Theory of spatial dispersion of dielectric and magnetic constants in magnetic uniaxial gyrotropic crystals

The theory of spatial dispersion of dielectric and magnetic constants of magnetic uniaxial crystals based on generalized Maxwell’s equations D = ε?E = (ε + inγ E = ?ns ^× H and B = μ?H = (μ + inδ)H = ns ^× E with spatial dispersion parameters γ and δ is considered. Generalized Fresnel’s and polarization equations for the obtained vectors E, D, H, and B are analyzed for the wave normal direction s ⊥ C (where C is the optic axis of a crystal). The possibility of the existence of a third natural wave in a crystal is proved.     

Magnetic properties of HoFe3(BO3)4

The magnetic properties of an antiferromagnet with trigonal symmetry, namely, HoFe₃(BO₃)₄, have been investigated theoretically. The calculations have been performed in the molecular field approximation and in the framework of the crystal field model for the rare-earth subsystem. Extensive experimental data on the magnetic properties of HoFe₃(BO₃)₄ have been interpreted and good agreement between theory and experiment has been achieved using the obtained theoretical dependences. The spontaneous spin-reorientation transition and the spin-reorientation transition induced by a magnetic field B ‖ a from the easy-axis to easy-plane state, as well as the spin-flop transition in a magnetic field B ‖ c, have been described. It has been shown that the spontaneous spin-reorientation transition is a magnetic analog of the Jahn-Teller effect. The temperature dependences of the initial magnetic susceptibility at temperatures ranging from 2 to 300 K, the nonlinear curves of magnetization for B ‖ c and B ⊥ c in a magnetic field up to 1.2 T (which indicate the occurrence of first-order phase transitions), and their evolution with variations in the temperature have been described, as well as the temperature and field dependences of the magnetization in a magnetic field up to 9 T. The parameters of the trigonal crystal field for the rare-earth ion Ho³⁺ and the parameters of the Fe-Fe and Ho-Fe exchange interactions have been determined in the course of interpretation of the experimental data.     

Bloch electron dynamics

New equations of motion for a Bloch electron [momentum p=h k,energy ε _n(p),zone number n, charge -e]: $$m_j \frac{{dv_j }}{{dt}} = - e(E + v \times B)_j $$ are proposed, where v≡?ε_n(p)/?p is the velocity, and {m_j}are the principal masses m _j ^? 1=?²ε_n/?p _j ² along the normal and the two principal axes of curvatures at each point of the constant-energy surface represented by ε=ε_n(p).Their advantages over the prevalent equations of motion where the left-hand-side is replaced by hk _j are demonstrated by examining de Haas-van Alphen oscillations and orientation-dependent cyclotron resonance peaks.     

Bis(2-Hydroxy-3-Isopropyl-6-Methyl-Benzaldehyde)Ethylenediamine: A Novel Cation Sensor

Novel substituted phenol-based new symmetrical bis(2-hydroxy-3-isopropyl-6-methyl-benzaldehyde)ethylenediamine (1) has been designed and synthesized. The compound 1 fluorometrically recognized Cu²⁺ ion in CH₃OH/H₂O (90:10, v/v) by exhibiting an increase in emission upon complexation. In addition, Cu²⁺ gave rise to a change in colour of the solution of compound 1, which was clearly visible to the naked eye under UV irradiation. The association constant (K) of compound 1 with Cu²⁺ ion was computed with the Benesi-Hildebrand plot and Scatchard plot at 43,000 M^?1 and 43,011 M^?1 respectively.     

A Novel Series Colorimetric and Off–On Fluorescent Chemosensors for Fe3+ Based on Rhodamine B Derivative

A novel series colorimetric and off–on fluorescent chemosensors (2a, 2b, 2c) were designed and synthesized, which showed reversible and highly selective and sensitive recognition toward Fe³⁺ over other examined metal ions. Upon addition of Fe³⁺, sensors (2a, 2b) exhibit remarkably and 2c exhibits moderate enhanced absorbance intensity and color change from colorless to pink in CH₃OH–H₂O(1:1, v/v). The three compounds (2a, 2b, 2c) may therefore be applicable as rhodamine-based turn-on type fluorescent chemosensors.     

