Effect of the donor–acceptor properties of ligands on the spectroscopic and electrochemical properties of mixed-ligand complexes of Pt(II) and Ir(III) with cyclometalated 2-phenylbenzothiazole

The results of the spectroscopic NMR (¹H, ¹³C, and ¹⁹⁵Pt), infrared, optical, and voltammetric characteristics of the mixed-ligand complexes of Pt(II) and Ir(III) with metalated 2-phenylbenzothiazole and tert-butylisocyanide (tBuNC), acetonitrile (AN), ethylenediamine (En), O-ethyldithiocarbamate (Exn^–), and diethyldithiocarbamate (Dtc–) ions are presented. It is demonstrated that the change in donor–acceptor interaction of ligands tBuNC, AN, En, Exn^–, and Dtc^– with metal leads to an increase in the energy of the highest occupied molecular orbital of the complexes and is accompanied by a shift of the cathode potential of the metal-centered oxidation, a bathochromic shift of the spin-allowed and spin-forbidden metal-tocyclometalated ligand optical charge transfer transitions, and an increase the degree of mixing of the ¹MLCT and triplet intraligand states, responsible for the phosphorescence of the complexes.     

The effect of adding aluminum and iron to Tb–Dy–Ho–Co multicomponent alloys on their structure and magnetic and magnetocaloric properties

A comprehensive analysis of the structure, phase composition, surface topology features, and magnetic and magnetocaloric properties of Tb_0.3Dy_0.35Ho_0.35Co_1.75 T _0.25 (T = Al, Fe) multicomponent alloys has been performed. The specifics of variations in the structure and functional properties induced by the partial substitution of cobalt atoms in the 3d sublattice of RCo₂ with aluminum or iron atoms have been determined.     

Temperature effect on emission lines and fluorescence lifetime of the ~4F_(3/2) state of Nd:YVO_4

By measuring the absorption and fluorescence spectra and the fluorescence lifetime of 4F3/2 state of Nd3+ ions in YVO4 (2 at.-%) crystal at different temperature, the effects of temperature on the spectra and the lifetime of F3/2 state have been investigated. As the temperature is increased, the line width of the 4F3/2 -4I11/2 transitions is found to increase and the spectral line toward the longer wavelength, which are duo to the ion-phonon interaction. The variation fluorescence lifetime of the 4F3/2 state of Nd:YVO4 is found to be anomalous in the measured range 8 - 300 K. It is about 81 us at room temperature and decreases to 30 us at 8 K. The experimental results are explained by ascribing to the thermal mixing between the two Stark levels of 4F3/2 state with different lifetime.     

The effect of perturbedk-selection and gap shrinkage on the optical transitions in III–V semiconductors

Optical transitions in direct semiconductors are governed according to simple one-electron treatment by ak-selection rule, which in doped or mixed crystals is but lifted to some extent (k) caused by 1) shallow impurities, 2) isoelectronic impurities or 3) alloy scattering. Values of k for these mechanisms are given and the implications for line shapes of optical spectra are discussed.Furthermore, as to the position of lines in the optical spectra of highly doped or highly excited crystals, gap shrinkage effects have to be considered, three main mechanisms of which can be distinguished: 1) Quadratic response of the band edges with respect to the fluctuating potential of the (screened) impurities, 2) polaron effects and 3) carrier exchange and correlation effects. Results of theoretical calculation are compared with experimental findings for GaAs and GaP. The practical importance of gap shrinkage effects for gain measurements and for the operation of (Ga, Al) As laser diodes is pointed out.From the Coulomb interaction of the carriers an additional mechanism for the lifting of thek-selection rule (especially valid for pure, but excited semiconductors) can be derived (plasmon coupling): Estimations show that the simplek-selection rule is almost never fulfilled within the energy range of emission spectra and that these spectra can be well explained simply assuming no-k-selection even for pure direct material.     

Effect of substituent on UV–visible absorption and photostability of liquid crystals: DFT study

The electronic transitions in the ultraviolet–visible (UV–Vis) range of two nematogens, namely 4′-cyanophenyl-4-n-pentylbenzoate and 4′-cyanophenyl-4-n-pentoxybenzoate, have been studied. The UV–Vis and circular dichroism spectra of these molecules have been simulated using the TDDFT/B3LYP/6-31+G(d) method. Mulliken atomic charges for each molecule have been compared with Loewdin atomic charges to analyze the molecular charge distribution and phase stability. The highest occupied molecular orbital and lowest unoccupied molecular orbital energies corresponding to the electronic transitions in the UV–Vis range have been reported. The excited states have been calculated via configuration interaction singles with semi-empirical Hamiltonian ZINDO (Zerner's intermediate neglect of differential overlap method). Further, the effect of substituent on ultraviolet absorption and photostability of the molecules has been discussed. The photostability of the molecules has been investigated in order to understand the application and operation with ultraviolet and visible light regions.     

