Single molecular orientation switching of an endohedral metallofullerene

The single molecular orientation switching of the Tb@C82 endohedral metallofullerene has been studied by using low-temperature ultrahigh vacuum (UHV) scanning tunneling microscopy (STM). An octanethiol self-assembled monolayer (SAM) was introduced between Tb@C82 and the Au111 substrate to control the thermal rotational states of Tb@C82. Scanning tunneling spectroscopy (STS) of Tb@C82 on an octanethiol SAM at 13 K demonstrated hysteresis including negative differential conductance (NDC). This observed hysteresis and NDC is interpreted in terms of a switching of the Tb@C82 molecular orientation caused by the interaction between its electric dipole moment and an external electric field.     

Interaction between fullerenes and single-wall carbon nanotubes: the influence of fullerene size and electronic structure

A series of fullerenes and endohedral metallofullerenes peapods have been synthesized by supercritical method in high filling rate. The interaction between SWNTs and various kinds of fullerenes (C60, C70, C78, C84) and metallofullerenes (Gd@C82, Er@C82, Ho@C82, Y@C82) has been further investigated. The slight blue shift of G-band in Raman spectra with respect to pristine SWNTs was attributed to the charge transfer from SWNTs to fullerenes cage. The obvious RBM shift strongly depended on the distance between the inner wall of the SWNTs and the fullerene cage and also partly associated with the electronic structure of the fullerene. These results indicated that the interaction between fullerenes and SWNTs, which was considered to be the van de walls interaction, can be influenced by the cage size and the kind of fullerenes.     

Quantitative analysis of endohedral metallofullerenes by Rutherford backscattering of protons

Samples containing endohedral metallofullerenes of gadolinium (Gd@C₈₂) and dysprosium (Dy@C₈₂) are investigated by the Rutherford backscattering of protons. It is shown that the concentration of endohedral metallofullerenes can be determined to within a few percent. The measured concentration of endohedral metallofullerenes Gd@C₈₂ and Dy@C₈₂ in samples prepared by selective multistep extraction is ∼60%. Pis’ma Zh. Tekh. Fiz. 25, 24–30 (May 26, 1999)     

Noble metal nanoparticles deposited on self-assembled monolayers by pulsed laser deposition show coulomb blockade at room temperature

Nanometer-sized noble-metal clusters are fabricated on top of alkylthiolate self-assembled monolayers (SAMs) on annealed gold by pulsed laser deposition at elevated pressures. The size distribution of the clusters depends on the metal and on the pressure during the deposition. Scanning tunneling microscopy (STM) and conductive probe atomic force microscopy (CP-AFM) showed that the metal clusters are insulated from the substrate on top of the SAM. Coulomb blockades could be measured at room temperature by STM for palladium clusters on decanethiol SAMs.     

Unique ordered domains of biphenylthiol self-assembled monolayers on Au(111)

The surface structure and adsorption conditions of biphenylthiol (BPT) self-assembled monolayers (SAMs) on Au(111) were examined using scanning tunneling microscopy (STM) and X-ray photoelectron microscopy (XPS). STM imaging revealed that the structural order of BPT SAMs formed in a 0.01 mM ethanol solution at 60 degrees C decreases with increasing immersion time. Interestingly, BPT SAMs formed after 30 min have unique ordered domains containing well-ordered (square root of 3 x square root of 3)R30 degrees structures and bright rows that are connected by small aggregated domains with a periodicity of approximately 10 angstroms, results that have never been observed for other thiol SAM systems. Distances between the bright rows were 20-35 angstroms. The bright small domains contained five or six BPT molecules each, which may have originated from differences in the adsorption orientations of biphenyl groups that were induced by localized interactions between them. XPS measurements for BPT SAMs on Au(111) showed the two sulfur peaks at 161.2 and 162.2 eV, implying the formation of chemisorbed monolayers. Our results are anticipated to be useful for understanding the formation and structure of BPT SAMs on gold surfaces.     

ISOLATION AND SPECTROSCOPIC STUDY OF A SERIES OF MONOTERBIUM ENDOHEDRAL METALLOFULLERENES

A series of monoterbium endohedral metallofullerenes Tb@C₈₀, Tb@C₈₆, and the second isomer of Tb@C₈₂ (II) has been produced and isolated from various hollow fullerenes and endohedral metallofullerenes by an efficient multi-stage chromatographic separation process for the first time. All these newly isolated metallofullerenes are characterized by laser-desorption time-of-flight (LD-TOF) mass spectrometry and UV-Vis-NIR absorption spectroscopy. Their possible molecular symmetries are discussed according to their HPLC retention time and absorption spectra.     

