C60 Cage Research Articles

Diels-Alder Reaction Mechanisms of La@C60 and Gd@C60 Studied Using Density Functional Theory.

Encapsulation of transition metals represents a crucial method for modifying the electronic structure and regulating the reactivity of fullerene, thereby expanding its applications. Herein, we present calculations with density functional theory methods to investigate the mechanisms of the Diels-Alder (DA) reactions of cyclopentadiene and La@C60 or Gd@C60 as well as their tricationic derivatives. Our findings indicate that the encapsulation of La and Gd into the C60 cage is thermodynamically favorable. The DA reactions are favored by the presence of La and Gd, with lower barriers, though the regioselectivity, favoring 6-6 bonds in the fullerene, is not affected. The effect of external electric fields has been also considered.

Electronic Structure, Aromaticity, and Magnetism of Minimum-Sized Regular Dodecahedral Endohedral Metallofullerenes Encapsulating Rare Earth Atoms.

A series of minimally sized regular dodecahedron-embedded metallofullerene REC20 clusters (RE = Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, and Gd) as basic units of nanoassembled materials with tunable magnetism and UV sensitivity have been explored using density functional theory (DFT). The contribution of the 4f orbital of the rare earth atom at the center of the C20 cage to the frontier molecular orbital of REC20 gives the REC20 cluster additional stability. The AdNDP orbitals of the four REC20 superatoms that conform to the spherical jellium model indicate that through natural population analysis and spin density diagrams, we observe a monotonic increase in the magnetic moment from Ce to Gd. This is attributed to the increased number of unpaired electrons in the 4f orbitals of lanthanide rare earth atoms. The UV-visible spectrum of REC20 clusters shows strong absorption in the mid-UV and near-UV bands. REC20 clusters encapsulating lanthanide rare earth atoms stand out for their tunable magnetism, UV sensitivity, and stability, making them potential new self-assembly materials.

Understanding the Electronic Structure and Chemical Bonding in the 2D Fullerene Monolayer.

Recently synthesized two-dimensional (2D) monolayer quasi-hexagonal-phase fullerene (qHPC60) demonstrates excellent thermodynamic stability. Within this monolayer, each fullerene cluster is surrounded by six adjacent C60 cages along an equatorial plane and is connected by both C-C single bonds and [2 + 2] cycloaddition bonds that serve as bridges. In this study, we investigate the stability mechanism of the 2D qHPC60 monolayer by examining the electronic structure and chemical bonding through state-of-the-art theoretical methodologies. Density functional theory (DFT) studies reveal that 2D qHPC60 possesses a moderate direct electronic band gap of 1.46 eV, close to the experimental value (1.6 eV). It is found that the intermolecular bridge bonds play a crucial role in enhancing the charge flow and redistribution among C60 cages, leading to the formation of dual π-aromaticity within the C60 sphere and stabilizing the 2D framework structure. Furthermore, we identify a series of delocalized superatom molecular orbitals (SAMOs) within the 2D qHPC60 monolayer, exhibiting atomic orbital-like behavior and hybridization to form nearly free-electron (NFE) bands with σ/π bonding and σ*/π* antibonding properties. Our findings provide insights into the design and potential applications of NFE bands derived from SAMOs in 2D qHPC60 monolayers.

Nature of partial sigma bond.

This study investigates the formation of partial sigma (σ) covalent bonds in experimentally synthesizable biradicals formed from hydrogenated and fluorinated C8, C20, and C60 cage structures, by assessing their stability, geometry, and bonding character in singlet and triplet states using restricted B3LYP-D3/6-31+G(d,p) theory, natural bond orbital (NBO) analysis, and complete active space self-consistent field (CASSCF) method. The results show that these partial σCC bonds have Wiberg bond orders of 0.38 to 0.48 and bond lengths ranging from 2.62 Å to 5.93 Å. Cage size influences the characteristics of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), with electrons favoring more antibonding orbitals in smaller cages where electrons reside more on the exterior of the cage and favoring bonding orbitals in larger ones where electrons are more in the interior. Fluorination enhances electron density on bonding orbitals. The analysis further clarified that the differentiation between antibonding and bonding features of HOMOs and LUMOs extends beyond merely electron transfer from s- to p-atomic orbitals, also noting possible interactions of the same symmetry repel. The study also introduces hyperconjugation from α-position CH bonds as a factor in stabilizing partial σ-bond formation. The results also caution against the use of broken symmetry methodology in unrestricted SCF wavefunctions for biradicals, such as those in this study as it may cause large spin contamination and thus errors in the calculated electronic properties results.

