Ternary Clusters Research Articles

Complex Dance of Molecules in the Sky: Choreography of Intermolecular Structure and Dynamics in the Cyclopentene-CO2-H2O Hetero Ternary Cluster.

This study delves into driving forces behind the formation of a hetero ternary cluster consisting of volatile organic compounds from industrial or combustion sources, specifically cyclopentene, alongside greenhouse gases like carbon dioxide, and water vapor. While substantial progress has been made in understanding binary complexes, the structural intricacies of hetero ternary clusters remain largely uncharted. Our research characterized the cyclopentene-CO2-H2O hetero ternary cluster utilizing Fourier transform microwave spectroscopy. The observed isomer in the pulsed jet has CO2 and H2O aligning above the cyclopentene ring, with water undergoing an internal rotation approximately about its C2 symmetry axis. Theoretical analyses support these observations, identifying an O-H⋅⋅⋅π hydrogen bond and a secondary C⋅⋅⋅O tetrel bond within this cluster. This study marks a critical step towards comprehending the molecular dynamics and interactions of VOCs, greenhouse gases, and water in the atmosphere, paving the way for further investigations into their roles in climate dynamics and air quality.

Dimers and 2D Networks of Adamantane-Related Ternary Organosilicon Coinage Metal Sulfide Clusters.

Adamantane-type organotin sulfide clusters were recently shown to react with coinage metal phosphine complexes under replacement of an organic substituent by a metal-phosphine unit. An extension of such studies involving the silicon-based congener [(PhSi)4S6] (A) revealed that the cluster core will be partly disassembled and a {PhSi} moiety is replaced by a coinage metal phosphine complex to form [(Et3PAg)3(PhSi)3S6] (B) and [Na2(thf)2.33][(Me3PCu)(PhSi)3S6] (C). Herein, we present an extension of this work upon variation of the reactants and reaction conditions. Besides the isolation of crystalline precursor complexes [CuCl(PMe2Ph)3] (1) and [AgCl(PMe2Ph)2]2 (2), the study addresses reactions of A with AgCl and a phosphine ligand in CH2Cl2, upon which A is completely disassembled to form [(Ph3P)3Ag(μ-S)SiCl2Ph] (3). In another case a CH2 group, most likely stemming from CH2Cl2, was attached to the ligand, thus generating [{PhCl(S)SiSCH2P(Ph2)CH2CH2}2] (4). Upon using CuCl and 1,4-bis(diphenylphosphino)butane (dppb) we isolated the phosphine-bridged analog of B, [{(dppbCu2)CuP(Ph2)(CH2CH2)(PhSi)3S6}2] (5). In order to receive the yet elusive silver homolog of C, we used PMe2Ph as a bulkier ligand. This way we generated a 2D coordination polymer of the desired composition, [Na2(thf)1.5][(Me2PhPAg)(PhSi)3S6] (6). UV-visible spectra of 6 indicated a bandgap of 3.89 eV, thus blue-shifted in regards to B and C.

Room-Temperature Formation of CdTeSe Magic-Size Clusters from Oleate-Capped CdTe Precursor Compounds via CdSe Monomer Substitution.

We report the first room-temperature synthesis of ternary CdTeSe magic-size clusters (MSCs) that have mainly the surface ligand oleate (OA). The MSCs display sharp optical absorption peaking at ∼399 nm and are thus referred to as MSC-399. They are made from prenucleation-stage samples of binary CdTe and CdSe, which are prepared by two reactions in 1-octadecene (ODE) of cadmium oleate (Cd(OA)2) and tri-n-octylphosphine chalcogenide (ETOP, E = Te and Se) at 25 °C for 120 min and 80 °C for 15 min, respectively. When the two binary samples are mixed at room temperature and dispersed in a mixture of toluene (Tol) and octylamine (OTA), the CdTeSe MSC-399 develops. Also, when the CdSe sample is added to CdTe MSC-371 in a dispersion, the transformation from CdTe MSC-371 to CdTeSe MSC-399 is seen. We propose that the MSCs develop from their precursor compounds (PCs) that are relatively transparent in optical absorption, such as CdTeSe MSC-399 from CdTeSe PC-399 and CdTe MSC-371 from CdTe PC-371. The formation of CdTeSe PC-399 undergoes monomer substitution and not anion exchange, which is the reaction of CdTe PC-371 and the CdSe monomer to produce CdTeSe PC-399 and the CdTe monomer. Our study provides evidence of monomer substitution for the transformation from binary CdTe to ternary CdTeSe PCs.

