4，4’，5-三甲基四硫富瓦烯 | 49868-52-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二硫醇
• 中文名称: 4，4’，5-三甲基四硫富瓦烯
• 英文名称: 4,4’,5-trimethyltetrathiafulvalene
• 英文别名: 3,3',4'-trimethyltetrathiafulvalene；4',3,4-trimethyltetrathiafulvalene；4,4',5-trimethyltetrathiafulvalene；3,6,7-trimethyltetrathiafulvalene；trimethyltetrathiafulvalene；4,5-Dimethyl-2-(4-methyl-1,3-dithiol-2-ylidene)-1,3-dithiole
• CAS: 49868-52-2
• 化学式: C₉H₁₀S₄
• mdl: MFCD00270147
• 分子量: 246.442
• InChiKey: RJWAYFAUEIUPCS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.333
• 拓扑面积：
  101
• 氢给体数：
  0
• 氢受体数：
  4

安全信息

• 危险品标志：
  Xi
• 危险类别码：
  R43

反应信息

• 作为反应物：
  描述：

  4，4’，5-三甲基四硫富瓦烯 在 lithium diisopropylamide mono(tetrahydrofuran) 作用下， 以 乙醚 、 环己烷 为溶剂， 反应 1.5h， 生成 (4,3',4'-trimethyltetrathiafulvalen-3-yl)lithium
  参考文献：
  名称：

  Functionalised Trimethyltetrathiafulvalene (TriMe-TTF) Derivatives via Reactions of Trimethyltetrathiafulvalenyllithium with Electrophiles: X-ray Crystal Structures of Benzoyl-TriMe-TTF and Benzoylthio-TriMe-TTF

  摘要：

  报告了三甲基四硫杂戊烯的高产合成，并通过三甲基四硫杂戊烯锂与亲电物的反应制备了一系列官能化衍生物。

  DOI：

  10.1055/s-1995-3972
• 作为产物：
  描述：

  1-[2-(2-diethoxyphosphoryl-4,5-dimethyl-1,3-dithiol-2-yl)-4-methyl-1,3-dithiol-2-yl]piperidine 以30%的产率得到
  参考文献：
  名称：

  LERSTRUR, K.;JONANNSEN, I.;JZHUSTORGENSEN, M., SYNTH. MET., 27,(1988) N-4, C. B9-B13

  摘要：

  DOI：

文献信息

• Synthesis and characterization of TTF-type precursors for the construction of conducting and magnetic molecular materials
  作者：S. Bouguessa、A.K. Gouasmia、S. Golhen、L. Ouahab、J.M. Fabre

  DOI：10.1016/j.tetlet.2003.10.067

  日期：2003.12

  New TTF precursors for the construction of conducting and magnetic materials have been synthesized by using the palladium-catalyzed cross-coupling reaction between a mono- or a bis(trialkylstannyl)tetrathiafulvalene and a series of heteroaryl halides. The redox potential and some crystallographic data of these new building blocks are presented and discussed.

  通过使用单或双（三烷基锡烷基）四硫富瓦烯与一系列杂芳基卤化物之间的钯催化交叉偶联反应，已经合成了用于导电和磁性材料构造的新型TTF前体。介绍并讨论了这些新构件的氧化还原电势和一些晶体学数据。
• Sb⋯S and S⋯S interactions in the first neutral and oxidized diphenylstibino (Ph₂Sb–) derivatives of the redox active tetrathiafulvalene (TTF) core
  作者：Srinivasan S. Kuduva、Narcis Avarvari、Marc Fourmigué

  DOI：10.1039/b205594p

  日期：——

  The preparation of the monostibines o-Me2TTF–SbPh2 (1) and Me3TTF–SbPh2 (2), the ortho distibine o-Me2TTF(SbPh2)2 (3) and the tetrastibine TTF(SbPh2)4 (4) is described together with their electrochemical properties and the X-ray crystal structures of the neutral 1 and 3. In the former, one intermolecular Sb⋯S contact completes the co-ordination sphere of the antimony atom while in 3 the TTF moieties stack on top of each other with no evidence for Sb⋯S interactions. Electrocrystallisation of 2 in the presence of [n-Bu4N]2[Mo6O19] affords a 2 ∶ 1 salt, [2]2[Mo6O19] where the 2+˙ cation radical species are associated into diamagnetic [2]22+dyads through a strong HOMO⋯HOMO overlap interaction, separated from each other by the [Mo6O19]2− counter ions.

