Ligand-field regulated superalkali behavior of the aluminum-based clusters with distinct shell occupancy

Li, Jun; Cui, Mei; Yang, Huan; Chen, Jing; Cheng, Shi‐Bo

doi:10.1016/j.cclet.2022.02.039

Cited by 8 publications

(3 citation statements)

References 49 publications

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“…These calculated E b values are higher than the previously reported systems Al 13 (C 5 N 2 H 8 ) (about 2.40 eV), Al 13 (CNC 6 H 4 NC) (about 1.30 eV), and Al 13 (EP) (1.11 eV). 30,33,37 Therefore, the interaction between the Al 13 cluster and the dianhydride ligand is relatively strong. In these previously reported systems, the aluminum clusters are bonded to organic molecules through an Al−Al−C/N/O bond.…”

Section: Structural Characteristics and Stabilitymentioning

confidence: 99%

“…Superatoms are the stable assembly of atoms that exhibit a behavior similar to that of atoms and can be used as building blocks for various nanoscale materials with unique properties. , Superhalogens are one of the most important members of the superatomic family and have been widely used in the design of new materials. The Al 13 cluster is referred to as a superhalogen and has been studied theoretically and synthesized experimentally. − Researchers have conducted a series of studies on the interactions between the Al 13 cluster and inorganic/organic ligands, including superalkalis, benzene, tetrahydrofuran, N -ethyl-2-pyrrolidone (EP), 1,3-dimethylimidazol-2-ylidene, and amino acid. − EP and amino acid molecules prefer to bind to Al 13 via the O or N atom. Their charge analysis showed that the electronic charge was transferred from the ligand to Al 13 .…”

Section: Introductionmentioning

confidence: 99%

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Design of High-Performance Inorganic–Organic Hybrid Nonlinear Optical Materials Using Superhalogen Al₁₃ and Dianhydrides

Hou,

Yan,

Liu

2024

J. Phys. Chem. A

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Novel inorganic−organic hybrid complexes Al 13 −X (X represents the dianhydrides PMDA, NTCDA, and PTCDA) are theoretically designed and studied using density functional theory (DFT) and time-dependent DFT. These conjugated dianhydrides containing four acceptor carbonyl groups are commonly used as electron acceptor materials. These compounds possess large binding energies, reflecting the sufficient binding of Al 13 to the dianhydride molecule. The binding nature of the complexes is of charge transfer type, i.e., electrons are transferred from the aluminum cluster to the dianhydride. All of the aimed complexes have large mean polarizability (α 0 ) and first hyperpolarizability (β 0 ). The β 0 values are explained on the basis of electronic transitions in crucial excited states using the TD-DFT method. Additionally, the hole−electron distribution was analyzed, revealing the nature of electronic excitation. Absorption spectra analysis shows that these complexes have an excellent infrared (IR) transparent region (1000−5000 nm). Therefore, these inorganic−organic hybrid complexes with high stability can be considered as potential candidates for new IR nonlinear optical molecules.

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Section: Structural Characteristics and Stabilitymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Design of High-Performance Inorganic–Organic Hybrid Nonlinear Optical Materials Using Superhalogen Al₁₃ and Dianhydrides

Hou,

Yan,

Liu

2024

J. Phys. Chem. A

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“…The grafting of external ligands at the metal center to build chemical bonds can effectively affect the geometric environmental symmetry and d orbital state of the active metal site of the spinel oxides, thereby enhancing catalytic performance. [17,18] Encouraged by this, the introduction of additional radicals with intense electron-capturing capability can offer the opportunity to trap electrons with high e g orbital occupancy state through the metal-to-ligand charge transfer, thereby changing the regularity of crystal fields and optimizing the e g orbital configuration. Therefore, NiFe 2 O 4 -based spinel was selected as the model catalyst, where the electronic configuration of Fe 3+ and Ni 2+ in the octahedral site (t 2g 3 e g 2 , t 2g 6 e g 2 ) is an undesirable e g occupancy for the OER, implying the necessity of further modulation.…”