Difference in effect of temperature on absorption and Raman spectra between all-trans-β-carotene and all-trans-retinol

<正>Temperature dependencies(81℃-18℃) of visible absorption and Raman spectra of all-trans-β-carotene and all-trans-retinol extremely diluted in dimethyl sulfoxide are investigated in order to clarify temperature effects on different polyenes.Their absorption spectra are identified to be redshifted with temperature decreasing.Moreover, all-trans-β-carotene is more sensitive to temperature due to the presence of a longer length of conjugated system.The characteristic energy responsible for the conformational changes in all-trans-β-carotene is smaller than that in all-transretinol. Both of the Raman scattering cross sections increase with temperature decreasing.The results are explained with electron-phonon coupling theory and coherent weakly damped electron-lattice vibrations model.     

A comparative study on the effects of salt and filler on transport and structural properties of organic–inorganic hybrid electrolytes

Organic–inorganic hybrid electrolytes based on the reaction of tri-block copolymer poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol) bis(2-aminopropyl ether), poly(ethylene glycol diglycidyl ether, and (3-glycidyloxypropyl)trimethoxysilane doped with LiClO₄ and SiO₂ nanoparticles were synthesized by a sol–gel process. The structural and dynamic properties of the materials thus obtained were systematically investigated by Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, alternate current impedance, and ¹³C solid-state NMR measurements. A maximum ionic conductivity of 3.2?×?10^?5 S cm^?1 was obtained at 30 °C for the solid hybrid electrolyte with a [O]/[Li] ratio of 16 and 7 wt% of SiO₂ nanoparticles. A Vogel–Tamman–Fulcher-like temperature dependence of ionic conductivity was observed for the hybrid electrolytes, implying that the diffusion of charge carriers was assisted by the segmental motions of the polymer chains.     

The effect of thermomechanical treatment regimes on microstructure and mechanical properties of V–Me(Cr,W)–Zr–C alloys

The regularities of the formation of a heterophase structure in dispersion-strengthened vanadium V–Me(Cr, W)–Zr–C alloys are studied as a function of the regimes of their thermomechanical treatment. The regimes of treatment providing a substantial increase in the dispersity and homogeneity of spatial distribution of ZrC particles, temperature of recrystallization, and high-temperature (at T = 800°C) short-time strength are found in comparison to conventional treatment regimes.     

UV–visible,infrared absorption spectra of undoped and TiO2-doped lead phosphate glasses and the effect of gamma irradiation

Undoped and TiO₂-doped lead phosphate glasses were prepared. Ultraviolet (UV)–visible and Fourier transform-infrared (IR) absorption spectra of the prepared samples were measured before and after being subjected to doses of 30 and 60 kGy of gamma irradiation. The parent undoped lead phosphate glass reveals charge transfer UV absorption bands which are attributed to the presence of unavoidable iron impurities contaminated within the raw materials used for the preparation of the glasses and the sharing of divalent lead (Pb²⁺) ions. Experimental spectral data indicate that the doped titanium ions are involved in such glasses in two valences, namely the trivalent and tetravalent states. The predominant trivalent titanium (Ti³⁺) ions are characterized by its purple color and exhibiting two visible absorption bands at about 500–550 and 700–720 nm. The lesser tetravalent titanium (Ti⁴⁺) ions belong to the d⁰ configuration and generally exhibit only an UV absorption band. Spectral data show that gamma irradiation causes noticeable changes in the undoped and TiO₂-doped samples in the UV range while the effects are limited in the visible range. The observed changes in the UV region are attributed to photochemical reactions while TiO₂-doped samples show retardation or shielding toward continuous gamma irradiation together with the sharing of heavy Pb²⁺ ions. IR absorption spectra reveal the vibrations of several phosphate groups including the metaphosphate chains as the main structural building units together with the possible Pb?O vibrations.     

Beneficial effect of Co substitution on the structure and magnetic properties of mechanically alloyed (Pr,Tb)–Fe–(C,B) magnets

The effect of Co substitution on the structure and magnetic properties of mechanically alloyed Pr₁₄Tb₂Fe_76−xCo_xC₆B₂ and Pr₁₆Fe_76−xCo_xC₆B₂ (x=0–20$x=0–20$) alloys has been studied systematically. The main phase in the alloys is Pr₂Fe₁₄C-type carbide, coexisting with a small amount of α-Fe and rare-earth-rich phases. In addition to the increasing of the Curie temperature of the Pr₂Fe₁₄C-type phase, Co substitution can affect the magnetic properties by adjusting the α-Fe fraction of the alloys. The increase of both coercivity and remanence has been realized in a certain composition range. This increase may be attributed mainly to the enhancement of the effective anisotropy constant _Keff$K_{\mathrm{eff}}$ of the magnets due to the reduced α-Fe fraction with a small Co addition. The highest coercivity _iH_c of 20.3 kOe and the optimum energy product (BH)_max of 10.3 MG Oe have been obtained for the Pr₁₄Tb₂Fe_69.5Co_6.5C₆B₂ alloy.     

