An observation of electron phase transition in SmB6 at low temperatures

In order to reveal the nature of the ground state of archetypal intermediate-valence compound SmB₆, a comprehensive study of its transport and magnetic properties was carried out on high-quality single crystals at temperatures of 1.8-300 K in magnetic fields up to 7 T. A drastic enhancement of negative magnetoresistance was observed below 14 K, with the maximum absolute value of Δρ/ρB²∼2.2×10⁻³ T⁻² at T≈5.2 K. This effect seems to be attributable to anomalous magnetic scattering of many-body (exciton-polaronic) complexes induced by fast valence fluctuations on Sm sites. The observed anomalies of magnetotransport, thermoelectric and magnetic characteristics are discussed in terms of electron phase transition to the coherent state of interacting many-body complexes occurring at T^*∼5 K.     

Synthesis and anion binding properties of 2,5-diamidothiophene polypyrrole Schiff base macrocycles

[reaction: see text] Two easy-to-synthesize polypyrrolic 2,5-diamidothiophene Schiff base macrocycles are reported, along with their anion binding properties as determined via UV-vis spectroscopic titrations carried out in dichloroethane. There is a striking difference between the interactions with anions of the two macrocycles, a finding ascribed to differences in their rigidity. For example, the more flexible dipyrromethane-derived macrocycle displays a 1.2:1 hydrogen sulfate versus nitrate selectivity, while its more rigid bipyrrole-derived congener shows a 7.4:1 selectivity in favor to hydrogen sulfate.     

Fluoropolyethers end‐capped by polar functional groups. III. Kinetics of the reactions of hydroxy‐terminated fluoropolyethers and model fluorinated alcohols with cyclohexyl isocyanate catalyzed by organotin compounds

The kinetics of the dibutyltin dilaurate (DBTDL)‐catalyzed urethane formation reactions of cyclohexyl isocyanate (CHI) with model monofunctional fluorinated alcohols and fluoropolyether diol Z‐DOL H‐1000 of various molecular weights (100–1084 g mol^?1) in different solvents were studied. IR spectroscopy and chemical titration methods were used for measuring the rate of the total NCO disappearance at 30–60 °C. The effects of the reagents and DBTDL catalyst concentrations, the solvent and hydroxyl‐containing compound nature, and the temperature on the reaction rate and mechanism were investigated. Depending on the initial reagent concentration and solvent, the reactions could be well described by zero‐order, first‐order, second‐order, or more complex equations. The reaction mechanism, including the formation of intermediate ternary or binary complexes of reagents with the tin catalyst, could vary with the concentration and solvent and even during the reaction. The results were treated with a rate expression analogous to those used for enzymatic reactions. Under the explored conditions, the rate of the uncatalyzed reaction of fluorinated alcohols with CHI was negligible. Moreover, there was no allophanate formation, nor were there other side reactions, catalysis by urethane in the absence of DBTDL, or a synergetic effect in the presence of the tin catalyst. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3771–3795, 2002     

Thermal properties of rare earth dodecaborides

We have measured heat capacity and thermal expansion of rare earth dodecaborides REB₁₂ (RE=Y, Tb-Tm, Lu). YB₁₂ and LuB₁₂ are diamagnetics whereas the other dodecaborides are ordered antiferromagnetically. The amplitude of the heat capacity discontinuity at the Néel temperature and the shape of the heat capacity variation in the critical region for all these antiferromagnetics are characteristics for amplitude-modulated magnetic structures. In the ordered state TbB₁₂ reveals two first-order phase transitions, most likely due to magnetic structure changes. The heat capacity of ErB₁₂ just below the Néel point shows an anomaly of unclear origin. From the Schottky contribution to the heat capacity we have determined crystal field parameters. They are completely different than that is estimated from Point Charge Model.     