  本文描述了单锑化合物o-Me2TTF–SbPh2 (1) 和Me3TTF–SbPh2 (2)，邻二锑化合物o-Me2TTF(SbPh2)2 (3) 以及四锑化合物TTF(SbPh2)4 (4) 的制备，同时介绍了它们的电化学性质和中性化合物1和3的X射线晶体结构。在化合物1中，一个分子间的Sb–S接触完成了锑原子的配位球，而在3中，TTF部分相互堆叠，没有发现Sb–S相互作用的证据。在存在[n-Bu4N]2[MO6O19]的条件下对化合物2进行电晶体化，可以得到盐 [2]2[MO6O19]，其中2+·阳离子自由基通过强HOMO–HOMO重叠相互作用聚集成顺磁性的[2]22+二聚体，彼此之间由[MO6O19]2−反离子隔开。
• Synthesis and crystal engineering of new halogenated tetrathiafulvalene (TTF) derivatives and their charge transfer complexes and radical ion salts
  作者：Andrei S. Batsanov、Martin R. Bryce、Antony Chesney、Judith A. K. Howard、Derek E. John、Adrian J. Moore、Clare L. Wood、Hagit Gershtenman、James Y. Becker、Vladimir Y. Khodorkovsky、Arkady Ellern、Joel Bernstein、Igor F. Perepichka、Vincent Rotello、Mark Gray、Alejandro O. Cuello

  DOI：10.1039/b101866n

  日期：——

  Efficient syntheses are reported for tetraiodotetrathiafulvalene 2, 4-iodo-5-methyl-4′,5′-bis(methylsulfanyl)TTF 3, and 4-iodo-4′,5′-bis(methylsulfanyl)TTF 4 by iodination, using perfluorohexyl iodide, of lithiated derivatives of the corresponding TTF system. Bromination and chlorination of lithiotrimethylTTF using 1,2-dibromotetrafluoroethane and hexachloroethane gave 4-bromo- and 4-chloro-4′,5,5′-trimethylTTF 6 and 7, respectively. Phosphite-induced self-coupling or cross-coupling reactions of 4-iodo-1,3-dithiole-2-thione or 4,5-diiodo-1,3-dithiole-2-thione(one) half-units resulted in TTF derivatives with partial loss of the iodine substituent(s). 4,5-Dibromo-4′,5′-bis(cyanoethylsulfanyl)TTF 15 was prepared by cross-coupling methodology, and converted into 4,5-dibromo-4′,5′-bis(methylsulfanyl)TTF 16 by reaction with caesium hydroxide and then methyl iodide. EPR data are reported for the electrochemically generated cation radicals of trimethylTTFX derivatives (X = I, Br and Cl) 5–7, respectively. For the neutral donors, the X-ray crystal structures are reported for 2, 5, 6, tetramethylTTF 8 and 15. Structure 2 is characterised by a particularly dense packing with continuous chains of intra-stack I⋯I contacts (4.17–4.19 Å). The crystals of 6 and 8 are isomorphous, while the structure of 5 is different. The iodo-substituent in 5 affects the packing in a way the bromo-substituent in 6 does not, due to differences in specific interactions rather than steric demands of I and Br, which are similar. Structure 15 comprises face-to-face dimers with inter-dimer Br⋯Br (3.57 Å) and Br⋯S (3.55 Å) contacts: a remarkable difference in bond distances between the Br and S-substituted dithiole rings is observed. The 1 ∶ 1 charge-transfer (CT) complexes 3·TCNQ and 4·TCNQ (TCNQ = 7,7,8,8-tetracyano-p-quinodimethane, 17) display mixed stair-like stacks of alternating D and A moieties: the overall degree of CT is estimated from bond length analysis to be 0.2 e and 0.3 e, respectively. In 3·TCNQ either position of the disordered iodine atom has one short (inter-stack, but intra-layer) contact with a cyano group (I⋯N distances of 3.14 and 3.18 Å). In 4·TCNQ a similar I⋯N contact is much longer (3.35 Å). In the structure of 5+·I3−·½I2 the cation radical is disordered; dimeric cation radicals display short intra-dimer contacts (S⋯S 3.38–3.39 Å, C⋯C 3.35 Å) consistent with electron coupling. Each dimer is surrounded by four I3− anions. The crystal structure of 16+·I3− is comprised of layers with interplanar separations of 3.55 Å. Cations of one layer overlap with anions of the next, and the packing can be described as mixed stacks parallel to the a axis. The remarkably high conductivity of this salt for a system of 1 ∶ 1 stoichiometry (σrt = 8 × 10−2 S cm−1) is ascribed to partial charge transfer (the charge on the TTF moiety is estimated as +⅔ from bond length analysis) and a continuous system of short non-bonding contacts.

