2,4,5,7-tetranitro-9-dicyanomethylenefluorene | 15517-55-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: 2,4,5,7-tetranitro-9-dicyanomethylenefluorene
• 英文别名: 9-dicyanomethylene-4,5,7-trinitrofluorene-2-carboxylic acid；2-(2,4,5,7-Tetranitrofluoren-9-ylidene)propanedinitrile
• CAS: 15517-55-2
• 化学式: C₁₆H₄N₆O₈
• 分子量: 408.243
• InChiKey: QLTDNDIVGHGWIX-UHFFFAOYSA-N

物化性质

• 熔点：
  >360 °C
• 沸点：
  635.9±55.0 °C(Predicted)
• 密度：
  1.819±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  30
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  231
• 氢给体数：
  0
• 氢受体数：
  10

安全信息

• 海关编码：
  2926909090

反应信息

• 作为反应物：
  描述：

  2,4,5,7-tetranitro-9-dicyanomethylenefluorene 在 sodium iodide 作用下， 以 乙腈 为溶剂， 反应 0.5h， 生成
  参考文献：
  名称：

  基于TTF和9-二氰基亚甲基芴衍生物的溶剂化有机电荷转移复合物的晶体生长和表征†

  摘要：

  通过TTF（四硫富瓦烯）与三种9-二氰基亚甲基芴衍生物的反应合成了一系列的1：1有机配合物：9-二氰基亚甲基-2,7-二硝基芴（DDF），9-二氰基亚甲基-2,4,7-三硝基芴（ DTF）和9-二氰基亚甲基-4,5,7-三硝基芴-2-羧酸（DC2TF）。通过这些化合物的X射线衍射和元素分析确定了以下公式：（TTF-DDF）·CH 3 CN（1），（TTF-DDF）·0.5PhCl（2），（TTF-DTF）·CH 3 CN（3），（TTF-DTF）·0.5Me 2 CO（4）和（TTF-DC2TF）·H 2 O（5）。还获得了具有不同化学计量比的第六溶剂化化合物（TTF）3（DC2TF）2 ·2CH 3 CN（6）。通过IR和拉曼光谱法估计了1-5中的电荷转移程度。晶格溶剂，乙腈，氯苯或丙酮从配合物1-4的晶体中缓慢释放，导致电荷转移随时间的推移而显着下降。这些晶体经过数月会聚，趋向接近中性

  DOI：

  10.1039/c5ce01059d
• 作为产物：
  描述：

  2,4,5,7-四硝基-9-芴酮 、 丙二腈 以 N,N-二甲基甲酰胺 为溶剂， 反应 1.0h， 以96%的产率得到2,4,5,7-tetranitro-9-dicyanomethylenefluorene
  参考文献：
  名称：

  Electron Acceptors of the Fluorene Series. 7.¹ 2,7-Dicyano-4,5-dinitro-9-X-fluorenes:  Synthesis, Cyclic Voltammetry, Charge Transfer Complexation with N-Propylcarbazole in Solution, and X-ray Crystal Structures of Two Tetrathiafulvalene Complexes

  摘要：

  The synthesis and physical properties of a series of novel fluorene pi-electron accepters (7-9) are described. Cyclic voltammograms of 7 and 8 exhibit three separate reversible (or quasi-reversible) one-electron redox waves, characteristic of strong electron accepters. Spectroelectrochemical experiments show the appearance in the long-wavelength visible region of absorption bands at appropriate potentials which were attributed to the transformations A --> A(.-) and A(.-) --> A(2-). Charge-transfer complexation with N-propylcarbazole in dioxane shows the formation of 1:1 complexes with parameters characteristic for other fluorene accepters. The single-crystal X-ray structures of 1:1 charge-transfer complexes of tetrathiafulvalene with the electron acceptor 8 and with the strongest fluorene acceptor 1f both show ..A...D...A...D.. stacking in the crystal.

  DOI：

  10.1021/jo9803481

文献信息

• Electron acceptors of the fluorene series. Part 5. Intramolecular charge transfer in nitro-substituted 9-(aminomethylene)fluorenes
  作者：Igor F. Perepichka、Anatolii F. Popov、Tatyana V. Orekhova、Martin R. Bryce、Alexander N. Vdovichenko、Andrei S. Batsanov、Leonid M. Goldenberg、Judith A. K. Howard、Nikolai I. Sokolov、Joanne L. Megson

