Stability Of Fullerenes Research Articles

(Invited) Is the [5,5] C120-D5d Fullertube a Metal?

Single-walled nanotubes (SWNTs) with a roll-up vector (n = m) have long been predicted to exhibit metallic behavior at infinite nanotube lengths.1 Moreover, in contrast with normal metals, armchair nanotubes e.g., [5,5] should result in exceptional ballistic transport properties.2 However, the question remains at what finite length of a SWNT or fullertube does metallic character begin, if at all. From a computational viewpoint, Cioslowski has shown that the HOMO-LUMO bandgap decreases to ~1 eV in an oscillatory fashion in approaching [5,5] C200 fullertubes.3 Although the HOMO-LUMO gap has been extensively used to predict the kinetic stability of fullerenes and metallofullerenes with less than 100 carbon atoms, Fowler has argued that the HOMO-LUMO gap can not be used to predict the kinetic stability of large fullerenes.4 More recently, Lilijeroth and coworkers have measured the experimental and DFT HOMO-LUMO gap for graphene nanoribbons (GNR) and find that GNRs with lengths of 5 nm have bandgaps of ~0.1 eV.5 These workers also point out that DFT calculated HOMO-LUMO bandgaps are always overestimated relative to experimental values. In this presentation, I will present the evidence in support of metallic character for [5,5] C120-D5d.6,7

Structural and optical properties of C70 fullerenes in aqueous solution

The simple method of preparation of highly stable and purified C70 fullerene aqueous solution (C70FAS) is proposed. The features of structural stabilization of C70 fullerenes in an aqueous solution by studying their structural and optical properties using Raman, photoluminescence, infrared reflection-absorption, UV–VIS absorption, and dynamic light scattering spectroscopy methods were analyzed. The experimental results showed that the most likely mechanism for C70 fullerenes stabilization in water is surface hydroxylation with covalent attachment of water hydroxyls to C70 fullerene carbons. Raman and infrared absorption spectra of C70FAS showed characteristic vibrational bands of C70 fullerenes with a slight broadening and low-frequency shift of ∼1 cm−1, indicating the attachment of water hydroxyls to the C70 fullerene carbons. The photoluminescence spectra showed excitonic emission bands of C70 molecules with intensity depending on their content. UV–VIS absorption spectra demonstrate the absorption bands typical for monomeric C70 fullerene. Finally, the dynamic light scattering data confirmed that C70FAS is a typical colloidal fluid containing both individual C70 molecules and their nano aggregates up to 100 nm. These findings provide insights into the stabilization mechanism of C70 fullerenes in water and may have implications for their potential application in nanobiotechnology.

Enhancing the Mechanical Stability of 2D Fullerene with a Graphene Substrate and Encapsulation.

Recent advancements have led to the synthesis of novel monolayer 2D carbon structures, namely quasi-hexagonal-phase fullerene (qHPC60) and quasi-tetragonal-phase fullerene (qTPC60). Particularly, qHPC60 exhibits a promising medium band gap of approximately 1.6 eV, making it an attractive candidate for semiconductor devices. In this study, we conducted comprehensive molecular dynamics simulations to investigate the mechanical stability of 2D fullerene when placed on a graphene substrate and encapsulated within it. Graphene, renowned for its exceptional tensile strength, was chosen as the substrate and encapsulation material. We compared the mechanical behaviors of qHPC60 and qTPC60, examined the influence of cracks on their mechanical properties, and analyzed the internal stress experienced during and after fracture. Our findings reveal that the mechanical reliability of 2D fullerene can be significantly improved by encapsulating it with graphene, particularly strengthening the cracked regions. The estimated elastic modulus increased from 191.6 (qHPC60) and 134.7 GPa (qTPC60) to 531.4 and 504.1 GPa, respectively. Moreover, we observed that defects on the C60 layer had a negligible impact on the deterioration of the mechanical properties. This research provides valuable insights into enhancing the mechanical properties of 2D fullerene through graphene substrates or encapsulation, thereby holding promising implications for future applications.