  报道了四碘四硫富瓦烯的高效合成方法，4-碘-5-甲基-4′,5′-双(甲基硫巴)TTF 3，以及4-碘-4′,5′-双(甲基硫巴)TTF 4，该方法通过用全氟己基碘对相应TTF体系的锂化衍生物进行碘化反应。使用1,2-二溴四氟乙烷和六氯乙烷对锂三甲基TTF进行溴化和氯化，分别得到了4-溴-和4-氯-4′,5,5′-三甲基TTF 6和7。由磷酸酯诱导的4-碘-1,3-二噁烯-2-硫酮或4,5-二碘-1,3-二噁烯-2-硫酮(一个)半单元的自偶联或交叉偶联反应导致TTF衍生物伴有部分碘取代基的损失。通过交叉偶联方法合成了4,5-二溴-4′,5′-双(氰乙基硫巴)TTF 15，并通过与氢氧化铯和随后与碘甲烷的反应转化为4,5-二溴-4′,5′-双(甲基硫巴)TTF 16。报告了为电化学生成的三甲基TTF衍生物(X = I, Br和Cl)的阳离子自由基进行的电子顺磁共振(EPR)数据。对于中性给体，报告了2、5、6、四甲基TTF 8和15的X射线晶体结构。结构2的特征在于具有特别密集的堆积形态，形成连续的堆叠内I⋯I接触(4.17–4.19 Å)。6和8的晶体是同构的，而5的结构则不同。由于特定相互作用的差异，而不是I和Br相似的立体要求，使得5中的碘取代基影响了堆积，而6中的溴取代基则没有。结构15由面对面二聚体组成，具有二聚体间的Br⋯Br(3.57 Å)和Br⋯S(3.55 Å)接触：观察到Br和S取代的二噁烯环之间的键长距离存在显著差异。1:1电荷转移(CT)复合物3·TCNQ和4·TCNQ(TCNQ = 7,7,8,8-四氰基-p-奎诺二甲烷，17)显示出交替的D和A基团的混合阶梯状堆叠：通过键长分析估计的CT整体程度分别为0.2 e和0.3 e。在3·TCNQ中，无序的碘原子在某个位置与一个氰基之间有一个短的(堆叠间，但层内)接触(I⋯N距离为3.14和3.18 Å)。在4·TCNQ中，类似的I⋯N接触则较长(3.35 Å)。在结构5+·I3−·½I2中，阳离子自由基无序；二聚阳离子自由基显示短的二聚内接触(S⋯S 3.38–3.39 Å, C⋯C 3.35 Å)，与电子耦合一致。每个二聚体周围都有四个I3−阴离子。16+·I3−的晶体结构由层组成，层间距离为3.55 Å。一个层的阳离子与下一个层的阴离子重叠，堆积可描述为沿a轴的混合堆叠。这种1:1化学计量比体系的盐具有显著高的导电性(σrt = 8 × 10−2 S cm−1)，归因于部分电荷转移(通过键长分析估计TTF基团的电荷为+⅔)和一种连续的短非键接触体系。
• (N-Methylthiocarbamoyl)tetrathiafulvalene derivatives and their radical cations: synthetic and X-ray structural studies
  作者：Adrian J. Moore、Martin R. Bryce、Andrei S. Batsanov、Julie N. Heaton、Christian W. Lehmann、Judith A. K. Howard、Neil Robertson、Allan E. Underhill、Igor F. Perepichka

