3,5-bis[2-[4-[1,6,9-tris(4-tert-butylphenoxy)perylene-3,4-dicarboximido]-3,5-diisopropylphenyl]ethynyl]benzaldehyde | 468083-02-5

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二芳基庚烷
• 英文名称: 3,5-bis[2-[4-[1,6,9-tris(4-tert-butylphenoxy)perylene-3,4-dicarboximido]-3,5-diisopropylphenyl]ethynyl]benzaldehyde
• 英文别名: 3,5-Bis[2-[3,5-di(propan-2-yl)-4-[5,12,20-tris(4-tert-butylphenoxy)-15,17-dioxo-16-azahexacyclo[12.6.2.12,6.011,21.018,22.010,23]tricosa-1(20),2(23),3,5,7,9,11,13,18,21-decaen-16-yl]phenyl]ethynyl]benzaldehyde
• CAS: 468083-02-5
• 化学式: C₁₃₉H₁₂₈N₂O₁₁
• 分子量: 2002.55
• InChiKey: MKDARVIJHUDWGY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  37.9
• 重原子数：
  152
• 可旋转键数：
  29
• 环数：
  21.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  147
• 氢给体数：
  0
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  吡咯 、 3,5-bis[2-[4-[1,6,9-tris(4-tert-butylphenoxy)perylene-3,4-dicarboximido]-3,5-diisopropylphenyl]ethynyl]benzaldehyde 在 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 0.17h， 以93%的产率得到5-[3,5-bis(2-{4-[1,6,9-tris(4-tert-butylphenoxy)perylene-3,4-dicarboximido]-3,5-diisopropylphenyl}ethynyl)phenyl]dipyrromethane
  参考文献：
  名称：

  Synthesis of perylene–porphyrin building blocks and rod-like oligomers for light-harvesting applications

  摘要：

  我们展示了四种用于Glaser、Sonogashira或Suzuki聚合的苝–卟啉构件的合成。这些构件在锌卟啉的反式（5,15）美索位点上带有合成手柄（4-乙炔基苯基、4-碘苯基、溴）并在卟啉的非连接美索芳香环的3,5位上附有两个或四个苝单酰亚胺染料。每个苝单酰亚胺上都有三个4-叔丁基苯氧基取代基（位于1、6和9位）和两个异丙基（在N-芳基单元上），以提高溶解度。在每种情况下，介导链是一个二芳基乙炔单元，连接苝的N-酰亚胺位和卟啉的美索位。苝–卟啉构件的制备方法包括：（1）将二苝-二吡咯烷与醛反应生成反式A2B2-卟啉；（2）将二苝-醛与二吡咯烷反应生成反式A2B2-卟啉；（3）将二苝-二吡咯烷与二吡咯烷-二醇反应生成反式AB2C-卟啉或ABCD-卟啉。这些构件在Glaser、Sonogashira或Suzuki偶联条件下进行处理，以便制备包含通过4,4'-二苯基丁炔（dpb）、4,4'-二苯乙炔（dpe）或1,4-苯基链接（p）连接的卟啉的低聚物。骨架中的每个卟啉附有两个或四个悬挂的苝单酰亚胺染料。Glaser和Sonogashira反应产生了低聚物的分布，而Suzuki反应则未成功。所制备的低聚物在如甲苯、THF或CHCl3等溶剂中可溶，便于常规操作。使用苝可以导致（1）在卟啉相对透明的绿色光谱区域内，光捕获效率的提高；（2）相比仅使用卟啉，获得更高的溶解度。这些可溶的苝–卟啉低聚物在基于分子的太阳能电池中作为光捕获材料具有吸引力。

  DOI：

  10.1039/b205680a
• 作为产物：
  描述：

  3,5-二乙炔基苯甲醛 、 1,6,9-tris(4-tert-butylphenoxy)-N-(2,6-diisopropyl-4-iodophenyl)perylene-3,4-dicarboximide 在 tris(dibenzylideneacetone)dipalladium (0) 、 三乙胺 、 三(邻甲基苯基)磷 作用下， 以 甲苯 为溶剂， 反应 2.0h， 以42%的产率得到3,5-bis[2-[4-[1,6,9-tris(4-tert-butylphenoxy)perylene-3,4-dicarboximido]-3,5-diisopropylphenyl]ethynyl]benzaldehyde
  参考文献：
  名称：

  Practical synthesis of perylene-monoimide building blocks that possess features appropriate for use in porphyrin-based light-harvesting arrays