Effect of small magnetic field on the absorption property of superconducting Y–Ba–Cu–O (the magnetic memory effect)

A magnetic memory effect is observed in the absorption of electromagnetic waves of 20–70 MHz in YBa₂Cu₃O₇at 77–300 K.     

Theoretical study of structural, mechanical and spectroscopic properties of boehmite (γ-AlOOH)

The structural, mechanical and spectroscopic properties of boehmite (AlOOH polymorph) were investigated by means of first-principle density functional theory (DFT) and semiempirical density functional based tight binding (DFTB) methods. Apart from a marginal underestimation of interlayer hydrogen bond distances the DFT method well reproduces the experimental equilibrium low-pressure structure. For the DFTB method similar good agreement was obtained for lattice parameters, however bond lengths and angles showed a larger deviation from experiment in comparison to DFT results. The experimental spectrum of the OH stretching region was interpreted by means of the calculated frequencies within the frame of the harmonic approximation and by calculating the power spectra of the hydroxyl groups obtained from molecular dynamics simulations. Using the latter approach, the strong coupling between the individual OH modes was demonstrated. Isostatic structural compression of the boehmite structure was performed in order to obtain the bulk modulus and the dependence of the vibrational spectrum on the pressure. The DFT method gives a value of 97 GPa in the athermal limit. Comparison with available bulk moduli for other AlOOH polymorphs reveals that boehmite shows the highest compression, for which mainly a strong shortening mechanism of interlayer hydrogen bonds is responsible. The DFT method also described correctly the dependence of the OH stretch frequencies upon compression resulting in a strong red shift. Although good performance is observed for the low-pressure region, the DFTB method is not found to be suitable for high-pressure studies in cases such as boehmite.     

Hypersensitivity in the 4f–4f absorption spectra of tris (acetylacetonato) neodymium(III) complexes with imidazole and pyrazole in non-aqueous solutions. Effect of environment on hypersensitive transitions

The optical absorption spectra of [Nd(acac)₃(H₂O)₂]·H₂O, [Nd(acac)₃(im)₂] and [Nd(acac)₃(pz)₂] (where acac is the anion of acetylacetone, im is imidazole and pz is pyrazole) complexes in the visible region have been analyzed. The transition ⁴G_5/2←⁴I_9/2 located near the middle of the visible region (17,500 cm^?1) is hypersensitive. Its behavior is in sharp contrast to many other typically weak and consistently unvaried, normal 4f–4f transitions. It is overlapped by a less intense transition ²G_7/2←⁴I_9/2. The band shapes of the hypersensitive transition show remarkable changes on passing from aqueous solution to various non-aqueous solutions, which is the result of changes in the environment about the Nd(III) ion in the various solutions and suggests coordination of a solvent molecules. Pyridine has been found especially effective in promoting 4f–4f electric-dipole intensity. The DMSO invades the complexes and replaces the water molecules and heterocyclic amines from the coordination sphere. Two DMSO molecules coordinate and the complexes acquire similar structure, [Nd(acac)₃(DMSO)₂] in solution. The oscillator strength and the band shape of the hypersensitive transition of all the complexes remains the same in this solvent. The IR spectra and the NMR spectra of the complexes have also discussed.     

Study on the Cofluorescence Effect of Europium (III)–Yttrium (III)–Balofloxacin–Sodium Dodecyl Sulfate System and Its Analytical Application

A new fluorescence enhancement phenomenon in the europium(III)–balofloxacin–sodium dodecyl sulfate system was observed when yttrium(III) was added. Based on this, a sensitive cofluorescence assay for the estimation of balofloxacin was established. Under the optimized conditions, the enhanced fluorescence signal was linear over the concentration of balofloxacin ranging from 3.0 × 10^?9 to 7.0 × 10^?6 mol L^?1 with a correlation coefficient of 0.9993. The detection limit (3 σ) was determined as 8.3 × 10^?10 mol L^?1. The presented method was successfully applied to determination of balofloxacin in pharmaceutical preparations, human serum, and urine. The possible fluorescence enhancement mechanism was also discussed.