Synthesis and Characterization of U≡C Triple Bonds in Fullerene Compounds.

Despite decades of efforts, the actinide-carbon triple bond has remained an elusive target, defying synthesis in any isolable compound. Herein, we report the successful synthesis of uranium-carbon triple bonds in carbide-bridged bimetallic [U≡C-Ce] units encapsulated inside the fullerene cages of C72 and C78. The molecular structures of UCCe@C2n and the nature of the U≡C triple bond were characterized through X-ray crystallography and various spectroscopic analyses, revealing very short uranium-carbon bonds of 1.921(6) and 1.930(6) Å, with the metals existing in their highest oxidation states of +6 and +4 for uranium and cerium, respectively. Quantum-chemical studies further demonstrate that the C2n cages are crucial for stabilizing the [UVI≡C-CeIV] units through covalent and coordinative interactions. This work offers a new fundamental understanding of the elusive uranium-carbon triple bond and informs the design of complexes with similar bonding motifs, opening up new possibilities for creating distinctive molecular compounds and materials.

Actinide-lanthanide single electron metal-metal bond formed in mixed-valence di-metallofullerenes.

Understanding metal-metal bonding involving f-block elements has been a challenging goal in chemistry. Here we report a series of mixed-valence di-metallofullerenes, ThDy@C2n (2n = 72, 76, 78, and 80) and ThY@C2n (2n = 72 and 78), which feature single electron actinide-lanthanide metal-metal bonds, characterized by structural, spectroscopic and computational methods. Crystallographic characterization unambiguously confirmed that Th and Y or Dy are encapsulated inside variably sized fullerene carbon cages. The ESR study of ThY@D3h(5)-C78 shows a doublet as expected for an unpaired electron interacting with Y, and a SQUID magnetometric study of ThDy@D3h(5)-C78 reveals a high-spin ground state for the whole molecule. Theoretical studies further confirm the presence of a single-electron bonding interaction between Y or Dy and Th, due to a significant overlap between hybrid spd orbitals of the two metals.

Three-dimensional organization of pyrrolo[3,2-b]pyrrole-based triazine framework using nanostructural spherical carbon: enhancing electrochemical performance of materials for supercapacitors.

Covalent triazine-based frameworks have attracted much interest recently due to their high surface area and excellent thermal and electrochemical stabilities. This study shows that covalently immobilizing triazine-based structures on spherical carbon nanostructures results in the organization of micro- and mesopores in a three-dimensional manner. We selected the nitrile-functionalized pyrrolo[3,2-b]pyrrole unit to form triazine rings to construct a covalent organic framework. Combining spherical carbon nanostructures with the triazine framework produced a material with unique physicochemical properties, exhibiting the highest specific capacitance value of 638 F g-1 in aqueous acidic solutions. This phenomenon is attributed to many factors. The material exhibits a large surface area, a high content of micropores, a high content of graphitic N, and N-sites with basicity and semi-crystalline character. Thanks to the high structural organization and reproducibility, and remarkably high specific capacitance, these systems are promising materials for use in electrochemistry. For the first time, hybrid systems containing triazine-based frameworks and carbon nano-onions were used as electrodes for supercapacitors.

Two Metastable Endohedral Metallofullerenes Sc2C2@C1(39656)-C82 and Sc2C2@C1(51383)-C84: Direct-C2-Insertion Products from Their Most Stable Precursors.

Endohedral metallofullerenes (EMFs) are sub-nano carbon materials with diverse applications, yet their formation mechanism, particularly for metastable isomers, remains ambiguous. The current theoretical methods focus mainly on the most stable isomers, leading to limited predictability of metastable ones due to their low stabilities and yields. Herein, we report the successful isolation and characterization of two metastable EMFs, Sc2C2@C1(39656)-C82 and Sc2C2@C1(51383)-C84, which violate the isolated pentagon rule (IPR). These two non-IPR EMFs exhibit a rare case of planar and pennant-like Sc2C2 clusters, which can be considered hybrids of the common butterfly-shaped and linear configurations. More importantly, the theoretical results reveal that despite being metastable, these two non-IPR EMFs survived as the products from their most stable precursors, Sc2C2@C2v(5)-C80 and Sc2C2@Cs(6)-C82, via a C2 insertion during the post-formation annealing stages. We propose a systematic theoretical method for predicting metastable EMFs during the post-formation stages. The unambiguous molecular-level structural evidence, combined with the theoretical calculation results, provides valuable insights into the formation mechanisms of EMFs, shedding light on the potential of post-formation mechanisms as a promising approach for EMF synthesis.