  摘要：

  Perylene-monoimide dyes with solubilizing aryloxy substituents at the perylene perimeter and a synthetic handle on the N-aryl group are valuable building blocks for incorporation as accessory pigments in porphyrin-based light-harvesting arrays. A family of such dyes has been prepared by reaction of 1,6,9-tris(4-tert-butylphenoxy)perylene-3,4-dicarboxylic anhydride with a set of 4-iodo/ethynyl anilines (with or without 2,6-diisopropyl substituents) in the presence of Zn(OAc)(2)(.)2H(2)O in imidazole/mesitylene at 130degreesC. The workup procedures throughout the synthesis have been streamlined for scale-up purposes, minimizing chromatography. Two bis(perylene)porphyrin building blocks were prepared in a rational manner and examined in Sonogashira and Glaser polymerizations. The two isopropyl groups on the N-aryl group and the three 4-tert-butylphenoxy groups at the perylene perimeter are essential for high solubility of the bis(perylene)porphyrins and corresponding oligomers in organic solvents. (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(03)00020-6

文献信息

• [EN] SYNTHESIS OF PERYLENE-PORPHYRIN BUILDING BLOCKS AND POLYMERS THEREOF FOR THE PRODUCTION OF LIGHT-HARVESTING ARRAYS<br/>[FR] SYNTHESE D'ELEMENTS CONSTITUTIFS A BASE DE PERYLENE-PORPHYRINE ET POLYMERES ASSOCIES DESTINES A LA PRODUCTION DE RESEAUX COLLECTEURS DE LUMIERE
  申请人：UNIV NORTH CAROLINA STATE

  公开号：WO2003105237A1

  公开（公告）日：2003-12-18

  The present invention provides methods, compounds, and compositions for the synthesis of light harvesting arrays, such arrays comprising: (a) a first substrate comprising a first electrode; and (b) a layer of light harvesting rods electrically coupled to said first electrode, each of said light harvesting rods comprising a polymer of Formula (I): wherein m is at least 1; X1 is a charge separation group, and X2 through Xm+1 are chromophores. At least one of X2 through Xm+1 has at least one perylene group coupled thereto.

  本发明提供了一种用于合成光收集阵列的方法、化合物和组合物，所述阵列包括：(a)包括第一电极的第一衬底；以及(b)与所述第一电极电性耦合的光收集棒层，其中每个所述光收集棒包括化学式(I)的聚合物：其中m至少为1；X1是一个电荷分离基团，X2至Xm+1是色素。X2至Xm+1中至少有一个与之耦合的苯菲啰基团。
• Synthesis and Photophysical Properties of Light-Harvesting Arrays Comprised of a Porphyrin Bearing Multiple Perylene-Monoimide Accessory Pigments
  作者：Kin-ya Tomizaki、Robert S. Loewe、Christine Kirmaier、Jennifer K. Schwartz、Jennifer L. Retsek、David F. Bocian、Dewey Holten、Jonathan S. Lindsey

  DOI：10.1021/jo0258002

  日期：2002.9.1

  excited porphyrin product. For the array containing four perylenes per porphyrin in both nonpolar (toluene) and polar (benzonitrile) media and for the array containing eight perylenes per porphyrin in toluene, the photoexcited perylene-monoimide dye (PMI) decays rapidly ( approximately 3.5 ps) and predominantly (>or=90%) by energy transfer to the zinc porphyrin to form the excited zinc porphyrin (Zn)

  我们提出了新的光收集阵列的合成和表征，该阵列包含附着在锌卟啉上的两个，四个或八个per-单酰亚胺辅助颜料。每个per被一个或三个4-叔丁基苯氧基取代基取代。4,3'-或4,2'-二芳基乙炔连接基连接NN-酰亚胺位和卟啉内消旋位，分别提供发散或会聚的结构。该体系结构旨在提供在有机介质中的高溶解度和容易的per到卟啉的能量转移，同时避免了激发的卟啉产物的电荷转移猝灭。对于在非极性（甲苯）和极性（苄腈）介质中每个卟啉含四个four的阵列，以及对于在甲苯中每个卟啉含八个eight的阵列，光激发的per-单酰亚胺染料（PMI）迅速衰减（约3.5 ps），并主要通过能量转移至卟啉锌形成激发态的锌卟啉（Zn）衰变（寿命= 90％） ，荧光产量）可与分离的生色团相比（约10％以内）。对于在苄腈中包含八个per的阵列，PMI通过能量转移（形成Zn）衰减大约80％，通过空穴转移（形成PMI- Zn +）大约衰
• Synthesis of perylene-porphyrin building blocks and polymers thereof for the production of light-harvesting arrays
  申请人：——

  公开号：US20030075216A1

  公开（公告）日：2003-04-24

  The present invention provides methods, compounds, and compositions for the synthesis of light harvesting arrays, such arrays comprising: (a) a first substrate comprising a first electrode; and (b) a layer of light harvesting rods electrically coupled to said first electrode, each of said light harvesting rods comprising a polymer of Formula I: X 1 &Parenopenst;X m+1 ) m (I) wherein m is at least 1; X 1 is a charge separation group, and X 2 through X m+1 are chromophores. At least one of X 2 through X m+1 has at least one perylene group coupled thereto.