Indole-based Fluorescent Sensors for Selective Detection of Hg2+

A series of indole-based fluorescent chemosensors 1–4 were prepared and investigated characteristick features with transition metal ions. Sensors 1 and 2 were selective for Hg²⁺ ion among a series of metal ions in H₂O–DMSO with association constants of 4.60×10⁴ and 5.90×10⁴?M^?1 and detection limits of 140 and 101.6 μM, respectively.

Influence of the ground state of the Pr<Superscript>3+</Superscript> ion on magnetic and magnetoelectric properties of the PrFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> multiferroic

The magnetic, magnetoelectric, and magnetoelastic properties of a PrFe₃(BO₃)₄ single crystal and the phase transitions induced in this crystal by the magnetic field are studied both experimentally and theoretically. Unlike the previously investigated ferroborates, this material is characterized by a singlet ground state of the rare-earth ion. It is found that, below T _N = 32 K, the magnetic structure of the crystal in the absence of the magnetic field is uniaxial (l ∥ c), while, in a strong magnetic field H ∥ c (H _cr ～ 43 kOe at T = 4.2 K), a Fe³⁺ spin reorientation to the basal plane takes place. The reorientation is accompanied by anomalies in magnetization, magnetostriction, and electric polarization. The threshold field values determined in the temperature interval 2–32 K are used to plot an H-T phase diagram. The contribution of the Pr³⁺ ion ground state to the parameters under study is revealed, and the influence of the praseodymium ion on the magnetic and magnetoelectric properties of praseodymium ferroborate is analyzed.     

Urea Based Dipodal Fluorescence Receptor for Sensing of Fe3+ Ion in Semi-Aqueous Medium

Urea based fluorescent chemosensor 1 was synthesized. Receptor 1 shows unique selectivity for the Fe³⁺ion and no such significant response was noticed with other metal ions (Cr³⁺, Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, Hg²⁺, Pb²⁺ and Bi³⁺) in DMSO/H₂O (50:50,v/v) semi-aqueous solution. The binding features have been established by absorption and fluorescence spectroscopic methods. The binding constant (K) values obtained from Benesi-Hildebrand, Scatchard and Connor plot for receptor 1 is (8.3?±?0.3) × 10³ M^?1 and has good detection limit 0.7?μM. The stoichiometry of 1.Fe³⁺ complex was confirmed by mass spectroscopy and Job’s plot.

9, 10-Bis(8-Quinolinoxymethyl)Anthracene—A Fluorescent Sensor for Nanomolar Detection of Cu2+ with Unusual Acid Stability of Cu2+-Complex

In this work, the dipod 9,10-bis(8-quinolinoxymethyl)anthracene (1) and for comparison, monopod 9-(8-quinolinoxymethyl)anthracene (2) have been synthesized. The fluoroionophore 1 in pH 7.1 HEPES buffered CH₃CN:H₂O (4:1 v/v) solution shows quenching only with Cu²⁺ with lowest limit of detection 150 nM, amongst various metal ions. Fluoroionophore 1 could also be applied to sense Co²⁺ with lowest limit of detection 600 nM. By modulating the pH of the solution and concentration of Cu²⁺, 1 shows respective “On-Off-On” and “On-Off” fluorescent switching. The self-assembly of two Cu²⁺ ions and two molecules of fluoroionophore 1 to form closed structure [Cu₂(L)₂]⁴⁺ seems to be responsible for nanomolar sensitivity towards Cu²⁺. The combination of delayed second protonation of 1 (pK_a2?=?2.6) and stepwise protonation of [Cu₂ L ₂]⁴⁺ causes unusual stability of [Cu(LH)₂]⁴⁺ even at pH?<?2.

Magnetic, thermal and hyperfine behaviours of Tm3+ in TmPO4, YPO4 and LuPO4: a comparative study