  DOI：10.1039/a802037j

  日期：——

  Lithiation of 4,5-bis(methylsulfanyl)-TTF 9, 4,5-(ethylenedisulfanyl)-TTF 10, 4,5-dimethyl-TTF 11 and 4,5,5′-trimethyl-TTF 12 (TTF=tetrathiafulvalene) followed by reaction with methyl isothiocyanate affords the corresponding (N-methylthio-carbamoyl)-TTF derivatives 14–17, respectively, in 54–70% yields. These new TTF derivatives display a broad intramolecular charge-transfer band in their UV–VIS spectra arising from conjugation between the donor TTF ring and the acceptor N-methylthiocarbamoyl moiety. Steric hindrance between the adjacent N-methylthiocarbamoyl and methyl substituents in 17 causes a marked hyposchromic shift in this band (λmax 395 nm) compared to compounds 14–16 (lambda;max 435–467 nm). Consistent with the electron-withdrawing properties of the N-methylthiocarbamoyl substituent, its attachment to the TTF ring raises slightly the oxidation potential of the system. Charge transfer complexes of these donors and (N-methylthiocarbamoyl)-TTF 2 with 7,7,8,8-tetracyano-p-quinodimethane (TCNQ) and salts with bromide anions are reported, some of which have high room temperature conductivity values. The X-ray crystal structures are presented for 16, 17 and the salts 2·Br, 14·TCNQ and (17)2·20. The structure of 16 comprises orthogonal dimers (kappa packing) while in the structure of 17 individual molecules are orthogonal to each other. There is weak intermolecular hydrogen bonding in both 16 and 17. In the structure of 2·Br, the radical cations 2+· are almost planar and they form an infinite stair-like stack of dimers, with bromide anions situated between the stacks, and linked with the cation by a strong N–H‥Br bond. The structure of 14·TCNQ comprises mixed ‥DDAADD‥ stacks; the N-methylthiocarbamoyl group engages in an interstack N–H‥N bond with a TCNQ anion. Analysis of the bond lengths in the structure suggests that there is partial charge transfer from 14 to TCNQ. In the structure of (17)2·20 molecules form mixed ‥DDADDA‥ stacks and analysis of bond lengths suggests that there is only a small degree of charge transfer from donor to acceptor. The geometries of compounds 2, 14, 16, 17 were optimised using the PM3 semi-empirical method and the results compare favourably with the X-ray structural data.