  本发明提供了用于合成光收集阵列的方法、化合物和组合物，其中所述阵列包括：(a)第一基底，包括第一电极；以及(b)与所述第一电极电性耦合的光收集棒层，每个所述光收集棒包括式I：X1&Parenopenst;Xm+1)m(I)的聚合物，其中m至少为1；X1是一个电荷分离基团，X2至Xm+1是色团。X2至Xm+1中至少有一个与至少一个苝基团耦合。
• US6916982B2
  申请人：——

  公开号：US6916982B2

  公开（公告）日：2005-07-12
• Synthesis of perylene–porphyrin building blocks and rod-like oligomers for light-harvesting applications
  作者：Robert S. Loewe、Kin-ya Tomizaki、W. Justin Youngblood、Zhishan Bo、Jonathan S. Lindsey

  DOI：10.1039/b205680a

  日期：——

  We present the synthesis of four perylene–porphyrin building blocks for use in Glaser, Sonogashira, or Suzuki polymerizations. The building blocks bear synthetic handles (4-ethynylphenyl, 4-iodophenyl, bromo) at the trans (5,15) meso-positions of a zinc porphyrin and contain two or four perylene-monoimide dyes attached at the 3,5-positions of the non-linking meso-aryl rings of the porphyrin. Each perylene-monoimide bears three 4-tert-butylphenoxy substituents (at the 1-, 6-, and 9-positions) and two isopropyl groups (on the N-aryl unit) for increased solubility. In each case the intervening linker is a diarylethyne unit that bridges the N-imide position of the perylene and the meso-position of the porphyrin. The perylene–porphyrin building blocks were prepared by (1) reaction of a diperylene-dipyrromethane with an aldehyde yielding a trans-A2B2-porphyrin, (2) reaction of a diperylene-aldehyde with a dipyrromethane yielding a trans-A2B2-porphyrin, and (3) reaction of a diperylene-dipyrromethane with a dipyrromethane-dicarbinol yielding a trans-AB2C-porphyrin or ABCD-porphyrin. The building blocks were subjected to Glaser, Sonogashira, or Suzuki coupling conditions in an effort to prepare oligomers containing porphyrins joined via 4,4′-diphenylbutadiyne (dpb), 4,4′-diphenylethyne (dpe), or 1,4-phenylene linkers (p), respectively. Each porphyrin in the backbone bears two or four pendant perylene-monoimide dyes. The Glaser and Sonogashira reactions afforded a distribution of oligomers, whereas the Suzuki reaction was unsuccessful. The oligomers were soluble in solvents such as toluene, THF, or CHCl3 enabling routine handling. The use of perylenes results in (1) increased light-harvesting efficiency particularly in the green spectral region where porphyrins are relatively transparent and (2) greater solubility than is achieved with the use of porphyrins alone. The soluble perylene–porphyrin oligomers are attractive for use as light-harvesting materials in molecular-based solar cells.

  我们展示了四种用于Glaser、Sonogashira或Suzuki聚合的苝–卟啉构件的合成。这些构件在锌卟啉的反式（5,15）美索位点上带有合成手柄（4-乙炔基苯基、4-碘苯基、溴）并在卟啉的非连接美索芳香环的3,5位上附有两个或四个苝单酰亚胺染料。每个苝单酰亚胺上都有三个4-叔丁基苯氧基取代基（位于1、6和9位）和两个异丙基（在N-芳基单元上），以提高溶解度。在每种情况下，介导链是一个二芳基乙炔单元，连接苝的N-酰亚胺位和卟啉的美索位。苝–卟啉构件的制备方法包括：（1）将二苝-二吡咯烷与醛反应生成反式A2B2-卟啉；（2）将二苝-醛与二吡咯烷反应生成反式A2B2-卟啉；（3）将二苝-二吡咯烷与二吡咯烷-二醇反应生成反式AB2C-卟啉或ABCD-卟啉。这些构件在Glaser、Sonogashira或Suzuki偶联条件下进行处理，以便制备包含通过4,4'-二苯基丁炔（dpb）、4,4'-二苯乙炔（dpe）或1,4-苯基链接（p）连接的卟啉的低聚物。骨架中的每个卟啉附有两个或四个悬挂的苝单酰亚胺染料。Glaser和Sonogashira反应产生了低聚物的分布，而Suzuki反应则未成功。所制备的低聚物在如甲苯、THF或CHCl3等溶剂中可溶，便于常规操作。使用苝可以导致（1）在卟啉相对透明的绿色光谱区域内，光捕获效率的提高；（2）相比仅使用卟啉，获得更高的溶解度。这些可溶的苝–卟啉低聚物在基于分子的太阳能电池中作为光捕获材料具有吸引力。