A Far-Infrared Study of the Structures of Tris(Methyl Methyl Phosphonate) Iron(III), Tris(EthylEthylphosphonate) Iron(III), and Tris(IsopropylMethylphosphonate) Iron(III)

In articles by Kokalas et al.^1,2 studies were made of the interaction of FeCl₃ with diisopropyl methylphosphonate (DIMP), diethyl ethylphosphonate (DEEP), and dimethyl methyl phosphonate (DMMP) and structures were proposed for the reaction products. When the reactions are run under much milder conditions, there is much evidence^3–5 to support a different mechanism than that proposed by Kokalas and an altogether different structure of the complexes formed. In the structures proposed by Kokalas et al. the iron atom is surrounded by six oxygen atoms and these are the only bonding atoms to the iron. But on the other hand, in donor-acceptor complexes as are formed in chemisorption reactions,^3–5 some of these sites are filled by chloride ions and this difference should be ascertained quite easily by far-infrared spectroscopy. It was the purpose of this study to look at the far-infrared data and either further substantiate the structures proposed or to propose new ones.     

The Enfrared Spectra of tris (Methyl Methylphosphonate) Iron(III), Tris (Ethyl Ethylphosphonate) Iron(III), and Tris (Isopropyl Methylphosphonate) Iron(III)

The literature contains few references to the reactions of phosphonate esters with iron salts. Guilbault et al. ¹ recently studied the infrared spectrs of diisopropyl methylphosphonate (DIMP) and dimethyl methylphosphonate (DIMP) chemisorbed on solid FeCl ³ and made infrared band assignments. We wish to report the results of a study of the products of the homogeneous reaction of DIMP, DMMP and diethyl ethylphosphonate (DEEP) with ferric chloride. On the basis of elemental analysis and infrared absorption data, the products isolated were identified as tris (methylmethylphosphonate) iron (III), tris (ethyl ethylphosphonate) iron (III), and tris (isopropyl methylphosphonate) iron (III).     

Tris (8-Hydroxyquinoline) Aluminium Nanostructure Film and Its Fluorescence Properties

Tris (8-hydroxyquinoline) aluminium (Alq3) nano-structured films are fabricated by the gas evaporation method, and their fluorescent properties are investigated in detail. Compared with the conventional amorphous Alq3 films, the fluorescent efficiency of the nanostructure films is enhanced to a certain extent.     

Fluorimetric Determination of Thyroxine Hormone with Eu(III)-(Pyridine-2,6-Dicarboxylate) Tris Complex

We describe a method for the determination of thyroxine (Thy) using its quenching effect on Eu(PDA)₃ ^3- tris complex fluorescence. The relative fluorescence intensities are measured at fixed _exc = 282 nm, _em = 615 nm by titrating the metal complex with Thy in piperazine buffer solution at pH 6.5. Data indicated an associative type of reaction of two molecules valid between 0.0 < R < 1.0, R being the mole ratio of Eu(PDA)₃ ^3- to Thy. Over this ratio and up to (R 1.0) collisional quenching of Eu(PDA)₃ ^3- complex ion emission is seen as a result of heavy atom effect, intermolecular energy transfer playing the main role. This is also confirmed by the Stern-Volmer equation. In optimized experimental conditions, the L- form of Thy is determined in a range of 15.5–551.6 g/ml (2.0 × 10^–5 – 7.1 × 10^–4 M) with relative error of ±1.17%.     

Photoluminescence of Homoleptic Lanthanide Complexes With Tris(benzotriazol-1-yl)borate

Bright photoluminescent neutral complexes having general formula [Ln(tbtz)₃] (Ln?=?Eu, Tb; tbtz?=?tris(benzotriazol-1-yl)borate) were obtained by reacting K[tbtz] with EuCl₃ and TbCl₃. The emissions in the visible range, related to the f-f transitions of the trivalent lanthanide ions, are observable upon excitation with wavelengths shorter than 350 nm. The most intense emission bands correspond to the ⁵D₀?→?⁷F₄ transition at 699 nm for the europium complex and to the ⁵D₄?→?⁷F₅ transition at 542 nm for the terbium derivative. The luminescence is in all the cases mostly associated with the antenna-effect from the coordinated tbtz ligands. The synthetic approach was successfully extended to the preparation of the analogous yttrium and gadolinium derivatives. Tricapped trigonal prismatic geometry was attributed to the complexes on the basis of luminescence data and DFT calculations. Highly photoluminescent plastic materials were obtained by embedding small amounts of [Eu(tbtz)₃] or [Tb(tbtz)₃] in poly(methyl methacrylate).