Stone-Wales defective C60 fullerene for hydrogen storage

Hydrogen energy is one of promising non-polluting and renewable energy sources. In this paper, we present a first principal study of hydrogen storage in pure C60 fullerene cage and Stone-Wales (SW) defective C60 cages using density functional theory (DFT) with applying both the exchange functional B3LYP and the dispersion correction wb97xd at 6–31+g(d,2p) basis set. In addition, the counterpoise correction is applied, and the basis set superposition error is calculated. The calculations underscore that the hydrogenation binding energy of C60 cages occurs through an endothermal process for C60Hin with a hydrogen binding energy of 0.09 eV and through an exothermal process for C60Hout, C60SW66Hout, and C60SW65Hout, cages with hydrogen binding energies of −2.17 eV, −2.96 eV, and −2.20 eV, respectively. Remarkably, for the first time, the intermediate hydrogen binding energy is found inside C60SW66Hin fullerene, and C60SW65Hin fullerene cages with energies of −0.26 eV and −0.81 eV, respectively. The hydrogen adsorption inside the cavity of C60SW66 fullerene cage is thermodynamically possible below 289.8 K and entire pressure range considered. Our results highlight, for the first time, that the endohedral cavity of C60SW66 is a promising new medium for hydrogen storage due to its binding energies (−0.26 eV) and its hydrogen storage weight percentage (5.3%) that are close to the optimal conditions specified by DOE for commercial use. In addition, this study opens up a new discovery of Stone-Wales defective C60 fullerene for further endohedral cavity applications.

Nanoscale Dodecahedral and Fullerene-Type Organoboroxine and Borazine Cages from Planar Building Units.

Boroxine- and borazine-cage analogs to C20, C60, and C70 were calculated and compared in terms of structure, strain indicators, and physical properties relevant to nanoscale applications. The results show C60 and C70 type cages are less strained than the smaller congener, primarily due to minimized bending in the B-arylene-B segments. The smallest cage calculated has a diameter of 2.4 nm, which increases up to 4.9 nm by either variation of the polyhedron (C20 < C60 < C70-type cage) or organic spacer elongation between boron centers. All calculated cages are porous (apertures ranging from 0.6 to 1.9 nm). Molecular electrostatic potential and Hirshfeld population analysis revealed both nucleophilic and electrophilic sites in the interior and exterior cage surfaces. HOMO-LUMO gaps range from 3.98 to 4.89 eV and 5.10-5.18 eV for the boroxine- and borazine-cages, respectively. Our findings provide insights into the design and properties of highly porous boroxine and borazine cages for nanoscience.

Translational eigenstates of He@C60 from four-dimensional abinitio potential energy surfaces interpolated using Gaussian process regression.

We investigate the endofullerene system 3He@C60 with a four-dimensional potential energy surface (PES) to include the three He translational degrees of freedom and C60 cage radius. We compare second order Møller-Plesset perturbation theory (MP2), spin component scaled-MP2, scaled opposite spin-MP2, random phase approximation (RPA)@Perdew, Burke, and Ernzerhof (PBE), and corrected Hartree-Fock-RPA to calibrate and gain confidence in the choice of electronic structure method. Due to the high cost of these calculations, the PES is interpolated using Gaussian Process Regression (GPR), owing to its effectiveness with sparse training data. The PES is split into a two-dimensional radial surface, to which corrections are applied to achieve an overall four-dimensional surface. The nuclear Hamiltonian is diagonalized to generate the in-cage translational/vibrational eigenstates. The degeneracy of the three-dimensional harmonic oscillator energies with principal quantum number n is lifted due to the anharmonicity in the radial potential. The (2l + 1)-fold degeneracy of the angular momentum states is also weakly lifted, due to the angular dependence in the potential. We calculate the fundamental frequency to range between 96 and 110 cm-1 depending on the electronic structure method used. Error bars of the eigenstate energies were calculated from the GPR and are on the order of ∼±1.5 cm-1. Wavefunctions are also compared by considering their overlap and Hellinger distance to the one-dimensional empirical potential. As with the energies, the two abinitio methods MP2 and RPA@PBE show the best agreement. While MP2 has better agreement than RPA@PBE, due to its higher computational efficiency and comparable performance, we recommend RPA as an alternative electronic structure method of choice to MP2 for these systems.