Pathway of Room-Temperature Formation of CdSeS Magic-Size Clusters from Mixtures of CdSe and CdS Samples.

The synthetic application of prenucleation-stage samples of colloidal semiconductor quantum dots (QDs) is in its infancy. It is shown that when two prenucleation-stage samples of binary CdSe and CdS are mixed, ternary CdSeS magic-size clusters (MSCs) grow at room temperature in dispersion. As the amount of the CdS sample increases, the optical absorption of the CdSeS MSCs blueshifts from ≈380 to ≈360 nm. It is proposed that the cluster in the CdSe sample reacts with the CdS monomer from the CdS sample. The monomer substitution reaction of CdSe by CdS can proceed continuously; thus, CdSeS MSCs with tunable compositions are obtained. The present study provides compelling evidence that clusters formed in the prenucleation stage of QDs. The clusters are precursor compounds (PCs) of MSCs, transforming at room temperature with the thermoneutrality principle of isodesmic reactions. The nucleation and growth of QDs follows a multi-step non-classical instead of one-step classical nucleation model.

Boosting Zinc‐Ion Batteries with Innovative Ternary Electrolyte for Enhanced Interfacial Electrochemistry and Temperature‐Resilient Performance

AbstractThe practical application of Zn‐ion batteries (ZIBs) faces several challenges, particularly regarding poor reversibility and the reactivity of water in the electrolytes across a wide temperature range. Herein, this study presents the design of a ternary electrolyte with significant intermolecular interactions based on tetrahydrofurfuryl alcohol (THFA), H2O, and Zn(OTf)2 to address these challenges from −40 to 60 °C. The ether alcohol compound THFA effectively mitigates the side reactions about water, by disrupting and suppressing the reactivity of the dominant water‐based clusters. Through experimental and theoretical investigations, the structural and mechanistic insights of ternary solvation clusters are uncovered. The hydrogen‐bond‐induced interactions of THFA facilitate the participation of OTf− in solvation clusters and bidentate chelation coordination with Zn2+ ensures the formation of lean‐water solvation clusters. Furthermore, the interfacial electrochemistry on the Zn surface is also regulated to exhibit a preferential layer‐by‐layer (0 0 2) oriented deposition with a stable solid electrolyte interface (SEI). As a result, The Zn||VO2 battery using ternary electrolyte maintains a capacity of 237.5 mAh g−1 with an 86.71% retention after 500 cycles at 60 °C and 3 A g−1, while it exhibits stable cycle even at −40 °C over 200 cycles with almost no capacity decrease.

Clustering in gallium ion beam sputtered compound materials driven by bond strength and interstitial/vacancy reaction

The investigation of chemical reactions during ion irradiation is a frontier for the study of the ion–material interaction. In order to probe the chemistry of ion produced nanoclusters, valence electron energy loss spectroscopy (VEELS) was exploited to investigate Ga+ ion damage in Al2O3, InP, and InGaAs, where each target material has been shown to react differently to the interaction between impinging ions, recoil atoms, and vacancies: metallic Ga, ternary InGaP clusters, and metallic In clusters are formed in Al2O3, InP, and InGaAs, respectively. Supporting simulations based on Monte Carlo and crystal orbital Hamiltonian calculations indicate that the chemical constitution of cascade induced nano-precipitates is a result of a competition between interstitial/vacancy consumption rates and preferential bond formation due to differing bond strengths.

