5-(tetrathiafulvalenyl)penta-2,4-dienal | 208449-60-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 5-(tetrathiafulvalenyl)penta-2,4-dienal
• 英文别名: (E)-5-(tetrathiafulvalenyl)penta-2,4-dien-1-al；5-(tetrathiafulvalenyl)penta-2,4-dien-1-al；(2E,4E)-5-[2-(1,3-dithiol-2-ylidene)-1,3-dithiol-4-yl]penta-2,4-dienal
• CAS: 208449-60-9
• 化学式: C₁₁H₈OS₄
• 分子量: 284.448
• InChiKey: GOHQZJDHJNWPQJ-ZPUQHVIOSA-N

物化性质

• 熔点：
  151-152 °C
• 沸点：
  358.5±42.0 °C(Predicted)
• 密度：
  1.556±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  118
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  3-(二氰基亚甲基)靛酮 、 5-(tetrathiafulvalenyl)penta-2,4-dienal 以 乙酸酐 为溶剂， 生成 3-dicyanomethylene-2-(5-tetrathiafulvalenyl-2,4-pentadienyliden)-1-indanone
  参考文献：
  名称：

  Second-order nonlinear optical properties of tetrathiafulvalene-π-3-(dicyanomethylidene)indan-1-one chromophores

  摘要：

  Novel conjugated donor-acceptor chromophores, based on the strong electron donating tetrathiafulvalene moiety and the strong electron-withdrawing 3-(dicyanomethylidene)indan-1-one acceptor, exhibit large second-order optical nonlinearities. The effect of increasing the length of the polyenic spacer on the NLO properties of the new molecules has been studied by using the electric field-induced second harmonic generation (EFISH) method. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(99)01801-8
• 作为产物：
  描述：

  四硫富瓦烯 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 6.0h， 生成 5-(tetrathiafulvalenyl)penta-2,4-dienal
  参考文献：
  名称：

  四硫富瓦烯-多氯三苯甲基二元化合物：桥和开壳特性对线性和非线性光学性质的影响

  摘要：

  通过将四硫富瓦烯（TTF）电子给体单元通过不同长度的亚乙烯基单元桥接到聚氯三苯甲基（PTM）电子受体基团上，制备了三个共轭的供体-π-受体基团（1a - 1c）。分子内电荷转移对共轭桥的长度的依赖性已经通过不同的电化学和光谱技术进行了分析。通过将系统1 a – 1 c与非自由基类似物（2 a – 2 c）进行比较，可以计算出这些导数的线性光学性质和二阶非线性光学（NLO）响应。有趣的是，对于二元组1a，预计NLO反应增强– 1 c以自由基形式的PTM用于具有较长亚乙烯基桥的化合物。计算证实了桥在供体TTF和受体PTM单元之间进行电子通信方面所起的积极作用。

  DOI：

  10.1002/chem.201701623

文献信息

• A convenient one-step synthesis of formyltetrathiafulvalene vinylogs: Building blocks for new NLO materials
  作者：Mar González、Nazario Matín、JoséL. Segura、Javier Garín、Jesús Orduna

  DOI：10.1016/s0040-4039(98)00467-5

  日期：1998.5

  A new method for the synthesis of formyltetrathiafulvalene vinylogs in which tetrathiafulvalene (TTF) or a substituted derivative of TTF is metalated with lithium diisopropylamide and then reacted with a vinylogous amide to yield the corresponding short polyenals in a one-pot process is described.

  描述了一种合成甲酰基四硫富瓦烯乙烯基酯的新方法，其中将四硫富瓦烯（TTF）或TTF的取代衍生物与二异丙基氨基化锂金属化，然后与一乙烯基酰胺反应，以一锅法生产相应的短多烯。
• Electronic and Structural Effects on the Nonlinear Optical Behavior in Push−Pull TTF/Tricarbonyl Chromiun Arene Complexes
  作者：Braulio Insuasty、Carmen Atienza、Carlos Seoane、Nazario Martín、Javier Garín、Jesús Orduna、Rafael Alcalá、Belén Villacampa

  DOI：10.1021/jo0493673

  日期：2004.10.1

  (η6-arene)chromium complex as the acceptor moiety through a systematically increased conjugated bridge of vinylene units (12a−c, 16a−c) have been synthesized by Wittig−Horner olefination reaction. The electronic spectra as well as the electrochemical data reveal a different behavior of TTF derivatives (12a−c) and of exTTF derivatives (16a−c). Cyclic voltammetry shows the influence of the tricarbonylchromium

  其中硫富瓦烯（TTF）和π共延伸的TTF作为强电子供体的新型d-π-A系统共价连接到一个三羰基（η 6 -arene）铬配合物作为通过系统地受体部分增加缀合的碳酸亚乙烯单元桥通过WiTTig-Horner烯烃化反应合成了（12a - c，16a - c）。电子光谱和电化学数据表明，TTF衍生物（12a - c）和exTTF衍生物（16a - c）的行为不同。循环伏安法表明三羰基铬芳烃对化合物中氧化电位的影响参见图12a - c，对于exTTF（16a - c）没有观察到明显的作用。12a - c和16a - c的非线性光学性质通过使用从头算CPHF / 6-31G * // B3P86 / 6-31G *模型进行计算，并且时变密度泛函理论（TD-DFT）方法已用于电子跃迁的计算。计算表明，配体内部的电荷转移跃迁（ILCT）和金属到配体的电荷转移跃迁（MLCT）引起了非线性响应。此外，由基态
• Synthesis of Conjugated Tetrathiafulvalene (TTF)-π-Acceptor Molecules − Intramolecular Charge Transfer and Nonlinear Optical Properties
  作者：Martin R. Bryce、Andrew Green、Adrian J. Moore、Dmitrii F. Perepichka、Andrei S. Batsanov、Judith A.K. Howard、Isabelle Ledoux-Rak、Mar González、Nazario Martín、José L. Segura、Javier Garín、Jesús Orduna、Rafael Alcalá、Belén Villacampa

