2,3-bis(bromomethyl)ethylenedithiotetrathiafulvalene | 225798-11-8

• 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: 2,3-bis(bromomethyl)ethylenedithiotetrathiafulvalene
• 英文别名: 2-[4,5-Bis(bromomethyl)-1,3-dithiol-2-ylidene]-5,6-dihydro-[1,3]dithiolo[4,5-b][1,4]dithiine
• CAS: 225798-11-8
• 化学式: C₁₀H₈Br₂S₆
• 分子量: 480.378
• InChiKey: QFNGBXIIKMZYPB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  152
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2,3-bis(bromomethyl)ethylenedithiotetrathiafulvalene 、 alkaline earth salt of/the/ methylsulfuric acid 在 reductive elimination reagent 作用下， 生成 1,2-cyclohexenyl-(ethylenedisulfanyltetrathiafulvalene)-[60]fullerene
  参考文献：
  名称：

  10.1016/s0022-2860(02)00240-5

  摘要：

  DOI：

  10.1016/s0022-2860(02)00240-5
• 作为产物：
  描述：

  4,5-bis(methoxycarbonyl)-1,3-dithiole-2-one 在 sodium tetrahydroborate 、 三溴化磷 、 lithium chloride 、 亚磷酸三乙酯 作用下， 以 四氢呋喃 、 甲醇 、 四氯化碳 为溶剂， 反应 5.83h， 生成 2,3-bis(bromomethyl)ethylenedithiotetrathiafulvalene
  参考文献：
  名称：

  四硫富瓦烯冠醚[60]富勒烯衍生物的合成及金属离子络合研究

  摘要：

  描述了含有电子供体四硫富瓦烯和金属络合冠醚的两种新型 [60] 富勒烯衍生物的合成，并通过固液萃取技术、循环伏安法和 1 H NMR 光谱研究了它们与碱金属阳离子的络合能力。

  DOI：

  10.1002/1099-0690(200004)2000:7<1157::aid-ejoc1157>3.0.co;2-z

文献信息

• Rigidified tetrathiafulvalene–[60]fullerene assemblies: towards the control of through-space orientation between both electroactive units
  作者：David Kreher、Michel Cariou、Sheng-Gao Liu、Eric Levillain、Jaume Veciana、Concepció Rovira、Alain Gorgues、Piétrick Hudhomme

  DOI：10.1039/b201695h

  日期：2002.6.21

  Our recent works on fused TTF–C60 dyads, (TTF)n–C60 polyads and C60–TTF–C60 dumbbell triads in which the acceptor C60 is doubly tethered to the donor tetrathiafulvalene through a rigidified cyclohexene ring are presented. This approach was developed in order to control the relative orientation as well as the distance between both donor and acceptor entities. Thereby, through-space interactions which are of great importance for photoinduced electron- and/or energy-transfer processes are expected to dominate because of the special topology of the molecules. The two linked C60 and TTF chromophores in such adducts are not only in close proximity but also have optimal orbital orientations, thus facilitating these through-space electronic interactions. These new C60-based assemblies were synthesized by [4 + 2] Diels–Alder cycloaddition reactions. The different methodologies considered for their synthesis are discussed, their analytical, spectroscopic characterizations and electrochemical properties are also described. The selective electro-oxidation or reduction afforded the corresponding radical cation and radical anion which were characterized by EPR. These C60-based assemblies were studied for their nonlinear optical and optical limiting applications. Moreover, intramolecular photoinduced charge-separation and charge-recombination processes in a fused C60–TTF–C60 dumbbell triad which was designed to be soluble in organic solvents were investigated by time-resolved absorption and fluorescence techniques. Appreciable interaction between the C60 moiety and TTF moiety in the ground state was suggested by steady-state absorption spectra and the fluorescence spectra showed considerable interaction in the singlet excited state. The nanosecond transient absorption spectra displayed the formation of the charge-separated radical pair C60–TTF˙+–C60˙−, characterized by a lifetime of ca. 20 ns in benzonitrile.

  我们最近的研究工作集中在融合的TTF–C60二聚体、(TTF)n–C60多聚体和C60–TTF–C60哑铃三聚体，这些体系中受体C60通过刚性的环己烯环与供体四硫富瓦烯双重连接。此方法的开发旨在控制供体和受体之间的相对方向和距离。因此，由于分子的特殊拓扑结构，空间内的相互作用在光诱导电子及/或能量转移过程中预计将占主导地位。这种加合物中连接的C60和TTF色团不仅相互接近，而且具有最佳的轨道取向，从而促进这些跨空间的电子相互作用。这些新的基于C60的组装体是通过[4 + 2]迪尔斯－阿尔德环加成反应合成的。文中讨论了其合成过程中考虑的不同方法，并描述了它们的分析、光谱特性及电化学性质。选择性电氧化或还原生成了相应的自由基阳离子和自由基阴离子，这些都通过电子顺磁共振（EPR）进行了表征。这些基于C60的组装体也被研究用于其非线性光学和光限制应用。此外，设计为可溶于有机溶剂的融合C60–TTF–C60哑铃三聚体中的分子内光诱导电荷分离和电荷重组过程通过时间分辨吸收和荧光技术进行了研究。在基态中，稳态吸收光谱表明C60基团与TTF基团之间存在显著的相互作用，而荧光光谱则显示在单重激发态中也存在较强的相互作用。纳秒瞬态吸收光谱显示了电荷分离的自由基对C60–TTF˙+–C60˙–，其在苯腈中表征的寿命约为20纳秒。
• Novel [60]fullerene–TTF cyclohexene fused polyadducts: unprecedented tri- and tetra-Diels–Alder adducts of dimethylidene[2H]tetrathiafulvalenes with C60
  作者：David Kreher、Sheng-Gao Liu、Michel Cariou、Piétrick Hudhomme、Alain Gorgues、Marta Mas、Jaume Veciana、Concepció Rovira

  DOI：10.1016/s0040-4039(01)00494-4

  日期：2001.5

  The title compounds, which are formed in very low yields by treating 2,3-bis(bromomethyl)tetrathiafulvalenes with naked iodide in the presence of C60, can be obtained in much higher yields by successive similar treatments of the major adducts produced at each step. The electrochemical properties of the unprecedented tri- and tetra-TTF/C60 assemblies are also presented.

  通过在C 60存在下用裸碘化物处理2,3-双（溴甲基）四硫富瓦烯以极低的收率形成标题化合物，可以通过连续地对每种化合物产生的主要加合物进行类似的处理，以高得多的收率获得这些化合物。步。还介绍了空前的三-和四-TTF / C 60组件的电化学性能。
• New versatile building blocks in tetrathiafulvalene (TTF) chemistry: 2,3-bis(bromomethyl) and tetrakis(bromomethyl)TTFs
  作者：P. Hudhomme、S.G. Liu、D. Kreher、M. Cariou、A. Gorgues

  DOI：10.1016/s0040-4039(99)00325-1

  日期：1999.4

  Efficient syntheses of novel 2,3-bis(bromomethyl)TTF derivatives 1 and tetrakis(bromomethyl)TTF 2, prone to generate corresponding 2,3-dimethylene[2H]-TTF 3 and tetramethylene[4H]-TTF 4 respectively, are reported. (C) 1999 Published by Elsevier Science Ltd. All rights reserved.