4,5,9,10-四溴-2,7-二辛基苯并[lmn][3,8]菲咯啉-1,3,6,8-四酮 | 954374-43-7

• 物质功能分类: 化学试剂 - 有机试剂 - 多环化合物
• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 中文名称: 4,5,9,10-四溴-2,7-二辛基苯并[lmn][3,8]菲咯啉-1,3,6,8-四酮
• 英文名称: 2,3,6,7-tetrabromonaphthalene-1,8,4,5-tetracarboxylic acid N,N-dioctyldiimide
• 英文别名: 2,3,6,7-tetrabromo-dioctyl-naphthalene diimide；4,5,9,10-tetrabromo-2,7-dioctylbenzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone；2,3,9,10-tetrabromo-6,13-dioctyl-6,13-diazatetracyclo[6.6.2.04,16.011,15]hexadeca-1,3,8,10,15-pentaene-5,7,12,14-tetrone
• CAS: 954374-43-7
• 化学式: C₃₀H₃₄Br₄N₂O₄
• 分子量: 806.227
• InChiKey: UNEXNPKMEOJLCQ-UHFFFAOYSA-N

物化性质

• 熔点：
  258 °C
• 沸点：
  771.1±60.0 °C(Predicted)
• 密度：
  1.652±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  10.7
• 重原子数：
  40
• 可旋转键数：
  14
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  74.8
• 氢给体数：
  0
• 氢受体数：
  4

安全信息

• 危险性防范说明：
  P261,P264,P270,P271,P280,P301+P312,P302+P352,P304+P340,P305+P351+P338,P330,P332+P313,P337+P313,P362,P403+P233,P405,P501
• 危险性描述：
  H302,H315,H319,H335
• 储存条件：
  | 室温 干燥 |

反应信息

• 作为反应物：
  描述：

  4,5,9,10-四溴-2,7-二辛基苯并[lmn][3,8]菲咯啉-1,3,6,8-四酮 在 1,1'-双(二苯基膦)二茂铁 、 tris-(dibenzylideneacetone)dipalladium(0) 、 lead dioxide 作用下， 以 1,4-二氧六环 、 氯仿 为溶剂， 反应 0.62h， 生成 5-bromo-2,7-dioctyl-1,3,6,8-tetraoxo-1,2,3,6,7,8-hexahydro[3,8] phenanthrolino[1,10-abc]phenazine-4-carbonitrile
  参考文献：
  名称：

  Cyanated Diazatetracene Diimides with Ultrahigh Electron Affinity for n-Channel Field Effect Transistors

  摘要：

  Several diazatetracene diimides with high electron affinity (up to 4.66 eV!) were prepared and well characterized. The LUMO energy level of these electron-deficient molecules was found to be closely related to their material stability. Compound 7 with ultrahigh electron affinity suffered from reduction and hydrolysis in the presence of silica gel or water. The stable compounds 3 and 6 showed n-channel FET behavior with an average electron mobility of 0.002 and 0.005 cm(2) V-1 s(-1), respectively, using a solution processing method.

  DOI：

  10.1021/ol400082c
• 作为产物：
  描述：

  四(4-甲酰基苯基)硅烷 在 三溴化磷 、 溶剂黄146 作用下， 以 甲苯 为溶剂， 反应 0.5h， 生成 4,5,9,10-四溴-2,7-二辛基苯并[lmn][3,8]菲咯啉-1,3,6,8-四酮
  参考文献：
  名称：

  A near-infrared fluoride sensor based on a substituted naphthalenediimide–anthraquinone conjugate

  摘要：

  The synthesis and characterization of a highly selective fluoride receptor based on a naphthalene diimide substituted with an anthraquinone (NDI-AQ) moiety is described. In CHCl3, the receptor was shown to be highly selective for fluoride (K-a similar to 10(3) M-1) over other anions (AcO-, HSO4-, Br-, Cl-, I-, ClO4-, H2PO4-, and NO3-) with pronounced changes in absorption characteristics, that is, red-shift of the absorption band to 790 nm (NIR). The visual color change, NIR shift in absorption, emission spectroscopy, and electrochemistry thus support an intramolecular charge transfer (ICT) effect upon fluoride binding to the NDI-AQ receptor. (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2015.06.050