Single-atomic platinum on fullerene C60 surfaces for accelerated alkaline hydrogen evolution.

The electrocatalytic hydrogen evolution reaction (HER) is one of the most studied and promising processes for hydrogen fuel generation. Single-atom catalysts have been shown to exhibit ultra-high HER catalytic activity, but the harsh preparation conditions and the low single-atom loading hinder their practical applications. Furthermore, promoting hydrogen evolution reaction kinetics, especially in alkaline electrolytes, remains as an important challenge. Herein, Pt/C60 catalysts with high-loading, high-dispersion single-atomic platinum anchored on C60 are achieved through a room-temperature synthetic strategy. Pt/C60-2 exhibits high HER catalytic performance with a low overpotential (η10) of 25 mV at 10 mA cm-2. Density functional theory calculations reveal that the Pt-C60 polymeric structures in Pt/C60-2 favors water adsorption, and the shell-like charge redistribution around the Pt-bonding region induced by the curved surfaces of two adjacent C60 facilitates the desorption of hydrogen, thus favoring fast reaction kinetics for hydrogen evolution.

Are U-U Bonds Inside Fullerenes Really Unwilling Bonds?

Previous characterizations of diactinide endohedral metallofullerenes (EMFs) Th2@C80 and U2@C80 have shown that although the two Th3+ ions form a strong covalent bond within the carbon cage, the interaction between the U3+ 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 U2@C2n species with 2n ≥ 50. DFT, CASPT2 calculations, and MD simulations for several fullerenes of different sizes and symmetries showed that thanks to the formation of strong U(5f3)-U(5f3) triple bonds, two U3+ ions can be incarcerated inside the fullerene. The formation of U-U bonds competes with U-cage interactions that tend to separate the U ions, hindering the observation of short U-U distances in the crystalline structures of diuranium endofullerenes as in U2@C80. Smaller cages like C60 exhibit the two interactions, and a strong triple U-U bond with an effective bond order higher than 2 is observed. Although 5f-5f interactions are responsible for the covalent interactions at distances close to 2.5 Å, overlap between 7s6d orbitals is still detected above 4 Å. In general, metal ions within fullerenes should be regarded as templates in cage formation, not as statistically confined units that have little chance of being observed.

[2,1,3]-Benzothiadiazole-Spaced Co-Porphyrin-Based Covalent Organic Frameworks for O2 Reduction.

Designing N-coordinated porous single-atom catalysts (SACs) for the oxygen reduction reaction (ORR) is a promising approach to achieve enhanced energy conversion due to maximized atom utilization and higher activity. Here, we report two Co(II)-porphyrin/ [2,1,3]-benzothiadiazole (BTD)-based covalent organic frameworks (COFs; Co@rhm-PorBTD and Co@sql-PorBTD), which are efficient SAC systems for O2 electrocatalysis (ORR). Experimental results demonstrate that these two COFs outperform the mass activity (at 0.85 V) of commercial Pt/C (20%) by 5.8 times (Co@rhm-PorBTD) and 1.3 times (Co@sql-PorBTD), respectively. The specific activities of Co@rhm-PorBTD and Co@sql-PorBTD were found to be 10 times and 2.5 times larger than that of Pt/C, respectively. These COFs also exhibit larger power density and recycling stability in Zn-air batteries compared with a Pt/C-based air cathode. A theoretical analysis demonstrates that the combination of Co-porphyrin with two different BTD ligands affords two crystalline porous electrocatalysts having different d-band center positions, which leads to reactivity differences toward alkaline ORR. The strategy, design, and electrochemical performance of these two COFs offer a pyrolysis-free bottom-up approach that avoids the creation of random atomic sites, significant metal aggregation, or unpredictable structural features.

USc2C2 and USc2NC Clusters with U-C Triple Bond Character Stabilized Inside Fullerene Cages.