In Ukrainian

The review examines experimental and theoretical works devoted to the description of modern methods for the preparation of iron endometal-fullerenes(EMF), as well as works that dispute such results due to the extremely low efficiency of the used methods. The paper also considers the advantages and disadvantages of synthesis, as well as the areas of possible application of synthesis products. It is shown that EMF is obtained mainly by two methods - arc discharge (plasma) and synthesis using ablation and implantation methods. Despite a very small number of works on iron-endometal-fullerenes, the group of authors managed to achieve some progress in their analysis. Thus, the fact of obtaining Fe-endometal-fullerenes with their isolation from a mixture of synthesis products was proved. In addition, the influence of the magnetic state of metal atoms on the stability of endohedral fullerenes was predicted, a relationship between the EMF output and the plasma temperature, as well as the chemical nature of the precursor of iron atoms, was established. In particular, it was established that with an increase in the atomic mass of the elements, the EMF output decreases exponentially. It was concluded that the magnetic properties of EMF make them perspective materials in the field of clinical diagnostics (for example, as contrast agents in MRI) and medicine (for magnetically controlled delivery of drugs directly to a diseased organ).

Room-temperature deposited fluorine-doped tantalum pentoxide for stable organic solar cells

Earth-abundant transition metal oxides deposited at room temperature with low-cost methods suitable for large area manufacturing can offer advances in many fields of energy related devices. Here we report the room-temperature deposition of a fluorine-doped tantalum pentoxide using a home-made, low-cost hot-wire deposition system. This novel tantalum oxyfluoride material is super hydrophobic, ultra-transparent within the visible spectrum, and possesses adequate conductivity and suitable valence band and conduction band extrema for acting as efficient hole extraction and electron blocking layer in organic solar cells with the forward architecture. By inserting this material in the form of nanoparticles deposited on top of the commonly used as hole transport layer poly(3,4-ethylenedioxythiophene) polystyrene sulfonate, higher efficiencies compared to the reference cells without the nanoparticles were demonstrated in solar cells based on blends of polymer donors with either a fullerene (where maximum achieved efficiency was improved from 6.07% to 7.90%) or a non-fullerene acceptor (reaching values of 13.48% compared to 11.32% of the reference cell). Moreover, significant improvement in device stability was achievd in unencapsulated devices continuously exposed in a humid environment for 500 h. This work demonstrates the unambiguous potential of well-designed metal oxide materials as charge transport and blocking interlayers and protective buffers in organic solar cells and beyond. Home-grown fluorine-doped tantalum pentoxide nanoparticles deposited on top of PEDOT:PSS hole transport layer results in around 19% improved power conversion efficiency and an improved stability in organic solar cells. • Room-temperature deposition of fluorine-doped tantalum pentoxide. • Improved hole extraction and electron blocking properties. • Ta 2 O 5 :F - an inorganic protective buffer layer. • A 19% improved efficiency in organic solar cells. • Improved stability of fullerene and non-fullerene acceptor.

Comprehensive theoretical study of the correlation between the energetic and thermal stabilities for the entire set of 1812 C60 isomers

The thermal stability of fullerenes plays a fundamental role in their synthesis and in their thermodynamic and kinetic properties. Here, we perform extensive molecular dynamics (MD) simulations using an accurate machine-learning-based Gaussian Approximation Potential (GAP-20) force field to investigate the energetic and thermal properties of the entire set of 1812 C60 isomers. Our MD simulations predict a comprehensive and quantitative correlation between the relative isomerization energy distribution of the C60 isomers and their thermal fragmentation temperatures. We find that the 1812 C60 isomers span over an energetic range of over 400 kcal mol−1, where the majority of isomers (∼85%) lie in the range between 90 and 210 kcal mol−1 above the most stable C60-Ih buckminsterfullerene. Notably, the MD simulations show a clear statistical correlation between the relative energies of the C60 isomers and their fragmentation temperature. The maximum fragmentation temperature is 4800 K for the C60-Ih isomer and 3700 K for the energetically least stable isomer, where nearly 80% of isomers lie in a temperature window of 4000–4500 K. In addition, an Arrhenius-based approach is used to map the timescale gap between simulation and experiment and establish a connection between the MD simulations and fragmentation temperatures.