     

八-羟基喹啉铝薄膜光致发光的厚度依赖性质

通过原位测量对八-羟基喹啉铝薄膜(Alq_3)光致发光的厚度依赖性质进行了研究.在 Alq_3向玻璃衬底沉积的初始阶段,Alq_3光致发光谱峰发生了显著红移,此后谱峰随着 Alq_3厚度的增加红移变缓并趋于饱和.Alq_3薄膜厚度从2nm 逐渐变化到500nm 时,Alq_3谱峰位总红移约为12nm.这种 Alq_3薄膜沉积的初始阶段 Alq_3谱峰的显著红移可归因于二维激子向三维激子态的转变.同时,由于激子同衬底的相互作用所引起的非辐射衰变,在 Alq_3沉积的初始阶段 Alq_3光致发光谱峰的强度呈现不同的变化,随后该谱峰的强度随 Alq_3薄膜厚度的增加而快速增加,并在薄膜厚度较大时,趋向于饱和.     

Concentration Dependence of Cobalt-59 Longitudinal Relaxation Times of Tris(acetylacetonato)cobalt(III) in Acetonitrile

The ⁵⁹Co longitudinal relaxation time of [Co(acac)₃] (acac⁻ = 2,4-pentanedionate ion) in acetonitrile was accurately measured over the concentration range between 20 and 110 mol m⁻³ at several temperatures. The relaxation rate was linearly dependent on the concentration of the complex up to approximately 80 mol m⁻³. The macroscopic viscosity of the solution was found to be the predominant factor in this dependence. The molar volume of the complex in acetonitrile was determined by applying the Debye-Stokes-Einstein model, and this value was compared to the corresponding values calculated from other experimental results.     

Photoinduced second harmonic generation studies on Tris(thiourea)copper(I) perchlorate Cu(SC(NH2)2)3(ClO4)

We have established a possibility to obtain the photoinduced optical second harmonic generation in the initially centrosymmetric single crystals of tris(thiourea)copper(I) perchlorate crystallized in the monoclinic system with the space group P2₁/c. The second‐order susceptibility of the investigated crystal was measured by inducing the crystal by external laser field. The results obtained are interesting and discussed in detail. We have established that the optical second harmonic generation achieves its maximum (about 0.84 pm/V) at photoinducing power density about 1430 kW/cm² for the fundamental wavelength 1064 nm. The maximal output second harmonic generation (SHG) was achieved at an angle of about 35° between the pumping and fundamental power beam's polarizations. Such maximum may be a consequence of a competition between the so formed anharmonic photothermal expansions and the thermal destruction that occurred because of the heating of the crystal surfaces. Our independent verifications have shown that the photoinduced surfaces were heated up to 8–12° C. This may cause occurrence of photothermal relaxation processes. The output SHG exists only immediately after the act of photoinduction. The obtained dependences are caused by specific features of the Raman spectra of the investigated crystals. Copyright © 2008 John Wiley & Sons, Ltd.     

Analysis of the solvent effect on the photophysics properties of 6-propionyl-2-(dimethylamino)naphthalene (PRODAN)

The absorption and emission spectroscopic properties of 6-propionyl-2-(dimethylamino)naphthalene (PRODAN) have been studied in a large number of protogenic, nonprotogenic, and amphiprotic solvents. The data obtained can be explained by the inclussion of a new term in the Lippert equation which takes into account the acidity of the solvent. This finding indicates that some precaution should be taken when using PRODAN as an indicator of the polarity of protein cavities if the environments involved include acid sites.     