Energy barriers of Be and B in passing through the C60 fullerene cage

We have studied the potential barriers for the penetration of atomic beryllium or boron inside the C60 fullerene by performing density functional theory (DFT) calculations with three variants for the exchange and correlation: B3LYP (hybrid functional), PW91, and PBE. Four principal trajectories to the inner part of C60 for the penetrating atom have been considered: through the center of six-member-carbon ring (hexagon), five-member-carbon ring (pentagon), and also through the center of the double C–C bond (D-bond) and the center of the single C–C bond (S-bond). Averaging over the three DFT variants yields the following barriers for beryllium penetrating inside a deformable fullerene: 3.2 eV (hexagon), 4.8 eV (S-bond), 5.3 eV (D-bond), 5.9 eV (pentagon). These barriers correspond to the slow and adiabatic penetration of Be, in contrast to the fast (non-adiabatic) penetration through the rigid cage of C60 resulting in 5.6 eV (hexagon), 16.3 eV (pentagon), 81.8 eV (S-bond), and 93.4 eV (D-bond). The potential barriers for the boron penetrating inside deformable/rigid C60 are 3.7/105.4 eV (D-bond), 4.0/86.8 eV (S-bond), 4.7/7.8 eV (hexagon), 6.8/14.0 eV (pentagon).

Local heating and Raman thermometry in a single molecule.

Because of the nonequilibrium nature of thermal effects at the nanoscale, the characterization of local thermal effects within a single molecule is highly challenging. Here, we demonstrate a way to characterize the local thermal properties of a single fullerene (C60) molecule during current-induced heating processes through tip-enhanced anti-Stokes Raman spectroscopy. Although the measured vibron populations are far from equilibrium with the environment, we can still define an "effective temperature (Teff)" statistically via a Bose-Einstein distribution, suggesting a local equilibrium within the molecule. With increased current heating, Teff is found to rise up to about 1150 K until the C60 cage is decomposed. Such a decomposition temperature is similar to that reported for ensemble C60 samples, thus justifying the validity of our methodology. Moreover, the possible reaction pathway and product can be identified because of the chemical sensitivity of Raman spectroscopy. Our findings provide a practical method for noninvasively detecting the local heating effect inside a single molecule under nonequilibrium conditions.

Two-dimensional fullerene-based monolayer materials assembled by C80 and Sc3N@C80.

Construction of two-dimensional (2D) materials using fullerenes as building blocks has attracted particular attention, primarily due to their ability to integrate desired functionalities into devices. However, realization of stable 2D phases of polymerized fullerenes remains a big challenge. Here, we propose two stable 2D monolayer phases with covalently bridged C80 cages, namely α-C80-2D and β-C80-2D, which are semiconductors with strong absorption in the long wave range and appreciable carrier mobility, respectively. The high stability originates from the bond energy released by the [2+2] cycloaddition polymerization of C80 is greater than the deformation energy of a cage. Starting from α-C80-2D, endohedral incorporation of the Sc3N molecule into each C80 cage leads to 2D semiconductors of α-Sc3N@C80-2D and α'-Sc3N@C80-2D, which possess exceptional stability and diverse physical properties, including unique electronic band structures, strong optical absorption in the visible (VIS) to near-infrared (NIR) regime, and anisotropic optical characteristics. Remarkably, a temperature-induced order-disorder transition in the α-Sc3N@C80-2D phase has been observed at elevated temperatures above 600 K. These findings expand the family of 2D carbon materials and provide useful clue for the potential applications of fullerene-assembled monolayer networks.

