Advances in cluster superatoms for a 3D periodic table of elements

Luo, Zhixun; Lin, Shiquan

doi:10.1016/j.ccr.2023.215505

Cited by 7 publications

(6 citation statements)

References 271 publications

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“…For these clusters, the orbitals located at lower energy (e.g., −20 eV for Ti 8 C 12 and −14 eV for Ti 14 C 13 ; Ti 17 C 2 and Ti 19 C 10 at −13 ∼ −14 eV) are dominantly contributed by the C(2s) electrons, while the C(2p) orbitals hybridize with Ti(3 d /4s) at higher energy levels. The PDOS compositions of Ti 17 C 2 and Ti 19 C 10 exhibit comparable patterns, with many hybridized orbitals above −8 eV showing vivid superatomic features. , Notably, the superatomic 1S and 1P z orbitals of Ti 17 C 2 are mainly composed of the 2s orbitals of the carbon atoms, while the superatomic 1P x , 1P y , 2S, 2P, and 1D orbitals are caused by hybridization of the valence C(2p) orbitals and Ti(3 d /4s) orbitals. This is analogous but partly different from the superatomic feature of nascent Ti 17 (Figure S23).…”

Section: Results and Discussionmentioning

confidence: 99%

Tailoring Titanium Carbide Clusters for New Materials: from Met-Cars to Carbon-Doped Superatoms

Cui,

Zhang,

et al. 2024

J. Am. Chem. Soc.

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Tailoring materials with prescribed properties and regular structures is a critical and challenging research topic. Early transition metals were found to form supermagic M 8 C 12 metallocarbohedrenes (Met-Cars); however, stable metal carbides are not limited to this common stoichiometry. Utilizing self-developed deep-ultraviolet laser ionization mass spectrometry, here, we report a strategy to generate new titanium carbides by reacting pure Ti n clusters with acetylene. Interestingly, two products corresponding to Ti 17 C 2 and Ti 19 C 10 exhibit superior abundances in addition to the Ti 8 C 12 Met-Cars. Using global-minimum search, the structures of Ti 17 C 2 and Ti 19 C 10 are determined to be an ellipsoidal D 4d and a rod-shaped D 5h geometry, respectively, both with carbon-capped Ti 4 C moieties and superatomic features. We illustrate the electronic structures and bonding nature in these carbon-doped superatoms concerning their enhanced stability and local aromaticity, shedding light on a new class of metal-carbide nanomaterials with atomic precision.

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Section: Results and Discussionmentioning

confidence: 99%

Tailoring Titanium Carbide Clusters for New Materials: from Met-Cars to Carbon-Doped Superatoms

Cui,

Zhang,

et al. 2024

J. Am. Chem. Soc.

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“…Furthermore, we present their current and potential applications in terms of their solubility and modifiability characteristics. It should be pointed out that the research based on Al−Al metal bonds 19 is not within the scope of this paper.…”

Section: Introductionmentioning

confidence: 99%

Induced Aggregation, Solvent Regulation, and Supracluster Assembly of Aluminum Oxo Clusters

Fang,

Xie,

Wang

et al. 2024

Acc. Chem. Res.

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Metrics & MoreArticle RecommendationsCONSPECTUS: Recent years have witnessed the development of cluster materials as they are atomically precise molecules with uniform size and solution-processability, which are unattainable with traditional nanoparticles or framework materials. The motivation for studying Al(III) chemistry is not only to understand the aggregation process of aluminum in the environment but also to develop novel low-cost materials given its natural abundance. However, the Al-related clusters are underdeveloped compared to the coinage metals, lanthanides, and transition metals. The challenge in isolating crystalline compounds is the lack of an effective method to realize the controllable hydrolysis of Al(III) ions. Compared with the traditional hydrolysis of inorganic Al(III) salts in highly alkaline solutions and hydrolysis of aluminum trialkyl compounds conducted carefully in an inert operating environment, we herein developed an effective way to control the hydrolysis of aluminum isopropanol through an alcoxalation reaction. By solvothermal/low melting point solid melting synthesis and using "ligand aggregation, solvent regulation, and supracluster assembly" strategies, our laboratory has established an organic-inorganic hybrid system of aluminum oxo clusters (AlOCs). The employment of organic ligands promotes the aggregation and slows the hydrolysis of Al(III) ions, which in turn improves the crystallization process. The regulation of the structure types can be achieved through the selection of ligands and the supporting solvents. Compared with the traditional condensed polyoxoaluminates, we successfully isolated a broad range of porous AlOCs, including aluminum molecular rings and Archimedes aluminum oxo cages. By studying ring expansion, structural transformation, and intermolecular supramolecular assembly, we demonstrate unique and unprecedented structural controllability and assembly behavior in cluster science. The advancement of this universal synthetic method is to realize materials customization through modularly oriented supracluster assembly. In this Account, we will provide a clear-cut definition and terminology of "ligand aggregation, solvent regulation, and supracluster assembly". Then we will discuss the discovery in this area by using a strategy, such as aluminum molecular ring, ring size expansion, ring supracluster assembly, etc. Furthermore, given the internal and external pore structures, as well as the solubility and modifiability of the AlOCs, we will demonstrate their potential applications in both the solid and liquid phases, such as iodine capture, the optical limiting responses, and dopant in polymer dielectrics. The strategy herein can be applied to extensive cluster science and promote the research of main group element chemistry. The new synthetic method, fascinating clusters, and unprecedented assembly behaviors we have discovered will advance Al(III) chemistry and will also lay the foundation for functional applications.

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“…More interestingly, the continuous study of aluminum clusters has yielded the concept of superatoms, which are a class of atomic clusters with special electronic structures that exhibit chemical properties similar to those of traditional atoms in the periodic table. To date, a lot of aluminum-based superatoms, − including superhalogens, , alkaline earth superatoms, superalkalis, , quasi-chalcogen superatoms, multiple valence superatoms, and noble gas superatoms have been reported.…”

Section: Introductionmentioning

confidence: 99%

Suzuki–Miyaura Cross-Coupling Reaction Catalyzed by Al₁₂M (M = Be, Al, C, and P) Superatoms with Different Numbers of Valence Electrons

Wang,

Zhang,

et al. 2024

Inorg. Chem.

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Advances in cluster superatoms for a 3D periodic table of elements

Cited by 7 publications

References 271 publications

Tailoring Titanium Carbide Clusters for New Materials: from Met-Cars to Carbon-Doped Superatoms

Tailoring Titanium Carbide Clusters for New Materials: from Met-Cars to Carbon-Doped Superatoms

Induced Aggregation, Solvent Regulation, and Supracluster Assembly of Aluminum Oxo Clusters

Suzuki–Miyaura Cross-Coupling Reaction Catalyzed by Al₁₂M (M = Be, Al, C, and P) Superatoms with Different Numbers of Valence Electrons

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Advances in cluster superatoms for a 3D periodic table of elements

Cited by 7 publications

References 271 publications

Tailoring Titanium Carbide Clusters for New Materials: from Met-Cars to Carbon-Doped Superatoms

Tailoring Titanium Carbide Clusters for New Materials: from Met-Cars to Carbon-Doped Superatoms

Induced Aggregation, Solvent Regulation, and Supracluster Assembly of Aluminum Oxo Clusters

Suzuki–Miyaura Cross-Coupling Reaction Catalyzed by Al12M (M = Be, Al, C, and P) Superatoms with Different Numbers of Valence Electrons

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Suzuki–Miyaura Cross-Coupling Reaction Catalyzed by Al₁₂M (M = Be, Al, C, and P) Superatoms with Different Numbers of Valence Electrons