Single crystals of thulium phosphates (TmPO₄) are grown and the principal magnetic susceptibility perpendicular to the symmetry axis ‘c’ of the crystal $$\left( {{\text{ $ \chi $ }}_ \bot } \right)$$ and the magnetic anisotropy $$\Delta {\text{ $ \chi $ }}\left( {{\text{ = $ \chi $ }}_\parallel - {\text{ $ \chi $ }}_ \bot } \right)$$ are measured in the temperature range 300–13.5 K and 300–80 K, respectively. Though $${\text{ $ \chi $ }}_ \bot $$ increases rapidly with the decrease of temperature, $${\text{ $ \chi $ }}_\parallel $$ increases very slowly with the lowering of temperature. The tetragonal crystal structure of TmPO₄ is similar to that of Tm³⁺ in YPO₄ and LuPO₄ and in all the cases the non-Kramers Tm³⁺ ion occupies a site of D_2d symmetry. Our observed magnetic data on TmPO₄ are analyzed using crystal field analysis where the Hamiltonian includes the atomic free ion and crystal field (one-electron) interaction term. The computed and measured paramagnetic susceptibilities of TmPO₄ agree very well in the temperature range of our study. The magnetic behaviours of Tm³⁺ in YPO₄ and LuPO₄ are also studied and the results are compared with that of TmPO₄. In all the cases the natures of thermal variations of average susceptibilities and magnetic anisotropies are mostly governed by the perpendicular susceptibilities as their values are higher and rapidly increase with the lowering of temperature compared to parallel susceptibilities. The computed nuclear quadruple splittings, electronic heat capacities of Tm³⁺ in three different hosts give some interesting results.     

Features of the magnetic and dielectric behavior of mesophases of chromium (III) complexes with azacyclic ligands

Two paramagnetic (1, 2) chromium metallomesogens were studied by the EPR, magnetic-susceptibility, and dielectric-spectroscopy methods. These mesogens possess columnar liquid-crystal phase polymorphism. For mesogen 1 in the columnar Col_xd phase, an irreversible structural phase transition was detected by the EPR method. An anomalous nonlinear temperature dependence of the resonance fields of the EPR line positions and of the fine-structure parameter D in the mesophases of compound 1 was observed. It was shown that this anomaly is associated with the soft mode of crystal lattice. The dielectric spectroscopy data provide support for the existence of the soft mode, which is probably due to the transition of the system from a paraelectric to a dipole-ordered state. The structure of the hexagonal columnar plastic phase of mesogen 2 is formed by a single type of paramagnetic monomer chromium center and does not exhibit any specific features.     

Magnetostriction and thermal expansion of HoAl3(BO3)4

The magnetostriction and thermal expansion of rare-earth aluminoborate HoAl₃(BO₃)₄ have been studied theoretically. The calculated field and temperature dependences of the multipole moments of the Ho³⁺ ion in HoAl₃(BO₃)₄ made it possible to describe the known experimental data and to predict possible anomalies of thermal expansion. It has been shown that, for the direction of the field B ‖ c, the nonmonotonic character of magnetostriction along the axis a is determined by the multipole moments, the main of which is β _J 〈O ₄ ⁰ 〉. For B ‖ a and B ‖ b, the maximum moments are β _J 〈O ₄ ² 〉and α _J 〈O ₂ ² 〉; their variation with the field and temperature explain well the form of magnetostriction. It has been established that the greater value of magnetostriction Δa/a for B ‖ b than for B ‖ a and the greater value of magnetostriction for the field in the basal plane than for B ‖ c are caused by greater variations in the field of actual multipole moments.     

Magnetic Properties of Sm0.7Ho0.3Fe3(BO3)4

The magnetic properties of a ferroborate single crystal of substituted composition Sm_0.7H_0.3Fe₃(BO₃)₄ with competing Sm-Fe and Ho-Fe exchange interactions are studied. The measured properties and effects are interpreted in terms of a general theoretical approach based on the molecular field approximation and calculations using the crystal field model for a rare-earth ion. The experimental temperature dependences of the initial magnetic susceptibility in the temperature range 2?C300 K, the anomalies in the magnetization curves for B ?? c and B ?? c in fields lower than 1.2 T, and the field and temperature dependences of magnetization in fields lower than 9 T are described. The crystal field parameters and the parameters of the R-Fe and Fe-Fe exchange interactions are determined during the interpretation of the experimental data.     