  DOI：10.1039/p29960002453

  日期：——

  Strong intramolecular charge transfer (ICT) in fluorenes 2 and 3 from a donor amino group to acceptor fluorene moiety leads to exceptionally easy rotation around the C(9)(α) bond that has been registered by 1H NMR spectroscopy; single crystal X-ray analysis of 2i confirms the changes in the bond numbers. Cyclic voltammetry (CV) of compounds 2 and 3 shows two closely spaced reversible single-electron reduction waves (in the range of –0.4 V to –1.16 V, E1red½– E2red½⩽ 0.16 V) resulting in radical anions and dianions, respectively, and a third reduction wave [E3red½≈–(1.31 – 1.53) V] resulting in radical trianions. E3red½ shows very little dependence on the structure of compounds 2 and 3, whereas E1red7½ and E2red½ correlate well with σp– constants of substituents in the fluorene ring. At +0.71 V to + 1.55 V a single-electron oxidation wave yielding radical cations of the compounds 2 and 3 is observed in CV. Parameters ρcv– for reduction (E1red½ and E2red½) and oxidation (Eox½) of compounds 2 and 3 are in the region of 0.12 V to 0.20 V. The influence of the structure and solvent effects on the ICT energies have been studied by UV–VIS spectroscopy. It has been found that the ICT energies also correlate well with σp– constants in the fluorene ring; however, in contrast to CV investigations which demonstrated close ρcv– values for both series of the compounds [ρ1red–(2)= 0.195 ± 0.005 V ≈ρ1red–(3) 0.175 ± 0.005 V, in acetonitrile], the sensitivity parameter ρICT–for 2 is approximately twice that for 3 (–0.175 ± 0.008 eV and –0.085 ± 0.008 eV, respectively, in acetonitrile). A quantitative estimation of solvent effects on the ICT energies using the four-parameter Koppel-Palm equation shows that only polarity and basicity of the solvent are statistically relevant in all the cases. Spectroelectrochemical studies on the compound 2i show the disappearance of the ICT band in the visible spectra when the negative potential yielding the radical anion and/or the dianion is applied. An increased electrophotographic sensitivity of poly-N-(2,3-epoxypropyl)carbazole (PEPC) films sensitized by compound 2d has been found in the ICT region; this phenomenon can be used for elaboration of photothermoplastic films with selective regions of the photosensitivity.

  在荧光苊（fluorenes） 2 和 3 中，强内分子电荷转移（ICT）发生在供体氨基团和受体荧光苊部分之间，导致围绕 C(9)(α) 键的旋转异常容易，这一点通过 1H NMR 谱学得到了验证；对 2i 的单晶 X 射线分析证实了键数的变化。化合物 2 和 3 的循环伏安法（CV）显示出两个紧密相邻的可逆单电子还原波（在 -0.4 V 至 -1.16 V 范围内，E1red½– E2red½⩽ 0.16 V），分别导致自由基阴离子和二阴离子的形成，以及一个第三个还原波 [E3red½≈–(1.31 – 1.53) V]，导致自由基三阴离子的形成。E3red½ 对化合物 2 和 3 的结构几乎没有依赖性，而 E1red½ 和 E2red½ 与荧光苊环中取代基的 σp– 常数有很好的相关性。在 +0.71 V 到 +1.55 V 的范围内，观察到产生化合物 2 和 3 自由基阳离子的单电子氧化波。化合物 2 和 3 的还原（E1red½ 和 E2red½）与氧化（Eox½）参数 ρcv– 在 0.12 V 至 0.20 V 的范围内。通过 UV–VIS 光谱研究了结构和溶剂效应对 ICT 能量的影响。发现 ICT 能量与荧光苊环中的 σp– 常数也有很好的相关性；然而，与 CV 研究结果相比，后者显示两组化合物具有接近的 ρcv– 值 [ρ1red–(2)= 0.195 ± 0.005 V ≈ ρ1red–(3) 0.175 ± 0.005 V，在乙腈中]，而 2 的灵敏度参数 ρICT– 约为 3 的两倍（在乙腈中分别为 -0.175 ± 0.008 eV 和 -0.085 ± 0.008 eV）。用四参数 Koppel-Palm 方程对溶剂效应对 ICT 能量的定量估计表明，只有溶剂的极性和碱性在所有情况下是统计上相关的。对化合物 2i 的光谱电化学研究表明，当施加负电位以产生自由基阴离子和/或二阴离子时，ICT 带在可见光谱中消失。发现用化合物 2d 感光的聚-N-(2,3-环氧丙基)喹喔烯（PEPC）薄膜在 ICT 区域具有提高的电光敏感性；这一现象可以用于开发具有选择性光敏区域的光热塑性薄膜。
• Engineering a Remarkably Low HOMO–LUMO Gap by Covalent Linkage of a Strong -Donor and a -Acceptor—Tetrathiafulvalene--Polynitrofluorene Diads: Their Amphoteric Redox Behavior, Electron Transfer and Spectroscopic Properties
  作者：Dmitrii F. Perepichka、Martin R. Bryce、Andrei S. Batsanov、Eric J. L. McInnes、Jing P. Zhao、Robert D. Farley