ZnOEP:Alq3掺杂体系的电致发光

采用八乙基卟啉锌（2,3,7,8,12,13,17,18,－octaethyl-21H23H-porphine zinc,ZnOEP）掺杂八羟基喹啉铝为发光层,在不同的掺杂浓度下,制备了结构为ITO/TPD/ZnOEP:Alq3/Alq3/Mg:Ag的多个器件,并测试了们的发光光谱、亮度－电流曲线以及亮度对时间的响应特性。结果发现,当ZnOEP掺杂浓度从05%变化到15%时,器件的发光光谱明显不同,可以分别得到从橙黄色到红色等不同发光颜色的器件,器件发光效率也从0.96cd/A变化到0.14cd/A。上述现象可由ZnOEP的自吸收和浓度猝灭效应来解释。另外,器件的驱动特性表明,Alq3和ZnOEP之间可能存在的能量传递过程。     

Growth of 4-(dimethylamino) benzaldehyde doped triglycine sulphate single crystals and its characterization

Single crystals of triglycine sulphate (TGS) doped with 1 mol% of 4-(dimethylamino) benzaldehyde (DB) have been grown from aqueous solution at ambient temperature by slow evaporation technique. The effect of dopant on the crystal growth and dielectric, pyroelectric and mechanical properties of TGS crystal have been investigated. X-ray powder diffraction pattern for pure and doped TGS was collected to determine the lattice parameters. FTIR spectra were employed to confirm the presence of 4-(dimethylamino) benzaldehyde in TGS crystal, qualitatively. The dielectric permittivity has been studied as a function of temperature by cooling the sample at a rate of 1 °C/min. An increase in the Curie temperature T_c=51 °C (for pure TGS, T_c=48.5 °C) and decrease in maximum permittivity has been observed for doped TGS when compared to pure TGS crystal. Pyroelectric studies on doped TGS were carried out to determine pyroelectric coefficient. The Vickers's hardness of the doped TGS crystals along (0 1 0) face is higher than that of pure TGS crystal for the same face. Domain patterns on b-cut plates were observed using scanning electron microscope. The low dielectric constant, higher pyroelectric coefficient and higher value of hardness suggest that doped TGS crystals could be a potential material for IR detectors.     

新型锌离子荧光探针(5-(二甲基氨基)-N-(4-(2-(2-喹啉亚甲基)甲酰肼基)苯基)萘-1-磺酰胺)的研究

以丹磺酰胺为荧光基团设计合成了新型Zn²⁺荧光探针DW1(5-(二甲基氨基)-N-(4-(2-(2-喹啉亚甲基)甲酰肼基)苯基)萘-1-磺酰胺)。通过紫外光谱、荧光光谱及电喷雾质谱研究了DW1对Zn²⁺的选择性识别作用。结果表明,DW1与Zn²⁺结合后荧光显著增强,荧光发射光谱由545 nm蓝移至515 nm,量子产率达到0.32,且对Zn²⁺具有较高的选择性,受常见离子的干扰较小。光谱滴定和ESI-MS谱表明DW1与Zn²⁺以1∶1的化学计量数形成配合物,平衡常数K=1.75×10⁴(mol/L)^-1。     

Synthesis of( E ) -5- ( dimethylamino ) -N- ( 4- ( 2- ( quinolin-2-ylmethylene ) -hydrazinecarbonyi ) phenyl ) naphthalene-1-sulfonamide for Detection of Zinc Ion

以丹磺酰胺为荧光基团设计合成了新型Zn2+荧光探针DW1(5-(二甲基氨基)-N-(4-(2-(2-喹啉亚甲基)甲酰肼基)苯基)萘-1-磺酰胺).通过紫外光谱、荧光光谱及电喷雾质谱研究了DW1对Zn2+的选择性识别作用.结果表明,DW1与Zn2+结合后荧光显著增强,荧光发射光谱由545nm蓝移至515nm,量子产率达到0.32,且对Zn2具有较高的选择性,受常见离子的干扰较小.光谱滴定和ESI-MS谱表明DW1与Zn2+以1:1的化学计量数形成配合物,平衡常数K=1.75×104(mol/L)-1.     

