Electrooptical effect in polymeric composites containing heterometallic Cu(II)/Mn(II) complexes

We studied the effect of an electric field on the transmission of linearly polarized light through films of composites based on polyvinylbutyral doped with particles of Cu(II)/Mn(II) complexes with “skeleton” and “planar” structures. The action of an electrostatic field causes light absorption to become anisotropic. The effect increases with increasing distance between the cation and anion. Its sign reverses if the spatial structure of the complex is changed. A phenomenological model is proposed according to which the electrooptical properties of the composites are due to a change in the mutual orientation of complex building blocks on exposure to an external electric field. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 4, pp. 481–484, July–August, 2007.     

Luminescent Properties of a Polymer Photoluminescent Composite Containing the Binuclear (EU,TB) Complex as an Emitter

Uninuclear europium (Eu), as well as binuclear Eu and terbium (Tb), complexes were synthesized using acrylic acid (AA) as the first ligand and 1,10-phenanthroline (Phen) as the second ligand. The relative weight ratio of the europium (III) (Eu³⁺) to terbium (III) (Tb³⁺) ions of the binuclear complex was 1:1 as determined via energy dispersive X-ray analysis. The structures of the Eu(AA)₃Phen and Eu_0.5Tb_0.5(AA)₃Phen complexes were characterized by Fourier transform infrared spectroscopy. A series of tri-cellulose acetate (TCA)/ the Eu(AA)₃Phen and TCA/Eu_0.5Tb_0.5(AA)₃Phen composites were prepared by solution blending, and their luminescent properties were investigated by fluorescence spectrophotometry. The excitation spectra of all composites indicated that the TCA matrix probably affected the energy absorption and transfer of organic ligands. In TCA/Eu_0.5Tb_0.5(AA)₃Phen composites the introduced Tb³⁺ ions had some influence on energy absorption and transfer of organic ligands; the energy transfer process of the complex is suggested to be as follows: Phen→AA→Tb³⁺ion→Eu³⁺ion. The emission spectra indicated that the luminescent intensity of the TCA/Eu_0.5Tb_0.5(AA)₃Phen composites was noticeably stronger than that of the TCA/Eu(AA)₃Phen composites, suggesting that the comparatively stable and high-efficiency energy transfer process was only slightly influenced by the TCA matrix. In summary, the TCA/Eu_0.5Tb_0.5(AA)₃Phen (90/10) composite possesses fine luminescent properties for potential usage as red fluorescent materials.     

Electrical conductivity and photoconductivity of polymer composites containing Cu(II)/Cr(III) heteropolynuclear complexes

The electrical conductivity and photoconductivity of films of composites based on electrically neutral poly(vinyl butyral) with additions of Cu(II)/Cr(III) heteropolynuclear complexes introduced in the form of solutions or mechanically ground polycrystalline powders are studied. Photocurrents in samples prepared in different ways differ no more than tenfold. The photoconductivity of the composite films increases with decreasing distance between the metal centers in the complexes. A phenomenological model of carrier photogeneration and transport in films of polymer composites with embedded particles of heteropolynuclear complexes prepared from a solution or by grinding is proposed. The slight difference in photocurrents between samples containing the same complexes but prepared by different methods can be accounted for by the close geometric sizes of particles of the complexes.     

叶绿素a锰（Ⅲ）和叶绿素a锰（Ⅱ）的合成和光谱

叶绿素ａ锰（Ⅲ）（Ｍｎ（Ⅲ）－Ｃｈｌ－ａ）由脱镁叶绿素（Ｐｈｅｏ－ａ）和醋酸锰（Ⅱ）合成而得，用反相高效液相色谱法分离纯化，叶绿素ａ锰（Ⅱ）（Ｍｎ（Ⅱ）－Ｃｈｌ－ａ）用Ｎａ２Ｓ２Ｏ４还原时绿素ａ锰（Ⅲ）获得，研究了它们的元素分析（ＥＡ），紫外可见吸附光谱（ＵＶ－Ｖｉｓ）和傅里叶红外吸收光谱（ＦＴ－ＩＲ）证明了此二种配合物的合成，并给出了（Ｍｎ（Ⅲ）－Ｃｈｌ－ａ）与（Ｍｎ（Ⅱ）－Ｃｈｌ－ａ）的组成分     

Specific features of the internal photoelectric effect of the Cu(II)/Fe(III) oxalate complex with ethylenediamine in an insulating polymer film

Physics of the Solid State - The electrical and photoconductive properties of films of the composites based on poly(vinyl alcohol) with additions of the (NH4)[Cu(en)2Fe(C2O4)3] · 2DMSO...     

