Synthesis,X-Ray Crystal Structures and Optical Properties of Novel Substituted Pyrazoly 1,3,4-Oxadiazole Derivatives

Novel pyrazoly 1,3,4-oxadiazole derivatives were synthesized and characterized by ¹H NMR, IR, HRMS and X-ray diffraction analysis. UV–vis absorption and fluorescence properties of these compounds in different solutions showed that the maximum absorption wavelength was not significantly changed in different solvents; however, maximal emission wavelength was red-shifted with the increase of solvent polarity. Absorption λ_max and emission λ_max was less correlated with substituent groups on aryl rings.     

An attempt of molecular design and synthesis of 3,4′/4,3′‐disubstituted benzylideneanilines with specified UV–Vis absorption maximum wavelength

Thirty‐one samples of 3,4′/4,3′‐disubstituted benzylideneanilines (XBAY) with specified UV–Vis absorption maximum wavelength (λ_max) were designed and synthesized by applying the equation (Eqn 1 ) which was abstracted from the UV–Vis absorption maximum wavelength energy (ν_max = 1/λ_max) of 4,4′‐disubstituted benzylideneanilines. Then, the UV–Vis data (λ_max) of the designed compounds were measured in anhydrous ethanol. The predicted UV–Vis data of designed compounds are in agreement with the experimental ones, in which the mean absolute error is 2.9 nm. The results show that Eqn 1 is applicative for the prediction of UV–Vis absorption λ_max values of both 4,4′‐disubstituted benzylideneanilines and 3,4′/4,3′‐disubstituted benzylideneanilines. For a same pair of groups (X and Y), one can at least get four disubstituted benzylideneaniline compounds which have different λ_max values. It perhaps provides a convenient method to design an optical material for benzylideneaniline compounds. Copyright © 2014 John Wiley & Sons, Ltd.     

Specific features of absorption and luminescence in CsBr: EuOBr crystals

The specific features of the absorption, photoluminescence, x-ray luminescence, thermally stimulated luminescence, and photostimulated luminescence spectra of CsBr: Eu²⁺ single crystals grown using the Bridgman method are investigated in the temperature range 80–500 K at the highest possible dopant content (0.1–0.4 mol % EuOBr in the batch) required for preparing perfect crystals. It is shown that an increase in the dopant content leads to a broadening of the absorption and photoluminescence excitation bands with maxima at wavelengths of 250 and 350 nm due to the interconfigurational transitions 4f⁷(⁸S_7/2) → 4f⁶5d(e _g , t_2g) in Eu²⁺ ions. The photoluminescence and photostimulated luminescence spectra of CsBr: EuOBr single crystals (0.1–0.4 mol % EuOBr) contain a band at a wavelength of λ_max=450 nm and bands at wavelengths of λ_max=508–523 and 436 nm. The last two bands are assigned to Eu²⁺-V_Cs isolated dipole centers and Eu²⁺-containing aggregate centers, respectively. It is revealed that the intensity of the luminescence associated with the aggregate centers (λ_max=508–523 nm) is maximum at an EuOBr content of less than or equal to 0.1 mol % and decreases with an increase in the dopant content. The possibility of forming CsEuBr₃-type nanocrystals that are responsible for the green luminescence observed at a wavelength λ_max=508–523 nm in CsBr: Eu crystals is discussed. The intensity of photostimulated luminescence in the CsBr: EuOBr crystals irradiated with x-ray photons is found to increase as the dopant content increases. It is demonstrated that CsBr: EuOBr crystals at a dopant content in the range 0.3–0.4 mol % can be used as x-ray storage phosphors for visualizing x-ray images with high spatial resolution.     

Luminescence of excitons and antisite defects in Lu<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript>:Ce single crystals and single-crystal films

