Design and Synthesis of <scp>Al7Ni2</scp> Heterometallic Clusters Based on Metal Substitution and Ligands Protection Strategies†

Liu, Ya‐Jie; Cui, Lianhua; Fang, Wei‐Hui; Zhang, Jian

doi:10.1002/cjoc.202200592

Cited by 6 publications

(3 citation statements)

References 43 publications

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“…The incorporation of lanthanide Lewis acid sites further facilitates the reaction and reaches a production of nearly 100% . In addition, transitional metal centers with unsaturated coordination sites employed facilitate interaction with substrate acetone and thus possess aldol condensation catalytic activity. − Based on the solubility and stability of clusters, our group investigated their homogeneous and heterogeneous catalytic performances, utilizing the solvent effect and supramolecular effect, inducing a high catalytic conversion efficiency for β-hydroxy ketone and α,β-unsaturated ketone …”

Section: Emerging Applicationsmentioning

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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Section: Emerging Applicationsmentioning

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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“…3) The Ce@AlMs dopant is highly miscible with polymer matrices and offers excellent stability due to the abundant peripheral phenyl groups. [38,39] Electrostatic repulsion between cationic clusters ensures a uniform distribution of the Ce@AlMs within the polymer, effectively overcoming the issues associated with traditional nanoparticle dopants, such as high surface roughness, dopant aggregation, defects, and low breakdown strength. Additionally, the well-dispersed Ce@AlMs in polymer matrices efficiently break dipole coupling and suppress polarization hysteresis loss even at high electric fields.…”

Section: Introductionmentioning

confidence: 99%

Breaking the Trade‐Off Between Polymer Dielectric Constant and Loss via Aluminum Oxo Macrocycle Dopants for High‐Performance Neuromorphic Electronics

Chen,

Sun,

et al. 2023

Advanced Materials

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The dielectric layer is crucial in regulating the overall performance of field‐effect transistors (FETs), the key component in central processing units, sensors, and displays. Despite considerable efforts being devoted to developing high‐permittivity (k) dielectrics, limited progress is made due to the inherent trade‐off between dielectric constant and loss. Here, a solution is presented by designing a monodispersed disk‐shaped Ce–Al–O‐macrocycle as a dopant in polymer dielectrics. The molecule features a central Ce(III) core connected with eight Al atoms through sixteen bridging hydroxyls and eight 3‐aminophenyl peripheries. The incorporation of this macrocycle in polymer dielectrics results in an up to sevenfold increase in dielectric constants and up to 89% reduction in dielectric loss at low frequencies. Moreover, the leakage‐current densities decrease, and the breakdown strengths are improved by 63%. Relying on the above merits, FETs bearing cluster‐doped polymer dielectrics give near three‐orders source‐drain current increments while maintaining low‐level leakage/off currents, resulting in much higher charge‐carrier mobilities (up to 2.45 cm2 V−1 s−1) and on/off ratios. This cluster‐doping strategy is generalizable and shows great promise for ultralow‐power photoelectric synapses and neuromorphic retinas. This work successfully breaks the trade‐off between dielectric constant and loss and offers a unique design for polymer composite dielectrics.

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“…Consequently, a series of new ligands with N and O coordination sites were designed and used in the development of actinide organometallic chemistry. [5][6][7][8][9][10][11][12][13][14][15][16][17][18] For instance, since the first example of an actinide complex supported by a triamidoamine ([(RNCH 2 CH 2 ) 3 N] 3− ) ligand (Tren) was reported by Scott and co-workers in 1994, 19 actinide organometallic chemistry with Tren ligands has flourished. 18,[20][21][22][23][24][25][26] With these trianionic ligands, a series of trivalent uranium complexes were isolated.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and reactivity of a uranium(iv) complex supported by a monoanionic nitrogen–phosphorus ligand

Li,

He,

Zhao

et al. 2023

Inorg. Chem. Front.

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Design and Synthesis of Al₇Ni₂ Heterometallic Clusters Based on Metal Substitution and Ligands Protection Strategies^†

Cited by 6 publications

References 43 publications

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

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

Breaking the Trade‐Off Between Polymer Dielectric Constant and Loss via Aluminum Oxo Macrocycle Dopants for High‐Performance Neuromorphic Electronics

Synthesis and reactivity of a uranium(iv) complex supported by a monoanionic nitrogen–phosphorus ligand

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Design and Synthesis of Al7Ni2 Heterometallic Clusters Based on Metal Substitution and Ligands Protection Strategies†

Cited by 6 publications

References 43 publications

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

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

Breaking the Trade‐Off Between Polymer Dielectric Constant and Loss via Aluminum Oxo Macrocycle Dopants for High‐Performance Neuromorphic Electronics

Synthesis and reactivity of a uranium(iv) complex supported by a monoanionic nitrogen–phosphorus ligand

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Design and Synthesis of Al₇Ni₂ Heterometallic Clusters Based on Metal Substitution and Ligands Protection Strategies^†