一种非对称的双稠合四硫富瓦烯衍生物的合成

以二硫化碳、二甲基甲酰胺为起始原料,亚磷酸三甲酯和亚磷酸三乙酯为偶联剂,利用多步Wittig交叉偶合反应,合成了一种双稠合的四硫富瓦烯衍生物2 (4′,5′ 二甲硫基 1′,3′二硫代环戊烯 2′叉) 5 (4′,5′ 二腈乙硫基 1′,3′二硫代环戊烯 2′叉) 1,3,4,6 四硫并环戊烯,该衍生物具有更为伸展的π共轭体系,因此有可能成为一种优良的电子给体。各步偶合反应的收率51 4%～82 4%。由于采用了交叉偶合反应及具有吸电子取代基,目的产物的收率高达82 4%。中间物及产物经IR和元素分析进行了结构鉴定。其中目标产物元素分析的实测值w(C)=33 59%,w(H)=2 30%,w(N)=4 18%与计算值w(C)=33 64%,w(H)=2 18%,w(N)=4 36%非常吻合,说明合成路线合理可行。     

四硫富瓦烯类衍生物的合成及表征

以金属钠和二硫化碳为起始原料,合成四硫富瓦烯(TTF)锌的配合物(TTF)Zn(NBu_4)_2。其与卤代烷烃或取代类酰氯反应得到16个对称的四硫富瓦烯硫酮类衍生物,再经醋酸汞氧化分别得到16个四硫富瓦烯氧酮类衍生物,其中13个未见文献报道。操作简单且收率达80%以上,其结构经~1H NMR、~(13)C NMR表征确证。     

双稠合四硫富瓦烯衍生物的制备及取代基对合成的影响

扩展TTF衍生物的π共轭体系,可以增进分子导体中分子间的S…S相互作用,改善分子导电性。基于这个目的,以二硫化碳、二甲基甲酰胺为起始原料,合成了二种双稠合的四硫富瓦烯衍生物2．(4′,5′-二甲硫基-1′,3′,二硫代环戊烯-2′叉)-5-(4′,5′-二腈乙硫基．1′,3′-二硫代环戊烯-2′叉)-1,3,4,6-四硫并环戊烯和2,5-二(4′,5′-二甲硫基-1′,3′-二硫：、己环戊烯-2′-叉)-1,3,4,6-四硫并环戊烯。这两种化合物具有更为伸展的π共轭体系,因此有可能成为优良的电子给体。中间物及锄物经IR和元素分析进行了结构鉴定。同时讨论了取代基性质对双稠合四硫富瓦烯衍生物的合成收率的影响。     

二氰基取代的四硫富瓦烯硫杂冠醚衍生物的合成及性质研究

在甲苯溶液中,在亚磷酸三乙酯存在下,采取高度稀释的方法,使4,5-二氰基-1,3-二硫杂环戊二烯-2-酮分别和多缩硫杂冠醚进行交叉偶联反应,成功地得到了不对称的2,3-二氰基四硫富瓦烯衍生物。用1HNMR、MSI、R和EA表征了其结构,并用循环伏安法研究了它们的电化学性质,用1HNMR初步评价了衍生物对钠离子的配合性能。     

四硫富瓦烯基四硫纶及其配合物的合成

以二硫化碳、N，N-二甲基甲酰胺（DMF）为起始原料，亚磷酸三丁酯为偶联剂，合成了2，3，6，7-四（2’-氰乙硫基）网硫富瓦烯四硫纶（TTFTT），并以TTFTT为桥配体、邻菲啰啉为封端配体，制得了中心金属离子为Zn^2＋、Ni^2＋的四硫富瓦烯基四硫纶双金属配合物。中间物及产物经IR和元素分析进行了结构表征，其中目标产物元素分析的实测值与计算值比较吻合，说明合成路线合理可行。     

合成四烃硫基四硫富瓦烯的研究进展

描述了四烃硫基四硫富瓦烯的4种合成方法及其研究进展.     

基于四硫富瓦烯衍生物的阳离子化学传感器研究进展

综述了基于四硫富瓦烯(TTF)冠醚、吡啶衍生物和基于化学反应的阳离子化学传感器研究进展,并展望了该领域的发展趋势.     

四硫富瓦烯基二硫纶及其配合物的合成

四硫富瓦烯-1,2-二硫纶(TTFDT)在有机金属导体领域有着良好的应用前景,通过恰当的分子设计可以开发出具有良好电导率的衍生物和配合物。设计、合成和表征了一种可作为配体前体的TTFDT衍生物,并且改进了其合成方法。     

“A-C≡C-TTF-C≡C-A”型四硫富瓦烯衍生物的合成与性质研究

四硫富瓦烯及其衍生物是性能优良的电子给体.本文利用Sonogashira反应将吡啶基团连接在四硫富瓦烯单元上,合成了"A-C≡C-TTF-C≡C-A"型四硫富瓦烯共轭体系衍生物4,4′(5′)-二-(4-吡啶乙炔基)-四硫富瓦烯(TTF4N).吸收光谱、电化学和Pb2+配位键合研究表明,三键作为桥基能够有效实现分子内的电荷转移.金属Pb2+离子与吡啶基团的配位能够引起TTF4N的吸收光谱、核磁氢谱和电化学性质的显著变化.     