Employing ternary fission of Pu242 as a probe of very neutron-rich matter

Detailed assessments of the ability of recent theoretical approaches to modeling existing experimental data for ternary fission confirm earlier indications that the dominant mode of cluster formation in ternary fission is clusterization in very neutron-rich, very low-density, essentially chemically equilibrated nucleonic matter. An extended study and comparison of these approaches applied to ternary fission yields in the thermal neutron induced reaction $^{241}\mathrm{Pu}({n}_{\mathrm{th}},\mathrm{f})$ has been undertaken to refine the characterization of the source matter. The resonance-gas approximation has been improved taking in-medium effects on the binding energies into account. A temperature of 1.29 MeV, density of $6.7\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}5}\phantom{\rule{0.16em}{0ex}}\mathrm{nucleons}/{\mathrm{fm}}^{3}$ and proton fraction ${Y}_{p}=0.035$ are found to provide a good representation of yields of the ternary emitted light particles and clusters. In particular, results for $Z=1$ and 2 isotopes are presented. Isotopes with larger $Z$ are discussed, and the roles of medium and continuum effects, even at very low density, are illustrated.

Nanoclusters and nanoalloys of group 13 elements (B, Al, and Ga): benchmarking of methods and analysis of their structures and energies.

We investigated the structural and energetic properties of nanoclusters and nanoalloys composed of group 13 elements (B, Al, and Ga) up to a cluster size of 12. We conducted a comprehensive benchmark analysis of density functional and post-Hartree-Fock methods to identify efficient and accurate approaches for studying these systems using our benchmark dataset (BAlGa16) consisting of sixteen dimers and trimers. We compared different density functionals and post-Hartree-Fock methods using bond length and binding energy as parameters. B2PLYP closely follows CCSD(T) for geometry optimization, while REVPBE, BPBE, and PBE show cost-accuracy balanced performances. MRACPF was used as the reference for benchmarking energies, with NEVPT2 being the most accurate method, followed by CCSD(T) and DLPNO-CCSD(T). M06 and range-separated hybrid functionals perform well. Based on a cost-accuracy analysis, we recommend M06/def2-SVP as the preferred method. Additionally, we explored the structural evolution of pure, binary, and ternary clusters of group 13 elements up to 12 atoms, uncovering global and local minima. Ga clusters exhibited more rectangular faces compared to the predominantly trigonal faces of B and Al clusters. Binary clusters showed B in center positions, while Ga preferred outer positions, confirming the higher cohesion of B. The most favorable size of binary clusters (12) exhibited similar compositions of Al and Ga atoms. Compositions with 16.67-40% B, 16.67-60% Al, and 20-50% Ga were estimated to have negative mixing energies, indicating their relative stability.

Room-Temperature Evolution of Ternary CdTeS Magic-Size Clusters Exhibiting Sharp Absorption Peaking at 381 nm.

Colloidal semiconductor ternary CdTeS magic-size clusters (MSCs) have not been reported. Here, we present the first synthesis of CdTeS MSCs at room temperature and our understanding of the evolution pathway. The MSCs exhibit sharp optical absorption peaking at 381 nm and are labeled MSC-381. CdTeS MSC-381 evolves when pre-nucleation-stage samples of binary CdTe and CdS that do not contain quantum dots (QDs) are separately prepared and then mixed and incubated at room temperature. We propose that CdTeS MSC-381 evolves from its precursor compound (PC) via quasi-isomerization. Synchrotron-based small-angle X-ray scattering suggests that PCs/MSCs of CdTe and CdTeS are similar in sizes. We propose further that the CdTeS PC forms from the substitution reaction between the CdTe PC and the CdS monomer/fragment (Mo/Fr). The present study paves the way to the room-temperature evolution of ternary MSCs and provides an in-depth understanding of the PC to MSC transformation.

Synthesis and Characterization of Ternary Clusters Containing the [As16]10- Anion, [MM'As16]4- (M = Nb or Ta; M' = Cu or Ag).

The [Nb@As8]3- anion was first isolated from solution in 1986, and a number of isostructural [M@Pn8]n- clusters (M = Nb, Cr, or Mo; Pn = As or Sb; n = 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'As16]4- (M = Nb or Ta; M' = Cu or Ag) units are found in compounds 2-5. These clusters contain a nortricyclane-like As7 cage and a [M@As8] crown, linked by a single As atom, and represent a fusion of two quite distinct branches of polyarsenide chemistry. Our analysis of the electronic structure confirms that the cluster retains many of the features of the component units. Electrospray ionization mass spectrometry reveals a series of smaller component ions containing 8-12 As atoms, the density functional theory-computed structures of which can be understood in terms of the pseudoelement concept. This work not only presents a new type of coordination mode for As clusters but also offers a point of entry for the rational design of multinary arsenic-based materials.