  DOI：10.1002/1521-3765(20021018)8:20<4656::aid-chem4656>3.0.co;2-1

  日期：2002.10.18

  incorporating very strong donor and acceptor moieties have been synthesized by condensation of the corresponding R3TTF-sigma-fluoren-9-one diads with malononitrile. Reversible five-step amphoteric redox behavior has been observed with an extremely low HOMO-LUMO gap (approximately 0.3 eV). For compound 14 a strong EPR signal is observed in the solid state, ascribed to intermolecular complexation: a less

  新型R3TTF-sigma-A化合物14、16和19（R3TTF =审判-kythtrathiafulvalene，sigma =饱和间隔基，A =聚硝基芴-9-二氰基亚甲基受体）结合了非常强的供体和受体部分，通过缩合相应的化合物R3TTF-sigma-fluoren-9-带有丙二腈的二价单体。已经观察到可逆的五步两性氧化还原行为，其HOMO-LUMO间隙极低（约0.3 eV）。对于化合物14，在固态下观察到很强的EPR信号，这归因于分子间的络合：在溶液中观察到的信号强度较小，相当于大约25。在室温下，有2％的分子以自由基形式存在。在二单元组14和16中的分子内电荷转移表现为在其电子光谱的近红外区域中的强吸收带。光谱电化学数据揭示了两种化合物在可见光和近红外区都有明显的电致变色行为。报告了芴自由基阴离子盐的第一X射线晶体结构，即2,4,5,7-四硝基-9-二氰基亚甲基芴的铜盐（化学计量为1：1）。
• ORGANIC LIGHT-EMITTING ELEMENT
  申请人：Sumitomo Chemical Company, Limited

  公开号：EP2562838A1

  公开（公告）日：2013-02-27

  An object of the invention is to provide an organic light emitting device having a high current density at the time of driving. A means for achieving the object is an organic light emitting device which has an anode and a cathode, has between the anode and the cathode a light emitting layer containing a light emitting organic compound, and has between the anode and the light emitting layer a first functional layer containing a first organic compound, a second functional layer containing a second organic compound and a hole transport layer in this order from the anode side, wherein the first organic compound is an electron accepting organic compound, and the second organic compound is an organic compound having a fused ring or not less than three aromatic rings.

  本发明的目的是提供一种在驱动时具有高电流密度的有机发光器件。实现该目的的一种方法是一种有机发光器件，该器件具有一个阳极和一个阴极，在阳极和阴极之间具有一个包含发光有机化合物的发光层，在阳极和发光层之间具有一个包含第一有机化合物的第一功能层、一个包含第二有机化合物的第二功能层以及一个从阳极侧依次排列的空穴传输层，其中第一有机化合物是一种接受电子的有机化合物，第二有机化合物是一种具有一个融合环或不少于三个芳香环的有机化合物。
• ACTUATOR ELEMENT USING CARBON ELECTRODE
  申请人：National Institute Of Advanced Industrial Science

  公开号：EP2833542A1

  公开（公告）日：2015-02-04

  An object of this invention is to create an actuator in which the amount of deformation is maintained and no displacement in the reverse direction occurs, even when a constant voltage is continuously applied for a long period of time. As a means for achieving the above object, the invention provides a conductive thin film comprising a polymer gel containing at least one organic molecule selected from the group consisting of electron-donating organic molecules and electron-withdrawing organic molecules, a nano-carbon material, an ionic liquid, and a polymer.

  本发明的一个目的是制造一种致动器，在这种致动器中，即使长时间连续施加恒定电压，也能保持一定的变形量，并且不会发生反向位移。 作为实现上述目的的一种方法，本发明提供了一种导电薄膜，该薄膜由聚合物凝胶组成，聚合物凝胶含有至少一种有机分子，该有机分子选自由电子供能有机分子和电子吸能有机分子、纳米碳材料、离子液体和聚合物组成的组。
• Actuator element using carbon electrode
  申请人：NATIONAL INSTITUTE OF ADVANCED INDUSTRIAL SCIENCE AND TECHNOLOGY

  公开号：US10367429B2

  公开（公告）日：2019-07-30

  An object of this invention is to create an actuator in which the amount of deformation is maintained and no displacement in the reverse direction occurs, even when a constant voltage is continuously applied for a long period of time. As a means for achieving the above object, the invention provides a conductive thin film comprising a polymer gel containing at least one organic molecule selected from the group consisting of electron-donating organic molecules and electron-withdrawing organic molecules, a nano-carbon material, an ionic liquid, and a polymer.

  本发明的一个目的是制造一种致动器，在这种致动器中，即使长时间连续施加恒定电压，也能保持一定的变形量，并且不会发生反向位移。 作为实现上述目的的一种方法，本发明提供了一种导电薄膜，该薄膜由聚合物凝胶组成，聚合物凝胶含有至少一种有机分子，该有机分子选自由电子供能有机分子和电子吸能有机分子、纳米碳材料、离子液体和聚合物组成的组。