P3HT/PMMA双层聚合物电双稳器件的研究

通过逐层旋涂的方法,制备了P3HT(poly(3-hexylthiophene))与PMMA(poly(methylmethacrylate))双层器件,并与二者的共混溶液制备的器件进行了性能对比。利用扫描电镜(SEM)表征了双层器件的横截面形貌;利用电流-电压(I-V)以及电流-读取次数(I-t)测试,测量了两种器件的开关比以及持续时间特性。其中,双层器件具有更好的开关比,可达1×10~3,同时反复读写测试表明器件性能非常稳定。为了解释电双稳现象产生的机理,对双层结构器件的电流-电压曲线进行了线性拟合,利用器件的能级图进行分析,得出了电荷在器件中的传输过程。研究结果表明,可以通过电荷俘获释放理论解释P3HT/PMMA双层器件电双稳特性产生的机理。     

High oxygen pressures and the stabilization of a new mixed valence Cu(III)/Cu(IV)

Abstract

The Cu(III) oxides were investigated first for the unusual copper oxidation state and then for the high-Tc superconductivity. In the last case this property is observed when a mixed copper valence is stabilized : Cu(I)/Cu(II) or Cu(II)/Cu(III). A new mixed valence Cu(III)/Cu(IV) has been stabilized in the three dimensional lattice of the perovskite-type oxide Lal_-xSr_xCuO₃ (0 ≥ ′ ≥ 0,25). Chemical analysis and XPS study confirm the mixed valence. This compound shows metallic properties with an broadening of the conduction band compared to LaCu0₃. Such a behaviour can be explained either by the increase of the covalence of the average Cu-0 bond or by the decrease of the structural distortion induced by the substitution of Sr(II) for La(III). No superconducting property has been detected down to 4K.     

A Rhodamine-Based Dual Chemosensor for Cu(II) and Fe(III)

An “off-on” rhodamine-based fluorescence probe for the selective signaling of Cu(II) and Fe(III) has been designed and synthesized. The optical properties of this compound have been investigated in acetonitrile-water (1:1) binary solution. Very interestingly, this compound showed sensitivity and selectivity towards Cu(II) during absorption process and towards Fe(III) during emission process. So this is a nice example of an excellent dual chemosensor for two biologically/physiologically very important transition metal ions using only the two very different techniques (absorption and emission); both cases displayed only intensity enhancement.     

EPR investigation of the spin-spin interactions in a Cu(II)-Gd(III)-Fe(III) heterospin system

The spin-spin interactions in a system that contains three different spin carriers, [{LCu}Gd(H₂O)₃×{Fe(CN)₆}] _n ·4nH₂O (1) [L²⁻, N,N-propylenedi(3-methoxysalicylideneiminato)], were investigated by electron paramagnetic resonance spectroscopy. Additional information was obtained by analyzing the discrete heterobinuclear system [LCu(OH₂)Gd(O₂NO)₃] (2), which contains the Cu(II)-Gd(III) pair also existing in the structure of 1, and the compounds [{LCu}Gd(H₂O)₃{Co(CN)₆}] _n ·3.5nH₂O and [{LCu}La(H₂O)₃×{Fe(CN)₆}] _n ·4nH₂O, which are isostructural with 1 and in which the paramagnetic low-spin Fe(III) and Gd(III) ions were replaced by diamagnetic low-spin Co(III) and La(III), respectively. The investigations were carried out in the temperature range of 293–4 K in both X- and Q-bands and also using a dual-mode X-band. The experimental spectra of the Cu(II)-Gd(III) pairs in 2 were interpreted as the sum of spectra of the ground spin state with total S = 4 and the excited state with S = 3 appearing due to the ferromagnetic exchange interaction between Cu(II) and Gd(III) ions. By fitting the experimental and simulated spectra, the zero-field splitting parameters of the Gd(III) ion are estimated and it is shown that no influence of the anisotropic interaction is detected. The magnetic properties of 1 are discussed from the perspective of the interaction of the Cu(II)-Gd(III) binuclear fragments with the Fe(III) ions.     

