Magnetic phase diagrams of the CrB- and FeB-type HoSi compounds

The temperature magnetic phase diagrams of the dimorphic HoSi compound were studied by neutron diffraction. The sample comprises 35.5% CrB- (Cmcm) and 64.5% FeB-type (Pnma) of structure. Both phases order antiferromagnetically below T_N=25 K and undergo first-order magnetic transitions at T_ic=16.5 K. Their T-phase diagrams comprise a low temperature (LT) 2.7 K−T_ic and a high temperature (HT) range T_ic−T_N with distinct wave vectors.The LT magnetic ordering of the CrB-type HoSi with the wave vector q₁=(1/2, 0, 1/2) corresponds to a uniaxial magnetic structure, with the Ho moments along the shortest axis c. At 2.7 K the ordered moment value is 8.6(2) μ_B/Ho atom. The HT ordering, described by the wave vector q₂=(q_2x, 0, q_2z) with a T-variable length, corresponds to an amplitude modulated structure.The magnetic ordering of the FeB-type HoSi requires two symmetry independent vectors q₃=(0, q_3y, q_3z) for the LT- and q₄=(q_4x, q_4y, 0) for the HT range. Both vectors correspond to sine wave modulated structures with the Ho magnetic moments confined along the shortest axis b. The q₃ vector has an almost invariable length vs. T close to ≈(0, 9/17, 1/11). At 2.7 K the amplitude of the wave is 10.9(1) μ_B/Ho atom. At T_icq₃ jumps to the wave vector q₄=(q_4x, q_4y, 0) with a T-variable length. At 17 K q₄=(0.092(1), 0.538(3), 0). Around T_ic there is a narrow coexistence range of the q₃ and q₄ competing phases. Various models are discussed and compared with the isomorphic RSi (R=rare earth) compounds counterparts of HoSi, a comparison that has led us to briefly review the magnetic structures available in the literature for this interesting class of compounds.     

Low-temperature magnetic structures in the DySi FeB-type compound 27.03.09

The low-temperature magnetic ordering of the dimorphic DySi compound has been studied at 1.5 K by neutron diffraction on two polycrystalline samples. The samples comprise various amounts of the two orthorhombic modifications: CrB-type (Cmcm Nr. 63, all atoms at 4c site: (0, y, )) and FeB-type (Pnma Nr. 62, all atoms at 4c site: (x, , z)), both order antiferromagnetically (T_N≈38 K). The CrB-type phase orders with a uniaxial structure with the wave vector q₁=(0, 0, ) requiring a doubling of the c-axis. The Dy moments point along the linear chain with the shortest distance c. At 1.5 K, the ordered moment value is 8.57(1) μ_B/Dy atom.Two symmetry independent wave vectors describe the 1.5 K magnetic ordering of the FeB-type phase: q₂=(0, , ) and q₃=(0, 0.484(1), 0.0892(1)), coexisting in form of domains. In both structures the magnetic moments are confined to the (0 0 1) plane at an angle of 2(2)° and 22(3)° from the shortest axis b, respectively. Both structures correspond to sine wave modulations. The amplitude of the q₂ wave is m_o=7.5(1) μ_B/Dy atom and that of q₃ 8.2(1) μ_B/Dy atom. The wave vector q₂ when referring to the (a, 2b, c) cell and the wave vector q=(0, 0, ) corresponds to a transversal modulation, which by a proper origin choice can be also described as an antiphase domain structure with two amplitudes. The moments point to the b-axis and are stacked in the sequence (+m_o/2, −m_o/2, −m_o, −m_o/2, +m_o/2, +m_o, …) along the c-direction, while t_b acts as an antitranslation. For the q₃ phase, the local moment value depends on the atom position in the wave. We also discuss the case where q₃ and q₂ act simultaneously in physical space.     

The nature of anharmonicity and anomalous piezoelectric properties of ferroelectric SbSBr crystal

The contribution of soft mode at Sb atom's sites, to the temperature dependences of Sb atom's equilibrium position's difference Δz(T) has been studied theoretically, when SbSBr crystal is deformed along a(x), b(y) and c(z)-axis in paraelectric phase and is deformed along c(z)-axis in ferroelectric phase. The largest change of Δz₃₃(T) occurs in the ferroelectric phase near the phase transition temperature in the range from 16 K to 21 K. The temperature dependence of Sb atom's equilibrium position's displacements Δz₃₃ is very similar to the temperature dependence of experimental piezoelectric modulus, when SbSBr crystal is deformed in the direction of c(z)-axis in ferroelectric phase.     