Unexpected Colloidal Stability of Fullerenes in Dimethyl Sulfoxide and Related Systems

It is known that fullerenes are poorly soluble in polar solvents, but readily form colloidal solutions in such media. These solutions are typically solvophobic (hydrophobic when prepared in water), that is, thermodynamically unstable colloidal systems with negatively charged particles. To understand the stability factors of a colloidal system, the thresholds for coagulation of a sol or suspension by electrolytes are of key importance. While hydrosols and aqueous suspensions coagulate at concentrations of 1:1 inorganic electrolytes about 0.1-0.2 M, in acetonitrile and methanol, the corresponding critical concentrations of coagulation are ca. 3 orders of magnitude lower. Given the wide variety of properties of organic solvents, it seemed important to complete the picture to study solvents with more basic properties. This is all the more reasonable since electrophilic fullerenes are in fact Lewis acids. Our choice was dimethyl sulfoxide, DMSO, and related solvent systems. The colloidal solutions of fullerenes C60 and C70 in DMSO and N,N-dimethyl formamide, DMF, are unexpectedly easy to prepare by mechanical methods, and addition of water leads to formation of relatively stable organo-hydrosols. UV-visible spectra and dynamic light scattering were used to characterize the solutions of C60 and C70 in DMSO, benzene-DMSO, acetonitrile-DMSO, and benzene-acetonitrile-DMSO systems, as well as in DMF. Our present study demonstrated that, in contrast to organosols in methanol and acetonitrile, colloids of C70 and C60 fullerenes in DMSO and DMF are surprisingly as stable with respect to electrolytes as the corresponding hydrosols are. Such high stability is caused by the non-DLVO interactions, or, in terms proposed by Churaev and Derjaguin, by the so-called structural effect. These results shed light on the nature of the solvation of colloidal fullerene particles in solvents of various chemical natures.

Dual modification to stabilize Non-IPR C72 fullerene: A new theoretical strategy

The stabilization of non-IPR fullerenes for their isolation and characterization is an area of recent interest. In the present study, we have explored the stabilization techniques of C72 isomers via endo and exo-modifications and finally approached dual modification. A total of four isomers of C72 have been considered in this study; among them, one is IPR derivative (1), and the rest are non-IPR derivatives with one (2) and two (3 and 4) fused pentagon rings. First, we have studied the endohedral modification by encapsulating one and two La atoms in the C72 cavity. Secondly, we have exohedrally modified the C72 isomers via chlorination by adding four and eight chlorides, respectively. Our final approach is to study the dual modification, where we have implemented both endo exo-modifications together. This dual modification can be achieved in two ways: exo followed by endo and endo followed by exo. For each modification, the relative stability of every modified C72 derivative has been checked by calculating the relative energy with respect to the most stable modified analogue. To find out whether these modifications are energetically feasible or not, we have calculated the binding energy of each modified C72 isomer. The binding energy calculation reveals that the encapsulation and exo-modification techniques are good enough to stabilize the non-IPR C72 derivatives. Moreover, the effectiveness of dual modification has also been established from the enhanced binding energy compared to either endo- or exo-modification. We have also studied the NPA charges on the encapsulated La atoms for each endo- and dual-modified C72 derivative. Furthermore, the AIM study has also been perceived to find out the interaction between the La atom and the fullerene cages for both mono- and di-encapsulated fullerene derivatives and also between La–La centres for di-encapsulated derivatives. Overall, the present theoretical study will provide an idea about the stability of the modified C72 derivatives, which will help the experimentalists to design new strategies for synthesizing modified non-IPR fullerene derivatives that have vast applications in the medicinal and industrial fields.