Synthesis and characterisation of the ternary intermetalloid clusters {M@[As8(ZnMes)4]}3- (M = Nb, Ta) from binary [M@As8]3- 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@As8]3− (M = Nb, Ta) can be used as synthetic precursors which, when combined with ZnMes2, generate ternary intermetalloid clusters with 12-vertex cages, {M@[As8(ZnMes)4]}3− (M = Nb, Ta). Structural studies are complemented by mass spectrometry and an analysis of the electronic structure using DFT. The synthesis of these clusters presents new opportunities for the construction of As-based nanomaterials.

Transformation Pathways in Colloidal CdTeSe Magic-Size Clusters.

A rarely studied transformation in colloidal ternary magic-size clusters (MSCs) is addressed. We report the first observation of the transformation from ternary CdTeSe MSC-399 to MSC-422, which occurs at room temperature. These two MSC types display sharp optical absorption resonances at 399 and 422 nm, respectively, and are related in that they are quasi isomers, together with their counterpart precursor compounds (PCs). Binary CdTe and CdSe samples were prepared in the prenucleation stage also called the induction period (IP). After they were mixed and placed in a mixture of toluene and octylamine, the transformation was found to take place and to be assisted by the addition of the CdSe IP sample. A binary IP sample contains corresponding binary PCs and monomers (Mo) and fragments (Fr). We argue that the transformation pathway is enabled by the corresponding ternary PCs, involving the substitution reaction, namely CdTeSe PC-399 + CdSe (Mo/Fr)-1 ⇒ CdTeSe PC-422 + CdSe (Mo/Fr)-2. The present study provides an in-depth understanding of the formation characteristics of the MSCs.

Germanium‐antimony‐selenium‐tellurium thin films: Clusters formation by laser ablation and comparison with clusters from mixtures of elements

AbstractQuaternary germanium‐antimony‐selenium‐tellurium (Ge‐Sb‐Se‐Te) thin films deposited from Ge19.4Sb16.7Se63.9−xTex (x = 5, 10, 15, and 20) glass‐ceramics targets by radio frequency magnetron sputtering were studied using laser ablation quadrupole ion trap time of flight mass spectrometry. Binary, ternary, and quaternary GeaSbbSecTed clusters were formed and their stoichiometry was determined. By comparison of the clusters obtained from quaternary Ge‐Sb‐Se‐Te thin films and those from ternary Ge‐Sb‐Te materials, we found that Ge‐Te species are not detected from the quaternary system. Furthermore, Ge‐Se and Se‐Te species are missing in mass spectra generated from Ge‐Sb‐Se‐Te thin films. From the Ge‐Sb‐Se‐Te thin films, 16 clusters were detected while ternary Ge‐Sb‐Se glasses yielded 26 species. This might be considered as a signal of higher stability of Ge‐Sb‐Se‐Te thin films which is increasing with a higher content of Te. The missing (Se2+, GeaSb+ (a = 1–4), and GeSec+ (c = 1, 2)) and new (Ge+ and SbbTe+ (b = 1–3)) clusters may indicate that some of the structural features of the films (Ge2Se6/2 and Se2Sb‐SbSe2) were replaced by (GeSe4−xTex and SbSe3−xTex) ones. In addition, when comparing the stoichiometry of clusters formed from Ge‐Sb‐Se‐Te thin films with those from the mixtures of the elements, only Sb3+ and SbSe+ were observed in both cases. The knowledge gained concerning clusters stoichiometry contributes to the elucidation of the processes proceeding during plasma formation used for the chalcogenide thin films deposition.

