3,6-di(4-piperidinophenyl)-2,5-dihydro-pyrrolo[3,4-c]pyrrole-1,4-dione | 128454-77-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: 3,6-di(4-piperidinophenyl)-2,5-dihydro-pyrrolo[3,4-c]pyrrole-1,4-dione
• 英文别名: 1,4-bis(4-piperidin-1-ylphenyl)-2,5-dihydropyrrolo[3,4-c]pyrrole-3,6-dione
• CAS: 128454-77-3
• 化学式: C₂₈H₃₀N₄O₂
• 分子量: 454.572
• InChiKey: HFTNGZZCGXQAOC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.05
• 重原子数：
  34.0
• 可旋转键数：
  4.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  64.68
• 氢给体数：
  2.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  3,6-di(4-piperidinophenyl)-2,5-dihydro-pyrrolo[3,4-c]pyrrole-1,4-dione 、 2,4-二硝基氟苯 在 potassium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 144.0h， 以14%的产率得到2,5-bis(2,4-dinitrophenyl)-3,6-bis(4-(piperidin-1-yl)phenyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione
  参考文献：
  名称：

  HOMO and LUMO energy levels of N,N′-dinitrophenyl-substituted polar diketopyrrolopyrroles (DPPs)

  摘要：

  A series of four [3,4-c]pyrrole-1,4-diones (diketopyrrolopyrroles, DPPs) with (substituted) phenyl rings in 3,6-positions was prepared by direct N,N'-arylation of corresponding diketopyrrolopyrrole pigments with 1-fluoro-2,4-dinitro-benzene. While the energies of the HOMO levels depend strongly on the nature of the p-substituehts on the 3,5-phenyl rings, the LUMO levels obtained by cyclic and rotating disc voltammetry were found to be almost independent of the substituent. The absorption spectra show either a hypsochromic or bathochromic shift with respect to parent pigments, depending on the electron-donating and -accepting character of the p-substituents. This behaviour was rationalized by density functional theory calculations, showing that highest occupied molecular orbital is delocalized over the whole 3,6-diphenyl-diketopyrrolopyrrole conjugated system as in the parent pigments, while low-lying LUMO is completely different from the precursors, as it is localized exclusively on the 2,4-dinitrophenyl substituents, i.e. its shape and energy are not affected by a substitution on the 3,6-phenyl rings. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.dyepig.2014.03.005
• 作为产物：
  描述：

  4-哌啶-1-苯甲醛 、 丁二酸二异丙酯 在 iron(III) chloride 、 sodium 、 水 作用下， 以 2-甲基-2-丁醇 为溶剂， 以15%的产率得到3,6-di(4-piperidinophenyl)-2,5-dihydro-pyrrolo[3,4-c]pyrrole-1,4-dione
  参考文献：
  名称：

  Novel, soluble diphenyl-diketo-pyrrolopyrroles: Experimental and theoretical study

  摘要：

  Derivatives of diphenyl-diketo-pyrrolopyrrole, possessing electron-donating or withdrawing groups in the p-position of the phenyl, were synthesized and studied using optical characterization (absorption, fluorescence, time-resolved fluorescence) and quantum chemical calculation. An increase in absorption coefficient >= 10(5) dm(3) mol(-1) cm(-1) was observed using electron-donor groups; a bathochromic shift in both absorption and luminescence peaks was observed as a result of increased conjugation. Soluble derivatives were obtained by the introduction of alkyl groups (by N-alkylation) in the central pyrrolopyrrole unit. Calculated phenyl torsion angles using HF and B3LYP methods showed that the loss of molecule planarity reduced the extent of overlap between the pi-orbitals of the central pyrrolopyrrole unit and phenyls after N-alkylation. This treatment thus reduced both the bathochromic shift and increased absorption coefficient. The presence of the donor or acceptor groups in itself does not influence molecule planarity. (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.dyepig.2009.07.014

文献信息

• Rational Molecular Design towards Vis/NIR Absorption and Fluorescence by using Pyrrolopyrrole<i>aza</i>-BODIPY and its Highly Conjugated Structures for Organic Photovoltaics
  作者：Soji Shimizu、Taku Iino、Akinori Saeki、Shu Seki、Nagao Kobayashi

  DOI：10.1002/chem.201405761

  日期：2015.2.9

  formation reaction with heteroaromatic amines is a highly potential chromophore due to its intense absorption and fluorescence in the visible region and high fluorescence quantum yield, which is greater than 0.8. To control the absorption and fluorescence of PPAB, particularly in the near‐infrared (NIR) region, further molecular design was performed using DFT calculations. This results in the postulation