Oxidation of bridging groups by carboxylate coordinated ligands in palladium clusters

Thermolysis of tetranuclear palladium clusters Pd₄(-Q)₄ Pd₄(-Q)₄(-O₂CR)₄ (Q=CPh₂ or CO;R=Me, CMe₃, Ph, CH₂Cl or CF₃) has been found to involve innersphere oxidation of carbene or carbonyl ligands during which an oxygen atom transfer occurs from the carboxylate group to the carbene or carbonyl ligand. The thermolysis of the carbonyl clusters gives rise to the products of CO₂ insertion into the C–H bond of benzene or toluene used as solvents forming benzoic acid from benzene and a mixture of phenylacetic and toluic acids from toluene. The reaction of [Pd(OAc)₂(PPh₃)]₂ with HCO₂H includes the transfer of an O atom from formate ligand to the P atom and cleavage of the P-Ph bond accompanied by transfer of the Ph group from PPh₃ ligand to the palladium atom. The structure of the complex formed, [Pd(-O₂PPh₂)(C₆H₅)(PPh₃)]₂, has been resolved by X-ray analysis.     

On linear free energy correlations in liquid-phase catalytic hydrogenation of aromatic compounds

Application of linear free energy relationships (correlation between kinetics and thermodynamics) to catalytic hydrogenation of aromatic compounds in the liquidphase over supported metal catalysts is discussed.     

Reactions of 4,7‐dihydro‐1,2,4‐triazolo[1,5‐a]pyrimidines with α,β‐unsaturated carbonyl compounds

The reaction of 5,7‐diphenyl‐4,7‐dihydro‐1,2,4‐triazolo[1,5‐a]pyrimidine ( 1 ) with α,β‐unsaturated carbonyl compounds 2a‐f led to the formation of the alkylated heterocycles 3a‐f (Figure 1). However, the reaction of 5‐methyl‐7‐phenyl‐4,7‐dihydro‐1,2,4‐triazolo[1,5‐a]pyrimidine ( 5 ) with 2a‐c yielded under the same conditions the triazolo[5,1‐b]quinazolines 6a‐c (Figure 3). In this case, the alkylation is followed by a cyclocondensation. The structure elucidation of the products is based on ir, ms, ¹H and ¹³C nmr measurements and on an X‐ray diffraction study.     

Three polymorphs of 3‐(3‐phenyl‐1H‐1,2,4‐triazol‐5‐yl)‐2H‐1‐benzopyran‐2‐one formed from different solvents

The polymorphic study of 3‐(3‐phenyl‐1H‐1,2,4‐triazol‐5‐yl)‐2H‐1‐benzopyran‐2‐one, C₁₇H₁₁N₃O₂, was performed due to its potential biological activity and revealed three polymorphic modifications in the triclinic space group P, the monoclinic space group P2₁ and the orthorhombic space group Pbca. These polymorphs have a one‐column layered type of crystal organization. The strongest interactions between the molecules of the studied structures is stacking between π‐systems, while N—H…N and C—H…O hydrogen bonds link stacked columns forming layers as a secondary basic structural motif. C—H…π hydrogen bonds were observed between neighbouring layers and their role is the least significant in the formation of the crystal structure. Packing differences between the polymorphic modifications are minor and can be identified only using an analysis based on a comparison of the pairwise interaction energies.     

Poly[μ2‐chloro‐μ2‐1,4‐oxathiane‐κ2S:S‐copper(I)]

The title complex, [CuCl(C₄H₈OS)]_n, contains infinite spiral (CuS)_n chains linked by bridging Cl atoms into layers. The Cl atoms do not form polymeric fragments with Cu^I, but combine into isolated centrosymmetric Cu₂Cl₂ units. The compound is non‐isomorphous with the Br‐containing analogue, which contains Cu₈S₈ rings linked by Br atoms into chains. The O atom of the 1,4‐oxathiane mol­ecule does not realize its coordination abilities in the known copper(I)–halide complexes, while in copper(II)–halide complexes, oxathiane is coordinated via the S and O atoms. This falls into a pattern of the preferred inter­actions, viz. weak acid (Cu^I atom) with weak base (S atom) and harder acid (Cu^II atom) with harder base (O atom).