Developing efficient catalysts for the conversion of CO2 into fuels and value‐added chemicals is of great significance to relieve the growing energy crisis and global warming. With the assistance of DFT calculations, it was found that, different from Al12X (X=Be, Al, and C), the alkali‐metal‐like superatom Al12P prefers to combine with CO2 via a bidentate double oxygen coordination, yielding a stable Al12P(η2‐O2C) complex containing an activated radical anion of CO2 (i.e., CO2.−). Thereby, this compound could not only participate in the subsequent cycloaddition reaction with propylene oxide but also initiate the radical reaction with hydrogen gas to form high‐value chemicals, revealing that Al12P can play an important role in catalyzing these conversion reactions. Considering that Al12P has been produced in laboratory and is capable of absorbing visible light to drive the activation and transformation of CO2, it is anticipated that this work could guide the discovery of additional superatom catalysts for CO2 transformation and open up a new research field of superatom catalysis.

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The adsorption of 5-fluorouracil on B40 and its derivatives has been theoretically studied to provide some implications for the potential application of B40 in drug delivery.

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...

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.