Bis-Benzimidazolyl Diamide Based Fluorescent Probe for Copper(II): Synthesis, Structural and Fluorescence Studies

A new fluorescent probe based on a bis-benzimidazole diamide N ²,N ^2′-bis[(1-ethyl-benzimidazol-2-yl)methyl]biphenyl-2,2′-dicarboxamide ligand L ₁ with a biphenyl spacer group and a Copper(II) trinuclear metallacycle has been synthesized and characterized by X-ray single crystallography, elemental and spectral (FT-IR, ¹H & ¹³C NMR, UV-Visible) analysis. The fluorescence spectra of L ₁ in MeOH show an emission band centered at 300 nm. This band arises due to benzimidazolyl moiety in the ligating system. The diamide L ₁ in the presence of Cu²⁺ show the simultaneous ‘quenching’ of (300 nm) and ‘enhancement’ of (375 nm) emission band. Similar fluorescence behavior was found in water–methanol mixture (9:1). The new emission band at 375 nm is attributed to intra ligand π–π* transition of the biphenyl moiety. L ₁ exhibited high selectivity and sensitivity towards Cu²⁺ in both the medium over other common metal ions like Ni²⁺, Co²⁺, Mn²⁺, Mg²⁺, Zn²⁺, Pb²⁺ and Hg²⁺. The binding constant with Cu²⁺ was calculated by the Benesi-Hildebrand equation. Selective “off-on-off” behavior of L ₁ in methanol has also been studied. The fluorescent intensity of 375 nm bands in L ₁ enhances (turns-on) upon addition of Cu²⁺ and quenches (turn-off) upon addition of Na₂-EDTA.     

A study of some methods for measuring CKM CP violating phases

We study the influence of penguin (especially, electroweak penguin) effects on some methods of measuring the angles α, β, and γ in the CKM unitarity triangle. We use next-to-leading order effective Hamiltonian, and present numerical estimates based on the factorization approximation. We find that some techniques suggested in the literature, especially for α determination, are not workable in light of the electroweak penguin effects. Nevertheless, there are methods that would work for each angle determination. For angle β we consider B → D ⁺D^{～ -} mode and estimate the penguin contamination. For angle γ we consider a method based on SU(3) symmetry and carefully consider SU(3) breaking effects. We point out regions in the parameter space where this method could be used reliably.     

Electron paramagnetic resonance of Mn<Superscript>2+</Superscript> ions in single crystals of yttrium aluminum borate YAl<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript>

Single crystals of yttrium aluminum borate YAl₃(BO₃)₄ doped with manganese ions are studied using electron paramagnetic resonance spectroscopy. It is shown that manganese ions introduced at low concentrations into the sample predominantly occupy yttrium ion sites in the crystal structure. The shape of the electron paramagnetic resonance spectrum unambiguously indicates that the valence of manganese ions in this case is equal to 2+. The parameters of the spin Hamiltonian of Mn²⁺ ions in the YAl₃(BO₃)₄ matrix are determined at room temperature. The magnitude and sign of the fine structure parameter D allow the conclusion that the YAl₃(BO₃)₄ single crystals doped with manganese ions have a strong crystal field at the yttrium ion sites and easy-axis anisotropy.     

A Rhodamine-Based Off�COn Fluorescent Chemosensor for Selectively Sensing Cu(II) in Aqueous Solution

A novel chromogenic and fluorogenic chemosensor RhB-pMOSal comprising a rhodamine fluorophore and a salicylaldehyde receptor being connected by an iminohydrazine link was synthesized and fully characterized. Its sensing behavior toward various metal ions in neutral aqueous solution was investigated by absorption and fluorescence spectroscopy. RhB-pMOSal exhibited a reversible and sensitive ??turn-on?? response of absorption and fluorescence toward Cu²⁺ in aqueous acetonitrile solution. Approximate 65 and 6-fold enhancement in the absorbance at 556 nm and fluorescence intensity at 573 nm were estimated when equivalent Cu²⁺ was added to the RhB-pMOSal solution. Under the same conditions, RhB-pMOSal displayed more sensitive than a reported analogue RhB-Sal to Cu²⁺ ion. The competition experiments for Cu²⁺ mixed with common metal ions exhibited no obvious change in absorption and emission except Cr³⁺ ion that can induce the fluorescence quenching of RhB-pMOSal to some extent.     

