N-羟甲基-2,3-二丁硫基四硫富瓦烯并[6,7-c]吡咯的合成

从4,5-二丁硫基-1,3-二硫杂环戊二烯-2-酮和N-对苯磺酰基-2-硫代-1,3-二硫杂环戊二烯并[4,5-c]吡咯出发,经交叉偶联、去保护得2,3-二丁硫基四硫富瓦烯并[6,7-c]吡咯(4)。化合物4在碱存在下与甲醛水溶液(37%)反应生成N-羟甲基化的产物。用核磁共振氢谱研究了标题化合物在不同极性溶剂中的偶合行为。     

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。     

“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。     

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。     

D-π-A型四硫富瓦烯衍生物的合成及其性能研究

作为很强的有机电子给体,四硫富瓦烯能够在低电位被可逆氧化,失去一个或两个电子生成相应的正一价阳离子自由基或正二价阳离子．近年来它在众多领域显示出日益重要的作用．本论文设计合成了一系列具有D-π-A和A-π-D-π-A结构的四硫富瓦烯 (TTF)衍生物,系统研究了它们在基态发生分子内电荷转移的可能,并利用外界刺激改     

D-兀-A型四硫富瓦烯衍生物的合成及其性能研究

作为很强的有机电子给体，四硫富瓦烯能够在低电位被可逆氧化，失去一个或两个电子生成相应的正一价阳离子自由基或正二价阳离子，近年来它在众多领域显示出日益重要的作用，本论文设计合成了一系列具有D-兀-A和A-兀-D-兀-A结构的四硫富瓦烯（TTF）衍生物，系统研究了它们在基态发生分子内电荷转移的可能，并利用外界刺激改变分子内电荷转移的程度，取得了如下研究结果：     

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。     

氧化作用控制“四硫富瓦烯-蒽”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.     

Synthesis, spectroscopic, and electrochemical properties of two dyads consisted of tetrathiafulvalene and carbazole

Two donor-σ-acceptor molecules containing tetrathiafulvalene (TTF) and carbazole moieties were synthesized by the reaction of 9-(4-bromo-butyl)-carbazole (1) with 2,6-bis(hexylthio)-3-(2-cyanoethylthio)-7- (methylthio)-tetrathiafulvalene (2) or 2,6-bis(2-cyanoethylthio)-3, 7-bis(methylthio)tetrathiafulvalene (3) in the presence of CsOH·H2O, respectively. The structures of the molecules were characterized by ¹H NMR, ¹³C NMR, MS, and elemental analyses. They showed negligible intramolecular charge-transfer interaction in their ground states as indicated by their UV-Vis spectroscopics and cyclic voltammetry results. Compared with carbazole, their fluorescence was strongly quenched, which implied that a photo induced electron transfer (PET) interaction between TTF and carbazole moieties occurred.     

Tetrathiafulvalene. XXI. Synthese von Tetrathiafulvalenen aus 2-Alkylthio-, 2-Arylthio- und 2-Alkylseleno-1,3-dithioliumsalzen

Tetrathiafulvalenes. XXI. Syntheses of Tetrathiafulvalenes from 2-Alkylthio-, 2-Arylthio- and 2-Alkylseleno-1,3-dithiolium Salts In the reaction of 2-alkylthio-, 2-arylthio- or 2-alkylseleno-1, 3-dithiolium salts with trivalent phosphorus compounds in acetonitril tetrathiafulvalenes 2 are formed. As an intermediate we suppose a phosphorane, which reacts with further 1,3-dithiolium salt to provide the tetrathiafulvalene. By the application of a 2-alkylthio-1,3-dithiolium salt a monomethin dye is formed in a side reaction. When the reaction is carried out in methanol, the phosphorane is trapped by the solvent and a 2H-1,3-dithiolium salt is obtained.     

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.     

用改进的实数编码遗传算法估计反应动力学参数

通过理论分析和模拟实验研究了遗传算法中实数编码线性交叉操作的效率,提出了一种优化分布线性交叉操作策略,使子代个体在搜索空间内达到均匀分布,具有很高的搜索效率。用这种改进的实数编码遗传算法进行正丁烷选择氧化反应动力学参数估计,取得了良好的效果。     

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。     

Synthesis and properties of tetrathiafulvalene-fluorescein dyads

Two donor-acceptor molecular systems consisted of tetrathiafulvalene (TTF) and fluorescein were designed and synthesized. The target compounds and their key intermediates were characterized by 1H NMR, mass spectrography, and infrared spectroscopy, respectively. The UV-vis spectra implied intramolecular interaction in their ground state. Fluorescence spectra and fluorescence lifetimes indicated the photoinduced charge transfer (PET) interaction between the TTF and fluorescein units in their excited states.     

New Unsymmetrically Benzene-Fused Bis (Tetrathiafulvalene): Synthesis,Characterization, Electrochemical Properties and Electrical Conductivity of Their Materials

The synthesis of new unsymmetrically benzene-fused bis (tetrathiafulvalene) has been carried out by a cross-coupling reaction of the respective 4,5-dialkyl-1,3-dithiole- 2-selenone 6–9 with 2-(4-(p-nitrophenyl)-1,3-dithiole-2-ylidene)-1,3,5,7-tetrathia-s-indacene- 6-one 5 prepared by olefination of 4-(p-nitrophenyl)-1,3-dithiole-2-selenone 3 and 1,3,5,7-tetrathia-s-indacene-2,6-dione 4. The conversion of the nitro moiety 10a–d to amino 11a–d then dibenzylamine 12a–d groups respectively used reduction and alkylation methods. The electron donor ability of these new compounds has been measured by cyclic voltammetry (CV) technique. Charge transfer complexes with tetracyanoquino-dimethane (TCNQ) were prepared by chemical redox reactions. The complexes have been proven to give conducting materials.     

Chemical and Physical Properties of Capped and Uncapped Alkylthio Substituted Tetrathiafulvalenes and Their Charge Transfer Complexes

A series of tetrakis(n-alkylthio)tetrathiafulvalene (alkyl-methyl to octadecyl; TTC_n-TTF (n = 1-18) has been synthesized. Synthesis, structure, and some physical properties of these uncapped analogues of bis(ethylenedithiolo)tetrathiafulvalene (BEDT-TTF) are described and compared with those of BEDT-TTF. Several charge transfer complexes of TTC₁-TTF are presented in terms of their electrical conductivities, ionicity, structures, and intermolecular interactions and compared with those of BEDT-TTF compounds. Molecular conformation, mode of the sulfur-to-sulfur atomic contacts, and requirements for an organic metal are discussed from the viewpoint of the molecular design.