Specific features of the temperature characteristics of electrical conductivity and photoconductivity of polymer composites containing Cu(II)/Cr(III) heterometallic complexes

The temperature characteristics of the electric current and the photocurrent in films of composites based on electrically neutral poly(vinyl butyral) with additions of Cu(II)/Cr(III) heterometallic cation-anion complexes are investigated. The electrical conductivity and photoconductivity of the polymer composite films in the visible optical range increase with a decrease in the distance between the metal centers in the complexes and upon introduction of acceptor additions of the C₆₀ fullerene into the composition of the polymer binder and increase exponentially with increasing temperature. The activation energy of electrical conduction and photoconduction exceeds 1 eV and depends weakly on the strength of the external electric field. The temperature characteristics of the electrical conductivity and photoconductivity of the materials under investigation are explained by the specific features of trapping of charge carriers at the interface between particles of the heterometallic complex and the polymer binder.     

Formation,Structure and Magnetic Properties of Polymer Matrix Nanocomposites Processed by Thermal Decomposition of the Fe(III)Co(II) Acrylate Complex

Structure and magnetic properties of polymer matrix nanocomposites, processed by pyrolysis of the Fe(III)Co(II) acrylate complex, were investigated. It was shown that thermal transformation of the complex studied consisted of three macrostages: dehydration, solid state polymerisation and decarboxylation of a metallopolymer form. The main products of the decomposition were nanoparticles stabilised by polymeric matrix. The crystalline phases, which were found in the fully processed material, were Fe₃O₄, CoFe₂O₄ and CoO. The mean crystallite size was 10nm. In the intermediate stages of the thermolysis iron was present in the forms of Fe^III (trivalent low – spin iron), Fe²⁺(divalent high – spin iron) and Fe₃O₄. The hysteresis loops measured at temperatures below 200K were opened and shifted towards negative field. The coercivity and remanence showed room temperature values of 0.18T and 15.5mT, respectively.     

Optical,thermal and mechanical characterization of Al(III)/Sb(III)-doped tris(thiourea)zinc(II) sulphate crystals

The influence of Al(III)/Sb(III)-doping on the properties of tris(thiourea)zinc(II) sulphate (ZTS) crystals grown by slow evaporation solution growth technique is reported. The as-grown crystals belong to orthorhombic system and cell parameters are, a = 7.77 Å, b = 11.13 Å, c = 15.47 Å, V = 1338 Å³ (Al(III)-doped) and a = 11.1996 Å, b = 7.770 Å, c = 15.5598 Å, V = 1368.3 Å³ (Sb(III)-doped). The structure and the crystallinity of the materials are further confirmed by powder X-ray diffraction analysis. The modes of vibrations of different functional groups present are identified by Fourier transform infrared studies. Thermogravimetric/differential thermal analysis studies reveal the purity of the materials and no decomposition is observed up to the melting point. Surface morphological changes due to doping are observed by scanning electron microscopy. Microhardness study was carried out to elucidate the mechanistic behavior microhardness studies were carried out to elucidate the mechanistic behavior. Second harmonic generation activity is much better in the case of Sb(III)-doping. The specimen is also characterized by dielectric studies.     

Ferrimagnetic coupling in oxamido-bridged Mn(II)Cu(II) compounds: a combined CASPT2 and DDCI study

Multiconfigurational perturbation theory (CASPT2) and difference dedicated configuration interaction (DDCI) are applied to study the ferrimagnetic coupling in an oxamido-bridged Mn(II)Cu(II) molecular species. CASPT2 reproduces the experimental coupling very well. From the partition of the CASPT2 energy, the most important contributions to the coupling are established. Spin populations are calculated with DDCI. The successive improvement of the N-electron wave function allows us to analyse the contributions to the spin delocalization.     