Anisotropic resonant magnetoplasticity of NaCl crystals in the Earth’s magnetic field

Resonant relaxation of the dislocation structure under the action of crossed magnetic fields, i.e., constant magnetic field of the Earth (B _Earth) and alternating radio-frequency field ( $\tilde B$ ), has been experimentally studied in a series of dielectric (NaCl) crystals with various compositions of impurities under variations in the frequency, direction of the pumping field $\tilde B$ , and orientation of the samples in the Earth’s magnetic field. The frequency dependence of the dislocation path length l(ν) exhibits peaks with various heights (l _max) and resonant frequencies (ν_res). The maximum resonant effect has been observed for dislocations with the direction L orthogonal to the plane of crossed magnetic fields in a configuration of mutually perpendicular vectors {L, $\tilde B$ , B _Earth} belonging, together with sample edges {a, b, c}, to the 〈100〉 system. Variation of the concentration C of calcium impurity in crystals of the NaCl_Ca series only influenced the resonant peak height as $l_{\max } \propto 1/\sqrt C $ . Rotation of the magnetic field $\tilde B$ in the (b, c) plane from direction $\tilde B$ ⊥ B _Earth to $\tilde B$ ∥ B _Earth also did not influence the frequency of the resonance but changed its amplitude. Depending on the crystal type, this influence changed from rather insignificant (in crystals of the NaCl_LOMO series) to complete suppression of the effect for $\tilde B$ ∥ B _Earth (in the NaCl_Nik series). The resonant frequency ν_res is sensitive to orientation of the sample with respect to B _Earth. Upon rotation of the crystal by the angle θ = ∠(c, B _Earth) about the a ⊥ B _Earth edge, the initial peak for dislocations L ‖ a at the crystal orientation θ = 0 and the frequency ν _res ⁰ is replaced by a pair of peaks at frequencies ν_{1, 2} ≈ ν _res ⁰ cosθ_{1, 2}, where θ₁ = 90° ? θ and θ₂ = θ. Previously, these peaks were observed separately in NaCl_Nik crystals for $\tilde B$ ∥ c and $\tilde B$ ∥ b. In the present study, these peaks have been observed simultaneously for both orientations of $\tilde B$ in NaCl_LOMO and NaCl_Ca crystals, where the resonance is not completely suppressed for $\tilde B$ ∥ B _Earth.     

Sensitized luminescence properties of dinuclear lanthanide macrocyclic complexes bearing a benzophenone antenna

Dinuclear lanthanide (Ln=Tb³⁺ or Eu³⁺) complexes (Ln₂L2) of two octadentate macrocyclic polyaminopolycarboxylic ligands connected through a benzophenone (BP) moiety (L2) have been synthesized. Sensitized luminescence properties of Ln₂L2 in water have been studied in comparison to those of BP-conjugated mononuclear Ln complexes (LnL1). The luminescence intensity of Tb₂L2 is lower than that of TbL1 because of lower triplet quantum yield of the BP moiety. In contrast, Eu₂L2 shows higher intensity than EuL1. For both Eu complexes, energy level of triplet excited-state BP (³BP*) is only 3 kJ mol⁻¹ higher than that of ⁵D₂ excited-state of Eu³⁺. The ⁵D₂ state formed by a triplet-energy transfer (TET) from ³BP* is therefore deactivated by a back energy transfer (BET) to the ground-state BP, resulting in low luminescence intensity of EuL1. In contrast, within Eu₂L2, TET from ³BP* to ⁵D₀ state of two Eu³⁺ ions is accelerated, thus leading to higher luminescence intensity. Another notable feature of Eu₂L2 is the luminescence quantum yield independent of its concentration. In contrast, for EuL1 system, an intermolecular BET occurs from ⁵D₂ state of Eu³⁺ to the ground-state BP conjugated to another EuL1 complex, resulting in a yield decrease with the concentration increase.     

Paramagnetische Resonanz des dreiwertigen Gadoliniums in YPO4, YVO4 und YAsO4

The EPR spectra of Gd³⁺-doped isostructural single crystals of YPO₄, YVO₄, and YAsO₄ have been measured in X-band at room temperature and at nitrogen and helium temperatures. The zero-field splitting can be described by the five crystal-field parametersb ₂ ⁰ ,b ₄ ⁰ ,b _6/0,b ₄ ⁴ , and b ₆ ⁴ fitted to a tetragonal spin-Hamiltonian corresponding to the point symmetry D_2d of the Gd³⁺ site. The values ofg and b ₂ ⁰ vary significantly with host lattice and with temperature.