ISOLATION AND SPECTROSCOPIC STUDY OF A SERIES OF MONOTERBIUM ENDOHEDRAL METALLOFULLERENES

ABSTRACT

A series of monoterbium endohedral metallofullerenes Tb@C₈₀, Tb@C₈₆, and the second isomer of Tb@C₈₂ (II) has been produced and isolated from various hollow fullerenes and endohedral metallofullerenes by an efficient multi-stage chromatographic separation process for the first time. All these newly isolated metallofullerenes are characterized by laser-desorption time-of-flight (LD-TOF) mass spectrometry and UV-Vis-NIR absorption spectroscopy. Their possible molecular symmetries are discussed according to their HPLC retention time and absorption spectra.     

Golden interfaces: The Surface of Self-Assembled Monolayers

Self-assembled monolayers (SAMs) of alkanethiols and disulfides on gold form organic interfaces with properties largely controlled by the end groups of the molecules composing the film. SAMs provide a unique link between the science of organic surfaces and technologies that seek to exploit their adaptable character. Many techniques are useful for probing the structure of SAMs although only scanning tunneling microscopy (STM) at picoamperes reveals the details of the packing of their end groups at the sub-angstrom level. This review demonstrates that STM effectively tests new types of control over the microscopic structure–property relationships characteristic of SAMs on gold that should prove useful to their application.     

Assembly behavior and monolayer characteristics of OH-terminated alkanethiol on Au(111): in situ scanning tunneling microscopy and electrochemical studies

Self-assembled monolayers (SAMs) of 6-mercapto-1-hexanol (MHO) on an Au(111) electrode were prepared in an electrochemical system. The adsorption behavior of MHO and the time-dependent organization of the SAM were investigated by in situ scanning tunneling microscopy (STM) and cyclic voltammetry (CV). The results show that a potential higher than 0.28?V (relative to RHE) is required to induce the adsorption of MHO. At 0.28?V, the MHO molecules adsorb in a flat-lying orientation, forming an ordered striped phase with a molecular arrangement of ([Formula: see text]). However, the adlayer is not stable at this potential. The adsorbed striped phase may recover to the herringbone feature of the gold substrate due to the desorption of adsorbed MHO. At a higher potential (0.35?V), the adlayer becomes stable and can undergo a phase evolution from the striped phase to a condensed structure, identified as c([Formula: see text]). This structure can also be described as a c(4 × 2) superlattice of a [Formula: see text] hexagonal adlattice. The surface coverage of the MHO SAM is identical to the saturated structure of an 11-mercapto-1-undecanol (MUO) SAM reported in a previous work, [Formula: see text]. However, the STM image of MHO adlayer shows a modulation in intensity, reflecting the presence of various conformations of adsorbed molecules. This result is attributed to the shorter chain length of MHO, which gives a weaker?van der Waals interaction between adsorbed molecules. This effect also results in a higher charge permeability across the adlayer and a lower striping potential to an MHO SAM.     

Gas Phase Derivations of Endohedral Metallofullerenes by Ion-Molecular Reactions

Gas phase ion-molecular reactions of endohedral metallofullerenes with the self-chemical ionization ion system of vinyl acetate, benzene and acetone in the ion source of the mass spectrometer have been studied. Several derivatized endohedral metallofullerene cations [M@C₈₂-C₂H₃O]⁺, [M₂@C₈₀-C₂H₃O]⁺, [M@C₈₂-C₆H₆]⁺ and [M@C₈₂-CO-CH₃]⁺ are observed as the major products. The experimental results indicate that endohedral metallofullerenes have active gas phase reactivities and can be efficiently derivatized by some small organic cations.     

Biomedical activities of endohedral metallofullerene optimized for nanopharmaceutics

Endohedral metallofullerenes, a novel form of carbon-related nanomaterials, currently attract wide attention for their potential applications in biomedical fields such as therapeutic medicine. Most endohedral metallofullerenes are synthesized using C60 or higher molecular weight fullerenes because of the limited interior volume of fullerene. It is known that the encapsulated metal atom has strong electronic interactions with the carbon cage in metallofullerenes. Gd@C82 is one of the most important molecules in the metallofullerene family, known as Magnetic Resonance Imaging (MRI) contrast agent candidate for diagnostic imaging. Gadolinium endohedral metallofullerenol (e.g., Gd@C82(OH)22) is a functionalized fullerene with gadolinium trapped inside carbon cage. Our group previously demonstrated that the distinctive chemical and physical properties of Gd@C82(OH)22 are dependent on the number and position of the hydroxyl groups on the fullerene cage. The present article summarizes our latest findings of biomedical effects of Gd@C82(OH)22 and gives rise to a connected flow of the existing knowledge and information from experts in the field. It briefly narrates the synthesis and physico-chemical properties of Gd@C82(OH)22. The polyhydroxylated nanoparticles exhibit the enhanced water solubility and high purity, and were tested as a MRI contrast agent. Gd@C82(OH)22 treatment inhibited tumor growth in tumor-bearing nude mice. Although the precise mechanisms of this action are not well defined, our in vitro data suggest involvements of improved immunity and antioxidation by Gd@C82(OH)22 and its size-based selective targeting to tumor site. The review critically analyzed the relevant data instead of fact-listing, and explained the potential for developing Gd@C82(OH)22 into a diagnostic or therapeutic agent.     