  吡咯并吡咯氮杂在我们最近的研究中开发的‐BODIPY（PPAB）是由二酮吡咯并吡咯通过四氯化钛介导的与杂芳族胺的席夫碱形成反应形成的发色团，由于其在可见光区的强烈吸收和荧光作用以及较高的荧光量子产率，因此是一种潜在的发色团。大于0.8。为了控制PPAB的吸收和荧光，特别是在近红外（NIR）区域，使用DFT计算进行了进一步的分子设计。这导致假设，杂芳族部分和芳基取代基干扰了PPAB的HOMO-LUMO间隙。基于这种分子设计，合成了一系列新的PPAB分子，其中最大吸收红移和荧光最大值分别高达803和850 nm，对于由苯并噻唑环和叔噻吩基取代基组成的PPAB，获得了相同的收率。与PPAB的急剧吸收相反，通过PPAB单体的交叉偶联反应制得的PPAB二聚体在UV / Vis / NIR区域表现出全色吸收。有了这一系列的PPAB生色团，人们研究了PPAB作为光电材料的潜在应用。根据使用时间分辨的微波
• Absorption and fluorescence of soluble polar diketo-pyrrolo-pyrroles
  作者：Stanislav Luňák、Martin Vala、Jan Vyňuchal、Imad Ouzzane、Petra Horáková、Petra Možíšková、Zdeněk Eliáš、Martin Weiter

  DOI：10.1016/j.dyepig.2011.05.004

  日期：2011.12

  Six soluble derivatives of 3,6-diphenyl-2,5-dihydro-pyrrolo[3,4-c]pyrrole-1,4-dione N-alkylated on pyrrolinone ring with polar substituents in para positions of pendant phenyl rings were synthesized: five of them are reported for the first time. Absorption and fluorescence spectra were studied in solvents of different polarity. The compounds show small solvatochromism of absorption and a moderate positive solvatochromism of fluorescence, especially when substituted by strong electron-donating piperidino substituent. A significant decrease of fluorescence quantum yields and its biexponential decay for dipolar derivatives in polar solvents was tentatively ascribed to the formation of twisted intramolecular charge transfer (TICT) excited state. All six compounds show fluorescence in polycrystalline solid-state with the maxima covering a range over 200 nm in visible and near infrared region. (C) 2011 Elsevier Ltd. All rights reserved.
• Novel, soluble diphenyl-diketo-pyrrolopyrroles: Experimental and theoretical study
  作者：M. Vala、J. Vyňuchal、P. Toman、M. Weiter、S. Luňák

  DOI：10.1016/j.dyepig.2009.07.014

  日期：2010.2

  Derivatives of diphenyl-diketo-pyrrolopyrrole, possessing electron-donating or withdrawing groups in the p-position of the phenyl, were synthesized and studied using optical characterization (absorption, fluorescence, time-resolved fluorescence) and quantum chemical calculation. An increase in absorption coefficient >= 10(5) dm(3) mol(-1) cm(-1) was observed using electron-donor groups; a bathochromic shift in both absorption and luminescence peaks was observed as a result of increased conjugation. Soluble derivatives were obtained by the introduction of alkyl groups (by N-alkylation) in the central pyrrolopyrrole unit. Calculated phenyl torsion angles using HF and B3LYP methods showed that the loss of molecule planarity reduced the extent of overlap between the pi-orbitals of the central pyrrolopyrrole unit and phenyls after N-alkylation. This treatment thus reduced both the bathochromic shift and increased absorption coefficient. The presence of the donor or acceptor groups in itself does not influence molecule planarity. (C) 2009 Elsevier Ltd. All rights reserved.
• HOMO and LUMO energy levels of N,N′-dinitrophenyl-substituted polar diketopyrrolopyrroles (DPPs)
  作者：Martin Vala、Jozef Krajčovič、Stanislav Luňák、Imad Ouzzane、Jean-Philippe Bouillon、Martin Weiter

  DOI：10.1016/j.dyepig.2014.03.005

  日期：2014.7

  A series of four [3,4-c]pyrrole-1,4-diones (diketopyrrolopyrroles, DPPs) with (substituted) phenyl rings in 3,6-positions was prepared by direct N,N'-arylation of corresponding diketopyrrolopyrrole pigments with 1-fluoro-2,4-dinitro-benzene. While the energies of the HOMO levels depend strongly on the nature of the p-substituehts on the 3,5-phenyl rings, the LUMO levels obtained by cyclic and rotating disc voltammetry were found to be almost independent of the substituent. The absorption spectra show either a hypsochromic or bathochromic shift with respect to parent pigments, depending on the electron-donating and -accepting character of the p-substituents. This behaviour was rationalized by density functional theory calculations, showing that highest occupied molecular orbital is delocalized over the whole 3,6-diphenyl-diketopyrrolopyrrole conjugated system as in the parent pigments, while low-lying LUMO is completely different from the precursors, as it is localized exclusively on the 2,4-dinitrophenyl substituents, i.e. its shape and energy are not affected by a substitution on the 3,6-phenyl rings. (C) 2014 Elsevier Ltd. All rights reserved.