2,5,7-trinitrofluorene-4-carboxylic acid methyl ester | 164297-32-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: 2,5,7-trinitrofluorene-4-carboxylic acid methyl ester
• 英文别名: 2,5,7-trinitro-4-methoxycarbonylfluorene；5-methoxycarbonyl-2,4,7-trinitrofluorene；Methyl 2,5,7-trinitro-9H-fluorene-4-carboxylate
• CAS: 164297-32-9
• 化学式: C₁₅H₉N₃O₈
• 分子量: 359.252
• InChiKey: LPEVCHMOSUMYEE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  26
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  164
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  5-phenyl-3-methylthio-1,2-dithiolium iodide 、 2,5,7-trinitrofluorene-4-carboxylic acid methyl ester 以 N,N-二甲基甲酰胺 为溶剂， 生成 9-(5-phenyl-1,2-dithiol-3-ylidene)-2,5,7-trinitro-4-methoxycarbonylfluorene
  参考文献：
  名称：

  Mysyk, Dmitrii D.; Perepichka, Igor F., Phosphorus, Sulfur and Silicon and the Related Elements, 1994, vol. 96, # 1-4, p. 527 - 530

  摘要：

  DOI：
• 作为产物：
  描述：

  methyl 4-fluorenecarboxylate 在 硫酸 、 硝酸 作用下， 生成 2,5,7-trinitrofluorene-4-carboxylic acid methyl ester
  参考文献：
  名称：

  Electron Acceptors of the Fluorene Series. 9.¹ Derivatives of 9-(1,2-Dithiol-3-ylidene)-, 9-(1,3-Dithiol-2-ylidene)-, and 9-(1,3-Selenathiol-2-ylidene)fluorenes:  Synthesis, Intramolecular Charge Transfer, and Redox Properties

  摘要：

  The synthesis and physical properties of four series of novel fluorene push-pull compounds (4-7) of the D-pi-A type with intramolecular charge transfer (from 1,3- and 1,2-dithiole and 1,3-selenathiole donor (D) moieties) are described. The nature of the heteroatom (S or Se) in the donor fragment has no effect on the maxima of intramolecular absorption bands (lambda(ICT)), whereas a change of position of the heteroatoms in the dithiole moiety from 1,3 to 1,2 leads to a substantial bathochromic shift in lambda(ICT). Solvatochromism, thermochromism, and negative halochromism in these compounds are demonstrated. Cyclic voltammograms of 4-7 exhibit two, separate, single-electron reversible redox waves, the potentials of which (as well as the ICT energies in the molecules) are quantitatively described by sigma(p)(-) constants of the substituents in the fluorene ring. Compounds 4-7 exhibit reversible salt formation in sulfuric acid, and for compound 5g in diluted sulfuric acid an additional absorption in the near-IR region has been observed that we attribute to radical species formation from the equilibrium [5g-H](+) + 5g reversible arrow 5g(.+) + [5g-H](.).

  DOI：

  10.1021/jo990100r

文献信息

• Combining High Electron Affinity and Intramolecular Charge Transfer in 1,3-Dithiole–Nitrofluorene Push–Pull Diads
  作者：Dmitrii F. Perepichka、Igor F. Perepichka、Oleksandr Ivasenko、Adrian J. Moore、Martin R. Bryce、Lyudmila G. Kuz'mina、Andrei S. Batsanov、Nikolai I. Sokolov

  DOI：10.1002/chem.200701459

  日期：2008.3.17

  Attaching electron-rich 1,3-dithiol-2-ylidene moieties to polynitrofluorene electron acceptors leads to the formation of highly conjugated compounds 6 to 11, which combine high electron affinity with a pronounced intramolecular charge transfer (ICT) that is manifested as an intense absorption band in their visible spectra. Such a rare combination of optical and electronic properties is beneficial for

  将富含电子的1,3-二硫醇-2-亚甲基连接到聚硝基芴电子受体上会导致形成高度共轭的化合物6至11，这些化合物将高电子亲和力与明显的分子内电荷转移（ICT）结合在一起，表现为强烈的可见光谱中的吸收带。光学和电子特性的这种罕见组合对于光电学中的几种应用是有益的。因此，将芴-二硫醇衍生物6a结合到光电导膜中提供了光热可塑性存储介质，其在ICT区域中具有显着增加的光敏性。分子的二硫醇和芴部分的结构变化很大，显示出ICT能量和还原电势与取代基的Hammett参数之间的极佳相关性。尽管仅观察到ICT波段很小的溶剂变色现象，但加热溶液会导致明显的蓝移，这可能是由于连接芴和二硫键部分的C9 = C14键周围扭曲增加的结果。7a，8a，10a，11a和13a的X射线晶体学分析证实了分子基态中的ICT相互作用。供体和受体之间的C9 ＝ C14双键基本上被延长，并且其长度随着二硫醇部分的供体特性的增强而增加。图
• Fluorene acceptors with intramolecular charge-transfer from 1,3-dithiole donor moieties: novel electron transport materials
  作者：Igor F. Perepichka、Dmitrii F. Perepichka、Anatolii F. Popov、Igor F. Perepichka、Martin R. Bryce、Leonid M. Goldenberg、Antony Chesney、Adrian J. Moore、Judith A. K. Howard、Lyudmila G. Kuz’mina、Nikolai I. Sokolov