A Review on Endohedral Metallofullerenes: Structures and Properties

The present review deals with some recent results on endohedral metallofullerenes obtained by the Nagoya group. The present structural analyses reveal unique of endohedoral metallofullerenes: (1) the presence of structural isomers with different fullerene cage structures; (2) encaged metal atoms are situated close to the carbon cage and not in the center of the cage; (3) metal atoms in Y@C82 and Sc2@C84 are at a standstill, not moving around, even at room temperature.     

Electron‐Induced Dynamics of Heptathioether β‐Cyclodextrin Molecules

Variable‐temperature scanning tunneling microscopy (STM) and spectroscopy (STS) measurements are performed on heptathioether β‐cyclodextrin (β‐CD) self‐assembled monolayers (SAMs) on Au. The β‐CD molecules exhibit very rich dynamical behavior, which is not apparent in ensemble‐averaged studies. The dynamics are reflected in the tunneling current–time traces, which are recorded with the STM feedback loop disabled. The dynamics are temperature independent, but increase with increasing tunneling current and sample bias, thus indicating that the conformational changes of the β‐CD molecules are induced by electrons that tunnel inelastically. Even for sample biases as low as 10 mV, well‐defined levels are observed in the tunneling current–time traces. These jumps are attributed to the excitations of the molecular vibration of the macrocyclic β‐CD molecule. The results are of great importance for a proper understanding of transport measurements in SAMs.     

Intramolecular Electron Transfers in Donor/Acceptor Linked Molecules Based on Endohedral Lanthanide Metallofullerenes

Chemical syntheses and intramolecular electron transferring behaviors in the electron donor/acceptor conjugates based on endohedral metallofullerenes, La₂@C₈₀ and La@C₈₂, are overviewed. A study on the photo-induced excited states of a La₂@C₈₀ derivative connected with an electron donor revealed the formation of a distinct radical ion pair state. A La@C₈₂ derivative linked with an electron donor demonstrated an unprecedented ion/anion pair state, and La₂@C₈₀ tethered with an acceptor showed a fullerene donor system, in which the fullerene acts as an electron donor. Using endohedral lanthanide metallofullerenes for intramolecular electron transferring systems opens a new door for developing novel molecular materials.     

An alkyl spacer effect on the structure of 4-fluorobenzenethiol and 4-fluorobenzenemethanethiol self-assembled monolayers on Au(111)

Self-assembled monolayers (SAMs) formed by the adsorption of 4-fluorobenzenethiol (4-FBT) and 4-fluorobenzenemethanethiol (4-FBMT) on Au(111) were examined by scanning tunneling microscopy (STM) to understand the effect of a flexible methylene spacer between the sulfur head-group and phenyl group and the effect of solution temperature on the formation and structure of the SAMs. Although the adsorption of 4-FBT on Au(111) at room temperature for 24 h generated only disordered phase SAMs containing gold adatom islands, 4-FBT at 75 degrees C for 2 h formed mixed SAMs: disordered phases and ordered (2 x 12√(2))R10 degrees superlattice with a rectangular unit cell containing six adsorbed molecules. On the other hand, SAMs formed from 4-FBMT, with a methylene spacer, at room temperature for 24 h on Au(111) had irregularly ordered phases containing uniformly distributed VIs with lateral dimensions of 2-5 nm; SAMs formed from 4-FBMT at 75 degrees C for 2 h were composed of slightly improved ordered phases and larger VIs with lateral dimensions of 5-12 nm as a result of Ostwald ripening. From this study, we found that the methylene spacer plays an important role in controlling the structure of SAMs formed from p-substituted fluorinated aromatic thiols.     