聚乙烯基咔唑与8-羟基喹啉铝混合体系的荧光衰减

报道了8－羟基喹啉铝和聚乙烯基咔唑薄膜及其混合体系膜的荧光衰减特性。聚乙烯基咔唑／8－羟基喹啉铝重量比100：4的混合膜在波长540nm和460nm处的荧光衰减时间分别为6．47ns和8．5ns。重量比100：10混合膜在波长540nm和460nm处的荧光衰减时间分别为5．5ns和7．9ns。上述两波长对应8－羟基喹啉铝和聚乙烯基咔唑分子荧光发射。混合体系的荧光寿命仅为8－羟基喹啉铝分子荧光的40％,同时也低于聚乙烯基咔唑14ns的荧光寿命。荧光寿命的减少反映出两种分子之间存在较强的相互作用或形成了分子复合体。     

方波驱动法测定Alq3的电子迁移率

在非正弦波(方波)的驱动下,观察到了OLED中Alq₃的电致发光现象。在高段方波驱动下,Alq₃中的电子向阳极移动;在低段方波驱动下,Alq₃中的电子向阴极移动。当方波的周期是电子穿过Alq₃中所用时间的2倍时,Alq₃中的电致发光现象完全消失。由此,可以计算出Alq₃中的电子迁移率,得到的结果和文献的报道值相吻合。对Alq₃中电子迁移率和厚度的关系进行了研究,从而提出了一种简单易行的计算有机材料的电子迁移率的方法。     

Synthesis,Spectral, Solvent Dependent Linear and Nonlinear Optical Characteristics of (E)-N-(3-(3-(4(dimethylamino)phenyl)acryloyl) phenyl)quinolone-2-carboxamide

This paper presents the synthesis of novel organic compound (E)-N-(3-(3-(4(dimethylamino)phenyl)acryloyl)phenyl)quinolone-2-carboxamide, also known as Quinolinecarboxamide Chalcone (QCC) using aldol condensation and carboxamide formation method. The organic sample QCC was examined by FT-IR, ¹H NMR, ¹³C NMR and mass spectroscopic techniques, respectively. Linear and third-order nonlinear optical (TNLO) properties of QCC dissolved in polar solvents such as DMSO, DMF and Ethanol have also been studied. The order of nonlinear refractive index and nonlinear absorption coefficient of QCC was measured to be 10^?11 m²/W and 10^?5 m/W. The nonlinear refractive index (n₂) of QCC was attributed to negative nonlinearity due to self-defocusing effect, and nonlinear absorption coefficient (β) indicates the behaviors of saturable absorption (SA) and reverse saturable absorption (RSA). The real and imaginary features of the TNLO susceptibility (χ⁽³⁾) of QCC in polar solvents were calculated to be the order of 10^─7 esu. The spectral characteristics of solvent on TNLO susceptibility of QCC were discussed. The results divulged that the synthesized organic compound is a novel nonlinear optical (NLO) material for applications in photonics and optoelectronics.

     

Infrared Spectra of Tris(ethylendiamine) Cobalt(III) Complex Ion in Solid State and Dissolved in Light and Heavy Water

In recent years, at least two groups^1,2 have developed programmes for combined conformational and vibrational analysis of complicated molecular systems. A version of one of these systems² is currently being adapted for work on coordination complexes. In such work experimental data are needed, and they stem almost exclusively from x-ray structural determinations, and infrared spectra of solids. Most calculational schemes so far deal with isolated molecules, and as one objective of the calculations is to provide thermodynamic functions, which, as far as coordination complexes are concerned, are measured in aqueous solution, we consider it necessary to compare some key properties of the substances as measured in the solid state and in solution. In particular, we want to investi- gate the extent to which internal vibrations are independent of the surroundings of the complexion.     

Optical emission spectrum of the NO2+ dication

We recorded and rotationally analyzed a new emission band at 2563 Å obtained from a low-pressure, hot cathode and magnetically confined electric discharge through pure NO vapor. The available experimental data from photoion-fluorescence photon coincidence and translational energy loss spectroscopy, in conjunction with ab initio calculation, allowed assignment of the new band to the B²Σ⁺-X²Σ⁺ (0, 0) transition of the NO²⁺ ion.     

Polymer microenvironmental effects on the photophysics of cinchonine dication

Photophysical properties of cinchonine dication (C⁺⁺) have been studied in protic and aprotic polymers by monitoring steady state and time resolved measurements. It is found to be sensitive towards the microenvironment of polymers. Edge excitation red shifted emission (EERS) is observed in all polymeric matrices. However, the magnitude of EERS is relatively high in protic as compared to aprotic polymer. Isobestic point in excitation spectra and three decay components in time resolved measurements indicate more than two trapped chemical species in the heterogeneous environment of the polymer. Solute-polymer interactions are found to produce the third decay channel, unlike in solution phase and may be useful to understand the polymer microenvironment.