Fragile magnetic ground state in half-doped LaSr2Mn2O7

We investigated the orbital and antiferromagnetic ordering behaviors of the half-doped bilayer manganite La(2-2x)Sr(1+2x)Mn2O7 (x ? 0.5) by using Mn L(2,3)-edge resonant soft x-ray scattering. Resonant soft x-ray scattering reveals the CE-type orbital order below T(oo) ? 220 K, which shows partial melting behavior below T(m) ? 165 K. We also found coexistence CE- and A-type antiferromagnetic orders. Both orders involve the CE-type orbital order with nearly the same orbital character and are coupled with each other. These results manifest that the ground state with the CE-type antiferromagnetic order is easily susceptible to destabilization into the A-type one even with a small fluctuation of the doping level, as suggested by the extremely narrow magnetic phase boundaries at x ? 0.5±0.005.     

Spectroscopic and structural study of metal-metal bonded metalloporphyrinic derivatives: the case of rhodium-indium

The synthesis and spectroscopic characterization of heterometallic porphyrinate derivatives containing rhodium-indium metal-metal bonds are reported. The investigated compounds are represented by the formula [(Porph)RhIn(Porph')], where Porph and Porph' are OEP, TPP, beta-Cl(4)TPP, beta-Cl(8)TPP, or TPyP. UV-Visible spectroscopy of the title complexes confirms the presence of a strong pi-pi interaction between the macrocycles in each derivative and denotes the effect of the nontransition metal in their optical features. For comparison purposes, a new bimetallic complex with a rhodium-thallium metal-metal bond is also presented. According to (1)H and (13)C NMR data, we were able to distinguish two major NMR regions: the endo- between the metal-metal bonded macrocycles and the exo-, which are characteristic features of porphyrinic complexes at very close proximity. X-ray absorption spectroscopy (XAS) structural characterization of Rh-In bond was performed on the [(OEP)RhIn(OEP)] complex, in the fluorescence mode, and we essentially focused on the metal-metal distance determination. Finally, the distance of 2.543(3) A was deduced from the X-ray structure of a new [(TPP)RhIn(TPyP)] derivative.     

Synthesis of fused 4,5-disubstituted indole ring systems by intramolecular friedel-crafts acylation of 4-substituted indoles

4-Substituted indoles containing a variety of electrophiles and N-substituents undergo Friedel-Crafts acylation to give exclusively the products of cyclization at the 5-position of indole. These indanones and tetralones have been scarcely prepared and are subunits in natural products and analogues of potential biological significance.     

Spin excitations in an anisotropic bond-alternating quantum s = 1 chain in a magnetic field: contrast to haldane spin chains

Inelastic neutron scattering experiments on the S = 1 quasi-one-dimensional bond-alternating antiferromagnet Ni(C9D24N4)(NO2)ClO4 have been performed under magnetic fields below and above a critical field Hc at which the energy gap closes. Normal field dependence of Zeeman splitting of the excited triplet modes below Hc has been observed, but the highest mode is unusually small and smears out with increasing field. This can be explained by an interaction with a low-lying two magnon continuum at q(parallel) = pi that is present in dimerized chains but absent in uniform ones. Above Hc, we find only one excited mode, in stark contrast with three massive excitations previously observed in the structurally similar Haldane-gap material NDMAP [A. Zheludev, Phys. Rev. B 68, 134438 (2003)].     

Synthèse et étude structurale de dérivés substitués en -2 du thiazolidine carboxylate d'éthyle-4 (R)

Pharmacological properties of thiazolidine derivatives are of great interest. For this purpose we prepared two series: 2-hydroxyalkyl-4-carbethoxythiazolidines and 2-carbalkoxyalkyl-4-carbethoxythiazolidines. Their syntheses involve a condensation reaction between L-carbethoxy-cystein and several α-hydroxyketones or β-ketoesters. Compounds 4 and 5 was obtained as an unequal mixture of diastereoisomers. Protons nmr spectra at 300 MHz in the presence of trifluoroacetic acid shows a modification of diastereoisomer percentages which indicate the existence of an equilibrium through an imminium ion intermediate. Therefore, the stereoselectivity observed reflects the relative stability of the different diastereoisomers.     

Incommensurate magnetic order in TbTe3

We report a neutron diffraction study of the magnetic phase transitions in the charge-density wave (CDW) TbTe(3) compound. We discover that in the paramagnetic phase there are strong 2D-like magnetic correlations, consistent with the pronounced anisotropy of the chemical structure. A long-range incommensurate magnetic order emerges in TbTe(3) at T(mag1) = 5.78 K as a result of continuous phase transitions. We observe that near the temperature T(mag1) the magnetic Bragg peaks appear around the position (0, 0, 0.24) (or its rational multiples), that is fairly close to the propagation vector (0,0,0.29) associated with the CDW phase transition in TbTe(3). This suggests that correlations leading to the long-range magnetic order in TbTe(3) are linked to the modulations that occur in the CDW state.     

Molecular engineering of organic sensitizers for solar cell applications

Novel organic sensitizers comprising donor, electron-conducting, and anchoring groups were engineered at molecular level and synthesized. The functionalized unsymmetrical organic sensitizers 3-{5-[N,N-bis(9,9-dimethylfluorene-2-yl)phenyl]-thiophene-2-yl}-2-cyano-acrylic acid (JK-1) and 3-{5'-[N,N-bis(9,9-dimethylfluorene-2-yl)phenyl]-2,2'-bisthiophene-5-yl}-2-cyano-acrylic acid (JK-2), upon anchoring onto TiO2 film, exhibit unprecedented incident photon to current conversion efficiency of 91%. The photovoltaic data using an electrolyte having composition of 0.6 M M-methyl-N-butyl imidiazolium iodide, 0.04 M iodine, 0.025 M LiI, 0.05 M guanidinium thiocyanate, and 0.28 M tert-butylpyridine in a 15/85 (v/v) mixture of valeronitrile and acetonitrile revealed a short circuit photocurrent density of 14.0 +/- 0.2 mA/cm2, an open circuit voltage of 753 +/- 10 mV, and a fill factor of 0.76 +/- 0.02, corresponding to an overall conversion efficiency of 8.01% under standard AM 1.5 sunlight. DFT/TDDFT calculations have been performed on the two organic sensitizers to gain insight into their structural, electronic, and optical properties. Our results show that the cyanoacrylic acid groups are essentially coplanar with respect to the thiophene units, reflecting the strong conjugation across the thiophene-cyanoacrylic groups. Molecular orbitals analysis confirmed the experimental assignment of redox potentials, while TDDFT calculations allowed assignment of the visible absorption bands.