Fullerene Adducts Research Articles

Two-dimensional Fullerene-Based Ferroelectric Materials: Assembly and Effects on Charge Carrier Lifetime.

Manipulating the symmetry of fullerene-based low-dimensional materials is crucial to the development of electronic devices and modern nonvolatile memories. However, there have been few reports on studying the physicochemical properties of fullerene and its derivatives by controlling the symmetries. Herein, we demonstrate ferroelectricity in Sc3N@Ih-C80-Pd/Pt adducts with relatively strong spontaneous polarization. Polarization originates from subtle molecular interactions between Sc3N@Ih-C80 and Pd/Pt atoms, breaking the structural symmetry. Additionally, we investigate how a temperature-dependent polar-nonpolar phase transition affects the corresponding nonadiabatic electron-hole recombination process in the ferroelectric fullerene adduct Sc3N@Ih-C80-Pd. The results indicate that polarization has a greater impact than temperature effects, resulting in an extension of the carrier lifetime in the polar phase by over 3 times compared to that in the nonpolar phase. Our findings unveil new members of the ferroelectric fullerene family and provide guidance for improving the performance of optoelectronic materials.

C60–bicyclo[2.2.1]heptanes: new hybrid mono- and hexakis-adducts of the C60 fullerene

New fullerene derivatives keep attracting attention of chemists due to their possible applications. Fullerene adducts with saturated polycyclic hydrocarbons represent one of the promising classes of fullerene compounds but still have rare examples. To enhance molecular diversity of fullerene derivatives in this direction, we have synthesized the representatives of C60–bicyclo[2.2.1]heptanes. For this purpose, we first produced the unsubstituted organic hydrazones from various bicyclo[2.2.1]heptane derivatives and then used the organic precursors in the reactions with C60. New homofullerenes and methanofullerenes with one bicyclo[2.2.1]heptane fragment have been obtained under metal-complex catalysis conditions at the fullerene C60:hydrazone molar ratio equal to 1:1.5. If fullerene C60:hydrazone ratio was 1:10, homofullerenes with six bicyclo[2.2.1]heptane fragments were synthesized, which can be isomerized into methanofullerenes when boiling in o-dichlorobenzene.

Metabolite responses of cucumber on copper toxicity in presence of fullerene C60 derivatives

Copper (Cu) toxicity in crops is a result of excessive release of Cu into environment. Little is known about mitigation of Cu toxicity through the application of carbon-based nanomaterials including water-soluble fullerene C60 derivatives. Two derivatives of fullerene were examined: polyhydroxylated C60 (fullerenol) and arginine C60 derivative. In order to study the response of Cu-stressed plants (Cucumis sativus L.) to these nanomaterials, metabolomics analysis by gas chromatography-mass spectrometry (GC-MS) was performed. Excess Cu (15 μM) caused substantial increase in xylem sap Cu, retarded dry biomass and leaf chlorosis of hydroponically grown cucumber. In Cu-stressed leaves, metabolomes was disturbed towards suppression metabolism of nitrogen (N) compounds and activation metabolism of hexoses. Also, upregulation of some metabolites involving in antioxidant defense system, such as ascorbic acid, tocopherol and ferulic acid, was occurred in Cu-stressed leaves. Hydroponically added fullerene adducts decreased the xylem sap Cu and alleviated Cu toxicity with effectiveness has been most pronounced for arginine C60 derivative. Metabolic responses of plants subjected to high Cu with fullerene derivatives were opposite to that observed under Cu alone. Fatty acids up-regulation (linolenic acid) and antioxidant molecules (tocopherol) down-regulation might indicate that arginine C60 adduct can alleviate Cu induced oxidative stress. Although fullerenol slightly improved cucumber growth, its effect on metabolic state of Cu-stressed plants was not statistically significant. We suggest that tested fullerene C60 adducts have a potential to prevent Cu toxicity in plants through a mechanism associated with their capability to restrict xylem transport of Cu from roots to shoot, and to maintain antioxidative properties of plants.

Protective action of water-soluble fullerene adducts on the example of an adduct with l-arginine

We present radioprotective, antiglycating, and photoprotective properties of a water-soluble C60 fullerene derivative with l-arginine (C60-Arg) and composite films based on collagen containing C60-Arg. The synthesis of these materials is described. The identification of the synthesised materials was carried out using modern physicochemical methods of analysis. The physicochemical properties of aqueous solutions of C60-Arg, such as, particle size distribution, zeta potentials, distribution coefficient in the octan-1-ol–water system were measured. The computer simulation of the process of C60-Arg association in aqueous and isotonic solutions was carried out using Molecular Dynamics. Composite films based on collagen containing C60-Arg demonstrate significant improvement in mechanical properties, cell adhesion, and cell proliferation when the nano-modifier is added. This shows high potential for the use of the C60-Arg adduct in biomedicine.