Effect of C and SiC additions into in situ or mechanically alloyed MgB2 deformed in Ti sheath

Effect of 3.4 wt.% C and 5 wt.% SiC doping into the standard in situ (IN) process and mechanically alloyed (MA) MgB₂ was studied. Powders of IN and MA process were carried out in air and in argon filled glove box, respectively. Wire samples were prepared by two-axial rolling deformation of IN and MA powders inside the Ti tube. Titanium as sheath material allows to use higher sintering temperatures, we used 700 °C and 800 °C for 30 min in Argon. Critical current densities (J_c) were measured at variable temperatures 4.2 K, 10 K, 15 K and 20 K in the external magnetic fields ranging to 15 T. Critical temperatures, upper critical fields and irreversibility fields of IN and MA with SiC and C additions are compared and discussed. The highest transport properties were observed for wires with MA SiC doped MgB₂ in the whole scale of temperatures 4.2–20 K. Upper critical field was rapidly enhanced in the case of carbon doped MA samples at 4.2 K. MA samples have shown decreased J_c values for higher temperatures (15 K, 20 K), in some case even worse than for the not doped reference IN sample. Carbon substitution and grain connectivity of analyzed samples are compared and discussed. Presented results show that for 20 K applications some new ways (additions) have to be found for increasing the J_c substantially.     

Reversible photomagnetism in a cobalt layered compound coupled with photochromic diarylethene

Photomagnetism is one of the most attractive topics in recent research on molecular solids. In order to produce a photo-controllable magnet, we have synthesized a novel organic-inorganic hybrid system coupled with a photochromic diarylethene anion, 2,2′-dimethyl-3,3′-(perfluorocyclopentene-1,2-diyl)bis(benzo[b]thiophene-6-sulfonate) (1a) and cobalt LDHs (layered double hydroxides). Based on the elemental analysis, the title compound, which was synthesized by the anion exchange reaction between Co₂(OH)₃(CH₃COO)·H₂O (2) and 1a, has the chemical composition, Co₄(OH)₇(1a)_0.5·3H₂O (3). Powder X-ray diffraction analysis revealed the interlayer distance of c=27.8 Å. The magnetic susceptibility measurements elucidated the ferromagnetic intra- and inter-layer interactions and the Curie temperature of T_c=9 K. By UV irradiation of 313 nm, 3 shows the photo-isomerization of diarylethene anion from the open form to the closed one in solid state, which leads to the decreases in the coercive field and the remnant magnetization. Furthermore, the photo-excited state is returned to the initial state (open form) almost reversibly by visible irradiation of 550 nm.     

A new quasi-one-dimensional molecular solid based on Ni(mnt)2 anion: Crystal structure and spin-gap transition

A new molecular solid, [1-(4′-bromo-2′-fluorobenzyl)-4-dimetylaminopyridinium]-bis(maleonitriledithiolato)nickel(III), (BrFBzPyN(CH₃)₂(Ni(mnt)₂)(1), has been prepared and characterized by elemental analyses, IR, ESI-MS spectra, single crystal X-ray diffraction and magnetic measurements. Compound 1 crystallizes in the orthorhombic space group Pnma, a=20.579(4) Å, b=7.078(1) Å, c=17.942(4) Å, α=β=γ=90°, V=2613.3(9) Å³, Z=4. The Ni(III) ions of 1 form a quasi-one-dimensional Zigzag magnetic chain within a Ni(mnt)₂⁻ column through Ni?S, S?S, Ni?Ni, or π?π interactions with an Ni?Ni distance of 4.227 Å. Magnetic susceptibility measurements in the temperature range 2-300 K show that 1 exhibits a spin-gap transition around 200 K, and antiferromagnetic interaction in the high-temperature phase (HT) and spin gap in the low-temperature phase (LT). The transition for 1 is second-order phase transition as determined by DSC analyses.     

Indium-induced superstructures formed on Si(1 1 0) surfaces

Si(1 1 0) surfaces covered with small amounts of In deposit and then annealed at high temperature were investigated by RHEED, and two kinds of superstructures with A = 3a and B = −a + 4b, and A = 3a − 2b and B = −2a + 4b as primitive translational vectors are reported to form on the surfaces.     

