MnIII2 (5-Rsaltmen)2NiII(pao)2(L)]2+: an S(T)=3 building block for a single-chain magnet that behaves as a single-molecule magnet

Mn(III)-Ni(II)-Mn(III) linear-type trinuclear complexes bridged by oximate groups were selectively synthesized by the assembly reaction of [Mn2(5-Rsaltmen)2(H2O)2](ClO4)2 (5-Rsaltmen2-=N,N'-(1,1,2,2-tetramethylethylene) bis(5-R-salicylideneiminate); R=Cl, Br) with [Ni(pao)2(phen)] (pao-=pyridine-2-aldoximate; phen=1,10-phenanthroline) in methanol/water: [Mn2(5-Rsaltmen)2Ni(pao)2(phen)](ClO4)2 (R=Cl, 1; R=Br, 2). Structural analysis revealed that the [Mn(III)-ON-Ni(II)-NO-Mn(III)] skeleton of these trimers is in every respect similar to the repeating unit found in the previously reported series of 1D materials [Mn2(saltmen)2Ni(pao)2(L1)2](A)(2) (L(1)=pyridine, 4-picoline, 4-tert-butylpyridine, N-methylimidazole; A=ClO4-, BF4-, PF6-, ReO4-). Recently, these 1D compounds have attracted a great deal of attention for their magnetic properties, since they exhibit slow relaxation of the magnetization (also called single-chain magnet (SCM) behavior). This unique magnetic behavior was explained in the framework of Glauber's theory, generalized for chains of ferromagnetically coupled anisotropic spins. Thus, in these 1D compounds, the [Mn(III)-ON-Ni(II)-NO-Mn(III)] unit was considered as an S(T)=3 anisotropic spin. Direct-current magnetic measurements on 1 and 2 confirm their S(T)=3 ground state and strong uniaxial anisotropy (D/k(B) approximately -2.4 K), in excellent agreement with the magnetic characteristic deduced in the study on the SCM series. The ac magnetic susceptibility of these trimers is strongly frequency-dependent and characteristic of single-molecule magnet (SMM) behavior. The relaxation time tau shows a thermally activated (Arrhenius) behavior with tau0 approximately 1x10(-7) s and Delta(eff)/k(B) approximately 18 K. The effective energy barrier for reversal of the magnetization Delta(eff) is consistent with the theoretical value (21 K) estimated from |D| S2T. The present results reinforce consistently the interpretation of the SCM behavior observed in the [Mn2(saltmen)2Ni(pao)2(L1)2](A)2 series and opens new perspectives to design single-chain magnets.     

Practical synthesis of a neuropeptide Y antagonist via stereoselective addition to a ketene

[Reaction: see text]. The synthesis of neuropeptide Y antagonist 1, currently under clinical investigation for the treatment of obesity, is described. The convergent synthesis from trans-spirolactone carboxylic acid intermediate 2a and aminopyrazole 3 is predicated on a stereoselective route to the former. The coupling reaction of ethyl 4-oxocyclohexanecarboxylate (10a) with lithiated isonicotinamide 11 was investigated in detail, but even optimized conditions only provided a 45:55 ratio of trans:cis isomers (12a:12b). While selective crystallization schemes were developed to isolate the thermodynamically less stable trans isomer 2a, improved stereocontrol was subsequentially achieved by the application of ketene chemistry. The ketene formation and quench was investigated under a variety of conditions aimed at maximizing the trans:cis ratio. Reacting a mixture of carboxylic acids 2a and 2b with POCl3 in THF, followed by concomitant addition of tert-butyl alcohol in the presence of TMEDA at 35 degrees C provided a 4:1 ratio of trans:cis tert-butyl esters (18a:18b) via in situ ketene formation. Ester hydrolysis, followed by selective crystallization of undesired 2b as the HCl salt, led to isolation of 2a in 47% overall yield. Aminopyrazole intermediate 3 was synthesized via the condensation reaction of 2-fluorophenylhydrazine hydrochloride (4a) with acrylonitrile derivative 5 in 65-70% yield. Coupling of advanced intermediates 2a and 3b via activation with thionyl chloride gave a 92% yield of 1.     

