Are U-U Bonds Inside Fullerenes Really Unwilling Bonds?

Previous characterizations of diactinide endohedral metallofullerenes (EMFs) Th@C and U@C have shown that although the two Th ions form a strong covalent bond within the carbon cage, the interaction between the U ions is weaker and described as an "unwilling" bond. To evaluate the feasibility of covalent U-U bonds, which are neglected in classical actinide chemistry, we have first investigated the formation of smaller diuranium EMFs by laser ablation using mass spectrometric detection of dimetallic U@C species with 2 ≥ 50. DFT, CASPT2 calculations, and MD simulations for several fullerenes of different sizes and symmetries showed that thanks to the formation of strong U(5f)-U(5f) triple bonds, two U ions can be incarcerated inside the fullerene.

Unexpected Formation of Metallofulleroids from Multicomponent Reactions, with Crystallographic and Computational Studies of the Cluster Motion.

New multicomponent reactions involving an isocyanide, terminal or internal alkynes, and endohedral metallofullerene (EMF) Lu N@C yield metallofulleroids which are characterized by mass-spectrometry, HPLC, and multiple 1D and 2D NMR techniques. Single crystal studies revealed one ketenimine metallofulleroid has ordered Lu N cluster which is unusual for EMF monoadducts. Computational analysis, based on crystallographic data, confirm that the endohedral cluster motion is controlled by the position of the exohedral organic appendants.

A New Class of Molecular Electrocatalysts for Hydrogen Evolution: Catalytic Activity of MN@C (2 = 68, 78, and 80) Fullerenes.

The electrocatalytic properties of some endohedral fullerenes for hydrogen evolution reactions (HER) were recently predicted by DFT calculations. Nonetheless, the experimental catalytic performance under realistic electrochemical environments of these 0D-nanomaterials have not been explored. Here, for the first time, we disclose the HER electrocatalytic behavior of seven MN@2 (2 = 68, 78, and 80) fullerenes (GdN@(7)-C, YN@(7)-C, LuN@(7)-C, ScN@(7)-C, ScN@(6)-C, ScN@(5)-C, and ScN@(6140)-C) using a combination of experimental and theoretical techniques.

α-DTC Fullerene Performs Significantly Better than β-DTC as Electron Transporting Material in Perovskite Solar Cells.

In this work, two new C isomers, α and β bis(2-(thiophen-2-yl)ethyl)-C-fullerene mono-adducts (DTC), were synthesized, characterized and used as electron transporting materials (ETMs) in perovskite solar cells (PSCs). Our results show that the α isomer improves both the and FF values of the devices, when compared to the results for the β-isomer and to those for phenyl-C-butyric acid methyl ester (PCBM), used as control. Devices based on α-DTC achieved a power conversion efficiency (PCE) of 15.

Formation of C-C(11188)Cl: A Particularly Stable Non-IPR Fullerene.

Halogenation has been one of the most used strategies to explore the reactivity of empty carbon cages. In particular, the higher reactivity of non-IPR fullerenes, i.e.