Magnetic structure of the La3NiGe2-type Tb3NiGe2 and Mn5Si3-type Tb5NixGe3−x (x=0 and 0.3)

We present a neutron powder diffraction investigation of the magnetic structure of La₃NiGe₂-type Tb₃NiGe₂ and Mn₅Si₃-type Tb₅Ni_xGe_3−x (x=0, 0.3) compounds. It is found that below∼135 K Tb₃NiGe₂ exhibits a commensurate b-collinear ferrimagnetic ordering with C_2h′={1, m_z, 1′×2_z, 1′×1?} magnetic point group. The Mn₅Si₃-type Tb₅Ge₃ and Tb₅Ni_0.3Ge_2.7 compounds are found to present a flat spiral type antiferromagnetic ordering at 85 and ≥89 K, respectively. The Ni for Ge substitution is found to decrease the flat spiral ordered magnetic unit cell from a×a×40c of Tb₅Ge₃ (below 40 K) down to a×a×5c for Tb₅Ni_0.3Ge_2.7 (below ∼10 K).     

Synthesis, characterization and optical limiting effect of nickel complexes of multi-sulfur 1,2-dithiolene

Three nickel complexes with a new multi-sulfur 1,2-dithiolene ligand, (n-Bu₄N)[Ni(cddt)₂] 1, (Ph₄P)[Ni(cddt)₂] 2 and [Ni(cddt)₂] 3 (cddt=4a, 6, 7, 7a-5H-cyclopenta[b]-1,4-dithiin-2,3-dithiolate), have been synthesized and characterized by electrochemical measurements, IR, EPR and UV-Vis-NIR spectroscopies. The crystal structure of complex 2 is determined. Their optical nonlinearities are measured by the Z-scan technique with an 8 ns pulsed laser at 532 nm and all exhibit NLO absorptive abilities. Complexes 1 and 2 both exhibit effective self-defocusing performance (n₂=−5.81×10⁻¹⁰ esu for 1 and −4.51×10⁻¹⁰ esu for 2). The optical limiting (OL) effects were observed with nanosecond and picosecond laser pulses. The OL capability of complex 3 is superior to C₆₀ at the same experimental condition in ns measurements.     

Intermolecular photoinduced electron-transfer processes between C60 and aniline derivatives in benzonitrile

The quenching behavior of the triplets of C₆₀ by various aniline derivatives (1a-d and 2a-e) was investigated by means of laser flash photolysis in benzonitrile at 293 K. Electron transfer process was proposed to be the main mechanism because of the direct detection of radical ions of aniline derivatives and C₆₀ in time-resolved transient absorption spectra. The quenching rate constants (k_q) of by different substrates determined at 740 nm approach or reach the diffusion-controlled limit. DFT method was employed to calculate the unknown oxidation potentials of substrates in solution. With these E_ox values, free energy changes (ΔG) were obtained through Rehm-Weller equation. Dependence of observed quenching rate constants on the free energy changes further indicates the photoinduced reactions between ³C₆₀^* and substrates proceed through an electron transfer mechanism. Obtained k_q values for the aniline derivatives are impacted obviously by ground-state configurations and the kinds substituents quantified by Hammett σ constant. Good correlation between log k_q and σ values conforms to the empirical Hammett equation. A more negative ρ value (−3.356) was gained for anilines (2a-e) than that of N,N-dimethylanilines (1a-d) (−1.382), which suggests a more susceptible reactivity for the former substrates. Charge density distribution of reaction center “N” originated from quantum calculation supports this suggestion. In addition, a relationship between quenching rate constants and solvent viscosity was gained from C₆₀/dimethyl-p-toluidine system in altered mixtures of acetonitrile and toluene.     

Nonlinear optical absorption and fluorescence of phosphine-substituted bithiophenes in the violet-blue spectral region

The nonlinear optical absorptions of two 5,5′-bis(diphenylphosphino)-2,2′-bithiophene derivatives, Ph₂(X)P(C₄H₂S)₂P(X)Ph₂ (X = O, 1; S, 2), have been investigated by direct transmission measurement with both picosecond and nanosecond laser pulses from 420 nm to 480 nm. Saturated dichloromethane solutions of 1 and 2 exhibit strong nonlinear optical absorptions in this violet-blue spectral region with that of 2 being stronger at all wavelengths. In the picosecond regime, at 420 nm, the transmittance rapidly falls to 50% when the incident fluence is 0.22 J/cm² for 1 and 0.11 J/cm² for 2. Two-photon absorption appears to be the primary mechanism for this nonlinear absorption. The two-photon absorption coefficients β for 1 (2.1 cm/GW) and 2 (4.4 cm/GM) were obtained by fitting the measurement of transmittance as the function of incident beam intensity at 420 nm. These β values are comparable with some of the best results obtained for organic materials in the green, red and infrared spectral region. Both compounds also show fluorescence with an emission peak at 390 nm for 1 and 400 nm for 2. The fluorescence of 1 is considerably stronger than is that of 2. The combination of the wide band gap and strong fluorescence emission of 1 makes it a promising candidate as a host material for blue organic light emitting diodes.     