The chemistry of f-block metal-carbon multiple bonds is underdeveloped compared to well-established carbene complexes of the d-block transition metals. Herein, we report two new actinide-rare earth mixed metal carbides and nitrogen carbide cluster fullerenes, USc2C2@D5h(6)-C80 and USc2NC@D5h(6)-C80, which contain U-C bonds with triple bond character and were successfully synthesized and characterized by mass spectrometry, UV-vis-NIR spectroscopy, Fourier transform infrared spectroscopy, single crystal X-ray diffraction, and DFT calculations. Crystallographic studies show that the two previously unreported clusters, USc2C2 and USc2NC, are stabilized in the D5h(6)-C80 carbon cage and adopt unique trifoliate configurations, in which C2/NC units are almost vertically inserted into the plane defined by the U and two Sc atoms. Combined experimental and theoretical studies further reveal the bonding structure of USc2C2 and USc2NC, which contain C═U(VI)═C and C═U(V)═N bonding motifs. The electronic structures of the two compounds are determined as U6+(Sc2)6+(C4-)2@D5h(6)-C804- and U5+(Sc2)6+(N)3-(C)4-@D5h(6)-C804-, respectively. Quantum-chemical studies confirm that the U-C bonds in both molecules show unprecedented multicenter triple-bond character. The discovery of this unique U-C multiple bond offers a deeper understanding of the fundamentals of uranium chemistry.

A charged diatomic triple-bonded U≡N species trapped in C82 fullerene cages.

Actinide diatomic molecules are ideal models to study elusive actinide multiple bonds, but most of these diatomic molecules have so far only been studied in solid inert gas matrices. Herein, we report a charged U≡N diatomic species captured in fullerene cages and stabilized by the U-fullerene coordination interaction. Two diatomic clusterfullerenes, viz. UN@Cs(6)-C82 and UN@C2(5)-C82, were successfully synthesized and characterized. Crystallographic analysis reveals U-N bond lengths of 1.760(7) and 1.760(20) Å in UN@Cs(6)-C82 and UN@C2(5)-C82. Moreover, U≡N was found to be immobilized and coordinated to the fullerene cages at 100 K but it rotates inside the cage at 273 K. Quantum-chemical calculations show a (UN)2+@(C82)2- electronic structure with formal +5 oxidation state (f1) of U and unambiguously demonstrate the presence of a U≡N bond in the clusterfullerenes. This study constitutes an approach to stabilize fundamentally important actinide multiply bonded species.

Correction: Krízová et al. Fullerene Derivatives Prevent Packaging of Viral Genomic RNA into HIV-1 Particles by Binding Nucleocapsid Protein. Viruses 2021, 13, 2451.

The authors wish to make the following corrections to this paper [...].

Polymeric Network Hierarchically Organized on Carbon Nano-onions: Block Polymerization as a Tool for the Controlled Formation of Specific Pore Diameters.

The organization of specific pores in carbonaceous three-dimensional networks is crucial for efficient electrocatalytic processes and electrochemical performance. Therefore, the synthesis of porous materials with ordered and well-defined pores is required in this field. The incorporation of carbon nanostructures into polymers can create material structures that are more ordered in comparison to those of the pristine polymers. In this study we applied polymer-templated methods of carbon material preparation, in which outer blocks of the star copolymers form the carbon skeleton, while the core part is pore-forming. Well-defined 6-star-(poly(methyl acrylate)-b-poly(4-acetoxystyrene)) dendrimers were synthesized by reversible addition-fragmentation chain-transfer polymerization. They were then transformed into poly(4-vinylphenol) derivatives (namely 6-star-(poly(methyl acrylate)-b-poly(4-vinylphenol)), subjected to polycondensation with formaldehyde, and pyrolyzed at 800 °C. Cross-linking of phenolic groups provides a polymer network that does not depolymerize by pyrolysis, unlike poly(methyl acrylate) chains. The selected star polymers were attached to carbon nano-onions (CNOs) to improve the organization of the polymer chains. Herein, the physicochemical properties of CNO-polymer hybrids, including the textural and the electrochemical properties, were compared with those of the pristine pyrolyzed polymers obtained under analogous experimental conditions. For these purposes, we used several experimental and theoretical methods, such as infrared, Raman, and X-ray photoelectron spectroscopy, nitrogen adsorption/desorption measurements, scanning and transmission electron microscopy, and electrochemical studies, including cyclic voltammetry. All of the porous materials were evaluated for use as supercapacitors.

Cylindrical C96 Fullertubes: A Highly Active Metal-Free O2 -Reduction Electrocatalyst.