On the restricted three-body model of the dynamical behaviour of masses of C70 fullerenes at the nanoscale

The present study investigates the positions and stability of C70 fullerenes. Numerically, the positions and stability have been computed C70 fullerene at the nanoscale to show the effects of the parameters involved with the help of software MATHEMATICA. The total molecular energy evidenced refers to the total pairwise molecular interactions between two C 70 fullerenes, which is an approximation of a continuous approach. The attractive Vand der Waals forces between only molecules provide the centripetal forces between three fullerenes. The total pairwise molecular interactions between two C 70 fullerenes, which is an approximation of a continuous approach, is termed the total molecular energy evidenced. The attractive Vand der Waals forces between single molecules create the centripetal forces between three fullerenes. We have predicted the collective potential function, mutual force and angular velocity. The stationary points are collinearly lying on the ξ−axis which are symmetric about the η−axis as the molecules of the carbon atoms in the nucleus are evenly distributed. There is at least one complex root with the positive real part for each set of values, it has been discovered. The stationary points are thus unstable in the Lyapunov sense.

Effects of orbital angles on the modeling of conjugated systems with curvature.

The remaining p orbitals of carbon atoms form some conjugated systems, such as fullerenes. The non-parallel p orbitals of fullerene conjugated systems dominate their stability. In this work, a model is proposed with a good correlation between model outputs and relative energies of fullerenes. The model is built from the extended Hückel molecular orbital theory and geometrical features, especially the orbital axial angle characteristics. The extended charge stability index (XCSI) proposed in this paper offers a good representation of the stability from small cage to at least C70. The axial angle feature is no longer necessary in large carbon cages, which is similar to previous models based on fullerene deformation factors. In addition, a deep learning model based on spatial orientation features containing spherical harmonic functions yields surprising transferring results on the stability of charged fullerenes. We hope this work will assist in building more general models dealing with problems related to conjugated systems.

Newly elected Chinese Academy of Sciences academicians in chemistry division in 2021

Newly elected Chinese Academy of Sciences academicians in chemistry division in 2021

Characterization of titanium influences on structure and thermodynamic stability of novel C20-nTin nanofullerenes (n=1-5): a density functional perspective.

In this survey, effects of titanium heteroatom(s) on structural parameters and thermodynamic stability of C20 fullerene and its C20-nTin derivatives (n = 1-5) are compared and contrasted, at DFT levels of theory. The results show that in going from C19Ti1 to C15Ti5, binding energy increases while absolute value heat of atomization decreases. According to vibrational frequency analysis, excepting C16Ti4-1, the other optimized structures give no imaginary frequency as true minima. The calculated binding energy of 887.12kcalmol-1/atom displays C15Ti5 as the most thermodynamically stable heterofullerene. It has Cs symmetry and contains five titanium atoms alternatively in equatorial position. The substitutional doping of C20 fullerene leads to high Mülliken charge distribution upon the surfaces of the resulted heterofullerenes especially C19Ti1 as suitable hydrogen storage. The contour plots indicate the most negative electrostatic potential by red color for C atoms, whereas the most positive electrostatic potential by yellow color for Ti heteroatoms. The contour plots and multiwfn analysis exhibit charge transfer from titanium heteroatoms to the neighboring carbon atoms. Furthermore, the resulted electron density maps from multiwfn qualitatively confirm the contour plot's findings. The hydrogen adsorption is an endothermic process for C20 fullerene and exothermic process for C20-nTin heterofullerenes. Major criteria examined for thermodynamic stability; from C19Ti1 to C15Ti5, binding energy and hydrogen adsorption increase while heat of atomization decreases.

Snapshots of the Fragmentation for C70@Single-Walled Carbon Nanotube: Tight-Binding Molecular Dynamics Simulations.