Polypyrrole-modified tips for functional group recognition in scanning tunneling microscopy

Tailored chemical modification of scanning tunneling microscopy (STM) tips is a promising method for the recognition of specific chemical species and functional groups in STM images. The present study shows for the first time that tips modified with polypyrrole can be used to measure STM images with molecular resolution. A high conductivity of the polypyrrole film was found to be important for the observation of STM images, while the thickness of the polymer film did not affect the images significantly. Furthermore, it was shown that recognition of functional groups in STM images is possible with tips coated with conductive polypyrroles. 1-Octadecanol and 1-octadecanoic acid monolayers with polypyrrole-modified tips gave high-resolution STM images in which aligned OH and COOH residues were represented by easily recognizable elevated bands. These selective contrast enhancements resemble those observed by us previously with gold tips modified with self-assembled monolayers (SAMs) and seem to be due to hydrogen bond interactions between functional groups of the tip-modifying molecules and the sample. The reproducibility of contrast enhancements in this study was significantly higher than for SAM-modified tips, suggesting that polymer modification of STM tips is particularly promising for specific functional group recognition with chemically modified STM tips.     

Long-range order induced by cobalt porphyrin adsorption on aminothiophenol-functionalized Au(111): the influence of the induced dipole

Porphyrins are useful in materials science for optical, photoelectrochemical and chemical sensor applications. Solid films of oriented porphyrins on gold can be realized through a simple procedure and without synthesizing thiol-derivatized porphyrins. In order to immobilize the porphyrin rings on the surface, we prepared a 4-aminothiophenol (4-ATP) self-assembled monolayer (SAM) on gold(111) followed by axial legation, in situ, of cobalt(II) 5,10,15,20-tetrakis(4-tert-butylphenyl)-porphyrin (CoTBPP). Ultrahigh vacuum (UHV) Scanning Tunneling Microscopy (STM) studies performed on the SAMs revealed the Au(111) herringbone structure reconstruction, probably due to adsorption/desorption processes of molecules. STM images and Scanning Tunneling Spectroscopy (STS) measurements clearly showed that the immobilization of molecules also induced an electronic perturbation on the gold surface. This effect is ascribed to the presence of oriented molecular dipole layers between the metal and the organic material.     

Controlled synthesis of fullerenes and endohedral metallofullerenes in high frequency arc discharge

The article presents the high-frequency arc discharge setup operating in helium atmosphere and applicable for the syntheses of carbon condensate with different dispersion and structure, along with fullerenes and endohedral metallofullerenes. It also highlights how the change of helium pressure in chamber can control the amount and composition of products in carbon condensate. The setup can be applied for the purposes of analysis, for instance in order to obtain information about the process of fullerenes and endohedral met-allofullerenes formation. Also, the fact that the yield of higher fullerenes is increasing with the pressure rise, whereas the yield of endohedral metallofullerenes is decreasing suggests different formation mechanisms.     

Molecular-scale investigation of tolane disulfide self-assembled monolayers on Au(111) using scanning tunneling microscopy

Molecular-scale surface structures of self-assembled monolayers (SAMs) formed by the spontaneous adsorption of tolane disulfides (TDS) on Au(111) in a 1 mM mixed solution of ethanol/N, N'-dimethylformamide (9:1) were examined using scanning tunneling microscopy (STM). The STM study revealed that TDS SAMs formed after a 24 h immersion at room temperature were composed of two-dimensional (2D) ordered phases with inhomogeneous surface morphologies and no clear domain boundaries. However, after 2 h immersion at 50 degrees C, uniform 2D ordered domains with clear domain boundaries were observed, which could be described as c(3 x square root of 3) structures with centered rectangular unit cell. Interestingly, a unique intermediate ordered phase with a low surface coverage was also observed. After a longer immersion for 24 h at 50 degrees C, only the uniform c(3 x square root of 3) domains were observed with a corrugation that may have reflected surface reconstruction of the Au(111) surfaces. From this study, we found that 2D ordered TDS SAMs with large and uniform domains on Au(111) can be obtained by controlling the solution temperature and immersion time.     

Scanning tunneling microscopy with chemically modified gold tips: in situ reestablishment of chemical contrast

A method was developed for the reestablishment of chemical contrast in STM images obtained with chemically modified gold tips. Such tips display selective chemical contrast, which allows the selective imaging of specific species on the sample surface. Chemically modified STM tips can be fabricated by forming a self-assembled monolayer (SAM) on an electrochemically etched gold tip. One difficulty with this method thus far has been the relatively short lifetime of SAM-treated tips. The method described here utilizes the brief application of a high bias voltage between the sample and the tip to cause SAM molecules to reoccupy the tip apex, thereby allowing the tips to display selective chemical contrast in imaging. These treatments consist of applying a +1.9-V sample bias for 0.5-10 min under tunneling conditions. The usable lifetime of SAM-modified tips could be increased by more than 2 orders of magnitude, from hours to at least a month, dramatically increasing the efficiency of using SAM-modified gold tips. SAM molecules can also be removed from the tip apex by application of a negative sample bias (-2.0 V for 0.5-10 min) making it possible to alternate between conventional STM images and STM images with chemically enhanced contrasts.