氧化作用控制“四硫富瓦烯-葸”二元体系的荧光开关行为

利用Wittig反应将高荧光量子产率的蒽基团通过双键连接在四硫富瓦烯单元上，合成了二元共轭体系化合物TTFan．在氧化作用的控制下，四硫富瓦烯单元的给电子能力降低，TTFan的荧光发射强度增大至原来的十几倍，实现了荧光的“off-on”过程．     

“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.     

氧化还原荧光开关构建的新型高选择性多信号化学传感器的研究

2,3,6,7-四(2′-氰乙硫基)四硫富瓦烯在醇钠的作用下消除氰乙基生成四硫富瓦烯四硫盐,再与9-溴甲基蒽反应生成四(9-亚甲基蒽硫基)四硫富瓦烯,通过氧化还原法发现其荧光能够可逆地增强或减弱,因此它是一个新的氧化还原荧光开关。在多种金属离子中,该新型氧化还原开关只对Fe3+有识别性能,其荧光强度随Fe3+的量增大而增强,其他金属离子没有干扰。所以,它又是一种对Fe3+具有高选择性识别的荧光传感器。该文报告工作的新颖性已为安徽大学图书馆2009年4月30日出具的第2009006号《科技查新报告》所证实。     

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。     

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.     

带有3个四硫富瓦烯结构单元的三脚型电子给体化合物的合成

在DMF-MeOH体系中,2-氰乙硫基-3,6,7-三取代四硫富瓦烯与等物质的量的氢氧化铯作用,生成去保护的3,6,7-三取代四硫富瓦烯-2-硫负离子,后者与三(碘乙基)胺或1,3,5-三(溴甲基)苯反应生成带有3个四硫富瓦烯取代的三脚型电子给体化合物。用NMR、MS和元素分析等手段证实了产物的结构,并用CVs研究了它们的电化学性质。对循环伏安图进行电流微分结果证明,标题化合物的电极反应为分步过程。     

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。     

合成四烃硫基四硫富乙烯的研究进展

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。     

新品研发辑要

新型四硫富瓦烯硫杂冠醚衍生物的合成简介:由于四硫富瓦烯(以下简称TTF)是一种稳定的、可逆的两电子给体,故可以利用于具有电、光、磁等性质的超分子化合物的构筑上。1985年,Otsubo等首次把TTF结构单元和冠醚结构单元连接在一起合成出了有离子传感性质的TTF冠醚衍生物。     

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.     

Conjugated opto/electroactive ethynylene-carbazole polymers with TTF as pendant group

Three conjugated ethynylene-carbazole polymers with Tetrathiafulvalene (TTF) as pendant group (P1–P3) were synthesized by using sonogashira coupling reaction and characterized by ¹H NMR, GPC, CV, UV–Vis, FL, and TGA. CV and UV–Vis spectra showed that an intramoleular interaction existed between the electron-rich moiety TTF and electron-deficient moiety polyethynylcarbazole of the polymers. A strong fluorescence quench (ca. 99%) could be observed, compared to the polyethynylene-carbazole without TTF units, which could be ascribed to the photo-induced electron transfer (PET) interaction from TTF moiety to the polyethynylene-carbazole backbone. The observed onset decomposition temperatures (T _d) for P1–P3 varied from 256 to 298 °C. The polymers mentioned above exhibited good thermal properties and higher conductivity (neutral conductivity ~7–11 × 10⁻⁷ S cm⁻¹; doped conductivity ~6–11 × 10⁻⁴ S cm⁻¹).     

Anion complexation by calix[4]arene-TTF conjugates

Calix[4]arenes bearing tetrathiafulvalene (TTF) moieties appended to the upper rim via the amidic functions were synthesized and used for ¹H NMR and UV/Vis complexation studies towards selected anions. It was found that the complexation affinity towards H₂PO₄⁻ dramatically depends on the substitution pattern of the calixarene moiety. As a result, the proximally disubstituted derivative has a complexation constant by two orders of magnitude higher than the distally disubstituted analogue. The differences between proximal and distal receptors were also documented by their behaviour during the oxidation of the attached TTF units.     

