2-(2-Cyanoethylthio)-3-methylthio-6,7-bis(hexylthio)tetrathiafulvalene | 319003-70-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二硫醇
• 英文名称: 2-(2-Cyanoethylthio)-3-methylthio-6,7-bis(hexylthio)tetrathiafulvalene
• 英文别名: 3-[[2-[4,5-Bis(hexylsulfanyl)-1,3-dithiol-2-ylidene]-5-methylsulfanyl-1,3-dithiol-4-yl]sulfanyl]propanenitrile；3-[[2-[4,5-bis(hexylsulfanyl)-1,3-dithiol-2-ylidene]-5-methylsulfanyl-1,3-dithiol-4-yl]sulfanyl]propanenitrile
• CAS: 319003-70-8
• 化学式: C₂₂H₃₃NS₈
• 分子量: 568.039
• InChiKey: CPKVCEHPKHUPNY-UHFFFAOYSA-N

物化性质

• 沸点：
  589.7±50.0 °C(Predicted)
• 密度：
  1.30±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  9.8
• 重原子数：
  31
• 可旋转键数：
  16
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  226
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  2-(2-Cyanoethylthio)-3-methylthio-6,7-bis(hexylthio)tetrathiafulvalene 在 cesium hydroxide 、 sodium hydroxide 作用下， 以 四氢呋喃 、 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 4.5h， 生成 4-(4',5'-Bis-hexylsulfanyl-5-methylsulfanyl-[2,2']bi[[1,3]dithiolylidene]-4-ylsulfanylmethyl)-benzoic acid
  参考文献：
  名称：

  Synthesis of Novel Phthalocyanine−Tetrathiafulvalene Hybrids; Intramolecular Fluorescence Quenching Related to Molecular Geometry

  摘要：

  A number of silicon phthalocyanine bis-esters have been synthesized and characterized, with axial ligands containing one or more tetrathiafulvalene groups. Variations in the substitution positions around a central aromatic "hinge" within the ligands lead to different molecular geometries, and the fluorescence of the macrocyclic core is subsequently quenched to varying degrees by the electron-rich tetrathiafulvalene moiety, the magnitude of this effect being dependent upon both the relative separation of the two units and the flexibility of the linking group. Pc derivative 24, with a highly flexible linker group, and pc derivative 28, with a dendritic axial ligand, have the intensity of the macrocycle emission reduced by 99% and 96%, respectively, relative to a similar silicon pc reference compound lacking the TTF moieties. Molecular modeling studies of a series of such hybrids allow the degree of this fluorescence quenching to be related to the intramolecular spacing. Additionally, the potential for rapid electrochemical switching of the phthalocyanine fluorescence by oxidation of the appended tetrathiafulvalene units is explored.

  DOI：

  10.1021/jo020340y
• 作为产物：
  描述：

  3-(5-methylsulfanyl-2-oxo-1,3-dithiol-4-ylsulfanyl)propanenitrile 、 4,5-bis(hexylthio)-1,3-dithiole-2-thione 在 亚磷酸三乙酯 作用下， 反应 5.0h， 以68%的产率得到2-(2-Cyanoethylthio)-3-methylthio-6,7-bis(hexylthio)tetrathiafulvalene
  参考文献：
  名称：

  New Multi(tetrathiafulvalene) Dendrimers

  摘要：

  报告了以乙二醇链为分支的多(TTF)树枝状大分子的聚合合成方法。迭代步骤中的关键方法涉及利用瞬态TTF-硫醇盐阴离子对活性卤化物进行亲核取代。树枝状大分子的核心单元分别为1,3,5-三取代苯、TTF和六取代苯，提供了三向、四向和六向的核心结构。循环伏安法(CV)和薄层CV研究表明，树枝状大分子结构中保留了TTF的氧化还原化学，通过电化学氧化可以清晰地依次形成多(阳离子自由基)和多(二阳离子)物种。

