Fullerene Dimers Research Articles

Formation of Doubly and Triply Charged Fullerene Dimers in Superfluid Helium Nanodroplets.

Sequential ionization of fullerene cluster ions (C_{60})_{n}^{+} within multiply charged helium nanodroplets leads to the intriguing phenomenon of forming and stabilizing doubly and triply charged fullerene oligomers. While the formation of doubly charged dimers (C_{60})_{2}^{2+} has been predicted in earlier studies, the observation of even triply charged ones (C_{60})_{2}^{3+} is highly surprising. This remarkable resilience against Coulomb explosion is achieved through efficient cooling within the superfluid environment of helium nanodroplets and a sequential ionization scheme that populates covalently bound or physisorbed fullerene dimers. Calculations support the stability of four differently bonded (C_{60})_{2}^{2+} and (C_{60})_{2}^{3+} isomers and predict a low Coulomb barrier (<0.4 eV) preventing even dissociation of cold van der Waals complexes.

Solution Dynamics of Covalent Open-[60]Fullerene Dimers.

The translational diffusivity of covalent open-[60]fullerene dimers in an organic solvent was found to be well describable by a prolate ellipsoid model while a monomeric open-[60]fullerene behaves like a sphere model. The water association dynamics were examined for two open-[60]fullerene dimers, showing a higher water affinity for the sp3-linked dimer relative to sp2-linked dimer owing to an effective orbital-orbital overlap identified by π(fullerene)→σ*(H2O) interactions as suggested by theoretical calculations.

Thermal transport in fullerene-based molecular junctions: molecular dynamics simulations

We investigate phonon thermal transport of fullerene-based single-molecule junctions by employing classical molecular dynamics (MD) simulations. We compute the thermal conductances of C60 fullerene monomers, dimers, and trimers utilizing three distinct MD methods. We observe the equilibration dynamics in one approach, and employ two other nonequilibrium steady state simulation methods. We discuss technical aspects of each simulation technique, and show that their predictions for the thermal conductance agree. Our simulations reveal that while the thermal conductance of fullerene monomer and dimer junctions remains similar, that of trimer junctions experiences a significant reduction. This study could assist in the design of high-performing thermoelectric junctions, where low thermal conductance is desired.

Phosphine-Mediated Dimerization of Open-[60]Fullerenes.

By a reaction of trimethylphosphine with an open-[60]fullerene, corresponding dimers could be generated via two-fold deoxygenation processes even though the formation of β-oxo-phosphorous ylide is inevitable, a part of which is hydrolyzed to yield an α-methylene carbonyl derivative. Nevertheless, Wittig reaction and aldol condensation did not proceed well, indicating the presence of an unknown dimerization pathway. In the ylide formation, 1-phosphonium-3-carbabetaine was previously proposed as a key intermediate. Upon assuming that the betaine also participates in the dimerization process, we examined a possible reaction pathway computationally. As the results, the betaine formed by a reaction with the first phosphine was suggested to undergo nucleophilic addition to an unreacted molecule of the open-[60]fullerene, yielding an epoxide dimer which is then deoxygenated by the second phosphine to furnish the desired open-[60]fullerene dimer.

Electron-beam-promoted fullerene dimerization in nanotubes: insights from DFT computations.

Fullerene dimerization inside a peapod is analyzed at DFT level by characterizing the stationary points and deriving the energy profile of the initial and reversible process named phase 1. We find that the barriers for the radical cation mechanism are significantly lower than those found for the neutral pathway. The peapod is mainly providing one-dimensional confinement for the reaction to take place in a more efficient way. Car-Parrinello metadynamics simulations provide hints on structures for the initial steps of the irreversible phase 2 where bond formation and breaking lead to important structural reorganizations within the coalescence process.

Unexpected and divergent mechanosynthesis of furanoid-bridged fullerene dimers C120O and C120O2.

An unexpected, divergent and efficient approach toward furanoid-bridged fullerene dimers C120O and C120O2 was established under different solvent-free ball-milling conditions by simply using pristine C60 as the starting material, water as the oxygen source and FeCl3 as the mediator. The structures of C120O and C120O2 were unambiguously established by single-crystal X-ray crystallography. A plausible reaction mechanism is proposed on the basis of control experiments. Furthermore, C120O2 has been applied in organic solar cells as the third component and exhibits good performance.

