Designing an alkali-metal-like superatom Ca<sub>3</sub>B for ambient nitrogen reduction to ammonia

Ye, Ya‐Ling; Zhang, Li; Li, Xianghui; Yu, Dan; Chen, Jinghua; Sun, Wei‐Ming

doi:10.1039/d1cp01533h

Cited by 10 publications

(10 citation statements)

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“…In view of the strong reducibility of superalkalis, these species have been used to synthesize special charge-transfer salts , and activate stable gas molecules ,− to obtain high-value products. , More importantly, as a subset of superatoms, superalkalis can be assembled into nanostructured materials , with exciting physical and chemical properties, including supersalts, , superbases, molecular switch, molecular crystals, lead-free perovskites, and so on. In particular, superalkalis have been extensively used as excellent replacements for alkali metal atoms in designing nonlinear optical (NLO) materials, − or serve as NLO molecules themselves with significant static nonlinear optical responses. ,, …”

Section: Introductionmentioning

confidence: 99%

Designing Magnetic Superalkalis with Extremely Large Nonlinear Optical Responses

et al. 2022

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Predicting superatoms with multiple desired properties is of great interest and challenge. To achieve this goal, a series of organometallic M@36adz (M = Sc ∼ Zn) complexes have been obtained by embedding the 3d transition-metal atoms into the 36adamanzane (36adz) complexant. Under the intramolecular interaction between M and 36adz, the magnetic moments of M atoms are either enhanced or preserved in the resulting M@36adz complexes. Also, the αSOMO levels of M@36adz are significantly raised by the presence of the M impurities, resulting in their greatly lower adiabatic ionization energies (AIEs) of 1.78–2.56 eV than the IE (3.89 eV) of Cs atom. As a result, these complexes can be regarded as a new kind of magnetic superalkalis. Moreover, due to the existence of diffuse electrons in their αSOMO, most of the M@36adz complexes also exhibit remarkable nonlinear optical responses with large first hyperpolarizabilities (β0) of 1.56 × 106–6.33 × 107 au. Hence, this study provides a possible strategy to design a new kind of multifunctional species with high reducing ability, magnetic properties, and large NLO responses by doping various transition metals into such cage-like organic complexants.

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Section: Introductionmentioning

confidence: 99%

Designing Magnetic Superalkalis with Extremely Large Nonlinear Optical Responses

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“…35 Recently, alkali-metal-like superatom M 3 B (M = Be, Mg, and Ca) have been studied for reduction of N 2 to NH 3 . 36 In this study, the interaction of noble gases with Be 3 B + has been studied using density functional theory and coupled cluster methods.…”

Section: Introductionmentioning

confidence: 99%

Coordination of noble gases by alkali‐metal‐like superatom cationBe₃B⁺

et al. 2023

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Quantum chemical calculations were carried out to investigate the noble gas binding ability of Be3B+ cluster. Calculations reveal that heavier noble gas atoms (ArXe) form stable complexes with this cluster. Detailed bonding analyses reveal that the noble gas atoms act as donor fragment in the formation of Ng → Be donor–acceptor bonds. Three noble gas atoms can consecutively form bonds with the Be atom of the Be3B+ cluster.

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“…Owing to their excellent reducing ability, superalkalis can be used to synthesize unusual charge-transfer salts ( Zintl and Morawietz, 1938 ; Jansen, 1976 ) with the counterpart possessing relatively low electron affinity and activate stable CO 2 and N 2 molecules ( Park and Meloni, 2017 ; Zhao et al, 2017 ; Park and Meloni, 2018 ; Sun et al, 2019 ; Sikorska and Gaston, 2020 ) to produce high-value products ( Zhang et al, 2021a ; Zhang et al, 2021b ). In particular, as a special subset of superatom ( Reveles et al, 2009 ; Luo and Castleman, 2014 ), superalkalis can behave as alkali metal atoms and maintain their structural and electronic integrities when assembled into extended nanostructures ( Reber et al, 2007 ).…”

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confidence: 99%

Designing Special Nonmetallic Superalkalis Based on a Cage-like Adamanzane Complexant

Pan

et al. 2022

Front. Chem.

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In this study, to examine the possibility of using cage-like complexants to design nonmetallic superalkalis, a series of X@36adz (X = H, B, C, N, O, F, and Si) complexes have been constructed and investigated by embedding nonmetallic atoms into the 36adamanzane (36adz) complexant. Although X atoms possess very high ionization energies, these resulting X@36adz complexes possess low adiabatic ionization energies (AIEs) of 0.78–5.28 eV. In particular, the adiabatic ionization energies (AIEs) of X@36adz (X = H, B, C, N, and Si) are even lower than the ionization energy (3.89 eV) of Cs atoms, and thus, can be classified as novel nonmetallic superalkalis. Moreover, due to the existence of diffuse excess electrons in B@36adz, this complex not only possesses pretty low AIE of 2.16 eV but also exhibits a remarkably large first hyperpolarizability (β0) of 1.35 × 106 au, indicating that it can also be considered as a new kind of nonlinear optical molecule. As a result, this study provides an effective approach to achieve new metal-free species with an excellent reducing capability by utilizing the cage-like organic complexants as building blocks.

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Designing an alkali-metal-like superatom Ca₃B for ambient nitrogen reduction to ammonia

Abstract: Converting earth-abundant nitrogen (N2) gas into ammonia (NH3) under mild conditions is one of the most important issues but a long-standing challenge in chemistry. Herein, a new superatom Ca3B was...

Cited by 10 publications

References 61 publications

Designing Magnetic Superalkalis with Extremely Large Nonlinear Optical Responses

Designing Magnetic Superalkalis with Extremely Large Nonlinear Optical Responses

Coordination of noble gases by alkali‐metal‐like superatom cationBe₃B⁺

Designing Special Nonmetallic Superalkalis Based on a Cage-like Adamanzane Complexant

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Designing an alkali-metal-like superatom Ca3B for ambient nitrogen reduction to ammonia

Abstract: Converting earth-abundant nitrogen (N2) gas into ammonia (NH3) under mild conditions is one of the most important issues but a long-standing challenge in chemistry. Herein, a new superatom Ca3B was...

Cited by 10 publications

References 61 publications

Designing Magnetic Superalkalis with Extremely Large Nonlinear Optical Responses

Designing Magnetic Superalkalis with Extremely Large Nonlinear Optical Responses

Coordination of noble gases by alkali‐metal‐like superatom cationBe3B+

Designing Special Nonmetallic Superalkalis Based on a Cage-like Adamanzane Complexant

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Designing an alkali-metal-like superatom Ca₃B for ambient nitrogen reduction to ammonia

Coordination of noble gases by alkali‐metal‐like superatom cationBe₃B⁺