A new isolation protocol was recently reported for highly purified metallic Fullertubes D5h -C90 , D3d -C96 , and D5d -C100, which exhibit unique electronic features. Here, we report the oxygen reduction electrocatalytic behavior of C60 , C70 (spheroidal fullerenes), and C90 , C96 , and C100 (tubular fullerenes) using a combination of experimental and theoretical approaches. C96 (a metal-free catalyst) displayed remarkable oxygen reduction reaction (ORR) activity, with an onset potential of 0.85 V and a halfway potential of 0.75 V, which are close to the state-of-the-art Pt/C benchmark catalyst values. We achieved an excellent power density of 0.75 W cm-2 using C96 as a modified cathode in a proton-exchange membrane fuel cell, comparable to other recently reported efficient metal-free catalysts. Combined band structure (experimentally calculated) and free-energy (DFT) investigations show that both favorable energy-level alignment active catalytic sites on the carbon cage are responsible for the superior activity of C96 .

Diazonium functionalized fullerenes: a new class of efficient molecular catalysts for the hydrogen evolution reaction.

Considerable efforts are being made to find cheaper and more efficient alternatives to the currently commercially available catalysts based on precious metals for the Hydrogen Evolution Reaction (HER). In this context, fullerenes have started to gain attention due to their suitable electronic properties and relatively easy functionalization. We found that the covalent functionalization of C60, C70 and Sc3N@IhC80 with diazonium salts endows the fullerene cages with ultra-active charge polarization centers, which are located near the carbon-diazonium bond and improve the efficiency towards the molecular generation of hydrogen. To support our findings, Electrochemical Impedance Spectroscopy (EIS), double layer capacitance (Cdl) and Mott-Schottky approximation were performed. Among all the functionalized fullerenes, DPySc3N@IhC80 exhibited a very low onset potential (-0.025 V vs. RHE) value, which is due to the influence of the inner cluster on the extra improvement of the electronic density states of the catalytic sites. For the first time, the covalent assembly of fullerenes and diazonium groups was used as an electron polarization strategy to build superior molecular HER catalytic systems.

Fullerene Derivatives Prevent Packaging of Viral Genomic RNA into HIV-1 Particles by Binding Nucleocapsid Protein.

Fullerene derivatives with hydrophilic substituents have been shown to exhibit a range of biological activities, including antiviral ones. For a long time, the anti-HIV activity of fullerene derivatives was believed to be due to their binding into the hydrophobic pocket of HIV-1 protease, thereby blocking its activity. Recent work, however, brought new evidence of a novel, protease-independent mechanism of fullerene derivatives' action. We studied in more detail the mechanism of the anti-HIV-1 activity of N,N-dimethyl[70]fulleropyrrolidinium iodide fullerene derivatives. By using a combination of in vitro and cell-based approaches, we showed that these C70 derivatives inhibited neither HIV-1 protease nor HIV-1 maturation. Instead, our data indicate effects of fullerene C70 derivatives on viral genomic RNA packaging and HIV-1 cDNA synthesis during reverse transcription-without impairing reverse transcriptase activity though. Molecularly, this could be explained by a strong binding affinity of these fullerene derivatives to HIV-1 nucleocapsid domain, preventing its proper interaction with viral genomic RNA, thereby blocking reverse transcription and HIV-1 infectivity. Moreover, the fullerene derivatives' oxidative activity and fluorescence quenching, which could be one of the reasons for the inconsistency among reported anti-HIV-1 mechanisms, are discussed herein.

Carbon Nano-onions: Potassium Intercalation and Reductive Covalent Functionalization.

Herein we report the synthesis of covalently functionalized carbon nano-onions (CNOs) via a reductive approach using unprecedented alkali-metal CNO intercalation compounds. For the first time, an in situ Raman study of the controlled intercalation process with potassium has been carried out revealing a Fano resonance in highly doped CNOs. The intercalation was further confirmed by electron energy loss spectroscopy and X-ray diffraction. Moreover, the experimental results have been rationalized with DFT calculations. Covalently functionalized CNO derivatives were synthesized by using phenyl iodide and n-hexyl iodide as electrophiles in model nucleophilic substitution reactions. The functionalized CNOs were exhaustively characterized by statistical Raman spectroscopy, thermogravimetric analysis coupled with gas chromatography and mass spectrometry, dynamic light scattering, UV-vis, and ATR-FTIR spectroscopies. This work provides important insights into the understanding of the basic principles of reductive CNOs functionalization and will pave the way for the use of CNOs in a wide range of potential applications, such as energy storage, photovoltaics, or molecular electronics.