Synthesis of a bifunctional epoxy monomer containing anthracene moiety and properties of its cured polymer with phenol novolac

A new type of epoxy resin containing anthracene moiety in the backbone was synthesized and was confirmed by elemental analysis, infrared spectroscopy, and ¹H nuclear magnetic resonance spectroscopy. Thermal properties of its cured polymer with phenol novolac were examined by thermomechanical, dynamic mechanical, and thermogravimetric analyses. The cured polymer with phenol novolac showed higher glass transition temperature (T_g), lower thermal expansion, lower moisture absorption, and higher anaerobic char yield at 700°C than a cured polymer having a phenylene group in place of anthracene moiety. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 953–959, 1999     

Synthesis and photochemical transformations of an anthracene containing methacrylic copolymer

Summary : A new methacrylate monomer containing anthracene moiety connected with long flexible spacer was prepared and copolymerized with n-butyl methacrylate. It has been found that upon illumination in inert atmosphere photodimerization of the anthracene rings takes place to a considerable extend. The reverse decomposition of the photodimers by thermal treatment is also facilitated by the long flexible spacer. In ambient air the only photoreaction is endoperoxide formation. Received: 4 December 2000/Revised version: 21 May 2001/Accepted: 21 May 2001     

Synthesis and characterization of pyridine and anthracene containing bismaleimides,bisnadimides and polyaspartimides

Three different novel diamines containing pyridine and anthracene moiety were prepared and subsequently converted into bismaleimides (BMI) and bisnadimides (BNI) and their structure was confirmed by elemental analysis, FT-IR, ¹H-NMR and ¹³C-NMR techniques. Chain extension of bismaleimides and bisnadimides was accomplished by incorporating various ether or ester groups. Owing to pendant anthracene moiety, pyridine unit and flexible linkages, the bismaleimides and bisnadimides were found to possess an excellent balance of properties; solubility and thermal stability and the curing behaviour was investigated by differential scanning calorimeter. In addition, a series of polyaspartimides containing anthracene and pyridine unit was prepared by the polyaddition of bismaleimides with various diamines via a Michael-type addition. The thermal stability of bismaleimides, bisnadimides and polyaspartimides was evaluated by thermo gravimetric analysis. All the polyaspartimides are soluble in many organic solvents and exhibit T _g in the range of 189–242 °C and 10% weight loss (T ₁₀) takes place in the range of 389–487 °C in N₂.     

Tetrathiafulvalene. XXII [1] Redox- und spektroskopische Eigenschaften von Tetrathiafulvalenen (TTF) und Tetraselenafulvalenen (TSF) sowie deren Mono- und Dikationen

Tetrathiafulvalenes. XXII. Redox- and Spectroscopic Properties of Tetrathiafulvalenes (TTF) and Tetraselenafulvalenes (TSF) and their Mono- and Dications The polarographic oxidation potential of TTF is decreased by alkyl- and increased by aryl-substituents. The oxidation potentials of arylated TTF can be correlated with σ⁺-constants (σ  0,1). TSF are weaker donors than the respective TTF. Alkyl substitution at TTF causes a bathocromic shift and aryl substitution a hypsochromic shift of the longest wavelength absorption band. In the mono- and dications of TTF a bathochromic shift of this absorption band is observed by alkyl- as well as aryl-substituents which is especially pronounced, when the molecule is planar.     

Chelating ability of a conjugated redox active tetrathiafulvalenyl-acetylacetonate ligand

A novel tetrathiafulvalene (TTF) bearing a conjugated β-diketone moiety (TTFacacH) has been synthesized and fully characterized. The chelating ability of its enolate anion (TTFacac) has been investigated with [M^II(OAc)₂ · xH₂O] (OAc = acetate and M = Zn, Cu and Ni) leading to complexes, where the metal center is coordinated by two TTFacac. Modulation of the redox properties of the TTF can be achieved through the simple change of the two apical ligands which completed the octahedral coordination geometry. This redox active ligand shows promising features for the elaboration of hybrid organic–inorganic building blocks.     

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     

Tetrathiafulvalene. XVI. Spektroskopische und elektrische Eigenschaften von TTF und TTF-TCNQ-Komplexen

Tetrathiafulvalenes. XVI. Spectroscopic and Electrical Properties of TTF and TTF-TCNQ-Complexes UV-vis-spectra of mono- and dications of the TTF 2 show in comparison to those of TTF 1 and 3 that the aryl substituent in the TTF 2 is more twisted from the TTF-plane than in 1 and 3 . Absorption maxima of mono- and dications from TTF 1 and 3 lie at a significantly greater wavelength than absorption maxima of mono- and dications from TTF 2 , because a better electronic interaction between substituents in the aryl-group and the positively charged dithiolium-ring is possible. TCNQ-complexes of smoother TTF 3 also have a higher electrical conductivity than TCNQ-complexes of 2 .