In previously reported experimental studies, a yield of double-walled carbon nanotubes (DWCNTs) at C70@Single-walled carbon nanotubes (SWCNTs) is higher than C60@SWCNTs due to the higher sensitivity to photolysis of the former. From the perspective of pyrolysis dynamics, we would like to understand whether C70@SWCNT is more sensitive to thermal decomposition than C60@SWCNT, and the starting point of DWCNT formation, which can be obtained through the decomposition fragmentation of the nanopeapods, which appears in the early stages. We have studied the fragmentation of C70@SWCNT nanopeapods, using molecular dynamics simulations together with the empirical tight-binding total energy calculation method. We got the snapshots of the fragmentation structure of carbon nano-peapods (CNPs) composed of SWCNT and C70 fullerene molecules and the geometric spatial positioning structure of C70 within the SWCNT as a function of dynamics time (for 2 picoseconds) at the temperatures of 4000 K, 5000 K, and 6000 K. In conclusion, the scenario in which C70@SWCNT transforms to a DWCNT would be followed by the fragmentation of C70, after C70, and the SWCNT have been chemically bonding in the early stages. The relative stability of fullerenes in CNPs could be reversed, compared to the ranking of the relative stability of the encapsulated molecules themselves.

Substructural Approach for Assessing the Stability of Higher Fullerenes.

This review describes the most significant published results devoted to the study of the nature of the higher fullerenes stability, revealing of correlations between the structural features of higher fullerene molecules and the possibility of their producing. A formalization of the substructure approach to assessing the stability of higher fullerenes is proposed, which is based on a detailed analysis of the main structural features of fullerene molecules. The developed substructure approach, together with the stability of the substructures constituting the fullerene molecule, helps to understand deeper the features of the electronic structure of fullerenes.

Molecular Simulations for Understanding the Stabilization of Fullerenes in Water

Molecular Simulations for Understanding the Stabilization of Fullerenes in Water

Aromaticity Survival in Hydrofullerenes: The Case of C66 H4 with Its π-Aromatic Circuits.

The isolated-pentagon rule (IPR) is a determining structural feature that accounts for hollow fullerene stabilization and properties related to Cn (n≥60) cages. The recent characterization of an unprecedented non-IPR hydrofullerene, C2v C66 H4 , bearing two heptagons with adjacent fused-pentagon motifs, largely dismisses this feature. Herein, employing DFT calculations, the 13 C NMR spectroscopy and aromatic behavior of C2v C66 H4 are explored. The results show the presence of three π-aromatic circuits at the bottom boat section of C66 H4 , indicating the unique features of this hydrofullerene in comparison to those of pristine C60 . In addition, under specific orientations of the external field, certain π-aromatic circuits are enabled, resulting in a more aromatic fullerene than that of C60 , but lower than that of the spherical aromatic C60 6- fulleride. Notably, under a field aligned with the saturated carbon atoms, nonaromatic characteristics are exposed. This reveals that spherical-like cages can involve a complex magnetic response that heavily depends on the orientation of the applied field.

Thermochemical stabilities of giant fullerenes using density functional tight binding theory and isodesmic-type reactions.

We present a systematic assessment of the density functional tight binding (DFTB) method for calculating heats of formation of fullerenes with isodesmic-type reaction schemes. We show that DFTB3-D/3ob can accurately predict Δf H values of the 1812 structural isomers of C60 , reproduce subtle trends in Δf H values for 24 isolated pentagon rule (IPR) isomers of C84 , and predict Δf H values of giant fullerenes that are in effectively exact agreement with benchmark DSD-PBEP86/def2-QZVPP calculations. For fullerenes up to C320 , DFTB Δf H values are within 1.0 kJ mol-1 of DSD-PBEP86/def2-QZVPP values per carbon atom, and on a per carbon atom basis DFTB3-D/3ob yields exactly the same numerical trend of (Δf H [per carbon] = 722n-0.72 + 5.2 kJ mol-1 ). DFTB3-D/3ob is therefore an accurate replacement for high-level DHDFT and composite thermochemical methods in predicting of thermochemical stabilities of giant fullerenes and analogous nanocarbon architectures.

Synthesis and Stability of Actinium-225 Endohedral Fullerenes, 225Ac@C60.

