Convolutive Cyclic Voltammetry,Chronoamperometry and Chronopotentiometry Studies of C6Me6-isocloso-ruthenaborane Complex in Non-aqueous Medium at a Glassy Carbon Electrode

Electroreduction of the C₆Me₆‐isocloso‐ruthenaborane complex {(C₆Me₆)‐isocloso‐1‐RuB₁₀H₁₀} has been investigated using cyclic voltammetry, convolutive voltammetry, chronoamperometry and chronopotentiometry techniques at a glassy carbon electrode in 0.1 mol·L⁻¹ tetrabutyl ammonium perchlorate dissolved in methylene chloride. The investigated complex has been reduced via the consumption of two sequential electrons leading to the formation of monoanion and dianion, respectively. The electrode reaction pathway and the electrochemical parameters of the investigated system were determined. The extracted electrochemical parameters were verified via digital simulation treatments. Diffusion coefficient and heterogeneous electron transfer kinetics of the {(C₆Me₆)‐isocloso‐1‐RuB₁₀H₁₀} complex at low temperature were studied and discussed.     

Synthesis of 1,4-Bis(Chloromethyl)-2-Methoxy-5-Phenoxy Benzene

Much attention has been paid to Poly(p-Phenylene Vinylene) (PPV) because they are associated with good electro-optical characterization, especially electro-luminescence which first discovered by Burroughes in 1990^[1]. 1,4-bis(chloromethyl) benzene is an important tool to synthesize PPV by dehydrochlorination. So the chloromethylation of substituted benzene becomes active. We once synthesized a series of dialkoxyl bischloromethyl benzene^[2]. Unfortunately, short chain alkoxyl-substituted PPV has poor solubility, which limits its utility. There are little reports on aryloxy PPV up to now, while aryloxy-substituted PPV may has good mechanical properties.     

Electrochemical and optical characterization of p- and n-doped poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene

We study electrochemical p- and n-type doping in the well-known light-emitting polymer poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV). Doping reactions are characterized using cyclic voltammetry. Optical measurements including photoluminescence and UV/Vis/NIR transmission were performed on doped samples. We find that oxidation in MEH-PPV is a highly reversible reaction resulting in stable freestanding doped films, while the reduced form is unstable and the reaction irreversible. We discuss the dependence of doping reactions on scan rate, film thickness, salt type and concentration, and working electrode type. We observe the development of two additional broad absorption bands in both lightly and heavily doped films accompanied by a slight blueshift in the primary optical transition, suggesting bipolaron band formation. Finally we find that both p and n dopings result in extremely sensitive photoluminescence quenching. We propose a physical model for understanding electrochemical doping in MEH-PPV and the implications this has on the development of such technologies as polymer light-emitting electrochemical cells, electrochromic devices, actuators, and sensors.     

New viologen analogs: 1,4-bis[2-(pyridin-4-yl)ethenyl]benzene quaternary salts

Alkylation of 1,4-bis[2-(pyridin-4-yl)ethenyl]benzene with alkyl p-toluenesulfonates and dimethyl sulfate gave new viologen analogs, 1-alkyl-4-(2-{4-[2-(1-alkylpyridinium-4-yl)ethenyl]phenyl}ethenyl)-pyridinium bis(p-toluenesulfonates) and sulfate. Their derivatives with tetrafluoroborate and tetraphenylborate ions were also obtained. Spectral properties of the synthesized compounds were examined, and their structure was determined by X-ray analysis.     

Voltammetric Behavior of 1,4‐Dimethoxypillar[m]arene[n]quinones

The electrochemical properties of a series of 1,4‐dimethoxypillar[m]arene[n]quinones (DMP[m]A[n]Qs) and the interactions between individual quinone units have been investigated on glassy carbon electrode in acetonitrile. All the quinone units showed relative electron uptake behavior except 1,4‐dimethoxypillar[5]quinones (DMP[5]Q). The results have shown that the electrochemical behavior of the DMP[m]A[n]Qs is comparatively different from that of their related linear quinone analogues. The resultant properties were attributed to the close proximity of redox‐active sites as well as the delocalization of electrons on the aromatic rings. Another aspect to be considered responsible for their electronic properties was suggested to be the electrostatic repulsions between adjacent quinone units in these complex structures. Current studies provide a better understanding on the voltammetric behavior of pillararene derivatives with different numbers of quinone units as well as their future scope in certain future electrochemical applications.     

