Mesoscopic thermodynamics of an inhomogeneous colossal-magnetoresistive phase

Equilibrium conductivity fluctuations of mesoscopic domains are found in film and bulk single-crystal manganite colossal magnetoresistive material. Temperature and field dependences of the Boltzmann factors for a collection of two-state fluctuators give measures of the magnetic moment and entropy differences between the states, and of the fluctuator volumes. The large resistance step size implies dramatic current inhomogeneities. Occasional anomalous temperature dependences indicate that the film inhomogeneous phase is stabilized by a repulsive interaction between conducting regions.     

The matrix effect on stereoselectivity of olefin cyclopropanation by arylcarbene

Temperature studies of additon of phenylcarbene to styrene showed that stereoselectivity changed rather dramatically as the reaction phase changed.     

Exciton band structure of crystalline anthracene

The density of states in the first exciton band of crystalline anthracene has been obtained at room, dry-ice-alcohol, and liquid nitrogen temperatures by applying a thermal modulation technique to observe the hot band-first exciton band optical transition (1-0 transition). The density of states function obtained has been interpreted in terms of the exciton band structure and the Davydov splitting. The K dependent selection rule for the 1-0 transition is discussed. The bandwidth of the first exciton band is 0.09 eV.     

A novel traceless resin-bound guanidinylating reagent for secondary amines to prepare N,N-disubstituted guanidines

[reaction: see text]. We report the development of a solid support-linked guanidinylating reagent. This reagent consists of a urethane-protected triflyl guanidine attached to the resin via a carbamate linker. It allows for rapid synthesis of guanidines from a variety of amines. It provides access to N-alkyl/aryl- or N,N-dialkylguanidines under mild conditions. Cleavage with 50% TFA produces target molecules in high yields and purity. The ability to guanidinylate secondary amines is a significant feature of this guanidinylating reagent.     

High performance of N-alkoxycarbonyl-imines in triethylborane-mediated tin-free radical addition

Triethylborane-mediated tin-free radical alkylation of N-alkoxycarbonyl-imines, such as N-Boc-, N-Cbz-, and N-Teoc-imines, proceeded smoothly at a low temperature (-78 to -20 °C) to give the corresponding adducts in high yield. Although the formation of isocyanate was the major unfavorable reaction at room temperature, a one-pot conversion of N-Boc-imine to N-ethoxycarbonyl-adduct was possible through the corresponding isocyanate generated in situ. The higher performance of N-alkoxycarbonyl-imine than those of N-Ts- and N-PMP-imines is rationalized by a moderate electron-withdrawing character of an alkoxycarbonyl group that makes both addition of alkyl radical and trapping of the resulting aminyl radical by triethylborane efficiently fast.     

Multicritical end point of the first-order ferromagnetic transition in colossal magnetoresistive manganites

We have studied the bandwidth-temperature-magnetic-field phase diagram of RE0.55Sr0.45MnO3 colossal magnetoresistance manganites with ferromagnetic metal (FM) ground state. The bandwidth was controlled both via chemical substitution and hydrostatic pressure with a focus on the vicinity of the critical pressure p;{*} where the character of the zero-field FM transition changes from first to second order. Below p;{*} the first-order FM transition extends up to a critical magnetic field. It approaches zero on the larger bandwidth side where the surface of the first-order FM phase boundary is terminated by a multicritical end point. The change in the character of the transition and the decrease of the colossal magnetoresistance effect is attributed to the reduced charge-order and orbital-order fluctuations.     

Ferromagnetic enhancement of CE-type spin ordering in (Pr,Ca)MnO3

We present resonant soft x-ray scattering results from small bandwidth manganites (Pr,Ca)MnO(3), which show that the CE-type spin ordering (SO) at the phase boundary is stabilized only below the canted antiferromagnetic transition temperature and enhanced by ferromagnetism in the macroscopically insulating state (FM-I). Our results reveal the fragility of the CE-type ordering that underpins the colossal magnetoresistance effect in this system, as well as an unexpected cooperative interplay between FM-I and CE-type SO which is in contrast to the competitive interplay between the ferromagnetic metallic state and CE-type ordering.     

Generation, characterization, and kinetics of triplet Di[1,2,3,4,5,6, 7,8-octahydro-1,4:5,8-di(ethano)anthryl]carbene

The title carbene has been generated by photolysis of the corresponding diazo precursors and studied by spectroscopic means, i. e., electron paramagnetic resonance (EPR) and UV/vis spectroscopy in matrixes at low temperature and laser-flash photolysis in solution at room temperature, with the product analysis. The results are compared with triplet di(2,3,5,6-tetramethylphenyl)carbene, an open-chain counterpart, which revealed that bicycloalkyl groups are acting as a fairly good kinetic protector for the triplet carbene as opposed to the open-chain counterpart. The formation of all-hydrocarbon triplet carbenes having a half-life over a second under normal conditions was realized for the first time. Effects of para-substituents on the structure and reactivities of the carbene are also investigated and discussed in terms of polar and spin electronic effects.     

Diastereoselective and enantioselective synthesis of 1,2-disubstituted cycloalkanecarboxaldehydes

A highly useful method for diastereoselective and enantioselective synthesis of trans- and cis-1,2-disubstituted cycloalkanecarboxaldehydes (trans- and cis-10), useful chiral synthons having asymmetric tertiary and quaternary carbon atoms in vicinal positions in their rings, is devised starting from cycloalkenecarboxal-dehydes (5) t-Leucine t-butyl ester (2, R=Bu^t), a highly effective chiral auxiliary reagent in the present method, can be recovered for recycling without any loss of optical purity Some mechanistic explanations on the stereochemical courses of the reactions are presented