We report the first synthesis of 225Ac (t1/2 = 10 days) endohedral fullerenes,225Ac@C60. The 225Ac@C60 was produced with a 12 ± 2% efficiency by applying an electrical arc discharge between a source of α-particle emitter 225Ac (∼1 mCi, electroplated on a Pt disk) and a thin coat of “preformed” C60 on an Al disk (C60 thickness of ∼0.25 mg/cm2). After formation by electrical arc discharge, the resulting radiofullerenes on the Al disk were dissolved in toluene under anaerobic conditions and converted to a malonate derivative using the Bingel reaction. Subsequent to repeated washings of the organic phase with dilute acidic solutions to remove exohedral 225Ac, ∼45% of 225Ac activity was retained in the organic phase, which resisted extraction into the aqueous phase. Failure to extract the 225Ac from the organic phase provided definitive evidence that the 225Ac is located inside of the fullerene. The formation of 225Ac@C60 was further confirmed using a classical hot-atom chemistry technique in which the organic phase containing purified endohedral 225Ac@C60 malonate was contacted with fresh dilute acid to repeatedly extract the ionic 4.8 m 221Fr and 45.6 m 213Bi activities (decay daughters of 225Ac), which were released by molecular disruption due to nuclear recoil. The result from the extraction experiments was further supported by a series of thin-layer chromatography and high-pressure liquid chromatography analysis of the organic phase containing 225Ac@C60 or 225Ac@C60 malonate. Taken together, studies show that, like polydentate chelators, single-wall fullerenes are not capable of retaining the 225Ac decay daughters.

Persistent spectral graph.

Persistent homology is constrained to purely topological persistence, while multiscale graphs account only for geometric information. This work introduces persistent spectral theory to create a unified low-dimensional multiscale paradigm for revealing topological persistence and extracting geometric shapes from high-dimensional datasets. For a point-cloud dataset, a filtration procedure is used to generate a sequence of chain complexes and associated families of simplicial complexes and chains, from which we construct persistent combinatorial Laplacian matrices. We show that a full set of topological persistence can be completely recovered from the harmonic persistent spectra, that is, the spectra that have zero eigenvalues, of the persistent combinatorial Laplacian matrices. However, non-harmonic spectra of the Laplacian matrices induced by the filtration offer another powerful tool for data analysis, modeling, and prediction. In this work, fullerene stability is predicted by using both harmonic spectra and non-harmonic persistent spectra, while the latter spectra are successfully devised to analyze the structure of fullerenes and model protein flexibility, which cannot be straightforwardly extracted from the current persistent homology. The proposed method is found to provide excellent predictions of the protein B-factors for which current popular biophysical models break down.

Fullerene Thermochemical Stability: Accurate Heats of Formation for Small Fullerenes, the Importance of Structural Deformation on Reactivity, and the Special Stability of C60.

We have used quantum chemistry computations, in conjunction with isodesmic-type reactions, to obtain accurate heats of formation (HoFs) for the small fullerenes C20 (2358.2 ± 8.0 kJ mol-1), C24 (2566.2 ± 7.6), and the lowest-energy isomers of C32 (2461.1 ± 15.4), C42 (2629.0 ± 20.5), and C54 (2686.2 ± 25.3). As part of this endeavor, we have also obtained accurate HoFs for several medium-sized molecules, namely 216.6 ± 1.4 for fulvene, 375.5 ± 1.5 for pentalene, 670.8 ± 2.9 for acepentalene, and 262.7 ± 2.5 for acenaphthylene. We combine the energies of the small fullerenes and previously obtained energies for larger fullerenes (from C60 to C6000) into a full picture of fullerene thermochemical stability. In general, the per-carbon energies can be reasonably approximated by the "R+D" model that we have previously developed [Chan et al. J. Chem. Theory Comput. 2019, 15, 1255-1264], which takes into account Resonance and structural Deformation factors. In a case study on C54, we find that most of the high-deformation-energy atoms correspond to the sites of the C-Cl bond in the experimentally captured C54Cl8. In another case study, we find that C60 has the lowest value for the maximum local-deformation energy when compared with similar-sized fullerenes, which is consistent with its "special stability". These results are indicative of structural deformation playing an important role in the reactivity of fullerenes.