Deconvolution of damping forces with a nonlinear microresonator.

We report a fully electrical microcantilever device that utilizes capacitance for both actuation and detection and show that it can characterize various gases with a bare silicon microcantilever. We find the motion of the cantilever as it rings down when the oscillating force is removed, by measuring the voltage induced by the oscillating capacitance in the microcantilever∕counterelectrode system. The ringdown waveform was analyzed using an iterative numerical algorithm to calculate the oscillator motion, modeling the cantilever∕electrode capacitance to calculate the electrostatic force. We find that nonlinearity in the motion of the cantilever is not necessarily a disadvantage. After calibration, we simultaneously measure viscosity and density of several gaseous mixtures, yielding viscosities within ±2% and densities within ±6% of NIST values.

Lanthanum nitride endohedral fullerenes La3N@C2n (43

While the trimetallic nitrides of Sc, Y and the lanthanides between Gd and Lu preferentially template C(80) cages, M(3)N@C(80), and while those of Ce, Pr and Nd preferentially template the C(88) cage, M(3)N@C(88), we show herein that the largest metallic nitride cluster, La(3)N, preferentially leads to the formation of La(3)N@C(96) and to a lesser extent the La(3)N@C(88). This is the first time that La(3)N is successfully encapsulated inside fullerene cages. La(3)N@C(2n) metallofullerenes were synthesized by arcing packed graphite rods in a modified Krätschmer-Huffman arc reactor, extracted from the collected soot and identified by mass spectroscopy. They were isolated and purified by high performance liquid chromatography (HPLC). Different arcing conditions were studied to maximize fullerene production, and results showed that yields have a high La(2)O(3)/C dependence. Relatively high yields were obtained when a 1:5 ratio was used. Three main fractions, La(3)N@C(88), La(3)N@C(92), and La(3)N@C(96), were characterized by UV/Vis-NIR and cyclic voltammetry. Unlike other trimetallic nitride metallofullerenes of the same carbon cage size, La(3)N@C(88) exhibits a higher HOMO-LUMO gap and irreversible reduction and oxidation steps.

The influence of cage size on the reactivity of trimetallic nitride metallofullerenes: a mono- and bis-methanoadduct of Gd3N@C80 and a monoadduct of Gd3N@C84.

A reactivity study of the higher TNT EMFs of gadolinium is reported here showing that the reactivity substantially decreases when the fullerene cage gets larger.

Preparation and structural characterization of the Ih and the D5h isomers of the endohedral fullerenes Tm3N@C80: icosahedral C80 cage encapsulation of a trimetallic nitride magnetic cluster with three uncoupled Tm3+ ions.

We report an efficient method for the preparation and purification of the Ih and the D5h isomers of Tm3N@C80. Following preparation in a Kratschmer-Huffman electric-arc generator, the Tm3N@C80 isomers were obtained by a chemical separation process followed by a one-stage isomer selective chromatographic high-performance liquid chromatography (HPLC) separation (pyrenyl, 5PYE column). The HPLC chromatographic retention behavior on a pentabromobenzyl (5PBB) column suggests a charge transfer of approximately 6 electrons; [M3N] 6+@C80(6-) and the chromatographic retention mechanisms of the Ih and the D5h isomers of Tm3N@C80 on both 5PBB and 5PYE columns are discussed. Single-crystal X-ray diffraction data demonstrate that the Tm3N cluster has a planar structure but represents a tight fit for trapping the Tm3N cluster inside the I h - and the D 5h -C 80 cages. Specifically, the Tm atoms punch out the cage carbon atoms adjacent to them. The "punched out" effect can be demonstrated by cage radii and pyramidal angles at cage carbon atoms near the Tm atoms. The magnetic susceptibility (chiT) for Tm3N@ Ih -C80 was found to exhibit Curie-Weiss behavior with C = 23.4 emu.K/mol, which is consistent with the calculated value for three uncoupled Tm3+ ions by considering the spin and orbital contributions with no quenching of the orbital angular momentum ( L = 5, S = 1, and J = 6; Ccalcd = 23.3 emu.K/mol). The electrochemical measurements demonstrate that both the Ih and the D5h isomers of Tm3N@C80 have a large electrochemical gap.

New M(3)N@C(2n) endohedral metallofullerene families (M=Nd, Pr, Ce; n=40-53): expanding the preferential templating of the C(88) cage and approaching the C(96) cage.