A hard molecular nanomagnet from confined paramagnetic 3d-4f spins inside a fullerene cage

Reducing inter-spin distance can enhance magnetic interactions and allow for the realization of outstanding magnetic properties. However, achieving reduced distances is technically challenging. Here, we construct a 3d-4f metal cluster (Dy2VN) inside a C80 cage, affording a heretofore unseen metallofullerene containing both paramagnetic 3d and 4f metal ions. The significantly suppressed 3d-4f (Dy-V) distances, due to the unique cage confinement effect, were observed by crystallographic and theoretical analysis of Dy2VN@Ih(7)-C80. These reduced distances result in an enhanced magnetic coupling (Jtotal, Dy-V = 53.30 cm−1; Jtotal, Dy-Dy = −6.25 cm−1), leading to a high magnetic blocking temperature compared to reported 3d-4f single-molecule magnets and strong coercive field of 2.73 Tesla. Our work presents a new class of single-molecule magnets with both paramagnetic 3d and 4f metals confined in a fullerene cage, offering superior and tunable magnetic properties due to the unique cage confinement effect and the diverse composition of the entrapped magnetic core.

Synthesis and Characterization of Ionic Li+ @C70 Endohedral Fullerene.

Ion-endohedral-fullerene has attracted growing interest due to the unique electronic and structural characteristics arising from its distinctive ionic nature. Although there has been only one reported ion-encapsulated fullerene, Li+ @C60 , a significant number of fundamental and applied studies have been conducted, making a substantial impact not only in chemistry and physics but also across various interdisciplinary research fields. Nevertheless, studies on ion-endohedral fullerenes are still in their infancy due to the limitations in variety, and hence, it remains an open question how the size and symmetry of fullerene, as well as the motion and position of the encapsulated ion, affect their physical/chemical properties. Herein, we report the synthesis of lithium-ion-endohedral [70]fullerene (Li+ @C70 X- , X=PF6 - and TFSI- ), a novel ionic endohedral fullerene. X-ray crystallography confirmed the encapsulation of Li+ by C70 cage as well as its ion-pair structure stabilized by external TFSI- counter anion. The encapsulated Li+ drastically lowered the orbital energy of the C70 cage by Coulomb interactions but did not affect the orbital energy gap and degeneracy. DFT studies were also performed, which supported the experimentally observed electronic effects caused by the encapsulated Li+ .

Bandgap Engineering of Erbium-Metallofullerenes toward Switchable Photoluminescence.

Encapsulating photoluminescent lanthanide ions like erbium (Er) into fullerene cages affords photoluminescent endohedral metallofullerenes (EMFs). Few reported photoluminescent Er-EMFs are all based on encapsulation of multiple (two to three) metal atoms, whereas mono-Er-EMFs exemplified by Er@C82 are not photoluminescent due to its narrow optical bandgap. Herein, by entrapping an Er-cyanide cluster into various C82 cages to form novel Er-monometallic cyanide clusterfullerenes (CYCFs), ErCN@C82 (C2 (5), Cs (6), and C2 v (9)), the photoluminescent properties of CYCFs are investigated, and obvious near-infrared (NIR) photoluminescence only is observed for ErCN@C2 (5)-C82 . Combined with a comparative photoluminescence study of three medium-bandgap di-Er-EMFs, including Er2 @Cs (6)-C82 , Er2 O@Cs (6)-C82 , and Er2 C2 @Cs (6)-C82 , this study proposes that the optical bandgap can be used as a simple criterion for switching the photoluminescence of Er-EMFs, and the bandgap threshold is determined to be between 0.83 and 0.74eV. Furthermore, the photoluminescent patterns of these three di-Er-EMFs differ dramatically. It is found that the location of the Er atom within the same Cs (6)-C82 cage is almost fixed and independent on the endo-unit; thus the previous statement on the key role of metal position in photoluminescence of di-Er-EMFs seems erroneous, and the geometric configuration of the endo-unit, especially the bridging mode of two Er ions, is decisive instead.