The luminescence of excitons and antisite defects (ADs) was investigated, as well as the specific features of the excitation energy transfer from excitons and ADs to the activator (Ce³⁺ ion) in phosphors based on Lu₃Al₅O₁₂:Ce (LuAG:Ce) single crystals and single-crystalline films, which are characterized by significantly different concentrations of ADs of the Lu _Al ³⁺ type and vacancy-type defects. The luminescence band with λ_max = 249 nm in LuAG:Ce single-crystal films is due to the luminescence of self-trapped excitons (STEs) at regular sites of the garnet lattice. The excited state of STEs is characterized by the presence of two radiative levels with significantly different transition probabilities, which is responsible for the presence of two excitation bands with λ_max = 160 and 167 nm and two components (fast and slow) in the decay kinetics of the STE luminescence. In LuAG:Ce single crystals, in contrast to single-crystal films, the radiative relaxation of STEs in the band with λ_max = 253.5 nm occurs predominantly near Lu _Al ³⁺ ADs. The intrinsic luminescence of LuAG:Ce single crystals at 300 K in the band with λ_max = 325 nm (τ = 540 ns), which is excited in the band with λ_max = 175 nm, is due to the radiative recombination of electrons with holes localized near Lu _Al ³⁺ ADs. In LuAG:Ce single crystals, the excitation of the luminescence of Ce³⁺ ions occurs to a large extent with the participation of ADs. As a result, slow components are present in the luminescence decay of Ce³⁺ ions in LuAG:Ce single crystals due to both the reabsorption of the UV AD luminescence in the 4f-5d absorption band of Ce³⁺ ions with λ_max = 340 nm and the intermediate localization of charge carriers at ADs and vacancy-type defects. In contrast to single crystals, in phosphors based on LuAG:Ce single-crystal films, the contribution of slow components to the luminescence of Ce³⁺ ions is significantly smaller due to a low concentration of these types of defects.     

Influence of the methyl group at C=C bridging bond of stilbene on the longest wavelength maximum in ultraviolet absorption spectra

The compounds stilbenes XArCH=CHArY(XSBY) and 1,2‐diphenylpropylenes XArC(Me)=CHArY(XSMBY) have bridging groups CH=CH and C(CH₃)=CH, respectively, in which the C(CH₃)=CH has a side‐group CH₃ at the carbon‐carbon double bond. A series of XSMBY were synthesized, and their longest wavelength maximum λ_max (nm) in ultraviolet absorption spectra were measured in this work. We investigated the change regularity of the ν_max (cm^‐1, ν_max = 1/λ_max) of XSMBY and compared it with that of XSBY. The results indicate that (1) there is no good linear relationship between the ν_max of XSMBY and that of XSBY. (2) Because of the influence of the side‐group CH₃, in case of the same couple of groups X and Y, the λ_max of XSMBY is shorter than that of XSBY, that is, it has a blue shift. (3) The cross‐interaction between the side‐group CH₃ and Y has an important effect on the ν_max of XSMBY, while the cross‐interaction between the side‐group CH₃ and X has a little effect on the ν_max and can be ignored. (4) The specific cross‐interaction between X and Y has important effect on the ν_max of XSMBY, whereas it has no important effect on the ν_max of XSBY.     

Self-induced generation of an off-axis frequency shifted radiation from atoms

The transient resonant linear response at wavelength λ_a of an N two-level atom vapor driven by a strong pulse with wavelength λ_f = λ_a - |Δλ| is shown to promote an emission of radiation peaked at wavelength λ_c = λ_a + |Δλ| in a conical shell around the propagation axis of the incident beam. In the limit of weak excitation, i.e. for an incident Rabi frequency much smaller than the detuning, the cone angle is found to be equal to 2λμ(2N/ch|Δλ|)^{$\text{1}\text{2}$} where μ is the transition dipole moment.     

N-lines in the luminescence spectra of Cr3+-doped spinels: IV. Excitation spectra

Excitation spectra (T = 75–300 K; λ_exc = 450–630 nm) which were measured for the R-lines of Cr³⁺-doped oxides (α-Al₂O₃, β-Ga₂O₃) and for different luminescence lines (R-lines, N-lines) of Cr³⁺-doped spinels (MgAl₂O₄, ZnAl₂O₄, ZnGa₂O₄) are reported. The excitation maxima observed for different luminescence lines of a given compound exhibit considerable differences: 530 nm ? λ^max_exc ? 565 nm for MgAl₂O₄; 530 nm ? λ^max_exc ? 580 nm for ZnAl₂O₄; 545 nm ? λ^max_exc 555 nm for ZnGa₂O₄. According to the interpretation of N-lines to arise from different classes of Cr³⁺ ion swith different short range orderd, the excitation maximum of one distinct line should entirely correspond to the transition Δ : ⁴T₂ ← ⁴A₂ of that Cr³⁺ class from which the line arises. By this method spectroscopic data about the different kinds of Cr³⁺ ions present in a given sample can, therefore, be obtained which are not available from absorption measurements. The experimetal data were found to be in agreement with the results of model calculations. Restrictions which limit the accuracy and relevance of the data are discussed.     