Three new families of trimetallic nitride template endohedral metallofullerenes (TNT EMFs), based on cerium, praseodymium, and neodymium clusters, were synthesized by vaporizing packed graphite rods in a conventional Krätschmer-Huffman arc reactor. Each of these families of metallofullerenes was identified and characterized by mass spectroscopy, HPLC, UV/Vis-NIR spectroscopy, and cyclic voltammetry. The mass spectra and HPLC chromatograms show that these larger metallic clusters are preferentially encapsulated by a C(88) cage. When the size of the cluster is increased, the C(96) cage is progressively favored over the predominant C(88) cage. It is also observed that the smaller cages (C(80)-C(86)) almost disappear on going from neodymium to cerium endohedral metallofullerenes. The UV/Vis-NIR spectra and cyclic voltammograms confirm the low HOMO-LUMO gap and reversible electrochemistry of these M(3)N@C(88) metallofullerenes.

Gd3N@C2n (n = 40, 42, and 44): remarkably low HOMO-LUMO gap and unusual electrochemical reversibility of Gd3N@C88 .

High-performance liquid chromatography was used to isolate two new trimetallic nitride endohedral fullerenes, Gd3N@C2n (n = 42 and 44), and they were characterized by MALDI-TOF mass spectrometry, UV-vis-NIR, and cyclic voltammetry. It was found that their electronic HOMO-LUMO gaps depend pronouncedly on the size of the cage, from a large band gap for Gd3N@C80 (2.02 V) to a small band gap for Gd3N@C88 (1.49 V). The electrochemical properties also change dramatically with the size of the cage, going from irreversible for the C80 cage to reversible for Gd3N@C88. The latter is the largest trimetallic cluster inside C88 isolated and characterized to date. Gd3N@C88 has one of the lowest electrochemical energy gaps for a nonderivatized metallofullerene.

A reassignment of the EPR spectra previously attributed to Cu@C60.

EPR spectra attributed to the endohedral metallofullerene Cu@C60 are better explained by the previously characterized Cu(II) dithiocarbamate family of compounds.

Reactivity differences between carbon nano onions (CNOs) prepared by different methods.

The carbon nanoparticles obtained from either arcing of graphite under water or thermal annealing of nanodiamonds are commonly called carbon nano onions (CNOs), or spherical graphite, as they are made of concentric fullerene cages separated by the same distance as the shells of graphite. A more careful analysis reveals some dramatic differences between the particles obtained by these two synthetic methods. Physicochemical methods indicate that the CNOs obtained from nanodiamonds (N-CNOs) are smaller and contain more defects than the CNOs obtained from arcing (A-CNOs). These properties explain the enhanced reactivity of the N-CNOs in cycloaddition and oxidation reactions, as well as in reactions involving radicals. Given the easier functionalization of the N-CNOs, they are the most obvious choice for studying the potential applications of these multi-shelled fullerenes.

X-Ray crystallographic and EPR spectroscopic characterization of a pyrrolidine adduct of Y3N@C80.

Crystallographic data for the pyrrolidine adduct Y3N@C80C4H9N x 2.5CS2 reveals a slightly pyramidalized Y3N unit with idealized mirror symmetry that straddles the site of addition but does not directly interact with the addend.

Unexpected chemical and electrochemical properties of M3N@C80 (M = Sc, Y, Er).

The unexpected isomerization of N-ethyl [6,6]-pyrrolidino-Y3N@C80 to the [5,6] regioisomer is reported, as well as the synthesis, characterization, and electrochemical analysis of Er3N@C80 derivatives. A complete electrochemical study of the M3N@C80 species (M = Sc, Y, Er) and their derivatives is presented. We introduce electrochemistry as a new tool in the characterization of the [5,6] and [6,6] regioisomers of trimetallic nitride endohedral metallofullerenes.

Phthalocyanine-modulated isomerization behaviour of an azo-based photoswitch.

A photoswitchable azobenzene-phthalocyanine-azobenzene triad has been synthesized and its electrochemical properties determined. Energy transfer among the subunits allows for modification of the E-Z ratio by selective excitation of the phthalocyanine moiety.

Preparation and functionalization of multilayer fullerenes (carbon nano-onions).

Carbon nano-onions (CNOs) represent a still largely unexplored carbon allotrope. Promising properties of these unique carbon structures are driving the research efforts in this area, but many technical problems remain in their preparation, derivatization, separation and characterization. In this article, we report the preparation, partial purification, and multiple functionalization and solubilization of CNOs. With only one priorly published short communication describing CNO functionalization, the present work is the most comprehensive description of CNO functionalization and characterization to date.

A simple isomeric separation of D5h and Ih Sc3N@C80 by selective chemical oxidation.

Two electrochemical oxidation waves assigned to the D(5h) isomer of Sc(3)N@C(80) have been identified, and a 270-mV difference in the first electrochemical oxidation potentials of the I(h) and D(5h) isomers has been measured. On the basis of this oxidative potential difference, a strategy for isomeric purification involving a selective chemical oxidation of the D(5h) isomer is reported. Variable scan cyclic voltammetry of the resultingly pure Sc(3)N@C(80) I(h) isomer shows evidence of a rapid endohedral chemical reaction following the first reduction process.