Paramagnetic {[Fe(CO)2]2-μ2-η2:η2-η2:η2-(C60)2}2- Dimer Bridged by Iron Atoms and C-C Bonds: Effect of Starting Iron Carbonyls on Structures and Properties of Negatively Charged Iron-Bridged Fullerene Dimers.

The reaction between an excess of Fe(CO)5 with {Cryptand(K+)}(C60•-) produced the salt {Cryptand(K+)}2{[Fe(CO)2]2-μ2-η2:η2-η2:η2-(C60)2}2-·4C6H4Cl2 (1) containing negatively charged iron-bridged fullerene dimers. In these dimers, the C60 cages are linked via two Fe(CO)2 fragments, forming short Fe-C(C60) bonds with a length of 2.070(3) Å and via two intercage C-C bonds with a length of 1.566(3) Å. Interfullerene center-to-center distance is short, being 9.02 Å. Thus, the coordination-induced dimerization of fullerenes is observed in 1. The dimer is negatively charged, with additional negative electron density mainly localized on iron atoms and, to a lesser extent, on the C60 cages, as revealed by optical and electron paramagnetic resonance spectra. These dimers have a diamagnetic singlet ground state with a small singlet-triplet gap of 25 K; consequently, they transfer to a paramagnetic state with two S = 1/2 spins per dimer above 50 K. Previously, different dimers with isomeric structures were obtained starting from {Cryptand(K+)}(C60•-) and Fe3(CO)12. However, these dimers exhibit diamagnetic properties, owing to the formation of a Fe-Fe bond. In contrast, in dimer 1, the Fe atoms are positioned too far apart to form such a bond, preserving the spin on Fe. We assume that both dimers are formed through the same [Fe(CO)3](C60•-) intermediate, but the subsequent interaction of this intermediate with Fe3(CO)12 or its dimerization yields different dimers. Therefore, the starting carbonyls can control the structures and properties of the resulting dimers.

Steering Single-Electron Metal-Metal Bonds and Hyperfine Coupling between a Transition Metal-Lanthanide Heteronuclear Bimetal Confined in Carbon Cages.

Metal complexes bearing single-electron metal-metal bonds (SEMBs) exhibit unusual electronic structures evoking strong magnetic coupling, and such bonds can be stabilized in the form of dimetallofullerenes (di-EMFs) in which two metals are confined in a carbon cage. Up to now, only a few di-EMFs containing SEMBs are reported, which are all based on a high-symmetry icosahedral (Ih) C80 cage embedding homonuclear rare-earth bimetals, and a chemical modification of the Ih-C80 cage is required to stabilize the SEMB. Herein, by introducing 3d-block transition metal titanium (Ti) along with 4f-block lanthanum (La) into the carbon cage, we synthesized the first crystallographically characterized SEMB-containing 3d-4f heteronuclear di-EMFs based on pristine fullerene cages. Four novel La-Ti heteronuclear di-EMFs were isolated, namely, LaTi@D3h(5)-C78, LaTi@Ih(7)-C80, LaTi@D5h(6)-C80, and LaTi@C2v(9)-C82, and their molecular structures were unambiguously determined by single-crystal X-ray diffraction. Upon increasing the cage size from C78 to C82, the La-Ti distance decreases from 4.31 to 3.97 Å, affording fine-tuning of the metal-metal bonding and hyperfine coupling, as evidenced by an electron spin resonance (ESR) spectroscopic study. Density functional theory (DFT) calculations confirm the existence of SEMB in all four LaTi@C2n di-EMFs, and the accumulation of electron density between La and Ti atoms shifts gradually from the proximity of the Ti atom inside C78 to the center of the LaTi bimetal inside C82 due to the decrease of the La-Ti distance. The electronic properties of LaTi@C2n heteronuclear dimetallofullerenes differ apparently from their homonuclear La2@C2n counterparts, revealing the peculiarity of heteronuclear dimetallofullerenes with the involvement of 3d-block transition metal Ti.