Bay Functionalized Perylenediimide with Pyridine Positional Isomers: NIR Absorption and Selective Colorimetric/Fluorescent Sensing of Fe<Superscript>3+</Superscript> and Al<Superscript>3+</Superscript> Ions

Bay functionalized perylene diimide substituted with pyridine isomers, (2-pyridine (2HMP-PDI), 3-pyridine (3-HMP-PDI) and 4-pyridine (4-HMP-PDI)) have been synthesized and explored for selective coloro/fluorimetric sensing of heavy transition metal ions. HMP-PDIs showed strong NIR absorption (760–765 nm) in DMF. The absorption and fluorescence of HMP-PDIs have been tuned by make use of pyridine isomers. Reddish-orange color was observed for 2-HMP-PDI (λ_max = 437, 551, 765 nm) whereas 4-HMP-PDI exhibited light green (λ_max = 432, 522, 765 nm). 3-HMP-PDI showed orange-yellow (λ_max = 431, 524, 762 nm). The fluorescence spectra of 2-, 3- and 4-HMP-PDI showed λ_max at 585, 538, 546 nm, respectively. Interestingly, HMP-PDI dyes showed selective color change (intense pink color) and fluorescence quenching for Fe³⁺ and Al³⁺ metal ions in DMF. Absorbance spectra revealed complete disappearance of NIR absorption and intensification/appearance of new peak at lower wavelength. The concentration dependent studies suggest that 4-HMP-PDI can detect up to 36.52 ppb of Fe³⁺ and 43.12 ppb of Al³⁺ colorimetrically. The interference studies in presence of other metal ions confirmed the good selectivity for Fe³⁺ and Al³⁺. The mechanistic studies indicate that Lewis acidic character of Fe³⁺ and Al³⁺ ions were responsible for selective color change and fluorescence quenching.     

Abnormal effect of hydroxyl on the longest wavelength maximum in ultraviolet absorption spectra for bis‐aryl Schiff bases

Two sets of bis‐aryl Schiff bases that contain 4(or 4′)‐OH and 2(or 2′)‐OH were synthesized. The first set consists of 4‐HOArCH=NArY and XArCH=NArOH‐4′, and the second set consists of 2‐HOArCH=NArY and XArCH=NArOH‐2′. Their ultraviolet absorption spectra were measured and investigated. A very interesting phenomenon was observed by analyzing their wave number ν_max (cm^?1) of longest wavelength maximum λ_max (nm) of ultraviolet. Compared with the change regularity of the ν_max of XArCH=NArY (where the X and Y excluded OH), the 4′‐position hydroxyl (4′‐OH) and 2′‐position hydroxyl (2′‐OH) have abnormal performance. The details are the following: the 4′‐OH contributes an additional red shift to the ν_max of XArCH=NArOH‐4′ (λ_max increase), whereas the 2′‐OH contributes an additional blue shift to the ν_max of XArCH=NArOH‐2′ (λ_max decrease). In addition, there are ortho steric effects of all 2‐OH and 2′‐OH on the ν_max for 2‐HOArCH=NArY and XArCH=NArOH‐2′, and the ortho steric effect contributes a red shift to their ν_max. These experimental facts can provide an important theoretical reference for us using aryl Schiff base compounds as optical materials and performing the molecular design.     

Exciton luminescence of YAlO<Subscript>3</Subscript> single crystals and single-crystal films

The paper reports on a study of exciton luminescence in single crystals (SCs) and single-crystal films (SCFs) of YAlO₃, which have substantially different concentrations of vacancy-type and substitutional defects, under excitation by synchrotron radiation near the fundamental absorption edge. The radiative annihilation of excitons in SCFs was shown to occur primarily at regular perovskite lattice sites and to be accompanied by luminescence in a band peaking at λ_max = 295 nm with τ = 5.2 ns. In contrast to SCFs, the radiative exciton decay in YAlO₃ SCs takes place predominantly near vacancy-type defects (F⁺ and F centers) and is accompanied by luminescence in the bands at λ_max = 350 nm (τ = 2.5 ns) and 440 nm (τ₁ = 1.9 ns, τ₂ = 30 ms). Photoexcitation in the 175-nm band of YAlO₃ SCs revealed photoconversion of the centers F → F⁺.     

