronic structures and properties of dianionic pentacarbonyls [TM(CO)] (TM = Cr, Mo, W).

Density functional theory (DFT) calculations were employed to study the stabilities, electronic structures, and vibrational and bonding properties of dianionic pentacarbonyls [TM(CO)] (TM = Cr, Mo, W). A D symmetry structure with singlet state was found to be the ground state and C-O stretching vibrational frequencies range from 1719 to 1766 cm, which are in excellent agreement with the experimental observations. The calculation results on bond dissociation energy for the CO loss revealed their stabilities.

Ternary aromatic and anti-aromatic clusters derived from the hypho species [SnSb].

Heterometallic clusters have attracted broad interests in the synthetic chemistry due to their various coordination modes and potential applications in heterogeneous catalysis. Here we report the synthesis, experimental, and theoretical characterizations of four ternary clusters ([M(CO)SnSb] (M = Cr, Mo), and [(MSnSb)], (M = Cu, Ag)) in the process of capturing the hypho- [SnSb] in ethylenediamine (en) solution. We show that the coordination of the binary anion to transition-metal ions or fragments provides additional stabilization due to the formation of locally σ-aromatic units, producing a spherical aromatic shielding region in the cages.

Open Shells in Endohedral Clusters: Structure and Bonding in the [Fe@Ge] Anion and Comparison to Isostructural [Co@Ge].

The anionic cluster [Fe@Ge] has been characterized and shown to be isostructural to the known -symmetric α isomer of the cobalt analogue [Co@Ge]. Together with the known pair of compounds [Co@Ge] and [Fe@Ge], the title compound completes a set of four closely related germanium clusters that allow us to explore how the metal-metal and metal-cage interactions evolve as a function of size and of the identity of the metal. The results of spin-unrestricted density functional theory (DFT) and multiconfigurational self-consistent field (MC-SCF) calculations present a consistent picture of the electronic structure where transfer of electron density from the metal to the cage is significant, particularly in the Fe clusters where the exchange stabilization of unpaired spin density is an important driving force.

[BiMo(CO)]: a multiple local σ-aromatic cluster containing a distorted Bi triangular prism.

The first Zintl cluster containing a distorted Bi triangular prism, [BiMo(CO)], has been synthesized and structurally characterized. Quantum chemical calculations indicated that the distorted cage cluster features multiple local σ-aromaticity.

[Sn ] -Bridged Mixed-Valence Zn /Zn in {[K ZnSn (ZnMes)] } Inverse Sandwich-Type Cluster Supported by a Zn -Zn Bond.

Since [Sn ] was discovered from the solid-state phase in 2000, its solution chemistry has been elusive due to the high charges and chemical activity. Herein, we report the synthesis and characterization of an inverse sandwich-type cluster dimer {[K ZnSn (ZnMes)] } (1 a), in which the highly charged [Sn ] is captured by mixed-valence Zn /Zn to form the dimer {closo-[Zn Sn ]} moieties bridged by a Zn-Zn bond. Such Zn-Sn cluster not only exhibits a novel example of mixed-valence Zn /Zn for stabilizing highly active anion species, but also indicates the [Sn ] cluster can act as a novel bridging ligand, like arene, with a η :η -fashion.

Solution-Based Group 14 Zintl Anions: New Frontiers and Discoveries.

ConspectusGroup 14 Zintl anions [E] (E = Si-Pb, = 4, 5, 9, 10) are synthetically accessible, and their diverse chemical reactivity makes them valuable synthons in the construction of larger nanoclusters with remarkable structures, intriguing patterns of chemical bonding, and tunable physical and chemical properties. A plethora of novel cluster anions have now been isolated from the reactions of polyanionic [E] precursors with low-valent d-/f-block metal complexes, main-group organometallics, or organics in polar aprotic solvents. The range of products includes intermetalloid clusters with transition metal atom(s) embedded in main-group element cages, organometallic Zintl anions in which [E] acts as a ligand, intermetallic Zintl anions where [E] is bridged by ligand-free transition metal atom(s), organo-Zintl anions where [E] is functionalized with organic-group(s), and oligomers formed through oxidative coupling reactions.