Superatom Molecular Orbitals of Endohedral C82.

Understanding superatom molecular orbital (SAMO) states in fullerene derivatives has been in the limelight ever since the first discovery of SAMOs owing to the fundamental interest in this topic as well as to the possible applications in molecular switches and other organic electronics. Nevertheless, very few reports have been published on SAMO states of larger fullerenes so far. Using density functional theory, we attempt to partially remedy this situation by presenting a study on SAMO states in C82 and its Ca and Sc endohedrally doped derivatives, comparing results with previous relevant findings for C60. We find that C82 possesses higher SAMO energies compared to C60, as associated with the symmetry of the molecule, and that endohedral doping leads to energetically favorable side positions of Ca and Sc inside the C82 cage. Among the two, Sc@C82 has more stable SAMO states compared to Ca@C82 as reflected by the shift in the density of states, while the charge states are found to be similar. In the case of the monolayer form, the pz- and 2s-SAMO orbitals overlap with the nearest neighbors, causing parabolic band dispersion with the formation of near free electron states and that the SAMO state energies move closer to the Fermi energy compared to the related molecules. These findings provide promising information about the distribution of SAMO states in C82 fullerene, which can be further relevant in studies of SAMO states of higher fullerenes and for coming applications of these systems.

Quantum-Chemical Modeling of Two Er3N@C80 Isomers

Computations of the molecular parameters and relative populations are reported for the two isomers of Er3N@C80 experimentally known, i.e. produced by encapsulation into the isolated-pentagon-rule (IPR) C80 cages with I h and D 5h symmetries. The calculations are mostly based on the density-functional theory (DFT) treatments with the B3LYP functional. However, the inter-isomeric energetics is further refined with the B2PLYP method which places the D 5h endohedral higher in the potential energy by 18.8 kcal/mol. The isomeric populations are evaluated using the Gibbs energy in a broad temperature interval. The computations performed with the floating-encapsulate-model (FEM) treatment agree with the observation that Er3N@I h (7)-C80 represents the major isomer. The calculations also suggest some similarity between Er3N@C80 and Lu3N@C80 so that Er3N@C80 could possibly also produce a useful nanowire, like recently found with Lu3N@C80 and its interesting electrical-conductivity and switching behavior.

(Invited) Synthesis of Ion-Endohedral Fullerenes by Plasma Implantation

Endohedral metallofullerenes (EMFs), which are the hybrid materials consisting of fullerene cage and encapsulated metal(s), are one of the well-studied nanocarbon materials during the past 3 decades.[1] As a result of significant progress in the development of synthetic procedures and purification processes, a variety of different types of EMFs, such as mono-metallofullerenes, di-metallofullerenes and metal-cluster-fullerenes with various carbon-cage sizes, are currently available. We previously reported development of an efficient method to access EMFs, so-called plasma implantation.[2] This approach allowed us to achieve scalable synthesis of lithium-ion-encapsulated [60]fullerene Li+@C60 X−, a stable ionic form of lithium encapsulated fullerene. The compound can be regarded as “ion-endohedral fullerene” consisting of encapsulated ion, neutral fullerene cage and external counter anion X−, and it should not be categorized into general metallofullerenes because of its ion-pair structure. Despite the unique properties arising from its ionic natures, no other ionic metallofullerenes have been well studied so far.[3] For systematic and deeper studies on ion-endohedral fullerenes, we focused on Li+-endohedral [70]fullerene (Li+@C70) because C70 is the second abundant and therefore widely studied fullerene next to C60. The Li+@C70 was synthesized as PF6 − and TFSI− (TFSI=bis(trifluoromethanesulfonyl)imide) salts using our improved plasma implantation method followed by oxidative purification process. 7Li NMR spectrum showed a sharp singlet signal at −32.81 ppm (vs LiCl/D2O standard) indicating that the Li+ was encapsulated in the C70 cage. 13C NMR spectrum showed 5 aromatic peaks, which evidenced the defectless C70 structure. In addition to the NMR signals originated from the Li+@C70 core, 19F and 31P NMR spectra showed clear signals assigned to each external counter anion. The structure of Li+@C70 was unambiguously confirmed by X-ray crystal structure analysis of the TFSI− salt. The crystal structure showed encapsulation of Li+ by C70 cage as well as the 1:1 ion-paired structure of the cationic Li+@C70 core and external TFSI− anion.Moreover, we also performed collision experiments using sodium plasma to synthesize sodium-ion-endohedral [60]fullerene. Laser desorption ionization (LDI) mass spectrum of the crude products showed signals at m/z= 720 and 743 assignable to the molecular ion of empty C60 and the Na+@C60, respectively. The target compound was isolated as TFSI− salt by oxidative purification process followed by electrolyte-added HPLC. There was only a mass peak at m/z= 743 after the purification, which evidenced the complete removal of empty C60. 23Na NMR spectrum showed a sharp singlet signal at −59.6 ppm (vs NaCl/D2O standard), evidenced the formation of the target Na+@C60.