A theoretical and numerical consideration of the longitudinal and transverse relaxations in the rotating frame

We previously derived a simple equation for solving time-dependent Bloch equations by a matrix operation. The purpose of this study was to present a theoretical and numerical consideration of the longitudinal (R_1ρ = 1/T_1ρ) and transverse relaxation rates in the rotating frame (R_2ρ = 1/T_2ρ), based on this method. First, we derived an equation describing the time evolution of the magnetization vector (M(t)) by expanding the matrix exponential into the eigenvalues and the corresponding eigenvectors using diagonalization. Second, we obtained the longitudinal magnetization vector in the rotating frame (M_1ρ(t)) by taking the inner product of M(t) and the eigenvector with the smallest eigenvalue in modulus, and then we obtained the transverse magnetization vector in the rotating frame (M_2ρ(t)) by subtracting M_1ρ(t) from M(t). For comparison, we also computed the spin-locked magnetization vector. We derived the exact solutions for R_1ρ and R_2ρ from the eigenvalues, and compared them with those obtained numerically from M_1ρ(t) and M_2ρ(t), respectively. There was excellent agreement between them. From the exact solutions for R_1ρ and R_2ρ, R_2ρ was found to be given by R_2ρ = (2R₂ + R₁)/2 − R_1ρ/2, where R₁ and R₂ denote the conventional longitudinal and transverse relaxation rates, respectively. We also derived M_1ρ(t) and M_2ρ(t) for bulk water protons, in which the effect of chemical exchange was taken into account using a 2-pool chemical exchange model, and we compared the R_1ρ and R_2ρ values obtained from the eigenvalues and those obtained numerically from M_1ρ(t) and M_2ρ(t). There was also excellent agreement between them. In conclusion, this study will be useful for better understanding of the longitudinal and transverse relaxations in the rotating frame and for analyzing the contrast mechanisms in T_1ρ- and T_2ρ-weighted MRI.     

Sensitized luminescence of Eu and Tb macrocyclic complexes bearing benzophenone antennae

Sensitized luminescence behavior of lanthanide (Ln=Eu³⁺, Tb³⁺) macrocyclic cyclen (1,4,7,10-tetraazacyclododecane) complexes bearing one or four benzophenone (BP) moieties as antenna (LnL1 and LnL4) has been studied in water. Despite higher molar extinction coefficient of EuL4 owing to four antennae, it shows only one-thirtieth the luminescence intensity of EuL1. Energy level of triplet excited-state of BP antenna (E_T) is only a few kJ mol⁻¹ higher than that of ⁵D₂ excited-state of Eu³⁺, thus promoting a back energy transfer (BET) from ⁵D₂ of Eu³⁺ to ground-state BP antennae. On EuL4 bearing four antennae, BET occurs more rapidly than that on EuL1, thus exhibiting much weaker luminescence. For Tb complexes, the energy gap between E_T of BP antenna and ⁵D₄ excited state of Tb³⁺ is large enough (>13 kJ mol⁻¹), such that practically no BET occurs. The luminescence intensity of TbL4 is, however, lower (two-third) than that of TbL1. Time-resolved luminescence measurement reveals that hydration number of Tb³⁺ within TbL4 is twice that within TbL1. This is because the structural distortion of ligands on TbL4, caused by an intramolecular dipole-dipole interaction among the BP antennae, allows coordination of higher number of H₂O molecules to Tb³⁺, thus leading to a strong Tb luminescence quenching via O-H oscillators.     

Synthesis and luminescent properties of two Schiff-base boron complexes

Schiff bases N,N′-o-phenylenebis (salicylideneimine) (H₂L¹), N,N′-p-phenylenebis (salicylideneimine) (H₂L²) and their corresponding boron complexes (BF₂)₂L¹, (BF₂)₂L² were synthesized, respectively. The two boron complexes have been characterized by ¹H NMR, mass spectrometry and elemental analysis, while the luminescent properties of them were investigated with UV-VIS spectroscopy and photoluminescence spectroscopy. Then the three-layer devices [ITO/NPB (60 nm)/(BF₂)₂L¹ (50 nm)/Alq3 (20 nm)/LiF (1 nm)/Al (200 nm)] (device I) and [ITO/NPB (60 nm)/(BF₂)₂L² (50 nm)/Alq3 (20 nm)/LiF (1 nm)/Al (200 nm)] (device II) were fabricated by vacuum deposition. These two devices both exhibited blue green emission at 500 nm, but showed different luminances and efficiencies.     