  将 4,5-双（甲硫基）-TTF 9、4,5-（亚乙基二硫基）-TTF 10、4,5-二甲基-TTF 11 和 4,5,5′-三甲基-TTF 12（TTF=四硫代富勒烯）进行锂化，然后与异硫氰酸甲酯反应，可分别得到相应的（N-甲硫基氨基甲酰基）-TTF 衍生物 14-17，收率为 54-70%。这些新的 TTF 衍生物在其紫外-可见光谱中显示出宽阔的分子内电荷转移带，这是由于供体 TTF 环和受体 N-甲基硫代氨基甲酰基之间的共轭作用产生的。与 14-16 号化合物（λmax 435-467 nm）相比，17 号化合物中相邻的 N-甲基硫代氨基甲酰基和甲基取代基之间的立体阻碍导致该波段（λmax 395 nm）出现明显的低色度偏移。与 N-甲基硫代氨基甲酰取代基的吸电子特性相一致，N-甲基硫代氨基甲酰取代基与 TTF 环的连接会略微提高体系的氧化电位。据报道，这些供体和（N-甲基硫代氨基甲酰基）-TTF 2 与 7,7,8,8-四氰基对二醌甲烷（TCNQ）以及溴阴离子盐的电荷转移配合物，其中一些具有很高的室温电导率值。本文介绍了 16、17 以及盐类 2-Br、14-TCNQ 和 (17)2-20 的 X 射线晶体结构。16 的结构由正交二聚体（卡帕堆积）组成，而在 17 的结构中，单个分子彼此正交。16 和 17 中都存在微弱的分子间氢键。在 2-Br 的结构中，自由基阳离子 2+- 几乎是平面的，它们形成一个无限阶梯状的二聚体堆栈，溴阴离子位于堆栈之间，并通过强 N-H‥Br 键与阳离子相连。14-TCNQ 的结构由混合的 ‥DDAADD‥ 堆栈组成；N-甲基硫代氨基甲酰基与 TCNQ 阴离子在堆间形成 N-H‥N 键。对结构中键长的分析表明，14 与 TCNQ 之间存在部分电荷转移。在 (17)2-20 的结构中，分子形成了混合的‥DDADDA‥堆栈，对键长的分析表明，从供体到受体只有少量的电荷转移。利用 PM3 半经验方法对化合物 2、14、16 和 17 的几何结构进行了优化，结果与 X 射线结构数据相比非常理想。
• Relative basicities of the oxygen atoms of the Linquist polyoxometalate [Mo6O19]2− and their recognition by hydroxyl groups in radical cation salts based on functionalized tetrathiafulvalene π donors
  作者：Anne Dolbecq、Aude Guirauden、Marc Fourmigué、Kamal Boubekeur、Patrick Batail、Marie-Madeleine Rohmer、Marc Bénard、Claude Coulon、Marc Sallé、Philippe Blanchard

  DOI：10.1039/a809442j

  日期：——

  Electrocrystallization of three hydroxylated donor molecules derived from tetrathiafulvalene (TTF) or ethylenedithiotetrathiafulvalene (EDT-TTF), i.e. Me3TTF-CH2OH, EDT-TTF(CH2OH)2 and TTF(CH2OH)4, in the presence of [n-Bu4N+]2[Mo6O19]2– afforded 2∶1 cation radical salts, [donor+˙]2[Mo6O19]2–, whose crystal structures have been solved by X-ray diffraction. In the three different salts complex hydrogen bond networks develop in the solid state where the oxygen atoms of both the hydroxyl groups and the [Mo6O19]2– anions act as hydrogen bond acceptors. The observed hydrogen bonding directed toward one surface, bridging oxygen atom of [Mo6O19]2– is rationalized by an analysis of ab initio calculations of the distribution of electrostatic potentials.

  在[n-Bu4N+]2[Mo6O19]2â的存在下，从四噻吩富戊二烯（TTF）或亚乙基二硫代四噻吩富戊二烯（EDT-TTF）衍生的三种羟基化供体分子（即Me3TTF-CH2OH、EDT-TTF(CH2OH)2 和 TTF(CH2OH)4，在[n-Bu4N+]2[Mo6O19]2â的存在下生成 2â¶1 阳离子自由基盐[供体+Ë]2[Mo6O19]2â，其晶体结构已通过 X 射线衍射解决。在这三种不同的盐中，羟基和[Mo6O19]2â阴离子的氧原子都是氢键的受体，在固态下形成了复杂的氢键网络。通过对静电位分布的 ab initio 计算分析，可以合理地解释观察到的指向 [Mo6O19]2â 的一个表面桥接氧原子的氢键。