Push–pull substituent design of fullerene dimer at the buried interface toward stable and efficient perovskite solar cells

Push–pull substituent design of fullerene dimer at the buried interface toward stable and efficient perovskite solar cells

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.

(Ro)vibrational Spectroscopic Constants, Lifetime and QTAIM Evaluation of Fullerene Dimers Stability.

The iconic caged shape of fullerenes gives rise to a series of unique chemical and physical properties; hence a deeper understanding of the attractive and repulsive forces between two buckyballs can bring detrimental information about the structural stability of such complexes, providing significant data applicable for several studies. The potential energy curves for the interaction of multiple van der Waals buckyball complexes with increasing mass were theoretically obtained within the DFT framework at ωB97xD/6-31G(d) compound model. These potential energy curves were employed to estimate the spectroscopic constants and the lifetime of the fullerene complexes with the Discrete Variable Representation and with the Dunham approaches. It was revealed that both methods are compatible in determining the rovibrational structure of the dimers and that they are genuinely stable, i.e., long-lived complexes. To further inquire into the nature of such interaction, Bader's QTAIM approach was applied. QTAIM descriptors indicate that the interactions of these closed-shell systems are dominated by weak van der Waals forces. This non-covalent interaction character was confirmed by the RDG analysis scheme. Indirectly, QTAIM also allowed us to confirm the stability of the non-covalent bonded fullerene dimers. Our lifetime calculations have shown that the studied dimers are stable for more than 1 ps, which increases accordingly with the number of carbon atoms.

Synthesis of pendant fullerene dimers by an aminomethylation reaction of fulleropyrrolidines bearing ketone moieties.

An aminomethylation reaction of fulleropyrrolidines bearing ketone moieties in the presence of N-unsubstituted fulleropyrrolidines and paraformaldehyde with the aid of p-toluenesulfonic acid afforded a series of scarce pendant fullerene dimers. A simple change of reaction substrates from ketone to ketone-containing fulleropyrrolidines successfully realized the synthesis of a variety of novel pendant fullerene dimers, including those from methyl ketone-containing fulleropyrrolidines, which were considered to produce the known bridged fullerene dimers. It should be noted that pendant fullerene dimers are usually difficult to prepare by other methods and may have promising applications in perovskite solar cells. Density functional theory (DFT) has been employed to elucidate the regioselectivity of methyl ketone-containing fulleropyrrolidines to yield exclusively pendant fullerene dimers by investigating the Gibbs free energy profile of the reaction starting from methyl ketone-containing fulleropyrrolidines and iminium intermediates.

Fullerenols Prevent Neuron Death and Reduce Oxidative Stress in Drosophila Huntington's Disease Model.

Huntington's disease (HD) is one of the human neurodegenerative diseases for which there is no effective treatment. Therefore, there is a strong demand for a novel neuroprotective agent that can alleviate its course. Fullerene derivatives are considered to be such agents; however, they need to be comprehensively investigated in model organisms. In this work, neuroprotective activity of C60(OH)30 and C120O(OH)44 fullerenols was analyzed for the first time in a Drosophila transgenic model of HD. Lifespan, behavior, oxidative stress level and age-related neurodegeneration were assessed in flies with the pathogenic Huntingtin protein expression in nerve cells. Feed supplementation with hydroxylated C60 fullerene and C120O dimer oxide molecules was shown to diminish the oxidative stress level and neurodegenerative processes in the flies' brains. Thus, fullerenes displayed neuroprotective activity in this model.

Investigating the Role of Cathode Buffer Layers Based on Zinc Oxide with Surface‐Rich Graded Fullerene Isomers in Tuning the Interfacial Properties of Organic Solar Cells

