1,2-cyclohexenyl-(2-thioxo-1,3-dithiole)-[60]fullerene | 186826-03-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: 1,2-cyclohexenyl-(2-thioxo-1,3-dithiole)-[60]fullerene
• CAS: 186826-03-9
• 化学式: C₆₅H₄S₃
• 分子量: 880.945
• InChiKey: ILVXNTXNQSZCJL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  18.95
• 重原子数：
  68.0
• 可旋转键数：
  0.0
• 环数：
  34.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  1,2-cyclohexenyl-(2-thioxo-1,3-dithiole)-[60]fullerene 在 间氯过氧苯甲酸 作用下， 以 邻二氯苯 为溶剂， 反应 2.0h， 以78%的产率得到1,2-cyclohexenyl-(1,3-dithiolium)-[60]fullerene hydrogenosulfate
  参考文献：
  名称：

  Rigidified tetrathiafulvalene–[60]fullerene assemblies: towards the control of through-space orientation between both electroactive units

  摘要：

  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。

  DOI：

  10.1039/b201695h
• 作为产物：
  描述：

  足球烯 、 5,5-dioxo-1,3-dithiole-2-thione 以 苯甲腈 、 氯苯 为溶剂， 以41%的产率得到1,2-cyclohexenyl-(2-thioxo-1,3-dithiole)-[60]fullerene
  参考文献：
  名称：

  The first Diels–Alder adduct of [60]fullerene with a tetrathiafulvalene

  摘要：

  通过[60]富勒烯与 TTF 二烯前体的直接反应，合成了[60]富勒烯与四噻吩富勒烯 (TTF) 衍生物的 DielsâAlder 加合物；[60]富勒烯的正式中间体 1,3- 二硫杂环戊烯-2-硫酮衍生物的晶体结构显示，[60]富勒烯与 1,3- 二硫杂环戊烯-2-硫酮分子之间存在短接触。

  DOI：

  10.1039/a607857e

文献信息

• Persistent and Transient Open-Shell Species Derived from C₆₀−TTF Cyclohexene-Fused Dyads
  作者：Josep Llacay、Jaume Veciana、José Vidal-Gancedo、José Luis Bourdelande、Rafael González-Moreno、Concepció Rovira

  DOI：10.1021/jo980498b

  日期：1998.7.1

  A new series of donor-acceptor fused dyads consisting of a C-60 doubly tethered to a substituted TTF moiety has been synthesized. Cyclic voltammetry of the new fullerene derivatives in solution shows a modulation in the difference between the first reduction potential of the fullerene moiety and the first oxidation potential of the TTF moiety with the substituents of the TTF addend; Along with the neutral bichromophoric compounds;we also report the generation-and characterization by EPR and absorption spectroscopies of the corresponding persistent open-shell species obtained electrochemically, namely their radical cations and radical anions. Spin density distributions of radical cations and radical anions derived from dyads la-e are mainly located on the TTF and fullerene moieties, respectively, as ascertained from the g values and S-33 hyperfine coupling constants. Interestingly, the EPR of the radical anion derived from the bisadduct Id exhibits a structured signal (g = 2.0005) arising from the coupling of the unpaired electron with the hydrogen atoms of the addends. The modification of the donor strength of the TTF moiety: allows the tuning of the HOMO-LUMO gap of dyads,permitting a study of the interaction between the two electroactive centers of the molecules as a function: of the donor strength. Nanosecond-resolved flash photolysis in the UV-vis region of dyads 1a-c in degassed benzonitrile shows a rapid quenching of the corresponding excited triplet states, which indicates different lifetimes depending on the donor ability of their TTF addends. Excited triplet states of 1b and 1c evolve toward transient charge-separated open-shell species that have remarkably long lifetimes (1b, tau = 75 x 10(-6) s; 1c, tau = 79 x 10(-6) s) and show absorptions around 460 and 620 nm due to the radical cation on the TTF moiety. These biradical species are also observed by LESR, having in frozen solution spectra consistent with strong exchange coupling between bath electrons.
• [4+2] Cycloaddition of C60 to 2-(thi)oxo-4,5-bis(methylene)-1,3-dithioles: en route to the bis-linking of tetrathiafulvalene to C60
  作者：C. Boulle、M. Cariou、M. Bainville、A. Gorgues、P. Hudhomme、J. Orduna、J. Garín

  DOI：10.1016/s0040-4039(96)02220-4

  日期：1997.1

  The title reaction carried out from S-propargyl xanthate 3 or 2-(thi)oxo-4,5-bis(bromomethyl)-1,3-dithioles 4a and 4b with C-60 is presented and some conversions of the synthesized cycloadducts 2a and 2b in several 1,3-dithiole derivatives are described. Copyright (C) 1996 Published by Elsevier Science Ltd