四硫富瓦烯作为催化剂的研究进展

介绍了四硫富瓦烯作为自由基-极性交叉反应的催化剂的反应机理,以及四硫富瓦烯催化的自由基-极性交叉反应在四环生物碱等天然产物合成方面的研究进展,展望了其发展趋势。     

二茂铁表面活性剂的合成及其电化学行为研究

合成了具有可逆特性的二茂铁表面活性剂N,N-二甲基二茂铁甲基正辛烷基溴化铵(Fc8),并以玻碳电极为工作电极,采用循环伏安法研究了Fc8在0.1 mol/L NaCl溶液中的电化学行为,讨论了pH、扫描速度及底物浓度对Fc8电化学行为的影响。结果表明,Fc8在pH<8的条件下具有良好的可逆性,可在氧化态(I2+)与还原态(I+)之间实现变换;Fc8在玻碳电极上的氧化峰电流(Ipc)与扫描速度呈现线性关系(R2>0.998),说明Fc8的电化学行为是受扩散控制的可逆过程;Ipc和扩散系数(D)在Fc8的临界胶束浓度(CMC)附近出现突变,在CMC以上,Ipc与D随表面活性剂浓度缓慢变化,该规律与Fc8表面张力变化趋势吻合,表明峰电流和扩散系数随Fc8浓度变化较快。     

乙酰基二茂铁缩氨脲的合成及其电化学性质

以二茂铁为原料通过两步反应合成了标题化合物,其结构通过IR、1HNMR和元素分析予以确证。采用循环伏安法测定了该化合物在无水乙腈溶液中的电化学性能。实验结果表明,在扫描范围(-0.1～0.83 V)内,标题化合物出现了一对氧化还原峰;当扫描速度在100～500 mV/s范围时,其半波电位(E1/2)为0.476～0.466 V;峰电流比(Ipa/Ipc)为1.387～1.269,并且峰电流(Ip)与扫描速度平方根(ν1/2)呈良好的线性关系。     

Synthesis of poly(ferrocenylsilanes) with different molecular weight and their electrochemical behavior

A series of poly(ferrocenylsilanes) (PFS) with different molecular weight have been prepared via the thermal ring‐opening polymerization of the corresponding monomers. The electrochemical behavior of poly(ferrocenyldimethylsilane) (PFDMS) and poly(ferrocenylmethylphenylsilane) (PFMPS) in solutions were investigated by cyclic voltammetry (CV). It was found that PFS could be adsorbed and electrodeposited on the Pt electrode surface, and the electroactive multilayer films formed on the Pt electrode surface influenced the shape of the voltammogram. The redox potential varied with the molecular weight slightly, and ΔE_1/2 became smaller with the increase in molecular weight. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 473–477, 2006     

Facile and clean electrochemical synthesis of new acetaminophen derivatives through electrochemical oxidation of acetaminophen in the presence of thiouracil derivatives

The electrochemical oxidation of acetaminophen (1a) is carried out in the presence of thiouracil derivatives (3a–c), as nucleophiles, in an acetate buffer solution (0.15?M, pH 5) mixed with Dimethylformamide (DMF) using cyclic voltammetry and coulometry under a constant potential. The results obtained indicate that N-acetyl-p-benzoquinone-imine derived from acetaminophen participates in a 1,4-Michael-type addition reaction with thiouracils to form the corresponding acetaminophen derivatives (4a–c) in good yields and with high purities using a facile, catalyst-free, and one-pot electrochemical method using three carbon electrodes in an undivided cell under mild conditions. The products obtained were characterized after purification by IR, ¹H NMR, and ¹³C NMR spectroscopies, and by the elemental analysis method.     

双缩二氨基硫脲类化合物的合成及其电化学性质研究

由芳香醛、酮和1,3-二氨基硫脲合成了双缩二氨基硫脲类希夫碱,并用1H NMR、IR对其结构进行了确证。采用循环伏安法对其电化学性能进行测试,并由其紫外-可见光谱的带边吸收确定化合物的带隙,计算了其电子亲和势、电离能等电化学参数。结果表明,标题化合物的电子亲和势为3.8~4.0 eV,高于常用电子传输材料2-(4-联苯基)-5-(叔丁苯基)-1,3,4-噁二唑(2.82 eV),具有较好的电子传输性能。     

Electropolymerization and properties of 3,4‐ethylenedioxythiophene backbone polymer with tetrathiafulvalene as pendant