  DOI：10.1002/1099-0690(200105)2001:10<1927::aid-ejoc1927>3.0.co;2-4

  日期：2001.5

  new conjugated donor-π-acceptor (D-π-A) chromophores 7, 9, and 12−15 in which monosubstituted tetrathiafulvalene (TTF) and trimethyl-TTF units are the donor moieties, connected by ethylenic bridges to electron-deficient benzene derivatives as the acceptor moieties. These compounds display a broad intramolecular charge transfer (ICT) band in their solution UV/Vis spectra at λmax = ca. 500 nm. The second

  我们合成了新的共轭供体-π-受体 (D-π-A) 发色团 7、9 和 12-15，其中单取代的四硫富瓦烯 (TTF) 和三甲基-TTF 单元是供体部分，通过烯键连接到电子-缺乏苯衍生物作为受体部分。这些化合物在其溶液 UV/Vis 光谱中显示出宽的分子内电荷转移 (ICT) 带，λmax = ca。500 纳米。已经使用 EFISH 技术研究了这些衍生物的二阶非线性光学 (NLO) 特性，并通过半经验和从头理论方法计算。讨论了 TTF 部分中甲基取代基的影响和共轭桥的性质。通过化合物 9 的 X 射线衍射研究获得的键长分析揭示了固态的 ICT。
• Tetrathiafulvalene Derivatives as NLO-phores:  Synthesis, Electrochemistry, Raman Spectroscopy, Theoretical Calculations, and NLO Properties of Novel TTF-Derived Donor-π-Acceptor Dyads
  作者：Mar González、José L. Segura、Carlos Seoane、Nazario Martín、Javier Garín、Jesús Orduna、Rafael Alcalá、Belén Villacampa、Víctor Hernández、Juan T. López Navarrete

  DOI：10.1021/jo010717k

  日期：2001.12.1

  Novel pi -conjugated donor-acceptor chromophores, based on the strong electron-donating tetrathiafulvalene moiety and different electron-withdrawing acceptors, exhibit large second-order optical nonlinearities. The effect of increasing the length of the polyenic spacer and the influence of the nature of the acceptor moiety on the NLO properties have been studied by using the electric field-induced second-harmonic generation (EFISH) technique as well as by semiempirical and ab initio theoretical calculations. A charge-transfer band has been observed in the absorption spectra of these D-pi -A compounds that undergoes an hypsochromic shift when increasing the number of vinylenic spacer units connecting both donor and acceptor moieties. The degree of the intramolecular charge transfer from the donor to the acceptor has also been analyzed by means of Raman spectroscopy.
• Evidence for Two Separate One-Electron Transfer Events in Excited Fulleropyrrolidine Dyads Containing Tetrathiafulvalene (TTF)
  作者：Nazario Martín、Luis Sánchez、M Angeles Herranz、Dirk M. Guldi

  DOI：10.1021/jp9941458

  日期：2000.5.1

  1,3-Dipolar cycloadditions of TTF-azomethine ylides (TTF = tetrathiafulvalene) to C-60 have been used to synthesize a series of novel donor-bridge-acceptor dyads. In these dyads the pyrrolidine[3',4':1,2][60]fullerene is covalently attached to the electron donor TTF either directly (5) or alternatively through one (2a) or two (7) vinyl groups. In the ground state, dyads 2a, 5, and 7 undergo Four quasireversible one-electron reductions and two reversible oxidation steps. The former are associated with the reduction of the C-60 core, whereas the latter correspond to the formation of the radical cation and dication of the TTF moiety, respectively. Semiempirical PM3 calculations reveal donor-acceptor distances of 4.8 Angstrom (5), 7.6 Angstrom (2a), and 10.5 Angstrom (7), and a deviation from planarity between the TTF fragment and the vinylogous spacer. In relation to an N-methylfulleropyrrolidine, the emission of the fullerene singlet excited state in dyads 2a, 5, and 7 is substantially reduced. Furthermore, the fluorescence quantum yield correlates well with the solvent dielectric constant and also with the spatial separation of the donor and acceptor moieties in the dyads. These correlation suggest that intramolecular electron-transfer processes evolving from the fullerene singlet excited state generate the (C-60(.-))-(TTF.+) pair. Pico- and nanosecond-resolved transient spectroscopy further substantiate a rapid transformation of the initially formed singlet excited state into the charge-separated radical pair with intramolecular rates ranging between 1.17 x 10(10) s(-1) and 1.47 x 10(9) s(-1). In all cases, the product of back electron transfer is the triplet excited state, which is generated with markedly high quantum yields (0.61-0.97). The latter is, in addition to the rapid primary intramolecular electron transfer, subject to a slower, secondary intermolecular electron transfer with rate constants of 7 x 10(8) M-1 s(-1) (5) in benzonitrile and 1.6 x 10(9) M-1 s(-1) (5) in toluene.