Section: Introductionmentioning

confidence: 99%

Activating Octahedral Center in Co‐Doped NiFe₂O₄ via Bridging Amorphous MoS_x for Electrocatalytic Water Oxidation: A Case for e_g Orbital Regulation in Spinel Oxide

Zheng

et al. 2023

Small Methods

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Moderate e g filling for octahedral metal cations (M Oh ) is strongly correlated with the electrocatalytic water oxidation performance in the oxides system. Here, the e g fillings of Ni Oh and Fe Oh in NiFe 2 O 4 -based spinel are controllably regulated by introducing an external radical of catalytically inactive MoS x as an electron acceptor via a novel ultrasonic anchored pyrolysis strategy. The electron occupied in e g orbit of M Oh emigrates with the amount of Mo-S hanging on the apical of octahedral sites, and results in a salutary transition from high to medium e g occupancy state, as confirmed by the X-ray absorption spectroscopy and X-ray photoelectron spectroscopy. In addition, benefiting from the abundant unsaturated S atoms in amorphous MoS x , the M Oh at the surface furthest activates and consequently shows a superior water oxidation performance. Density functional theory also reveals that the e g fillings of Ni and Fe decrease to 1.4 and 1.2 after MoS x modification, which can effectively reduce the free energy of the OOH* intermediates in the oxygen evolution reaction process. This work opens an avenue for further releasing the electrocatalytic activity of octahedral sites through bridging external phases with rational electron-capturing/donating capability.

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Composite materials based on covalent organic frameworks for multiple advanced applications

Chen

Wang

et al. 2023

Exploration

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Covalent organic frameworks (COFs) stand for a class of emerging crystalline porous organic materials, which are ingeniously constructed with organic units through strong covalent bonds. Their excellent design capabilities, and uniform and tunable pore structure make them potential materials for various applications. With the continuous development of synthesis technique and nanoscience, COFs have been successfully combined with a variety of functional materials to form COFs‐based composites with superior performance than individual components. This paper offers an overview of the development of different types of COFs‐based composites reported so far, with particular focus on the applications of COFs‐based composites. Moreover, the challenges and future development prospects of COFs‐based composites are presented. We anticipate that the review will provide some inspiration for the further development of COFs‐based composites.

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Ligand-field regulated superalkali behavior of the aluminum-based clusters with distinct shell occupancy

Cited by 8 publications

References 49 publications

Design of High-Performance Inorganic–Organic Hybrid Nonlinear Optical Materials Using Superhalogen Al₁₃ and Dianhydrides

Design of High-Performance Inorganic–Organic Hybrid Nonlinear Optical Materials Using Superhalogen Al₁₃ and Dianhydrides

Activating Octahedral Center in Co‐Doped NiFe₂O₄ via Bridging Amorphous MoS_x for Electrocatalytic Water Oxidation: A Case for e_g Orbital Regulation in Spinel Oxide

Composite materials based on covalent organic frameworks for multiple advanced applications

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Ligand-field regulated superalkali behavior of the aluminum-based clusters with distinct shell occupancy

Cited by 8 publications

References 49 publications

Design of High-Performance Inorganic–Organic Hybrid Nonlinear Optical Materials Using Superhalogen Al13 and Dianhydrides

Design of High-Performance Inorganic–Organic Hybrid Nonlinear Optical Materials Using Superhalogen Al13 and Dianhydrides

Activating Octahedral Center in Co‐Doped NiFe2O4 via Bridging Amorphous MoSx for Electrocatalytic Water Oxidation: A Case for eg Orbital Regulation in Spinel Oxide

Composite materials based on covalent organic frameworks for multiple advanced applications

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Product

Resources

About

Design of High-Performance Inorganic–Organic Hybrid Nonlinear Optical Materials Using Superhalogen Al₁₃ and Dianhydrides

Design of High-Performance Inorganic–Organic Hybrid Nonlinear Optical Materials Using Superhalogen Al₁₃ and Dianhydrides

Activating Octahedral Center in Co‐Doped NiFe₂O₄ via Bridging Amorphous MoS_x for Electrocatalytic Water Oxidation: A Case for e_g Orbital Regulation in Spinel Oxide