Photochemical and electrochemical Z–E isomerization of 1,4-dialkoxy-2,5-bis[2-(thien-2-yl)ethenyl]benzene stereoisomers

The group of 1,4-dialkoxy-2,5-bis[2-(thien-2-yl)ethenyl]benzene stereoisomers was synthesized in which methoxy- and ethoxy-groups were used as alkoxy-substituents. These isomers were characterized as solution species both electrochemically and spectroscopically. As expected, these compounds, having a stilben like structure, are the subject of photoisomerization, which is described and discussed. It is demonstrated how electrochemical process may cause isomerization of the double CC bonds in that group of compounds. An attempt of using electrochemical methods to monitor the process of photoisomerization of these compounds is presented. Mechanism of the oxidatively induced electrochemical isomerization has been proposed and discussed. The electrochemical isomerization mechanism is verified by digital simulation, which allowed estimating basic kinetic parameters of the processes.     

Mono‐ and Bis(imidazolidinium ethynyl) Cations and Reduction of the Latter To Give an Extended Bis‐1,4‐([3]Cumulene)‐p‐carboquinoid System

An extended π‐system containing two [3]cumulene fragments separated by a p‐carboquinoid and stabilized by two capping N‐heterocyclic carbenes (NHCs) has been prepared. Mono‐ and bis(imidazolidinium ethynyl) cations have also been synthesized from the reaction of an NHC with phenylethynyl bromide or 1,4‐bis(bromoethynyl)benzene. Cyclic voltammetry coupled with synthetic and structural studies showed that the dication is readily reduced to a neutral, singlet bis‐1,4‐([3]cumulene)‐p‐carboquinoid as a result of the π‐accepting properties of the capping NHCs.     

Spectroscopic studies of photochemical reactions in organic solids: Photopolymerization of 1,4 bis[β-pyridyl(2)vinyl] benzene

The laser Raman phonon spectroscopic technique has been used to study the photopolymerization reaction of 1,4 bis[β-pyridyl(2)vinyl] benzene (P2VB). Raman and infrared spectroscopy have been used to study the intramolecular vibrations of the reactant and the product and to characterize them. Absence of any large Stokes' shift between absorption and emission bands of the monomer crystal shows that exciton–phonon coupling is weak, and the reaction is not likely to be phonon mediated. Phonon spectroscopy shows that the reaction proceeds by a heterogeneous mechanism. Sharp phonon bands of the product, however, suggests that the photopoly P2VB lattice is highly ordered.     

C60/C70键联1,4-二-(咔唑-9-亚甲基)苯的电化学行为与双光子吸收

设计合成了C60键联1,4-二-(咔唑-9-亚甲基)苯(5)和C70键联1,4-二-(咔唑-9-亚甲基)苯(6), 用红外、核磁共振和MALDI-TOF质谱进行了表征, 确认了化合物5和6的结构, 用循环伏安法研究了化合物5和6的电化学性质, 并用Z扫描对其双光子吸收性质进行了研究.     

Toward Electrochemically Controllable Tristable Three‐Station [2]Catenanes

Encouraged by the prospect of producing an electrochemical, color‐switchable red–green–blue (RGB) dye compound, we have designed, synthesized, and characterized two three‐station [2]catenanes. Both are composed of macrocyclic polyethers containing three π‐electron‐rich stations, which act as recognition sites for a π‐electron‐deficient tetracationic cyclophane. The molecular structures of the two three‐station [2]catenanes were characterized fully by mass spectrometry and ¹H NMR spectroscopy. To anticipate the relative occupancies of the three stations in each [2]catenane by the cyclophane, model compounds with the same constitutions in the vicinity of the stations were synthesized. The relative ground‐state populations of the three stations occupied in both [2]catenanes were estimated from the thermodynamic parameters for 1:1 complexes between all these model compounds and the cyclophane, obtained from isothermal titration calorimetry (ITC). The electrochemical and electromechanical properties of the three‐station [2]catenanes were analyzed by cyclic voltammetry (CV), differential pulse voltammetry (DPV), and spectroelectrochemistry (SEC). The first three‐station [2]catenane was found to behave like a bistable system, whereas the second can be described as a quasi‐tristable system.     