Isomerization and fluorescence characteristics of sterically hindered azobenzene derivatives

We report synthesis and isomerization behaviors of sterically hindered azobenzene derivatives (1 and 2) with decyloxy and hydroxy groups, respectively, and their fluorescence enhancement under UV light irradiation characterized by means of absorption and fluorescence spectroscopy measurements. Upon irradiation of as-prepared solution (1) with UV light (∼200 mJ/cm²) a cis-rich photostationary state was reached. Obviously different from 2 showing very fast thermal cis-to-trans isomerization within 2 min, slow cis-to-trans thermal back isomerization of 1 with a long alkyl chain at ambient temperature was observed on the time scale of weeks. In contrast to no striking changes in absorption and fluorescence spectra of compound 2, the azobenzene 1 showed green fluorescence upon prolonged irradiation with UV light (about 3-8 J/cm² exposure doses), although both the initial trans-rich and cis-rich states of azobenzene molecules were not fluorescent in solution. The stability of fluorescence efficiency caused by drying and redissolving processes was examined.     

Magnetic structure of the Mn5Si3-type Er5Ge3 compound

The Er₅Ge₃ compound (Mn₅Si₃-type, hP16, P6₃/mcm) at 4 K shows magnetic ordering of the antiferromagnetic type. Its magnetic structure consists of sine modulated collinear magnetic moments of Er that are parallel to the c axis (with a propagation vector k=[0 0 ±0.3]). This corresponds to the magnetic unit cell (a a 10c), the values of the magnetic moment of the Er atoms being, as a general formula, M_z≈M₀ cos [2π(Z–1/4)(1–kZ)], with M₀=9.2(2) μ_B at 4 K.     

Photophysical characteristics of 4,4′-bis(N-carbazolyl)tolan derivatives and their application in organic light emitting diodes

4,4′-bis(N-carbazolyl)tolan (BCT) and 4,4′-bis[N-(3,6-di-t-butyl)carbazolyl]tolan (BCT-t-Bu) were synthesized as π-expanded analogs of 4,4′-bis(N-carbazolyl)biphenyl. Their photophysical characteristics both in solution and films were thoroughly investigated. Interestingly, the phosphorescence spectrum of BCT was significantly medium-dependent, and the emission maximum was red-shifted by 131 nm from 489 nm in solution at 77 K to 620 nm in a deposited film at 5 K, suggesting the presence of strong intermolecular interactions in the film. BCT and BCT-t-Bu were found to be useful as host materials for fluorescence-based organic light emitting diodes (OLEDs). However, their low triplet energy levels in films negated their potential to act as hosts in phosphorescence-based OLEDs.     

EPR study of Cu(II) dopant ions in single crystals of bis(l-asparaginato)Zn(II)

We report an electron paramagnetic resonance (EPR) study at 33.9 GHz and room temperature of oriented single crystal samples of bis(l-asparaginato)Zn(II) doped with Cu(II). The variation of the spectra with magnetic field orientation was measured in three crystal planes (a*b, bc and a*c, with a*=b×c). These spectra display two groups of four peaks arising from the hyperfine interaction with the I_Cu=3/2 nuclear spins of copper. They were assigned to Cu(II) ions in two lattice sites related by a 180° rotation around the b-crystal axis. The g and hyperfine coupling (A) tensors of the Cu(II) ions were evaluated from the single crystal data. Some indeterminacy in the assignment of the signals was avoided measuring the EPR spectrum of a powder sample. Their principal values are g₁=2.060(1), g₂=2.068(2), g₃=2.283(2), and A₁≈0.1×10⁻⁴, A₂=13×10⁻⁴ and A₃=165×10⁻⁴ cm⁻¹. The eigenvectors corresponding to g₃ and A₃ are coincident within the experimental error; the other eigenvectors are rotated 5.6° in the perpendicular plane. Considering the crystal structure of bis(l-asparaginato)Zn(II), our EPR results indicate that the Cu(II) impurities replace Zn(II) ions in the host crystal. We propose a molecular model based on the EPR data and the structural information, and analyse the results comparing the measured values with those obtained in similar systems.