Monophotonically UV excited delayed luminescence in rigid solutions of aromatic amines

During a study of neutralization luminescence following photoionization of aromatic solutes in rigid organic glasses, a new type of long-lived luminescence has been observed simultaneously with the well-known neutralization luminescence following biphotonic ionization. It has been extensively studied for tetramethyl-p-phenylenediamine in methylcyclohexane or ethanol: it is one-photon excited but differs from the ordinary luminescence by the emission spectrum (λ_max 430 nm compared to λ_{max f.} 395 nm and λ_{max ph.} 490 nm in ethanol) and by the excitation spectrum, the present luminescence being observed only for short wavelength excitation. Finally the lifetime (of the order of seconds) depends on experimental conditions. Other solid and liquid phase studies suggest that the precursor of this new luminescence is a solute-solvent charge transfer state.     

Determining the excited‐state substituent constants of furyl and thienyl groups

Six series of styrene derivatives XCH═CHArY (total of 65) containing the styrene parent molecular skeleton were synthesized (here, Y is OMe, Me, H, F, Cl, CF₃, CN, and NO₂, and X is 2‐furyl, 3‐furyl, 2′‐methyl‐2‐furyl, 2‐thienyl, 3‐thienyl, and 2′‐methyl‐2‐theniyl). Their ultraviolet absorption spectra were measured in anhydrous ethanol, and their wavelength of absorption maximum λ_max was recorded. For the wavenumber ν_max (cm^?1, ν_max = 1/λ_max) of the obtained λ_max, a quantitative correlation analysis was performed, and 6 excited‐state substituent constants of groups X were obtained by means of curve‐fitting method. Taking the ν_max values of total 90 compounds of styrene derivatives as a data set (including 25 compounds from reference and 65 compounds of this work), a quantitative correlation analysis was performed, and the reliability of the obtained was verified. In addition, 12 samples of disubstituted Schiff bases (XCH═NArY) involving the above groups X were synthesized, and their ν_max values were recorded. Using these 12 ν_max together with the 14 ν_max values of Schiff bases taken from reference (total of 26 compounds), it was further verified that the values are reliable by means of quantitative correlation method.     

Solvatochromic Studies of Fluorescein Dianion in N,N-Dimethylformamide/Water and Dimethylsulphoxide/Water Mixtures

Abstract

The absorption, excitation and fluorescence spectra of the fluorescein dianion (FL^2?) in N, N-Dimethylformamide (DMF)/water (H₂O) and Dimethylsulphoxide (DMSO)/H₂O solvent mixtures have been investigated. It is found that the absorption λ_max and emission maxima EX, _nax are both hypsochromic shifted when the H₂O content in the solvent mixtures increases. However, the shoulder peaks λ_s remain constant at 483. 5nm within the range of H₂O mole fraction, x= 0 to 0. 518 in a DMF/H₂O solvent mixture and at 484. 4nm within the range, x=0 to 0. 304, in a DMSO/H₂O mixture. Further increases in H₂O content, cause a hypsochromic shift in λ_s. The molar energies for the electronic transition from the ground state (S₀) to S₁, the first excited singlet state, (E_T(1)) and to S₂, the 2nd excited singlet state, (E_T(2)) of FL^2?in the solvent mixtures are also plotted against x. Linear straight lines and intersection points are observed at x=0. 73 for E_T(1) and at x=0. 51 for E_T(2) in the DMF/H₂O mixture and at x=0. 71 for E_T(1) and at x=0. 31 &; 0. 69 for E_T(2) in the DMSO/H₂O mixture. Hydrogen-bonding stabilization effects are used to explain the above observations. The variation in relative fluorescence quantum yields of S₁ and S₂ of FL^2? with x in the aprotic solvent-H₂O mixtures to FL^2? in pure aprotic solvent are determined and discussed.     

IR absorption in p-type pb0.97Sn0.03Se

IR absorption in p-type melt grown Pb_0.97Sn_0.03Se crystals is reported. The results for the room temperature absorption coefficient (α) in the wavelength region 2–15 μm are analysed. The indirect absorption edge is found to be at 0.26 eV for this ternary alloy. In the longwavelength region α is found to be proportional to λ², in agreement with the classical free carrier absorption expression. The conductivity effective mass of holes is found to be 0.067 m₀ at 300°K.     

Free-carrier absorption in p-type Pb0.79Sn0.21Te

Results are presented of the room-temperature absorption coefficient (α) of Pb_0.79Sn_0.21Te (p_77K = 2 × 10¹⁶-6 × 10¹⁷cm^-3) in wavelength (λ) range 6–15 μm. At long wavelengths α exhibits a λ² dependence, in agreement with the classical free-carrier absorption expression, and in this region α is proportional to carrier density.     