Linear free‐energy relationships in semiquinone species and their Mn(II) and Cu(II) complexes

Linear free‐energy relationships for a series of functionalized semiquinone ligands and their Mn^II‐ and Cu^IIhydro‐tris(3‐cumenyl‐5‐methylpyrazolyl) borate complexes were examined. Quinone–semiquinone cycle half‐wave reduction potentials and semiquinone hydrogen hyperfine coupling constants (a_H) were determined and their correlation with Hammett σ parameters reported. A new σ parameter, σ_aH, has been proposed. Mn^II and Cu^II metal complex metal–ligand charge transfer and n → π* UV transitions were found to be modulated by substituents. Satisfactory Hammett correlations between UV transitions and various σ values have been determined and compared in a number of instances. Copyright © 2011 John Wiley & Sons, Ltd.     

Photoinduced Anisotropy in Poly(Methyl Methacrylate)/Sudan Red III Thin Films

The dynamic behavior of photoinduced optical anisotropy of amorphous PMMA/Sudan Red III thin films has been investigated using the pump-probe method. The results showed that the anisotropy increased rapidly in an exponential fashion in the first seconds of pumping, so that a photostationary state was reached as a result of the photoisomerization process cycles. The anisotropy relaxation phase decreased exponentially in a slow manner, which means the anisotropy did not disappear instantaneously when the irradiation was switched off. Evidence of the existence of the Angular Hole Burning (AHB) and the Angular Redistribution (AR) effects in the Sudan Red III molecules in the PMMA polymeric host is presented. The relative photoinduced optical anisotropy was calculated. The results showed that, at room temperature, the thermal isotropic relaxation of the photoisomer was negligible compared to the anisotropic reverse photoisomerization that occurred as soon as the pump beam was cut-off.     

过渡金属Mn（Ⅲ）,Fe（Ⅲ）,Rh（Ⅱ）和Pd（Ⅱ）卟啉配合物的共振拉…

讨论了金属离子Ｍｎ（Ⅲ），Ｆｅ（Ⅲ），Ｒｈ（Ⅲ）和Ｐｄ（Ⅱ）原卟啉Ⅸ－二甲酯（ＰＰ）和四苯基卟啉（ＴＰＰ）配合物及Ｐｄ（Ⅱ）间氯四苯基卟啉（ＴＰＰｍ－ｃｌ）配合物的共振拉曼光谱。利用金属离子外层ｄ电子与卟啉环的作用，解释了配合物结构灵敏带的变化规律，同时讨论了不同卟啉及卟啉环上取代基团对结构灵敏带的影响。     

Synthesis, Characterization and Reactivity Study of a New Penta-Coordinated Mn(II) Complex

A penta-coordinated Mn(II) compound [dqpMnCl₂] (1) (dqp = 2,6-di-(8-quinoline-yl)-pyridine) has been synthesized and its X-ray crystallographic structure is reported here. Magnetic susceptibility measurements confirmed a high-spin Mn(II) (S = 5/2) center in 1. The X-band EPR spectrum of 1 in dimethylformamide solution exhibits widely distributed transitions in the spectral range from 0 to 700 mT with particularly well-resolved hyperfine lines due to the ⁵⁵Mn (I = 5/2) nucleus. The abundance of highly resolved transition lines in the spectrum facilitated the electron paramagnetic resonance spectral simulation which revealed large zero-field splitting and g-anisotropies. When dissolved, 1 exists in equilibrium with a hexa-coordinated species, the latter probably resulting from disassociation of one chlorido-ligand allowing ligation of two solvent molecules. The redox behavior of 1 was studied and was compared to that of a structural analog for which water oxidation in the presence of a chemical oxidant has been shown. The results from water oxidation trials of 1 are discussed.     

Frequency Dependence of the Complex Conductivity of Thin Polymer Films

Technical Physics - A method to experimentally determine the components of complex thermal conductivity for thin polymer films has been developed. It is based on measuring the temperatures of both...