  DOI：

  10.1055/s-2000-8203

文献信息

• Synthesis, spectroscopic, and electrochemical properties of three tetrathiafulvalenes attached to perylene
  作者：Haixiao Qiu、Chengyun Wang、Jinfeng Xu、Guoqiao Lai、Yongjia Shen

  DOI：10.1007/s00706-008-0863-y

  日期：2008.11

  donor–acceptor dyads 1 – 3 comprising of a tetrathiafulvalene ( TTF ) unit linked with perylene by a simple σ-bond were synthesized and characterized. Spectroscopy and cyclic voltammetry provided an indication that intramolecular charge-transfer interactions in their ground states between TTF and perylene for dyads 1 – 3 are negligible. Compared with the compound perylene, dyads 1 – 3 exhibited large fluorescence

  三个供体-受体成对层 1 - 3 ，其包括硫富瓦烯（的 TTF 通过简单的σ键与苝连接）单元被合成和表征。光谱和循环伏安法提供的指示在它们之间的基态的分子内电荷转移相互作用 TTF 和苝为成对层 1 - 3 是可忽略的。与化合物苝相比，成对层 1 - 3 表现出大的荧光淬灭，这可能归因于间光诱导电子转移相互作用 TTF 处于兴奋状态和苝单元。
• Synthesis and properties of a tetrathiafulvalene–perylene tetracarboxylic diimide–tetrathiafulvalene dyad
  作者：Yu Zhang、Liang-Zhen Cai、Cheng-Yun Wang、Guo-Qiao Lai、Yong-Jia Shen

  DOI：10.1039/b719844b

  日期：——

  A donor–acceptor–donor dyad 4 involving 2-sulfur-3-methylthio-6,7-bis(hexylthio)tetrathiafulvalene (TTF) as a donor attached directly to N,N′-dibutylperylene-3,4,9,10-tetracarboxylic diimide (PDI) as an acceptor was synthesized by condensation of N,N′-dibutyl-1,6-dibromo-3,4,9,10-perylenetetracarboxylic diimide and 2-(2-cyanoethylthio-3-methylthio-6,7-bis(hexylthio)tetrathiafulvalene. The cyclic voltammetric (CV) data implied significant intramolecular interaction and the absorption spectrum indicated that there was an intramolecular charge transfer (ICT) interaction between TTF and PDI moieties in dyad 4. Comparing with PDI 13, the fluorescence emission intensity of dyad 4 was quenched almost quantitatively, which might result from the photo-induced electron transfer (PET) interaction between the PDI and TTF moieties in dyad 4. The fluorescence intensity of dyad 4 could be reversibly modulated by sequential oxidation and reduction of the TTF unit using chemical methods. Thus dyad 4 can be regarded as a new reversible fluorescence-redox dependent molecular switch.

  通过缩合 N,N²-二丁基-1,6-二溴-3,4,9,10-四羧酸二亚胺（PDI）作为受体，合成了供体-受体-受体四元化合物、通过缩合 N,N²-二丁基-1,6-二溴-3,4,9,10-过烯四羧酸二亚胺和 2-(2-氰基乙硫基-3-甲硫基-6,7-双(己硫基)四硫代富勒烯，合成了作为受体的 10-四羧酸二亚胺（PDI）。循环伏安（CV）数据表明存在显著的分子内相互作用，而吸收光谱则表明在对偶 4 中，TTF 和 PDI 分子之间存在分子内电荷转移（ICT）相互作用。与 PDI 13 相比，染料 4 的荧光发射强度几乎被定量淬灭，这可能是染料 4 中 PDI 和 TTF 分子之间的光诱导电子转移（PET）作用所致。使用化学方法依次氧化和还原 TTF 单元，可以可逆地调节染料 4 的荧光强度。因此，共轭物 4 可被视为一种新的可逆荧光-氧化还原依赖性分子开关。
• Synthesis and properties of polysilanes with tetrathiafulvalene as pendant group
  作者：Yibo Liu、Chengyun Wang、Meijiang Li、Guoqiao Lai、Yongjia Shen

