Analysis of lanthanide-induced NMR shifts of the Ce@C82 anion

The mapping of bond connectivity in the carbon cage of [Ce@C82]- and full assignment of the NMR lines were successfully achieved by means of 2D INADEQUATE NMR measurement. Paramagnetic NMR analysis shows that the Ce atom in [Ce@C82]- is located at an off-centered position adjacent to a hexagonal ring along the C2 axis of the C2v-C82 cage.     

Bicyclo[3.2.1]octanone catalysts for asymmetric alkene epoxidation: the effect of disubstitution

A series of 2-fluoro-8-oxabicyclo[3.2.1]octan-3-ones are prepared and tested as catalysts for alkene epoxidation with Oxone^®. These catalysts provide trans-stilbene oxide with up to 83% ee, but the highest ee value is obtained with the monofluorinated ketone 2: both 2,2- and 2,4-disubstituted catalysts afford epoxide of lower ee.     

Quantum mechanical Monte Carlo approach to electron transport at heterointerface

With the progress of LSI technology, the electronic device size is scaled down to the sub 0.1μ m region. In such an ultrasmall device, it is indispensable to take quantum mechanical effects into account in device modeling. In this paper, we present a newly developed quantum Monte Carlo device simulation applicable to ultrasmall semiconductor devices. In this model, the quantum effects are represented in terms of quantum mechanically corrected potential in the classical Boltzmann equation. It is demonstrated that the quantum transport effects such as tunneling and energy quantization in ultrasmall semiconductor devices are obtained for the first time by using the standard Monte Carlo techniques.     

Synthesis of donor-acceptor chromophores by the [2 + 2] cycloaddition of arylethynyl-2H-cyclohepta[b]furan-2-ones with 7,7,8,8-tetracyanoquinodimethane

Arylethynyl-2H-cyclohepta[b]furan-2-ones reacted with 7,7,8,8-tetracyanoquinodimethane (TCNQ) in a formal [2 + 2] cycloaddition reaction, followed by ring opening of the initially formed cyclobutene derivatives, to afford the corresponding dicyanoquinodimethane (DCNQ) chromophores in excellent yields. The intramolecular charge-transfer (ICT) interactions between the 2H-cyclohepta[b]furan-2-one ring and DCNQ acceptor moiety were investigated by UV/Vis spectroscopy and theoretical calculations. The redox behavior of the novel DCNQ derivatives was examined by cyclic voltammetry (CV) and differential pulse voltammetry (DPV), which revealed their multistep electrochemical reduction properties depended on the number of DCNQ units in the molecule. Moreover, a significant color change was observed by visible spectroscopy under electrochemical reduction conditions.     

Stereochemistry-dependent, mechanoresponsive supramolecular host assemblies for fullerenes: a guest-induced enhancement of thixotropy

Self-assembly behaviors of a series of systems (G1, G2, and G3) possessing same organic building blocks based on a substituted anthracene have been investigated in decalin. G2 and G3 are dominated by head-to-tail (ht) and head-to-head (hh) type dimers of G1, respectively. G1 gives a thermoresponsive gel that behaves ideally, showing frequency-independent elastic and viscous moduli. Interestingly, G2 produces a thixotropic gel that shows the signature of structural relaxation, signifying the dynamic nature of the system. In contrast, G3 remains fluidlike. As investigated by scanning electron microscopy (SEM), in the assembly process of G2, first disklike nanoaggregates are formed, and in the second step these aggregates interact to construct the densely packed secondary assembly. A transition from secondary assembly to primary assembly under shear initiates the mechanoresponsive destruction of the gel. In the self-assembly process, G1 propagates in a one-dimensional fashion, whereas G2 and G3 can propagate in a two-dimensionional fashion. The same side orientation of the substituents in G3 facilitates the formation of a compact closed-shell-type structure, which results in the generation of isolated nanocrystals. The long-range weak interaction together with the capability of propagating in two dimensions is found to be essential for the construction of such a mechanoresponsive assembly. C(60) and C(70) could be incorporated successfully in G2 assembly to develop mechanoresponsive fullerene assemblies. The presence of fullerenes not only enhances the elastic properties of G2 but also intensifies the thixotropy. C(70) appears to be a superior guest in terms of property enhancement due to its better size fitting with the concave-shaped host.     

Chemical understanding of carbide cluster metallofullerenes: a case study on Sc2C2@C2v(5)-C80 with complete X-ray crystallographic characterizations

Little is known about the chemical properties of carbide cluster metallofullerenes (CCMFs). Here we report the photochemical reaction of a newly assigned CCMF Sc(2)C(2)@C(2v)(5)-C(80) with 2-adamantane-2,3-[3H]-diazirine (AdN(2), 1), which provides a carbene reagent under irradiation. Five monoadduct isomers (2a-2e), with respective abundances of 20%, 40%, 25%, 5%, and 10%, were isolated and characterized with a combination of experimental techniques including unambiguous single-crystal X-ray crystallography. Results show that the two Sc atoms of the bent Sc(2)C(2) cluster tend to move in most cases, whereas the C(2)-unit is almost fixed. Accordingly, it is difficult to explain the addition patterns by considering the strain and charge density on the cage with a fixed cluster, and thus a moving cluster may account for the addition patterns. These results show that the situation of CCMFs is more complicated than those in other metallofullerenes. Furthermore, a thermal isomerization process from 2b to 2c was observed, confirming that the most abundant isomer 2b is a kinetically favored adduct. Finally, it is revealed that the electronic and electrochemical properties of pristine Sc(2)C(2)@C(2v)(5)-C(80) have been markedly altered by exohedral modification.     

Effects of substrate-induced-strain on the structural and transport properties of La0.7Ca0.3MnO3 thin films

We have studied the structural and electrical properties of epitaxial La_0.7Ca_0.3MnO₃ (LCMO) thin films prepared by metal organic deposition under different types and degrees of substrate-induced strain. 40-nm-thick films have been epitaxially grown on single-crystalline (LaAlO₃)_0.3?C(SrAlTaO₆)_0.7 (negligible tensile strain), SrTiO₃ (tensile strain) and LaAlO₃ (compressive strain) substrates. High-resolution X-ray diffraction and reciprocal space maps demonstrate a direct correlation between the crystalline quality and the substrate-induced strain. The electrical properties were found to be strongly dependent on the substrate used. The temperature dependence of resistivity curves was fitted using various approaches in different phases (below and above the ferromagnetic transition temperature T _P). In the ferromagnetic metallic phase, ??(T) follows a T ^?? power law. The obtained values of the coefficient ???(3.5?C4) indicate that the electrical transport in our films is a combination of spin wave scattering processes and electron?Cmagnon or two-magnon scattering phenomena. In the paramagnetic insulator phase, the activation energy E _A and the variable range hopping characteristics (characteristic temperature T ₀) were found to be strongly dependent on the strain-induced lattice mismatch between the LCMO and the substrate used.     

A Face of a Projective Triangulation Removed for Its Geometric Realizability

Let M be a map on a surface F ². A geometric realization of M is an embedding of F ² into a Euclidian 3-space ℝ³ with no self-intersection such that each face of M is a flat polygon. In Bonnington and Nakamoto (Discrete Comput. Geom. 40:141–157, 2008), it has been proved that every triangulation G on the projective plane has a face f such that the triangulation G−f on the M?bius band obtained from G by removing the interior of f has a geometric realization. In this paper, we shall characterize such a face f of G.