Discovery of Ferroelectricity in the Fullerene Adduct C60S8.

Fullerenes offer versatile functionalities and are promising materials for a widespread range of applications from biomedicine and energy to electronics. Great efforts have been made to manipulate the symmetries of fullerene and its derivatives for studying material properties and novel effects, such as ferroelectricity with polar symmetry; however, no documentary report has been obtained to realize their ferroelectricity. Here, for the first time, we demonstrated clear ferroelectricity in a fullerene adduct formed by C60 and S8. More is different: the combination of the most symmetric molecule C60 with the highest Ih symmetry and molecule S8 with high D4d symmetry resulted in the polar C60S8 adduct with a low crystallographic symmetry of the C2v (mm2) point group at room temperature. The presented C60S8 undergoes polar-to-polar ferroelectric phase transition with the mm2Fm notation, whose ferroelectricity was confirmed by a ferroelectric hysteresis loop and ferroelectric domain switching. This finding opens up a new functionality for fullerenes and sheds light on the exploration of more ferroelectric fullerenes.

Synthesis of hybrid molecules based on conjugated polycyclic hydrocarbons and С60 fullerene: application of thin films based on them in organic electronics

Hybrid molecules based on C60 fullerene and strained polycyclic hydrocarbons were synthesized for the first time using the Bingel-Hirsch reaction. Thin films based on the synthesized hybrid compounds were obtained, and the surface morphology of these films was studied. Based on thin films of С60 fullerene adducts containing fragments of conjugated polycyclic hydrocarbons, organic field-effect transistors were fabricated. The current-voltage characteristics of transistors were measured and the mobility of charge carriers was calculated.

Design, synthesis, and electrochemical studies of a new [60] fullerene pyrrolidine as a precursor for the construction of supramolecular systems

One of the challenges in fullerene chemistry is to prepare derivatives soluble in common solvents to study their chemical and physical properties in solution. In this context, a new highly soluble fullerene adduct was synthesized by the cycloaddition of a hydrazone-aldehyde derivative, which is prepared from the condensation of pyridincarboxaldehyde and pyridinhydrazine derivatives, and C60 in the presence of N-octyl glycine. The hydrazone derivative acting as a 1,3-dipole and [60] fullerene as a dipolarophile yielded adduct 7 with a 32% yield. The synthesized compounds were characterized by nuclear magnetic resonance (NMR) spectroscopy (1H, 13C, and COSY), elemental analysis, and mass spectrometry. The electronic properties of the fullerene adduct 7 were analyzed by UV-Vis spectroscopy in toluene and compared to those of [60]fullerene. The electrochemical properties of the fulleropyrrolidine were studied using cyclic and square wave voltammetry in tetrahydrofuran (THF) showing three reduction peaks at -1.11, -1.70, and -2.28 V, which are cathodically shifted when compared to [60]fullerene.

C60 adduct with L-arginine as a promising nanomaterial for treating cerebral ischemic stroke

The work aimed to investigate the biocompatibility and biological activity of the water-soluble fullerene adduct C60-Arg. It was found that the material is haemocompatible, is not cyto- and genotoxic, possesses pronounced antioxidant activity. Additionally, this paper outlines the direction of application of water-soluble fullerene adducts in the creation of neuroprotectors. It has been suggested that a putative mechanism of the protective action of the C60-Arg adduct is associated with its antioxidant properties, the ability to penetrate the blood-brain barrier, and release nitrogen monoxide as a result of the catabolism of L-arginine residues, which promote vascular relaxation. The action of the C60-Arg adduct was compared with the action of such an antioxidant as Edaravone, which is approved in Japan for the treatment of ischemic and haemorrhagic strokes.

Fullerene adducts from malonic esters of triethylene glycol and C60: electronic and electrochemical properties

In this work, dimeric and monomeric fullerene-C60 derivatives with triethylene glycol units were synthesised through the Bingel–Hirsch reaction and characterised with thermogravimetric analysis (TGA), Nuclear Magnetic Resonance (NMR) spectroscopy and Mass Spectrometry (MS) techniques. Also, the target compounds were studied from a physical chemistry perspective to investigate their photophysical and electrochemical properties using UV–Vis and fluorescence spectroscopy, Cyclic (CV), and Square Wave Voltammetry (SWV). All previous emphasised the aim to evaluate the features to be an electron transporting layer on perovskite solar cells (PSC), on this regard, both compounds exhibited good thermal stability and alignment of LUMO energy levels with MAPbBr3 as the perovskite semiconductor layer.