U@Cs(4)-C82: A Different Cage Isomer with Reactivity Controlled by U-Sumanene Interaction.

Actinide endohedral metallofullerenes (EMFs) are a fullerene family that possess unique actinide-carbon cage host-guest molecular and electronic structures. In this work, a novel actinide EMF, U@Cs(4)-C82, was successfully synthesized and characterized, and its chemical reactivity was investigated. Crystallographic analysis shows that U@Cs(4)-C82, a new isomer of U@C82, has a Cs(4)-C82 cage, which has never been discovered in the form of empty or endohedral fullerenes. Its unique chemical reactivities were further revealed through the Bingel-Hirsch reaction and carbene addition reaction studies. The Bingel-Hirsch reaction of U@Cs(4)-C82 shows exceptionally high selectivity and product yield, yielding only one major addition adduct. Moreover, the addition sites for both reactions are unexpectedly located on adjacent carbon atoms far away from the actinide metal, despite the nucleophilic (Bingel-Hirsch) and electrophilic (carbene addition) nature of either reactant. Density functional theory (DFT) calculations suggest that this chemical behavior, unprecedented for EMFs, is directed by the unusually strong interaction between U and the sumanene motif of the carbon cage in U@Cs(4)-C82, which makes the energy increase when it is disrupted. This work reveals remarkable chemical properties of actinide EMFs originating from their unique electronic structures and highlights the key role of actinide-cage interactions in the determination of their chemical behaviors.

Structural, electronic, thermal and mechanical properties of C60-based fullerene two-dimensional networks explored by first-principles and machine learning

Recent experimental reports on the realizations of two-dimensional (2D) networks of the C60-based fullerenes with anisotropic and nanoporous lattices represent a significant advance, and create exciting prospects for the development of a new class of nanomaterials. In this work, we employed theoretical calculations to explore novel C60-based fullerene lattices and subsequently evaluate their stability and key physical properties. After the energy minimization of extensive structures, we could detect novel 2D, 1D and porous carbon C60-based networks, with close energies to that of the isolated C60 cage. Density functional theory results confirm that the C60-based networks can exhibit remarkable thermal stability, and depending on their atomic structure show metallic, semimetallic or semiconducting electronic nature. Using the machine learning interatomic potentials, thermal and mechanical responses of the predicted nanoporous 2D lattices were investigated. The estimated thermal conductivity of the quasi-hexagonal-phase of C60 fullerene is shown to be in an excellent agreement with the experimental measurements. Despite of different atomic structures, the anisotropic room temperature lattice thermal conductivity of the fullerene nanosheets are estimated to be in the order of 10 W/mK. Unlike the majority of carbon-based 2D materials, C60-based counterparts noticeably are predicted to show positive thermal expansion coefficients. Porous carbon C60-based networks are found to exhibit superior mechanical properties, with tensile strengths and elastic modulus reaching extraordinary values of 50 and 300 GPa, respectively. The theoretical results presented in this work provide a comprehensive vision on the structural, energetic, electronic, thermal and mechanical properties of the C60-based fullerene networks.