文献信息

• Controlled Nanodimensional Supramolecular Self-Assembly of Tetra-Alkylated Naphthalene Diimide Derivatives
  作者：Sheshanath V. Bhosale、Namdev V. Ghule、Mohammad Al Kobaisi、Melissa M. A. Kelson、Sidhanath V. Bhosale

  DOI：10.1002/chem.201304117

  日期：2014.8.18

  employed to visualize the supramolecular self‐assembled nanostructures. The growth of these structures is mainly due to packing of hydrophobic alkyl chains and π–π stacking of the cNDI core. The present study paves the way to rational and controlled designs of nanostructures made of optically active dyes (naphthalene diimide); this may open a new avenue towards tuning nanodimensional morphology.

  通过非共价键在纳米到毫米尺度上构建热力学稳定的纳米结构在材料科学中起着重要作用。添加到核上的具有可变烷基链（C 8 H 17，C 12 H 25和C 16 H 33）的四烷基氨基核取代的萘二酰亚胺（cNDI）的自组装导致形成多种受控的形态和定义明确的纳米结构。这样的结构包括纳米棒，囊泡，带，扭曲的带和甜甜圈状形态（在CHCl 3 / MeOH和CHCl 3中形成/己烷混合物）通过疏溶剂控制产生。UV / Vis吸收和荧光光谱显示溶液中的分子聚集。此外，SEM被用于可视化超分子自组装纳米结构。这些结构的增长主要归因于疏水性烷基链的堆积和cNDI核的π–π堆积。本研究为光学活性染料（萘二酰亚胺）制成的纳米结构的合理和受控设计铺平了道路。这可能会为调整纳米形貌开辟新的途径。
• Room-Temperature Long-Lived Triplet Excited States of Naphthalenediimides and Their Applications as Organic Triplet Photosensitizers for Photooxidation and Triplet–Triplet Annihilation Upconversions
  作者：Song Guo、Wanhua Wu、Huimin Guo、Jianzhang Zhao

  DOI：10.1021/jo3003002

  日期：2012.4.20

  NDI (6) shows fluorescence, and no triplet excited state was populated upon excitation. The compounds were used as singlet oxygen (1O2) photosensitizers for the photooxidation of 1,5-dihydroxylnaphthalene (DHN). We found that 5 is more efficient than the conventional photosensitizer, such as Ir(ppy)2(bpy)[PF6]. The compounds were also used as organic triplet photosensitizers for triplet–triplet annihilation

  制备了具有2,6-或2,3,6,7-四溴或氨基取代基的萘二酰亚胺（NDI）衍生物。N，N'-二烷基-2,6-二溴NDI（化合物2）和N，N'-二烷基-2,3,6,7-四溴NDI（化合物4）分别在610或667 nm处显示磷光发射。从未观察到NDI衍生物的磷光。相反，N，N'-二烷基-2，6-二溴-3，7-二氨基NDI（化合物5）在526nm处显示强吸收，在551nm处显示荧光，未观察到磷光。然而，纳秒级时间分辨瞬态差分吸收光谱法证实了三重态激发态在光激发下填充5。2,3,6,7-四氨基NDI（6）显示荧光，并且激发时未填充三重态激发态。该化合物用作单线态氧（1 O 2）光敏剂，用于1,5-二羟基萘（DHN）的光氧化。我们发现5比传统的光敏剂（如Ir（ppy）2（bpy）[PF 6 ] ）更有效。这些化合物还用作有机三重态光敏剂，用于基于三重态-三重态an灭的上转换。观察到高达18.5％的上转换量子产率。
• Redox‐Switchable Cycloisomerization of Alkynoic Acids with Napthalenediimide‐Derived N‐Heterocyclic Carbene Complexes
  作者：César Ruiz‐Zambrana、Ana Gutiérrez‐Blanco、Sergio Gonell、Macarena Poyatos、Eduardo Peris

  DOI：10.1002/anie.202107973

  日期：2021.9

  that each one-electron reduction produces a decrease of the average ν(CO) of 9–10 cm−1, indicating a significant enhancement of the electron-richness of the metal. The [MCl(NDI-NHC)(COD)] complexes were tested in the catalytic cycloisomerization of alkynoic acids. The one-electron reduced forms showed greatly enhanced activities. For the cyclization of 5-hexynoic acid, the two-electron reduction of the

