A Delicate Balance between Antiferromagnetism and Ferromagnetism: Theoretical and Experimental Studies of A2MRu5B2 (A=Zr,Hf; M=Fe,Mn) Metal Borides

Metal-rich borides with the Ti₃Co₅B₂-type structure represent an ideal playground for tuning magnetic interactions through chemical substitutions. In this work, density functional theory (DFT) and experimental studies of Ru-rich quaternary borides with the general composition A₂MRu₅B₂ (A=Zr, Hf, M=Fe, Mn) are presented. Total energy calculations show that the phases Zr₂FeRu₅B₂ and Hf₂FeRu₅B₂ prefer ground states with strong antiferromagnetic (AFM) interactions between ferromagnetic (FM) M-chains. Manganese substitution for iron lowers these antiferromagnetic interchain interactions dramatically and creates a strong competition between FM and AFM states with a slight preference for AFM in Zr₂MnRu₅B₂ and for FM in Hf₂MnRu₅B₂. Magnetic property measurements show a field dependence of the AFM transition (T_N): T_N is found at 0.1 T for all phases with predicted AFM states whereas for the predicted FM phase it is found at a much lower magnetic field (0.005 T). Furthermore, T_N is lowest for a Hf-based phase (20 K) and highest for a Zr-based one (28 K), in accordance with DFT predictions of weaker AFM interactions in the Hf-based phases. Interestingly, the AFM transitions vanish in all compounds at higher fields (>1 T) in favor of FM transitions, indicating metamagnetic behaviors for these Ru-rich phases.     

Wireless Information Transmission System Powered by an Abiotic Biofuel Cell Implanted in an Orange

An “abiotic” biofuel cell composed of catalytic electrodes modified with inorganic nanoparticles (NPs) deposited on carbon black (CB) was used to activate a wireless information transmission system. The cathode and anode were made of carbon paper modified with Pt‐NPs/CB and buckypaper modified with Au₈₀Pt₂₀‐NPs/CB, respectively. The cathode/anode pair was implanted in orange pulp extracting power from its content (glucose and fructose in the juice). The open circuit voltage, V_oc, short circuit current density, j_sc, and maximum power produced by the biofuel cell, P_max, were found as 0.36 V, 1.3 mA cm^?2 and 182 µW, respectively. The voltage produced by the biofuel cell was amplified with an energy harvesting circuit and applied to a wireless transmitter. The present study continues the research line where different implantable biofuel cells are used for activation of electronic devices.     

Die Seltenerdmetallpolyselenide Gd8Se15, Tb8Se15−x,Dy8Se15−x,Ho8Se15−x,Er8Se15−x und Y8Se15−x (0 < x ≤ 0.3) – Zunehmende Fehlordnung in ausgedünnten,planaren Selenschichten

The Rare Earth Metal Polyselenides Gd₈Se₁₅, Tb₈Se_15?x, Dy₈Se_15?x, Ho₈Se_15?x, Er₈Se_15?x, and Y₈Se_15?x – Increasing Disorder in Defective Planar Selenium Layers Single crystals of the rare earth metal polyselenides Gd₈Se₁₅, Tb₈Se_15?x, Dy₈Se_15?x, Ho₈Se_15?x, Er₈Se_15?x, and Y₈Se_15?x (0 < x ≤ 0.3) have been prepared by chemical transport reactions (1120 K→ 970 K, 14 days, I₂ as carrier) starting from pre‐annealed powders of nominal compositions between LnSe₂ and LnSe_1.9. The isostructural title compounds adopt a 3 × 4 × 2 superstructure of the ZrSSi type and can be described in space group Amm2 with lattice parameters of a = 12.161(1) Å, b = 16.212(2) Å and c = 16.631(2) Å (Gd₈Se₁₅), a = 12.094(2) Å, b = 16.123(2) Å and c = 16.550(2) Å (Tb₈Se_15?x), a = 12.036(2) Å, b = 16.060(2) Å and c = 16.475(2) Å (Dy₈Se_15?x), a = 11.993(2) Å, b = 15.999(2) Å and c = 16.471(2) Å (Ho₈Se_15?x), a = 11.908(2) Å, b = 15.921(2) Å and c = 16.428(2) Å (Er₈Se_15?x), and a = 12.045(2) Å, b = 16.072(3) Å and c = 16.626(3) Å (Y₈Se_15?x), respectively. The structure consists of puckered [LnSe] double slabs and planar Se layers alternating along [001]. The planar Se layers contain a disordered arrangement of dimers, Se^2? and vacancies. All compounds are semiconducting and contain trivalent rare earth metals (Ln³⁺).     

Structural‐Distortion‐Driven Magnetic Transformation from Ferro‐ to Ferrimagnetic Iron Chains in B6‐based Nb6FeIr6B8

We report on a structural distortion of kinetically stable B₆‐based ferromagnetic Nb₆FeIr₆B₈ that induces an unprecedented transformation of a ferromagnetic Fe chain into two ferrimagnetic Fe chains through superstructure formation. Density functional theory calculations showed that the ferromagnetic Fe–Fe intrachain interactions found in the undistorted structure become ferrimagnetic in the distorted superstructure, mainly because the two independent iron atoms building each chain interact antiferromagnetically and carry different magnetic moments. High‐temperature SQUID magnetometry confirmed ferrimagnetic ordering at 525 K with a high and negative Weiss constant of ?972 K indicating the presence of strong antiferromagnetic interactions, as predicted. This finding paves the way for the development of low‐dimensional magnetic intermetallic systems based on Heisenberg ferrimagnetic chains, which have previously been studied only in molecular‐based compounds.     