  DOI：10.1039/b713819a

  日期：——

  Two polysilanes with tetrathiafulvalene (TTF) as pendant groups were synthesized by reaction of 2-cyanoethyl substituted TTF 1 with (chloromethylphenyl)dimethyl(phenyl)polysilane, or reaction of 4-vinylphenyl-TTF 2 with poly[methylsilane-co-methyl(phenyl)silane]. The structures and properties of TTF-polysilanes and their intermediates were characterized by 1H NMR, mass, GPC, UV/Vis, IR and cyclic voltammetry (CV). The results of UV/Vis and CV of these polysilanes indicated interaction between the TTF moieties and σ-electron delocalized Si–Si chain in the ground states. These polysilanes doped by I2 exhibited high conductivities (10−2 S cm−1).

  通过 2-氰乙基取代的 TTF 1 与（氯甲基苯基）二甲基（苯基）聚硅烷反应，或 4-乙烯基苯基-TTF 2 与聚[甲基硅烷-共甲基（苯基）硅烷]反应，合成了两种以四噻吩（TTF）为悬垂基团的聚硅烷。通过 1H NMR、质量、GPC、UV/Vis、IR 和循环伏安法（CV）对 TTF 聚硅烷及其中间体的结构和性质进行了表征。这些多聚硅烷的紫外可见分光光度法和紫外可见分光光度法的结果表明，在基态时，TTF 分子与σ-电子致焦的硅-硅链之间存在相互作用。这些掺杂了 I2 的聚硅烷表现出很高的导电率（10-2 S cm-1）。
• 3,4-Ethylenedioxythiophene Functionalizationed with Tetrathiafulvalene: Synthesis and Selective Esterification
  作者：Lei Zhang、Changzhi Wu、Chengyun Wang、Hujin Zuo、Yongjia Shen

  DOI：10.1002/jhet.1834

  日期：2014.9

  dimethyl 3,4‐dihydroxythiophene‐2,5‐dicarboxylate (1), which were isomers and difficult to separate. When they were esterified with tetrathiafulvalene carried carboxylic acid group, only 3,4‐(hydroxymethyl‐ethylenedioxy)thiophene (4) could be esterified. No such selectivity was observed when the isomers were esterified by lauric acid and benzoic acid, respectively.

  由3,4-二羟基噻吩-2,5-二羧酸二甲酯（1）合成3,4-（羟甲基-乙二氧基）噻吩（4）和3,4-（2'-羟丙二氧基）噻吩（4' '）是异构体，很难分离。当它们被四硫富瓦烯带有的羧酸基团酯化时，只能将3,4-（羟甲基-乙二氧基）噻吩（4）酯化。当异构体分别被月桂酸和苯甲酸酯化时，没有观察到这样的选择性。
• Synthesis and characterization of tetrathiafulvalene-σ-thiophene dyads
  作者：SHI-XIONG DENG、YU-HAO LI、PENG-FEI CAI、CHENG-YUN WANG、HAN WANG、YONG-JIA SHEN

  DOI：10.1007/s12039-020-01779-0

  日期：2020.12

  Meanwhile, the result of theoretical calculation indicated that TTF-Th-2 exhibited lower bandgap with the evident electron transfer in the LUMO energy level. Graphic abstractSynthesis and Characterization of TTF-σ-Thiophene Dyads

  摘要通过Steglich酯化反应和经典的SN 2反应，合成了3个TTF组装的噻吩富勒烯分子。UV和CV结果表明，分子组装形成的新分子存在不同的取代作用。在新分子中，最短的σ桥连接的TTF-Th-2（TTF-亚甲基噻吩）表现出最明显的取代作用。同时，理论计算结果表明，TTF-Th-2在LUMO能级上具有较低的带隙，并且具有明显的电子转移。 图形摘要TTF-σ-噻吩二烯的合成与表征