Three 3,4‐ethylenedioxythiophene (EDOT) derivatives, including an EDOT‐tetrathiafulvalene (TTF) derivative, were synthesized by Steglich esterification of carboxylic acids with hydroxymethyl EDOT (3,4‐ethylenedioxythiophene methanol). The UV spectra showed that there was no distinctive intramolecular interaction for the EDOT–TTF monomer between the EDOT and the TTF moieties in the ground state; however, the cyclic voltammetry responses implied that such intramolecular interaction occurred. Electropolymerization in excessive potential could bring in strong overoxidation effects and degradation in the polymer film. The polymers were simulated using density functional theory with Gaussian03 package and the optimized HOMO and LUMO state were figured out. The conductivity of TTF‐polymer was 6 S·cm^?1 obtained by galvano station and 4.8 × 10^?3 S·cm^?1 obtained by potentiostatic electropolymerization after doping with 7,7,8,8‐tetracyanoquinodimethane. The results indicated that this polymer was a reasonable candidate for conducting materials and it was meaningful to increase the conductive dimensions of TTF polymers by chemical doping. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

新型二元熔盐电解质LiTFSI/NaTf的热学和电化学性能

制备了由二（三氟甲基磺酰亚胺）锂（LiTFSI）和三氟甲基磺酸钠（NaTf）形成的二元低温熔盐电解质材料,采用差热分析、电化学阻抗和循环伏安法分别对熔盐电解质体系的热学性质、电导率和电化学窗口等进行了研究。测试结果表明,LiTFSI/NaTf熔盐体系的最低共熔温度为188℃,而且具有很高的热稳定性,在300℃以内没有明显热分解的迹象;LiTFSI/NaTf熔盐体系具有较好的电导率,电导率随着LiTFSI浓度的增加而减小;温度为230℃、摩尔配比为1∶3的LiTFSI/NaTf熔盐体系的电化学窗口为4.7 V,且随着温度的升高,电化学窗口减小幅度较小,表明该体系具有良好的电化学稳定性。     

Effect of microstructure on the electrochemical behavior of Pt/YSZ electrodes

Two types of O₂,Pt/YSZ electrode preparation (Pt/YSZ cermet and sputtered platinum film) have been characterized by SEM and by cyclic voltammetry and chronoamperometry at 450 °C in 20 kPa oxygen. Cyclic voltammetry on the cermet and on the as-sputtered non-porous film electrode evidenced the characteristics of the PtO _x /Pt couple. The corresponding redox reaction occurs at the metal/electrolyte interface and it manifests itself by an anodic wave and one of more cathodic peaks in the voltammogram. Heat treatment of the sputtered electrode at 700 °C in oxygen atmosphere resulted in a porous structure by coalescence of the film. Cyclic voltammetry of the porous film electrode featured the characteristics of the O₂/O²⁻ couple, i.e. the redox reaction of gaseous oxygen occurring at the tpb. Chronoamperometry at anodic potentials showed similar features for both electrode preparations: an initial inhibition, a current peak and a slow activation, the latter being related to the phenomenon of electrochemical promotion of catalysis.     

农药乐果的电化学性质及快速测定

利用电化学沉积法制备了纳米金修饰的金电极,通过循环伏安法研究了乐果在该电极上的电化学性质,实现了乐果的快速测定.实验结果表明,乐果在碱性环境中可以水解生成巯基化合物,吸附到电极表面从而获得电化学信号.纳米金能有效地促进电子传递,同时其大的比表面积能够增加对水解液中巯基化合物的吸附量,提高检测的灵敏度.利用循环伏安法在最优条件下对乐果进行了检测,检测范围为1.6×10-6～2.6×10-4 mol/L,检测限为8.5×10-7 mol/L.     

Synthesis and characterization of the polyaminophenol derivatives containing thiophene in side chain: Thermal degradation,electrical conductivity,optical‐electrochemical,and fluorescent properties

Novel polyaminophenols, poly‐2‐[3‐thienylmethylene]aminophenol (P‐2,3‐TP), poly‐3‐[3‐thienylmethylene]aminophenol (P‐3,3‐TP) and poly‐4‐[3‐thienylmethylene]amino phenol (P‐4,3‐TP), were synthesized by oxidative polycondensation reaction. Metal complexes of P‐2,3‐TP were also obtained. The structures of synthesized compounds were confirmed by FT‐IR, UV‐vis, ¹H NMR, and ¹³C NMR techniques. The characterization was made by TG‐DTA, DSC, and gel permeation chromatography (GPC) analyses in addition to solubility tests. Electrical conductivities of polymers were measured by four‐point probe technique. Fluorescence measurements were carried out in various solutions and optimum concentrations and maximal intensities were determined. The new synthesized polyaminophenols are good candidates for electronic, opto‐electronic, and photovoltaic applications due to polyconjugated structures. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011