Electronic absorption and fluorescence spectra and excited singlet-state dipole moments of biologically important pyrimidines

Electronic absorption and fluorescence emission spectra of several biologically important pyrimidines were measured at room temperature (298 K) in the following solvents: dioxane, ethyl ether, chloroform, ethyl acetate, 1-butanol, 2-propanol, methanol, dimethylformamide, acetonitrile, and dimethyl sulfoxide. The compounds studied were uracil, thymine, cytosine, 5-fluorouracil, 5-chlorouracil, 5-bromouracil, 5-iodouracil, 2-thiouracil, barbituric acid, and orotic acid. In combination with the ground-state dipole moments of the above compounds, these spectral data were used to determine their lowest excited singlet-state dipole moments using the soivatochromic method. The effects of the solvent upon the spectral properties and of the structure upon the ground and excited singlet-state dipole moments are discussed. For most of the compounds, the excited singlet-state dipole moments are higher than their ground-state counterparts.The theoretical dipole moments for all the pyrimidines listed above, as well as for pyrimidine, alloxan, and uracil-5-carboxylic acid, were calculated by two methods. One approach involved a combination of the PPP (-LCI-SCF-MO) method for the -contribution to the overall dipole moment and the -contribution obtained as a vector sum of the -bond moments and group moments. The second set of theoretical values was obtained by the CNDO/2 method. The results were compared with the experimental dipole moments.Presented, in part, at the XIth IUPAC Symposium on Photochemistry, Lisbon, Portugal, July 27–August 1, 1986, and at the 192nd National Meeting of the American Chemical Society, Anaheim, CA, September 7–12, 1986. Part of this work was carried out at the University of Texas at El Paso, El Paso, TX, during the tenure of one of the authors there (C. P.). This paper is dedicated to Dr. Rudolf Zahradník, the teacher of one of the authors (C. P.) and the authors' friend and colleague.     

Synthesis and Some Chemical Conversions of 2-([2,2]-5-Paracyclophanyl)pyrrole

2-([2,2]-5-Paracyclophanyl)pyrrole has been synthesized and nitration and formylation of it have been effected. The 1--cyanoethyl derivative and 2-formyl-5-paracyclophanyl-3H-pyrrolizine have been obtained from 5-formyl-2-([2,2]-5-paracyclophanyl)pyrrole by the action of acrylonitrile and acrolein respectively under Michael reaction conditions.     

Partial Fourier approximation of the Lamé equations in axisymmetric domains

In this paper, we study the partial Fourier method for treating the Lamé equations in three‐dimensional axisymmetric domains subjected to non‐axisymmetric loads. We consider the mixed boundary value problem of the linear theory of elasticity with the displacement û , the body force f̂ ϵ (L₂)³ and homogeneous Dirichlet and Neumann boundary conditions. The partial Fourier decomposition reduces, without any error, the three‐dimensional boundary value problem to an infinite sequence of two‐dimensional boundary value problems, whose solutions û _n (n = 0, 1, 2,…) are the Fourier coefficients of û . This process of dimension reduction is described, and appropriate function spaces are given to characterize the reduced problems in two dimensions. The trace properties of these spaces on the rotational axis and some properties of the Fourier coefficients û _n are proved, which are important for further numerical treatment, e.g. by the finite‐element method. Moreover, generalized completeness relations are described for the variational equation, the stresses and the strains. The properties of the resulting system of two‐dimensional problems are characterized. Particularly, a priori estimates of the Fourier coefficients û _n and of the error of the partial Fourier approximation are given. Copyright © 1999 John Wiley & Sons, Ltd.     

Effect of Substitution on the Hysteretic Phase Transition in a Bistable Phenalenyl-Based Neutral Radical Molecular Conductor

The ability to tune the physical properties of bistable organic functional materials by means of chemistry can facilitate their development for molecular electronic switching components. The butylamine-containing biphenalenyl boron neutral radical, [Bu]₂B, crystalline compound has recently attracted significant attention by displaying a hysteretic phase transition accompanied by simultaneous bistability in magnetic, electrical, and optical properties close to room temperature. In this report, substitutional doping was applied to [Bu]₂B by crystallizing solid solutions of bistable [Bu]₂B and its non-radical-containing counterpart [Bu]₂Be. With increasing doping degree, the hysteretic phase transition is gradually suppressed in terms of reducing the height, but conserves the width of the hysteresis loop as observed through magnetic susceptibility and electrical conductivity measurements. At the critical doping level of about 6 %, the abrupt transformation of the crystal structure to that of the pure [Bu]₂Be crystal packing was observed, accompanied by a complete collapse of the hysteresis loop. Further study of the structure–properties relationships of bistable neutral radical conductors based on the [Bu]₂B host can be conducted utilizing a variety of biphenalenyl-based molecular conductors.