Benzyne-induced ring opening reaction of thiiranes. Efficient synthesis of phenyl vinyl sulfides

A series of thiiranes react with benzyne to provide an efficient synthesis of phenyl vinyl sulfides. The reaction is stereospecific, thus producing cis-(phenylthio)-stilbene from cis-2,3-diphenylthiirane and trans-(phenylthio)stilbene from trans-2,3-diphenylthiirane.     

Changes in electronic structure upon lithium insertion into the A-site deficient perovskite type oxides (Li,La)TiO3

Investigation on variation of the electronic structure accompanying the electrochemical lithium insertion into the perovskite type oxide, (Li,La)TiO3, has been carried out by X-ray absorption spectroscopy (XAS). During the electrochemical lithium insertion, titanium ion reduced its oxidation state from Ti4+ to Ti3+, while La3+ does not contribute to the reduction reaction resulting from Ti K-edge and La L3-edge XAS, respectively. Furthermore, O K-edge XAS showed marked spectral changes with electrochemical lithium insertion, indicating the electronic structure around oxide ion affected by lithium insertion reaction. From the XAS measurement, we have concluded the variation observed in O K-edge XAS was related to the strong interaction with inserted Li ion. To confirm this, first-principles band calculations were performed for the perovskite structure before and after electrochemical lithium insertion. The calculated results showed that the electron originated from inserted Li transferred to neighboring oxide ion locally as well as to Ti ion. This may be due to local neutralization effect of Li to reduce the electrostatic interaction in the crystal.     

Structure and magnetic properties of the two-dimensional ferrimagnet (NEt4)[[Mn(salen)]2Fe(CN)6]: investigation of magnetic anisotropy on a single crystal

The title compound, (NEt(4))[[Mn(salen)](2)Fe(CN)(6)] (1), was synthesized via a 1:1 reaction of [Mn(salen)(H(2)O)]ClO(4) with (NEt(4))(3)[Fe(CN)(6)] in a methanol/ethanol medium (NEt(4)(+) = tetraethylammonium cation, salen(2)(-) = N,N'-ethylenebis(salicylidene)iminate). The two-dimensional layered structure of 1 was revealed by X-ray crystallographic analysis: 1 crystallizes in monoclinic space group P2(1)/c with cell dimensions of a = 12.3660(8) A, b = 15.311(1) A, c = 12.918(1) A, beta = 110.971(4) degrees, Z = 2 and is isostructural to the previously synthesized compound, (NEt(4))[[Mn(5-Clsalen)](2)Fe(CN)(6)] (5-Clsalen(2-) = N,N'-ethylenebis(5-chlorosalicylidene)iminate; Miyasaka, H.; Matsumoto, N.; Re, N.; Gallo, E.; Floriani, C. Inorg. Chem. 1997, 36, 670). The Mn ion is surrounded by an equatorial salen quadridentate ligand and two axial nitrogen atoms from the [Fe(CN)(6)](3-) unit, the four Fe[bond]CN groups of which coordinate to the Mn ions of [Mn(salen)](+) units, forming a two-dimensional network having [[bond]Mn[bond]NC[bond]Fe[bond]CN[bond]](4) cyclic repeating units. The network is spread over the bc-plane of the unit cell, and the layers are stacked along the a-axis. The countercation NEt(4)(+) is located between the layers. Compound 1 is a ferrimagnet with T(c) = 7.7 K and exhibits hysteresis with a remnant magnetization of 13.44 cm(3).mol(-1) (M/N mu(B) = 2.4) at zero field and a coercivity of 1000 Oe when the powder sample was measured at 1.9 K. Magnetic measurements of a direction-arranged single crystal were also carried out. The orientation of the crystallographic axes of a selected single crystal was determined by X-ray analysis, and magnetization was measured when an external field was applied in the a*, b, and c directions. The magnetization in the a* direction increased more easily than those in the b and c directions below the critical temperature. No hysteresis was observed only for the measurement in the a* direction, indicating the presence of strong structural anisotropy with potential anisotropy on Mn(III) ions.     