Fluorescence and absorption spectra of Rose-Bengal dye in the presence of surfactants

The fluorescence and absorption spectra of Rose Bengal dye in aqueous solution have been studied in the presence of various nonionic, anionic and cationic surfactants. With cationic and nonionic surfactants, shifts occur in the absorption and emission peaks of the dye solution, with a large enhancement in the absorption and fluorescence intensity at the shifted λ_max. No appreciable change in the absorption and fluorescence spectra of the dye has been observed on the addition of anionic surfactants.All the changes observed in the absorption and fluorescence spectra of the dye solution with surfactants may be attributed, to binding of the surfactant with dye molecules and the disaggregation of the dye multimer forms into the monomeric form.     

Spectroscopic studies on the luminescence properties of ternary europium complexes with different ligands

In this paper, ligand effect of several bi-dental oxygen (O) and nitrogen (N) ligands on the red luminescence properties of europium ion (Eu³⁺) was studied comprehensively. Absorption, emission, and excitation spectral properties of ternary europium complexes with different combinations of ligands including thenoyl trifluoroacetone (TTA), naphthyl trifluoroacetone (NTA), 2,2′-bipyridyl (bpy) and phenanthroline (Phen) were investigated. Efficient Eu³⁺ red emission was observed with all the combinations of the above mentioned ligands. The most intense emission was found with the all nitrogen coordinated complex Eu(bpy)₂(Phen)₂ while the longest wavelength excitation band was recorded with oxygen-nitrogen mixed NTA-bpy complex Eu(NTA)₁(bpy)₃. With change of the ligands combination and ratio, the Eu³⁺ emission peak changes slightly from 612 to 618 nm. The absorption and excitation spectra of the europium complexes were compared and analyzed referring to the individual absorption spectral properties of the ligands. The relation between ligand-to-metal charge transfer states and luminescence intensities for different complexes was studied.     

Luminescence of neodymium-doped yttria

Pulsed cathodoluminescence of Nd³⁺: Y₂O₃ nanopowders of the cubic and monoclinic phases and the ceramics synthesized from these nanopowders has been investigated in the spectral range 350–850 nm. It is found that the IR emission band of neodymium ions in the Nd³⁺: Y₂O₃ cubic phase is located at λ₁ ≈ 825 nm. When there is a monoclinic phase admixture, two additional luminescence bands of Nd³⁺ arise in the spectrum at λ₂ ≈ 750 nm and λ₃ ≈ 720 nm. The emission spectrum of all Nd³⁺: Y₂O₃ materials also contains a wide intrinsic band of yttrium oxide at λ ≈ 485 nm; however, the presence of neodymium decreases the intensity of this band and increases the its structurization. It is suggested that the structure of this band in Nd³⁺: Y₂O₃ materials is mainly determined by local absorption (self-absorption) of neodymium ions.     

Effect of pump spectra and axial mode separation on the single longitudinal mode performance in end pumped solid-state lasers with semi-monolithic gain medium

We present a theoretical model to study the effect of the pump spectrum and axial mode separation on the single longitudinal mode operation of a laser with a homogeneously broadened semi-monolithic gain medium of short absorption depth. The characterizing parameter is the ratio of the pump power up to which single longitudinal mode is possible to the pump power at the lasing threshold and is denoted by r_max. A numerical study using a Gaussian-shaped pump spectrum reveals that, for a small value of the axial mode separation and for a crystal with short absorption depth at the pump wavelength, the value of r_max reduces significantly with increase in the FWHM of the pump spectrum and thereby results in degradation of the single longitudinal mode performance of the system. However, for large value of the axial mode separation, the SLM performance was found to be nearly independent of the variations in the spectral bandwidth of the pump beam, location of its peak emission wavelength and its polarization.     

Measurement of collision broadening of the calcium resonance line by low resolution spectroscopy

The Lorentzian half-widths of the Ca λ4227 Å (4s²¹S₀?4s4p¹P₁) line in the impact regime have been measured by low resolution spectroscopy. They were determined from measurements of the total absorption of both a white source and an emission line of the same transition. The absorption cells contained calcium at about 410°C with a perturbing gas of argon at pressures of up to about 50 cm of Hg. Corrections were applied to account for the width of the emission line and the non-transparency of the absorption cells. High resolution measurements of absorption profiles from a grating spectrometer are also described and the results of both methods are compared.