1，4-双{2-[4-[2-苯并恶唑)苯基]乙烯基}苯及衍生物的合成

通过Wittig-Horner反应，以对苯二甲醛和2—(4-氯甲基苯基)苯并恶唑为主要 原料，合成了八个新型1，4-双{2-[4-(2—苯并恶唑)苯基]乙烯基}苯及衍生物．通 过IR，^1H NMR,UV-vis和元素分析等方法确认了它们的化学结构，分析数据表明各 标题化合物分子结构中的C=C双键均为反式结构特．     

Bis[2-(4-pyridyl)ethyl](2-cyanoethyl)phosphine Oxide: Synthesis and Reactions with 1,4-Dihalobutanes

Russian Journal of General Chemistry - Bis[2-(4-pyridyl)ethyl]phosphine reacts with acrylonitrile under mild conditions to form bis[2-(4- pyridyl)ethyl](2-cyanoethyl)phosphine which is readily...     

Synthesis of aromatic polyethers by Scholl reaction. V. Synthesis and polymerization of 1,3-bis[4-(1-naphthoxy) benzoyl]benzene, 1,4-bis[4-(1-naphthoxy)benzoyl]benzene,bis[4-(1-naphthoxy)phenyl]methane, 1,3-bis[4-(1-naphthoxy) phenylmethyl]benzene,and 1,4-bis-[4-(1-naphthoxy)phenylmethyl]benzene

This article describes the synthesis and the cation-radical polymerization (Scholl reaction) of 1,3-bis[4-(1-naphthoxy) benzoyl] benzene ( 6 ) and 1,4-bis[4-(1-naphthoxy) benzoyl]- benzene ( 7 ) initiated by FeCI₃. This polymerization produced poly(ether ether ketone ketone)s (PEEKK) of number average molecular weight (M?_n) up to 5400 g/mol. The synthesis of bis[4-(1-naphthoxy) phenyl] methane ( 8 ), 1,3-bis[4-(1-napthoxy) phenylmethyl] benzene ( 9 ), and 1,4-bis[4-(1-naphthoxy) phenylmethyl] benzene ( 10 ) are also described. Polyethers of M?_n up to 15400 g/mol at a FeCl₃/monomer molar ratio of 2/1 were obtained. An increased polymerizability of the monomers 9 and 10 containing two CH₂ groups versus that of the corresponding monomers containing two carbonyl groups ( 6 and 7 ) was observed. This enhanced polymerizability was explained based on the increased nucleophilicity of monomers 9 and 10 .     

Electron-Rich Phenothiazine Congeners and Beyond: Synthesis and Electronic Properties of Isomeric Dithieno[1,4]thiazines

A series of isomeric dithieno[1,4]thiazines is accessible through an intermolecular–intramolecular Buchwald–Hartwig amination starting from dihalodithienyl sulfides. The electronic properties of dithieno[1,4]thiazine isomers differ conspicuously over a broad range depending on the thiophene–thiazine anellation: a large cathodic (340 mV) or an anodic shift (130 mV) of the redox potentials relative to corresponding phenothiazines is possible. Structure–property relationships of the dithieno[1,4]thiazine constitution derived from DFT calculations and cyclic voltammetry not only reveal increased electron density but also different delocalization of the radical cations that determines the electrochemical properties significantly. In addition, photophysical properties (absorption and emission) qualify dithieno[1,4]thiazines as promising substitutes of phenothiazine and beyond due to increased tunable electron richness.     

Kinetics and mechanism of the electrochemical reduction of [1,2-bis(tert-butylperoxy)ethyl]benzene under conditions of the in situ recovery of a platinum surface

The behavior of [1,2-bis(tert-butylperoxy)ethyl]benzene (I) on Pt electrode is studied by means of cyclic voltammetry (CVA). A comparison of the electrochemical properties of I and the properties of previously studied bridge-type 1,2,4,5-tetraoxane ((1,4)-1,4-dimethyl-7-(4-methylbenzyl)-2,3,5,6-tetraoxabicyclo[2.2.1]heptane) (II) shows that the biperoxide studied in this work is reduced on a Pt electrode at lower cathodic potentials and is resistant to electrooxidation.     

