Dimethyl 2-(65,67-dithiatritriacontacyclo[62.3.0.03,58.03,62.04,20.05,57.06,18.07,55.08,17.09,53.010,15.011,52.012,49.013,47.014,44.016,43.019,42.021,41.022,62.023,39.024,61.025,37.026,35.027,60.028,33.029,59.030,56.031,54.032,51.034,50.036,48.038,46.040,45]heptahexaconta-1(64),4(20),5(57),6(18),7(55),8(17),9(53),10(15),11,13,16(43),19(42),21(41),22,24(61),25,27(60),28,30(56),31(54),32,34,36,38(46),39,44,47,49,51,58-triacontaen-66-ylidene)-1,3-dithiole-4,5-dicarboxylate | 190520-28-6

• 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: Dimethyl 2-(65,67-dithiatritriacontacyclo[62.3.0.03,58.03,62.04,20.05,57.06,18.07,55.08,17.09,53.010,15.011,52.012,49.013,47.014,44.016,43.019,42.021,41.022,62.023,39.024,61.025,37.026,35.027,60.028,33.029,59.030,56.031,54.032,51.034,50.036,48.038,46.040,45]heptahexaconta-1(64),4(20),5(57),6(18),7(55),8(17),9(53),10(15),11,13,16(43),19(42),21(41),22,24(61),25,27(60),28,30(56),31(54),32,34,36,38(46),39,44,47,49,51,58-triacontaen-66-ylidene)-1,3-dithiole-4,5-dicarboxylate
• CAS: 190520-28-6
• 化学式: C₇₂H₁₀O₄S₄
• 分子量: 1067.13
• InChiKey: SRFPSGQMIOTEFC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  19.3
• 重原子数：
  80
• 可旋转键数：
  4
• 环数：
  35.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  154
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  Dimethyl 2-(65,67-dithiatritriacontacyclo[62.3.0.03,58.03,62.04,20.05,57.06,18.07,55.08,17.09,53.010,15.011,52.012,49.013,47.014,44.016,43.019,42.021,41.022,62.023,39.024,61.025,37.026,35.027,60.028,33.029,59.030,56.031,54.032,51.034,50.036,48.038,46.040,45]heptahexaconta-1(64),4(20),5(57),6(18),7(55),8(17),9(53),10(15),11,13,16(43),19(42),21(41),22,24(61),25,27(60),28,30(56),31(54),32,34,36,38(46),39,44,47,49,51,58-triacontaen-66-ylidene)-1,3-dithiole-4,5-dicarboxylate 在 lithium bromide 作用下， 以 六甲基磷酰三胺 为溶剂， 以12.5%的产率得到1,2-(cyclohexenyltetrathiafulvalene)buckminsterfullerene
  参考文献：
  名称：

  Persistent and Transient Open-Shell Species Derived from C₆₀−TTF Cyclohexene-Fused Dyads

  摘要：

  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.

  DOI：

  10.1021/jo980498b
• 作为产物：
  描述：

  足球烯 、 2-(5,5-Dioxo-5,6-dihydro-4H-5λ⁶-thieno[3,4-d][1,3]dithiol-2-ylidene)-[1,3]dithiole-4,5-dicarboxylic acid dimethyl ester 以 苯甲腈 、 甲苯 为溶剂， 以47%的产率得到Dimethyl 2-(65,67-dithiatritriacontacyclo[62.3.0.03,58.03,62.04,20.05,57.06,18.07,55.08,17.09,53.010,15.011,52.012,49.013,47.014,44.016,43.019,42.021,41.022,62.023,39.024,61.025,37.026,35.027,60.028,33.029,59.030,56.031,54.032,51.034,50.036,48.038,46.040,45]heptahexaconta-1(64),4(20),5(57),6(18),7(55),8(17),9(53),10(15),11,13,16(43),19(42),21(41),22,24(61),25,27(60),28,30(56),31(54),32,34,36,38(46),39,44,47,49,51,58-triacontaen-66-ylidene)-1,3-dithiole-4,5-dicarboxylate
  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

• Isolation and Characterization of Four Isomers of a C₆₀ Bisadduct with a TTF Derivative. Study of Their Radical Ions
  作者：M. Mas-Torrent、R. A. Rodríguez-Mias、M. Solà、M. A. Molins、M. Pons、J. Vidal-Gancedo、J. Veciana、C. Rovira

  DOI：10.1021/jo010748f

  日期：2002.1.1

  which were studied by EPR spectroscopy. Spin density distributions of these radical cations and radical anions show that the unpaired electron is located mainly on the TTF and fullerene moieties, respectively. However, while the EPR signals obtained from the radical cations are very similar for all the isomers, the structured signals observed for the radical anions arising from the coupling of the

  合成了由刚性间隔基连接到两个相同的TTF部分的C（60）组成的三单元组，并通过紫外可见光谱，LDI-TOF-MS和HMBC NMR光谱对某些异构体进行了分离和表征。为了验证它们的分配，已经对偶极矩和不同异构体的形成热进行了AM1半经验计算。三单元组的氧化和还原提供了衍生的自由基离子系统TTF（+ *）-C（60）-TTF（+ *）和TTF-C（60）（-*）-TTF，已通过EPR光谱法进行了研究。这些自由基阳离子和自由基阴离子的自旋密度分布表明，未成对的电子分别主要位于TTF和富勒烯部分上。但是，尽管从自由基阳离子获得的EPR信号对于所有异构体都非常相似，由未配对电子与间隔基中亚甲基桥的氢原子偶合所产生的自由基阴离子所观察到的结构化信号表明，异构现象对自旋分布有很大影响。重要的是，自由基阴离子的自旋密度分布的理论计算与实验EPR结果非常吻合。