In organic solar cells (OSCs), improving the properties at the interface of the bulk heterojunction (BHJ) photoactive layer and the buffer layer is desired, but achieving a high‐quality interface between these two layers is inevitably challenging. Herein, a novel (PC61BM)‐doped zinc oxide, that is, a (PC61BM‐ZnO)DEZ hybrid thin film, is proposed for application as a cathode buffer layer (CBL) for OSCs based on both fullerene‐based acceptors and nonfullerene acceptors. These thin films require low annealing temperatures and can be deposited via a one‐step solution‐processable method using a hybrid precursor composed of PC61BM and diethylzinc solution (DEZ). The study reveals that the performance of devices with (PC61BM‐ZnO)DEZ hybrid thin films as a CBL exceeds that of devices with thin films of conventional ZnO as a CBL. Impedance analysis of the fabricated OSCs suggests improved charge collection efficiency in the devices with (PC61BM‐ZnO)DEZ thin film. Optical, electrical, morphological, and compositional characterizations of thin films used as CBLs confirm the presence of a PC61BM‐rich phase with traces of d‐C61 (fullerene dimer) at the surface of the hybrid (PC61BM‐ZnO)DEZ thin film. These phases help in tuning the interfacial properties by ensuring better coupling between the BHJ photoactive layer and the CBL.

Rational Design of a Low-Dimensional and Metal-free Heterostructure for Efficient Water Oxidation: DFT and Experimental Studies.

A nitrogen-doped fullerene dimer is synthesized and compounded with multi-walled carbon nanotubes (MWCNTs) to construct a low-dimensional and metal-free 0D-1D heterostructure for electrocatalytic water oxidation. The (C59N)2/MWCNTs heterostructure exhibits a highly efficient performance, as verified by both first-principles density functional theory and experimental studies. The *O → *OOH process is confirmed as the rate-determining step of water oxidation. The negatively charged N-doping leads to electronic redistribution and intermolecular charge transfer and thus reduces the uphill free energies of intermediates on the (C59N)2/MWCNTs interface. Therefore, the (C59N)2/MWCNTs heterostructure has great potential to emit light and heat in metal-free-based electrocatalytic water oxidation.

Interface engineering for achieving efficient and stable perovskite solar cells by Bphen-fullerene dimer

The design and synthesis of interface engineering materials with high superficial passivation and electron extraction performance is an effective strategy to improve the efficiency and long-time stability of perovskite solar cells (PSCs). Herein, a novel fullerene dimer, namely, 2C60-Bphen, is prepared by Prato reaction with a high yield and is first used to be an interface-modified material for PSCs. To passivate the surface defects of perovskite films and improve the interface contact the interface modification layer was introduced. 2C60-Bphen with two carbon cages can reduce the self-polymerization of phenanthroline molecules. The well-matched energy levels between 2C60-Bphen and perovskite and the high electron mobility of 2C60-Bphen are beneficial to the electron extraction and transportation of efficient PSCs. PSC achieves the highest photoelectric conversion efficiency of 20.24% when using 2C60-Bphen as the interface layer, and it can still maintain 85% efficiency after 500 h storage under environmental conditions. These results indicate that 2C60-Bphen has the potential to be used as interface material for high-performance PSCs.

Excited state modulation of C70 dimerization in a carbon nanotube under a variable electron acceleration voltage

Cinematographic recording of chemical reactions with transmission electron microscopy provides information unavailable by any other analytical methods. Studies have thus far remained mostly phenomenological, lacking information on the reactive species involved. To gain insight into the nature of the reactive species, we need to obtain kinetic information under various temperatures and variable acceleration voltages, i.e., electronic energy supply. We studied the mechanism of [2 + 2] dimerization of [70] fullerene in a carbon nanotube as an example. We describe herein a statistical analysis of individual reaction events of the dimerization that revealed dose-dependent first-order kinetics and voltage-dependent crossover from a singlet to a triplet mechanism, as highlighted by the pre-exponential factor (the frequency of excitation) that is a million times larger for the singlet reaction than for the triplet one. Comparison with the results of a recent study of [60] fullerene dimerization lets us propose that electron-impact excitation of the carbon nanotube is the first step, followed by energy transfer to fullerene molecules and their dimerization via an excited state. The results show that a variable-voltage kinetic study is indispensable for discussing the mechanism of chemical transformations under electron microscopic observation.

Studying the possibility of using fullerenes inside carbon nanotubes as a molecular engine

A simple model of a molecular engine is proposed, which consists of a fullerene dimer with a charge and a carbon nanotube. Calculations of molecular dynamics have been carried out, which help to estimate the efficiency of fullerene dimers as a molecular rotor. A dimer placed inside a carbon nanotube will move along the axis of the nanotube, but at the same time it needs to be given a lot of energy in order for it to leave it. The ability of molecules to move along a container is studied mechanically.