Theoretical investigation onto the reaction mechanism of dry reforming of methane on core–shell Cu-Ni-Pt ternary alloy clusters

Dry reforming of methane (DRM) can not only solve the problem of greenhouse gas emissions, but also be used as a precursor step for the production of clean energy. In this paper, based on Cu55 cluster, core–shell Cu-Ni-Pt ternary alloy clusters were constructed by density functional theory (DFT). Based on theoretical calculation, the adsorption of intermediate species and reaction mechanism of DRM on clusters were discussed in detail. Compared with Cu55 cluster, Cu-Ni-Pt ternary alloy clusters show much lower energy barrier in CHX activation, which indicates that the latter is much more suitable for DRM reaction than the former. The different species would be adsorbed on Top1, Top2, Hol1 and Bri2 site of the cluster. Hol2 was not the active adsorption site of DRM species. For Cu-Ni-Pt ternary alloy clusters, CH4 decomposes into CH3*, and then CO2 is directly activated into CO* and O*. CH3* collides with O* species to produce CH3O*, and CH3O* further decays H* to produce CH2O*. Two molecules H* in the system interact to form H2*. CH2O* continuously dissociates two H* and transforms into CO*. Finally, two H* are combined to form H2*. The rate-determining step of this reaction pathway is CO2* activation.

Laser ablation of Ga‐Sb‐Te thin films monitored with quadrupole ion trap time‐of‐flight mass spectrometry

AbstractLaser ablation of Ga‐Sb‐Te chalcogenide thin films prepared by radiofrequency magnetron co‐sputtering was monitored with quadrupole ion trap time‐of‐flight mass spectrometry (QIT‐TOF‐MS). The mass spectra of 11 thin films of various compositions (Ga: 0–53.1, Sb: 0–52.0, and Te: 0–100.0 at. %) were recorded. Several series of unary (Gax, Sby, and Tez) binary (GaxSby, GaxTez, and SbyTez), and ternary GaxSbyTez clusters were identified in both positive and negative ion modes. Stoichiometry of observed clusters was determined. Up to 18 binary clusters (positively and negatively charged) were detected for thin film with low Sb content of 6.5 at. %. The highest number (4) of ternary clusters was observed for thin film with high Te content of 66.7 at. %. The number of generated clusters and their peaks intensity varied according to the chemical composition of thin films. Altogether, 41 clusters were detected. The laser ablation monitoring shows laser‐induced fragmentation of thin film structure. The relation of clusters stoichiometries to the chemical composition of thin films is discussed. The fragmentation can be diminished by covering a surface of thin films with paraffin's, glycerol, or trehalose sugar thin layers. The stoichiometry of generated clusters shows partial structural characterization of thin films.

Ternary aromatic and anti-aromatic clusters derived from the hypho species [Sn2Sb5]3\u2212

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 ([M2(CO)6Sn2Sb5]3− (M = Cr, Mo), and [(MSn2Sb5)2]4−, (M = Cu, Ag)) in the process of capturing the hypho- [Sn2Sb5]3− 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. While in the case of [Mo2(CO)6Sn2Sb5]3− stabilization arises from locally σ-aromatic three-centre and five-centre two-electron bonds, aromatic islands in [(AgSn2Sb5)2]4− and [(CuSn2Sb5)2]4− render them globally antiaromatic. This work describes the coordination chemistry of the versatile building block [Sn2Sb5]3−, thus providing conceptual advances in the field of metal-metal bonding in clusters.

As3M(As3Pb3)]3− (M = Nb, Ta): Ternary Heterometallic Clusters with Early Transition Metal Atoms and Aromatic [Pb3]2−

Main observation and conclusionTwo ternary clusters, [As3Nb(As3Pb3)]3− 1 and [As3Ta(As3Pb3)]3− 2, were directly extracted from “K8NbPbAs5” and “K8TaPbAs5” intermetallic solid in the presence of ethylenediamine and 2.2.2‐crypt, respectively. Both 1 and 2, comprising an electron‐poor early transition metal‐atom Nb or Ta coordinated to a As3 triangle and a bowl‐like As3Pb3, were characterized by single crystal X‐ray diffraction, energy dispersive X‐ray (EDX) and electrospray ionization mass‐spectrometry (ESI‐MS). They also represent the first examples of the Pb‐As hybrid in solution‐based Zintl anion chemistry and DFT calculations revealed a σ‐aromaticity of the [Pb3]2− unit.