Synthesis, properties, and redox behavior of mono-, bis-, and tris[1,1,4,4,-tetracyano-2-(1-azulenyl)-3-butadienyl] chromophores binding with benzene and thiophene cores

Mono-, bis-, tris-, and tetrakis(1-azulenylethynyl)benzene and mono- and bis(1-azulenylethynyl)thiophene derivatives 5-10 have been prepared by Pd-catalyzed alkynylation of ethynyl arenes with 1-iodoazulene derivative or the 1-ethynylazulene derivative with tetraiodobenzene and iodothiophenes under Sonogashira-Hagihara conditions. Compounds 5-10 reacted with tetracyanoethylene in a [2+2] cycloaddition reaction to afford the corresponding 1,1,4,4,-tetracyano-2-(5-isopropyl-3-methoxycarbonyl-1-azulenyl)-3-butadienyl chromophores 12-16 in excellent yields, except for the reaction of the tetrakis(1-azulenylethynyl)benzene derivative. 1,1,4,4,-Tetracyano-2,3-bis(1-azulenyl)butadiene (17) was also prepared by the similar reaction of bis(1-azulenyl)acetylene (11) with tetracyanoethylene (TCNE). The redox behavior of novel azulene derivatives 12-17 was examined by cyclic voltammetry (CV) and differential pulse voltammetry (DPV), which revealed multistep electrochemical reduction properties. Moreover, a significant color change was observed by visible spectroscopy under electrochemical reduction conditions.     

Synthesis of [1,3]dithiole and spiro[1,3]dithiole thiopyran derivatives of the [1,2]dithiolo[1,4]thiazine ring system

We report the synthesis of some new polysulfur-nitrogen heterocycles by cycloaddition reactions to readily available tricyclic condensed 1,2-dithiole-3-thiones. Thus, treatment of bis[1,2]dithiolopyrrole ketothione 1 with diacyl acetylenes gave the bis-aducts 2a-d. On the other hand, cycloaddition of bis[1,2]dithiolo[1,4]thiazine ketothione 3 with 1 equiv of acyl or diacyl acetylenes gave [1,3]dithiolylidenyl[1,2]dithiolo[1,4]thiazines 4a-f in fair to high yields. Catalysis by scandium triflate was used in the reactions that implied the less reactive dipolarophiles. Treatment of 3 with 2 equiv of DBA gave the bis-aduct 5a, and reaction of 4c with DMAD gave the mixed bis-adduct 5b. Cyclic voltammetry of selected examples showed irreversible processes that were influenced by the electrochemical activity of peripheral groups bonded to the heterocyclic system.     

[CuCl3CPZ(O)H]络合物的合成及电化学行为的研究

盐酸氯丙嗪目前在精神病治疗中作为首选药物之一，在临床上应用于精神分裂症、狂躁症、焦虑症及更年期精神病等症．该药物吩唾咪环比较容易被氧化；1982年Geary等[1]合成了该药物的钯络合物，并对其进行了X-今线结构分析．Kawazura等[2,3]研究了该药物与体内微量元素之间的相互作用；Holbrok山研究表明用盐酸氯丙埃后脑内铜的浓度上升．而服用后药物先与蛋白质结合，与金属离子反应的可能性较小；为此本文制备了该药物的主要代谢产物之一的CPZ（0）HCI，并与体内微量元素铜（11）络合得到KUQa＊Pz问仰，对该络合物进行了元素分析和电…     

4-Alkoxycarbonyl-2-(2-pyridyl)thiazoles and their complexes with CuII and CoII. Molecular and crystal structure of copper 4-ethoxycarbonyl-2-(2-pyridyl)thiazole dichloride

The first synthesis of ethyl 2-(2-pyridyl)thiazole4-carboxylate ( 2) and bis[2-(2-pyridylthiazol-4-ylcarbonyloxy)ethyl] disulfide ( 4) is described. The complexation of compounds 2 and 4 with Cu^II, Co^II, and Ni^II chlorides and perchlorates has been studied. Electrochemical behavior of the ligands and complexes obtained has been investigated by cyclic voltammetry and using rotating disk electrode, which allowed us to confirm the possibility for the ligand 4 and its complexes to be adsorbed on the surface of a gold electrode.     

新型I型五聚四硫富瓦烯衍生物的合成和性质

利用2,3-二(2'-氰乙基硫基)-6,7-二烷硫基四硫富瓦烯在甲醇钠的作用下消除一个保护基团生成四硫富瓦烯单钠盐,与1,4-二(氯甲基)苯反应,形成单桥-双(四硫富瓦烯)衍生物,生成的单桥-双(四硫富瓦烯)衍生物再次在甲醇钠的作用下消除剩下的保护基团,形成单桥-双(四硫富瓦烯)衍生物二钠盐,最后与四(3'-碘丙硫基)四硫富瓦烯反应形成新型I型五聚TTF衍生物,并通过循环伏安法和化学氧化法分别对其氧化还原性质和紫外光谱进行了研究.