Relationship between molecular properties and degradation mechanisms of organic solar cells based on bis-adducts of phenyl-C61 butyric acid methyl ester.

Environmental stability remains a major challenge for the commercialisation of organic solar cells and degradation pathways remain poorly understood. Designing materials for improved device stability requires an understanding of the relationship between the properties of the donor or acceptor molecule and different degradation mechanisms. Here we study the correlations between various molecular parameters of the fullerene derivative bis-PCBM and the degradation rate of polymer:bis-PCBM organic solar cells, based on the same carbazole-alt-benzothiadiazole polymer, in aerobic and anaerobic conditions. We compare eight high purity bis-PCBM isomers with different electronic, chemical and packing properties along with PCBM and the mixture of bis isomers. In the case of aerobic photodegradation, we find that device degradation rate is positively correlated to the LUMO energy of the bis-PCBM isomer and to the degree of crystallinity of the isomer, while the correlation of degradation with driving force for epoxide formation is unclear. These results support the idea that in these samples, aerobic photodegradation proceeds via superoxide formation by the photogenerated polaron on the fullerene, followed by further chemical reaction. In the absence of air, photodegradation rate is correlated with molecular structure, supporting the mechanism of microstructural degradation via fullerene dimerization. The approach and findings presented here show how control of specific molecular parameters through chemical design can serve as a strategy to enhance stability of organic solar cells.

Covalently Bonded Fullerene Nano-Aggregates (C60)n: Digitalizing Their Energy–Topology–Symmetry

Fullerene dimers and oligomers are attractive molecular objects with an intermediate position between the molecules and nanostructures. Due to the size, computationally assessing their structures and molecular properties is challenging, as it currently requires high-cost quantum chemical techniques. In this work, we have jointly studied energies, topological (Wiener indices and roundness), and information theoretic (information entropy) descriptors, and have obtained regularities in triad ‘energy–topology–symmetry’. We have found that the topological indices are convenient to indicating the most and least reactive atoms of the fullerene dimer structures, whereas information entropy is more suitable to evaluate odd–even effects on the symmetry of (C60)n. Quantum chemically assessed stabilities of selected C120 structures, as well as linear and zigzag (C60)n, are discussed.

Synthesis and Electrochemistry of Novel Dumbbell-Shaped Bis-pyrazolino[60]fullerene Derivatives Formed Using Microwave Radiation.

The design of covalently linked [60]fullerene dimers has gained increased attention, as the linked electron donors or acceptors are in close proximity to the surface of the C60, providing a valuable approach to novel molecular electronic devices. Herein, new compounds involving C60 dumbbells covalently connected by the π-conjugated system from azobenzene and diaryl ether linkers were synthesized following the bifunctional cycloaddition reactions to C60 using microwave radiation. The structural identity of the fullerene dimers has been determined using spectroscopic techniques including Fourier transform infrared (FT-IR), matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF), and NMR spectroscopy, and the photophysical and the electrochemical properties for the new dumbbells have been examined using UV–vis spectroscopy, fluorescence spectroscopy, cyclic voltammetry, and square wave voltammetry. Both new dimers show electronic interaction with the fullerene cage and higher electron affinity than the pristine C60.

(Invited) Structural Studies of Open-Cage Fullerenes

Open-cage fullerenes, fullerenes with orifices created by breaking some of the C-C bonds in a fullerene such as C60, are molecules that allow chemical access to both the external and the internal surfaces of the carbon cage. We have found such molecules to be challenging to crystallize and thereby fully structurally characterize through single crystal X-ray diffraction studies. We have also found that the reactivity of these open cage fullerenes can differ significantly from that of the parent fullerene (see A. Aghabali, S. Jun, M. M. Olmstead, A. L. Balch, Silver(I)-Mediated Modification, Dimerization, and Polymerization of an Open-Cage Fullerene. J. Am. Chem. Soc. 2016, 138, 16459-16465.) This talk will report recent studies of the crystallographically determined structures and reactivities of several open-cage fullerenes with particular attention given to the accessibility of the cage opening to chemical reactions.