Decomposition of solid C60–indene adducts by retro Diels Alder reaction – A kinetic and thermodynamic study

Diels-Alder cycloaddition is a common synthetic approach to functionalize fullerenes. However, the stability of such fullerene adducts is hampered by the existence of the Retro Diels-Alder (RDA) reaction. Herein, the RDA reactions in the solid phase of the mono and bisadducts of C60 with indene, IC60MA and IC60BA, were studied by differential scanning calorimetry and thermogravimetric analysis. The RDA reaction in solid IC60MA occurs at a higher temperature than in IC60BA. IC60MA decomposition follows a first-order rate law and in IC60BA it is described by two consecutive first-order reaction steps. The decomposition of both adducts yields a metastable C60 solid. The higher decomposition temperature of IC60MA is due to higher activation energy, Ea, and lower pre-exponential factor, A. The values of Ea for the RDA reactions differ due to crystal packing efficiency in the solids. The measured A values were found to reflect the statistical weight of C60–Indene bonds that can be broken. A reaction mechanism was proposed for the decomposition of the fullerene adducts. The enthalpies of sublimation of IC60MA and IC60BA were estimated based on the enthalpies of their respective RDA reactions. Additionally, the heat capacities of the solid fullerenes (C60, IC60MA, and IC60BA), at T = 298.15 K, were measured by high-precision heat capacity drop calorimetry, indicating that the rotational motion of C60 in the crystal increases its expected heat capacity.

Balancing Attraction and Repulsion: The Influence of London Dispersion in [10]Cycloparaphenylene-Fullerene Complexes.

Herein we present a systematic study of the influence of different alkyl chains in malonyl ester fullerene adducts with [10]cycloparaphenylene ([10]CPP]) and a tert-butyl (tBu) ester-substituted [10]CPP analogue. The association constants between the nanoring hosts and the fullerene guests were determined by fluorescence quenching experiments. The trends in association were rationalized by an interplay of repulsion arising from an extended volume and London dispersion as an attractive counterpart.

Enantioselective fullerene functionalization through stereochemical information transfer from a self-assembled cage.

The regioselective functionalization of C60 remains challenging, while the enantioselective functionalization of C60 is difficult to explore due to the need for complex chiral tethers or arduous chromatography. Metal-organic cages have served as masks to effect the regioselective functionalization of C60. However, it is difficult to control the stereochemistry of the resulting fullerene adducts through this method. Here we report a means of defining up to six stereocentres on C60, achieving enantioselective fullerene functionalization. This method involves the use of a metal-organic cage built from a chiral formylpyridine. Fullerenes hosted within the cavity of the cage can be converted into a series of C60 adducts through chemo-, regio- and stereo-selective Diels-Alder reactions with the edges of the cage. The chiral formylpyridine ultimately dictates the stereochemistry of these chiral fullerene adducts without being incorporated into them. Such chiral fullerene adducts may become useful in devices requiring circularly polarized light manipulation.

Biocompatibility and biological activity of C70 fullerene adduct with L-threonine (C70(C4H9NO3)2)

The aim of this work is to synthesise and study the biocompatibility and biological activity of the C70 fullerene adduct with l-threonine (C70-Thr). The obtained adduct was identified using a complex of physicochemical methods, namely, 13C NMR spectroscopy, IR spectroscopy, thermogravimetric analysis, electron spectroscopy, elemental analysis, and high-performance liquid chromatography. The study of biocompatibility and biological activity of the C70-Thr adduct included the study of haemocompatibility (haemolysis, platelet aggregation, plasma coagulation haemostasis, binding to human serum albumin, esterase activity), antiradical activity, cytotoxicity, cell proliferation, and interaction with DNA (determination of the DNA binding constant and genotoxicity).

Adducts of Lower Fullerenes and Amino Acids: Synthesis, Identification, and Quantum-Mechanical Modeling of Their Physicochemical Properties

Different ways of synthesizing bis-, tris-, and octakis-adducts of C60 and C70 lower fullerenes are considered, and their yield and purity are described. The adducts are identified by physicochemical means: elemental analysis, IR, electron spectroscopy, Raman spectroscopy, HPLC, mass spectrometry, and complex thermal analysis. Their physicochemical properties are modeled using computers, density functional theory, and molecular dynamics at the atomic-molecular level.