Tuning the Electronic Structure of Atomically Precise Sn/Co/Se Nanoclusters via Redox Matching of Tin(IV) Surface Sites.

A new strategy is reported to tailor the electronic properties of a superatomic metal chalcogenide cluster by redox matching the cluster core with surface tin(IV) sites. Two ternary clusters (SnR2)3Co6Se8L6 (R = Me, nBu) are synthesized by salt metathesis from the hexalithiated salt [Li2(py)2]3Co6Se8L6 and R2SnCl2. Cyclic and differential-pulse voltammetry studies reveal that the tristannylated clusters feature two new, near-degenerate, electronic states within the highest occupied molecular orbital-lowest unoccupied molecular orbital gap of the Co6Se8 core, which are attributed to the reduction of a surface tin site. Single-crystal X-ray diffraction analysis reveals that no Sn···Se coordination is present in the solid state. The single-crystal X-ray structure of the hexalithiated salt starting material is reported for the tetrahydrofuran (THF) adduct variant [Li2(THF)2]6Co6Se8L6.

Ternary antimony–chalcogen iron carbonyl complexes and their derivatives: Syntheses, structures, reactivities, and low-energy-gap characteristics

A novel series of ternary antimony–chalcogen iron carbonyl clusters, [{SbTeFe3(CO)9}{Te2Fe3(CO)9}]– (1), [{SbSeFe3(CO)9}{Se2Fe2(CO)6}]– (2), and [{SbSFe3(CO)9}{SFe3(CO)9}]– (3), were synthesized in moderate yields from reactions of [EFe3(CO)9]2– (E = Te, Se, S) with SbCl3. X-ray analyses revealed that complexes 1–3 each can be viewed as a square pyramidal geometry [SbEFe3(CO)9] (E = Te, Se, S), where the Sb atom was further coordinated with pendant cluster fragments [Te2Fe3(CO)9], [Se2Fe2(CO)6], and [SFe3(CO)9], respectively. Interestingly, the oxidation state of the Sb atom in complexes 1–3 was 0, which was evidenced by XPS and XANES. Complexes 1–3 showed high electrophilicity toward a series of metal carbonylates, which produced transmetallated products, the “spiked” square pyramidal complexes [{SbEFe3(CO)9}{M(CO)x}] [M(CO)x = Fe(CO)4, E = Te, 1-Fe; Se, 2-Fe; S, 3-Fe; M(CO)x = Cr(CO)5, Se, 2-Cr; S, 3-Cr] and the Mn(CO)4-bridged di-ESbFe3(CO)9-based clusters [{SbEFe3(CO)9}2Mn(CO)4]– (E = Se, 2-Mn; S, 3-Mn). Furthermore, the diffuse reflectance spectra showed that these ternary and quaternary antimony-chalcogenide metal carbonyl clusters possessed low energy gaps of 0.84–1.48 eV, suggesting possible electron transports within the frameworks, which was supported by crystal packings and DFT calculations.

Binary and ternary Pt-based clusters grown in a plasma multimagnetron-based gas aggregation source: electrocatalytic evaluation towards glycerol oxidation.

Platinum (Pt), platinum–bismuth (PtBi), platinum–copper (PtCu) and platinum–bismuth–copper (PtCuBi) clusters were grown in a gas aggregation source (GAS) equipped with three in-plane plasma magnetrons located in a single region of the gas aggregation zone. The X-ray diffraction results have shown that PtCu clusters form alloys as the decrease of the lattice parameter occurs when the Cu atomic content increases. PtBi clusters do not form alloys, but the presence of secondary Bi oxide phases was detected. Scanning transmission electron microscope mapping images revealed that simultaneously adding Bi and Cu to Pt leads to PtCu alloyed clusters decorated with Bi or CuBi species on the surface. The electrochemical results indicated that the shell might be composed of a metastable CuBi phase. Electrochemical measurements have shown that the addition of Bi or Cu to the Pt clusters enhances the catalytic activity for glycerol oxidation by decreasing the oxidation onset potential.