  两种萘二酰亚胺 (NDI) 双咪唑鎓盐已被用作 N-杂环卡宾 (NHC) 前体，用于制备通式 [MCl(NDI-NHC)(COD)] 的 NDI 功能化铑和铱配合物（ M=Rh，Ir；NDI-NHC=NDI-官能化的NHC配体）。配合物 [IrCl(NDI-NHC)(CO) 2 ] 及其相关的一电子和二电子还原形式的红外光谱比较表明，每次单电子还原都会导致平均 ν(CO) 的减少9–10 cm -1 ，表明金属的电子丰富度显着增强。在炔酸的催化环异构化中测试了[MCl(NDI-NHC)(COD)]配合物。单电子还原形式显示出大大增强的活性。对于5-己烯酸的环化，配体的双电子还原进一步增强了催化活性，因此表明催化剂可以在具有三种不同催化活性的三种氧化还原物质之间切换。
• Core-Fluorinated Naphthalene Diimides: Synthesis, Characterization, and Application in n-Type Organic Field-Effect Transistors
  作者：Zhongyi Yuan、Yingjie Ma、Thomas Geßner、Mengmeng Li、Long Chen、Michael Eustachi、R. Thomas Weitz、Chen Li、Klaus Müllen

  DOI：10.1021/acs.orglett.5b03489

  日期：2016.2.5

  A series of difluoro- and tetrafluoro-substituted naphthalene diimides (NDIs) were synthesized by halogen exchange reactions of corresponding bromo-NDIs with CsF in dioxane. Two strong electron acceptor molecules 6 and 8 with low-lying LUMO energy levels of −4.27 and −4.54 eV were obtained, starting from tetrafluoro-NDI. Organic field-effect transistors (OFETs) based on these fluorinated NDIs were

  通过相应的溴-NDI与CsF在二恶烷中的卤素交换反应，合成了一系列二氟和四氟取代的萘二酰亚胺（NDI）。从四氟-NDI开始，获得了两个低电子的LUMO能级分别为-4.27和-4.54 eV的强电子受体分子6和8。基于这些氟化NDI的有机场效应晶体管（OFET）是通过气相沉积法制造的，在环境条件下具有n沟道场效应特性，其迁移率最高为0.1 cm 2 V –1 s –1。
• Regioselectivity in Sequential Nucleophilic Substitution of Tetrabromonaphthalene Diimides
  作者：Sabin-Lucian Suraru、Frank Würthner

  DOI：10.1021/jo400320a

  日期：2013.6.7

  Nucleophilic substitution of tetrabromosubstituted naphthalene diimides (NDIs) with aniline was studied in detail to explore the regioselectivity as three different diamino-substituted regioisomeric products can be formed. We found that the regioselectivity of the nucleophilic disubstitution of 2,3,6,7-tetrabromonaphthalene diimide with aniline is dependent on reaction solvents and additives. In dichloromethane

  详细研究了用苯胺对四溴取代的萘二酰亚胺（NDI）进行亲核取代，以探索区域选择性，因为可以形成三种不同的二氨基取代的区域异构体。我们发现2,3,6,7-四溴萘二酰亚胺与苯胺的亲核性解离的区域选择性取决于反应溶剂和添加剂。在没有添加剂的二氯甲烷和氯仿中，2,7-二氨基-3,6-二溴-NDI异构体是区域选择性形成的，而在DMF中，在相似的反应条件下，可以观察到2,3-二氨基-6,7-二溴异构体为主要的区域异构体。如果可能的话，形成第三种可能的区域异构体2，6-二氨基-3，7-二溴产物的量很小。四丁基氟化铵（TBAF）添加剂对该反应的区域选择性具有显着影响，因为在没有TBAF的二氯甲烷中，2,7-二氨基异构体是区域选择性形成的，而在没有TBAF的二氯甲烷中，仅形成2,3-二氨基异构体。TBAF的显着效果可以合理化，如在此顺序反应的第一步中生成的单氨基-三溴-NDI的去质子化作用，作为氟离子的中间产