Biocompatibility, antioxidant activity and collagen photoprotection properties of C60 fullerene adduct with L-methionine

Functionalization of the fullerene core with amino acids has become a new and promising direction in the field of nanochemistry. The biologic activity of water-soluble fullerene derivatives is based on such properties as lipophilicity, electron deficiency and photosensitivity. The complex of above-mentioned properties can be used to develop protection of biomolecules (in particular, proteins) from external physical and chemical influences. Thus, development and up-scaling of synthesis procedures, as well as investigation of the biological properties of these derivatives, are extremely important. This paper presents new data on the biocompatibility studies of C60 fullerene adduct with L-methionine (C60[C5H11NO2S]3; C60-Met). Antiradical activity, binding to human serum albumin (HSA), collagen and deoxyribonucleic acid (DNA), hemocompatibility, photodynamic properties, genotoxicity and cytotoxicity were studied. In addition, it was found that C60-Met increases the photostability of the collagen molecule, and this effect is dose-dependent.

Physicochemical Properties of Adducts of Light Fullerenes and Amino Acids

Physicochemical Properties of Adducts of Light Fullerenes and Amino Acids

Physicochemical investigation of water-soluble C60(C2NH4O2)4H4 (C60-Gly) adduct

The article presents a comprehensive physicochemical and biological study of water-soluble fullerene adduct with glycine. The investigation included density, speed of sound, and viscosity temperature and concentration data with subsequent calculation of thermodynamic characteristics; correlation of the obtained results using fourth-order polynomial; determination of associate sizes; measurements of isobaric heat capacity; binding to human serum albumin; antiradical activity in the reaction with 2,2-diphenyl-1-picrylhydrazyl radical.

In Vitro and In Silico Investigation of Water-Soluble Fullerenol C60(OH)24: Bioactivity and Biocompatibility.

Light fullerenes, C60 and C70, have significant potential in biomedical applications due to their ability to absorb reactive oxygen species, inhibit the development of tumors, inactivate viruses and bacteria, and as the basis for developing systems for targeted drug delivery. However, the hydrophobicity of individual fullerenes complicates their practical use; therefore, creating water-soluble derivatives of fullerenes is increasingly important. Currently, the most studied soluble adducts of fullerenes are polyhydroxy fullerenes or fullerenols. Unfortunately, investigations of fullerenol biocompatibility are fragmental. They often lack reproducibility both in the synthesis of the compounds and their biological action. We here investigate the biocompatibility of a well-defined fullerenol C60(OH)24 obtained using methods that minimize the content of impurities and quantitatively characterize the product's composition. We carry out comprehensive biochemical and biophysical investigations of C60(OH)24 that include photodynamic properties, cyto- and genotoxicity, hemocompatibility (spontaneous and photo-induced hemolysis, platelet aggregation), and the thermodynamic characteristics of C60(OH)24 binding to human serum albumin and DNA. The performed studies show good biocompatibility of fullerenol C60(OH)24, which makes it a promising object for potential use in biomedicine.

Emergence of dynamical disorder and phase metastability in carbon nanobowls

The condensed phases of the carbon-based nanobowl corannulene are herein investigated in the temperature range 200–573 K, combining differential scanning calorimetry, synchrotron X-ray diffraction, and quasielastic neutron-scattering. For the first time, we identify the presence of a well-defined thermal event at 382 K, a figure well below a melting point of 540 K. Contrary to naïve expectation, detailed analysis of the neutron-scattering data below and above this pre-melting transition signals the emergence of correlated stochastic dynamics within both thermodynamically stable solid phases of the material. We find that these are progressively responsible for the suppression of molecular and supramolecular order over mesoscopic length scales, and are associated with the formation of high-symmetry rotor-like states exhibiting localized stochastic motions. Upon cooling from the melt, we have also discovered a robust hysteresis associated with the existence of hitherto-unknown metastable liquid (deep-supercooled) and disordered-solid phases. This behaviour is markedly different from that observed in the quintessential Buckminsterfullerene C60 or other chemically substituted fullerene adducts studied to date at this level of detail. These results evince new and yet-to-tapped opportunities for the use of the stable and metastable phases of carbon-based nanobowls in novel applications exploiting the emergence of dynamical disorder at the nanoscale.

Synthesis of Fused Dihydroazepine Derivatives of Fullerenes by a Rh‐Catalyzed Cascade Process

AbstractA synthetic methodology is reported that functionalizes C60 and C70 fullerenes with dihydroazepine rings by a cascade reaction encompassing a rhodium‐catalyzed cycloisomerization of 1,5‐bisallenes and a [4+2] cycloaddition. This transition metal‐catalyzed cascade reaction provides a versatile and step‐economical approach to the synthesis of 6,7‐membered polyheterocyclic fullerene adducts. Electrochemical characterization of the products obtained ventures their application in organic and perovskite photovoltaic devices.magnified image