  DOI：10.1039/a800912k

  日期：——

  The synthesis, solution redox behaviour and intramolecular charge transfer properties of novel D(CH–CH)nA compounds (n = 0, 1, 3; D and A are 1,3-dithiole and nitrofluorene moieties, respectively) are reported.

  报道了新型D(CH–CH)nA化合物（n = 0, 1, 3；D和A分别为1,3-二噻烷和硝基芴基部分）的合成、溶液氧化还原行为及分子内电荷转移特性。
• Electron acceptors of the fluorene series
  作者：Dmitrii F. Perepichka、Igor F. Perepichka、Anatolii F. Popov、Martin R. Bryce、Andrei S. Batsanov、Antony Chesney、Judith A.K. Howard、Nikolai I. Sokolov

  DOI：10.1016/s0022-328x(01)00948-2

  日期：2001.12

  structures for ferrocene derivatives 8a, 8g, and 11d were determined by single-crystal X-ray diffraction. Tetranitro derivative 8a shows substantial distortion, caused by steric repulsion between the nitro groups in positions 4 and 5, which precludes the formation of stacks, and pairs of fluorene moieties contact face-to-face (interplanar distance 3.8 Å). In di- and trinitro derivatives 8g and 11d the

  二茂铁甲醛13及其乙烯基化合物（E，E）-1-二茂铁基-4-甲酰基-1,3-丁二烯（16）与硝基芴作为CH酸的反应会生成Fc-π型推挽式化合物-芴（8a - g，12a - e）。根据芴结构，在单或双缩合产物，OHCFcCH芴（11d，e）或芴CHFcCH芴和芴CHRcCH芴（9a – c，10a – c）。化合物8中的分子内电荷转移（ICT）导致降低了CH double芴双键周围的旋转势垒，并易于在溶液中进行E-Z异构化。循环伏安法（CV）实验显示FcCH芴的可逆单电子氧化（8）产生阳离子，两个可逆单电子还原波产生自由基阴离子和二价阴离子（对于8a – e），它们合并成两个-电子还原波8f – h。ICT还表现在8 – 12的电子吸收光谱中发现，和ICT的能量（以及在CV还原电位）来显示极好的相关性（ř ≥0.99）用哈米特型取代基常数（σ p - ）的芴基部分。化合物8
• Skabara, Peter J.; Serebryakov, Igor M.; Perepichka, Igor F., Journal of the Chemical Society. Perkin Transactions 2 (2001), 1999, # 3, p. 505 - 513
  作者：Skabara, Peter J.、Serebryakov, Igor M.、Perepichka, Igor F.

  DOI：——

  日期：——
• Electron Acceptors of the Fluorene Series. 9.¹ Derivatives of 9-(1,2-Dithiol-3-ylidene)-, 9-(1,3-Dithiol-2-ylidene)-, and 9-(1,3-Selenathiol-2-ylidene)fluorenes:  Synthesis, Intramolecular Charge Transfer, and Redox Properties
  作者：Dmitrii D. Mysyk、Igor F. Perepichka、Dmitrii F. Perepichka、Martin R. Bryce、Anatolii F. Popov、Leonid M. Goldenberg、Adrian J. Moore

  DOI：10.1021/jo990100r

  日期：1999.9.1

  The synthesis and physical properties of four series of novel fluorene push-pull compounds (4-7) of the D-pi-A type with intramolecular charge transfer (from 1,3- and 1,2-dithiole and 1,3-selenathiole donor (D) moieties) are described. The nature of the heteroatom (S or Se) in the donor fragment has no effect on the maxima of intramolecular absorption bands (lambda(ICT)), whereas a change of position of the heteroatoms in the dithiole moiety from 1,3 to 1,2 leads to a substantial bathochromic shift in lambda(ICT). Solvatochromism, thermochromism, and negative halochromism in these compounds are demonstrated. Cyclic voltammograms of 4-7 exhibit two, separate, single-electron reversible redox waves, the potentials of which (as well as the ICT energies in the molecules) are quantitatively described by sigma(p)(-) constants of the substituents in the fluorene ring. Compounds 4-7 exhibit reversible salt formation in sulfuric acid, and for compound 5g in diluted sulfuric acid an additional absorption in the near-IR region has been observed that we attribute to radical species formation from the equilibrium [5g-H](+) + 5g reversible arrow 5g(.+) + [5g-H](.).