Effects of beta-sheet breaker peptide polymers on scrapie-infected mouse neuroblastoma cells and their affinities to prion protein fragment PrP(81-145)

The effects of Soto's 'beta-sheet breaker peptide' and its polymer on PrPSc formation in ScN2a cells were investigated. Surface plasmon resonance study indicated that direct binding between PrP(81-145) and the 'beta-sheet breaker peptide' is not specific and may not play a major role in the inhibition of PrPSc formation.     

Mapping analyses of Fe-diffused mc-Si using M?ssbauer microscope and photoluminescence

Twenty CK chondrites collected in the Antarctica Continent were characterized by inductively-coupled plasma mass spectrometry (ICP-MS), prompt gamma ray analysis (PGA), instrumental neutron activation analysis (INAA), X-ray diffractometry (XRD) and ⁵⁷Fe-M?ssbauer spectroscopy. As a result of elemental analysis, it was revealed that 18.2~26.4 mass% of iron was included in the each chondrite. M?ssbauer spectrum of LEW86258, classified as a typical CK chondrite, was found to be composed of two paramagnetic doublets and two magnetic sextets. M?ssbauer spectra were assigned to the absorption due to forsterite (Mg_1.36Fe_0.64SiO₄) and magnetite (Fe₃O₄), as also confirmed by XRD. XRD study of LAP03834, reclassified from CK to R chondrite, revealed the presence of crystalline phase due to forsterite. These results indicate that LAP03834 and related chondrites, i.e., MET01149, LAP03923 and MAC02453, should be reclassified as R or LL chondrite.     

Physical and Chemical Properties of Four-Membered Bis(triphenylphosphane)platinum(II) Sulfenato Thiolato Complexes

The reaction of isolable dithiirane 1-oxides with (Ph 3 P) 2 Pt( m 2 -C 2 H 4 ) provided the title complexes in high yields. 31 P NMR spectroscopy of the phosphine ligands of the complexes and x-ray crystallographic analysis of a complex were reported.     

Superconducting Properties in Metallic Phase of NbS3

Metallic phase of NbS₃ was synthesized by heating the crystal of semiconducting NbS₃. Metallic NbS₃ undergoes superconducting transition around 2 K. The analysis of the angular dependence of the upper critical magnetic field suggests that the effect of filmy or fibrous morphology plays an important role in the superconducting properties.     

Thermal and evolved gas analyses of the oxidation of a cellulose/copper(II) oxide mixture

Cellulosic biomass is a promising alternative energy resource from the viewpoint of sustainability. The use of waste materials as cellulosic biomass could additionally contribute to a recycling society. It is thus essential to develop safer processes in order to expand utilization of cellulosic biomass as a useful resource in the future. For example, in some cases, construction wastes contain wood preservatives, including metal oxides that can act as catalysts for the oxidation of organic materials. Copper(II) oxide (CuO) is a major component in wood preservatives and is known to catalyze the oxidation of cellulose. There is, therefore, possibility for spontaneous ignition within large piles of wood chips from construction wastes. In this study, we focused on the thermal behavior of a cellulose/CuO mixture, measured using a Calvet-type heat flux calorimeter. In addition, Fourier transform infrared spectroscopy and gas chromatography were applied to analyze the oxidative decomposition gases of the cellulose/CuO mixture, and a reaction mechanism was proposed. It was revealed that CuO promotes the oxidative decomposition of cellulose and increases the quantity of the gases that evolved from cellulose with a catalytic cycle. The influence of CuO on oxidation of cellulose is greater at lower temperatures and spontaneous ignition, fires, and explosions are likely to increase when wood chips containing CuO are stored for long periods of time.