Linking the Defective Structure of Boron-Doped Carbon Nano-Onions with Their Catalytic Properties: Experimental and Theoretical Studies.

Defects are widely present in nanomaterials, and they are recognized as the active sites that tune surface properties in the local region for catalysis. Recently, the theory linking defect structures and catalytic properties of nanocatalysts has been most commonly described. In this study, we prepared boron-doped carbon nano-onions (B-CNOs) by applying an annealing treatment of ultradispersed nanodiamond particles and amorphous boron. These experimental conditions guarantee doping of CNOs with boron atoms in the entire carbon nanostructure, thereby ensuring structural homogeneity. In our research, we discuss the correlations between defective structures of B-CNOs with their catalytic properties toward SO2 and tert-butanol dehydration. We show that there is a close relationship between the catalytic properties of the B-CNOs and the experimental conditions for their formation. It is not only the mass of the substrates used for the formation of B-CNOs that is crucial, that is, the mass ratio of NDs to amorphous B, but also the process, including temperature and gas atmosphere. As it was expected, all B-CNOs demonstrated significant catalytic activity in HSO3- oxidation. However, the subsequent annealing in an air atmosphere diminished their catalytic activity. Unfortunately, no direct relationship between the catalytic activity and the presence of heteroatoms on the B-CNO surface was observed. There was a linear dependence between catalytic activity and Raman reactivity factors for each of the B-CNO materials. In contrast to SO2 oxidation, the B-CNO-a samples showed higher catalytic activity in tert-butanol dehydration due to the presence of Brønsted and Lewis acid sites. The occurence of three types of boron-Lewis sites differing in electron donor properties was confirmed using quantitative infrared spectroscopic measurements of pyridine adsorption.

UCN@Cs(6)-C82: An Encapsulated Triangular UCN Cluster with Ambiguous U Oxidation State [U(III) versus U(I)].

Understanding the chemical behavior of actinide elements is essential for the effective management and use of actinide materials. In this study, we report an unprecedented η2 (side-on) coordination of U by a cyanide in a UCN cluster, which was stabilized inside a C82 fullerene cage. UCN@Cs(6)-C82 was successfully synthesized and fully characterized by mass spectrometry, single crystal X-ray crystallography, cyclic voltammetry, spectroscopy, and theoretical calculations. The bonding analysis demonstrates significant donation bonding between CN- and uranium, and covalent interactions between uranium and the carbon cage. These effects correlate with an observed elongated cyanide C-N bond, resulting in a rare case where the oxidation state of uranium shows ambiguity between U(III) and U(I). The discovery of this unprecedented triangular configuration of the uranium cyanide cluster provides a new insight in coordination chemistry and highlights the large variety of bonding situations that uranium can have.

Crystallographic Characterization of U@C2n (2n = 82-86): Insights about Metal-Cage Interactions for Mono-metallofullerenes.

Endohedral mono-metallofullerenes are the prototypes to understand the fundamental nature and the unique interactions between the encapsulated metals and the fullerene cages. Herein, we report the crystallographic characterizations of four new U-based mono-metallofullerenes, namely, U@Cs(6)-C82, U@C2(8)-C84, U@Cs(15)-C84, and U@C1(12)-C86, among which the chiral cages C2(8)-C84 and C1(12)-C86 have never been previously reported for either endohedral or empty fullerenes. Symmetrical patterns, such as indacene, sumanene, and phenalene, and charge transfer are found to determine the metal positions inside the fullerene cages. In addition, a new finding concerning the metal positions inside the cages reveals that the encapsulated metal ions are always located on symmetry planes of the fullerene cages, as long as the fullerene cages possess mirror planes. DFT calculations show that the metal-fullerene motif interaction determines the stability of the metal position. In fullerenes containing symmetry planes, the metal prefers to occupy a symmetrical arrangement with respect to the interacting motifs, which share one of their symmetry planes with the fullerene. In all computationally analyzed fullerenes containing at least one symmetry plane, the actinide was found to be located on the mirror plane. This finding provides new insights into the nature of metal-cage interactions and gives new guidelines for structural determinations using crystallographic and theoretical methods.