2,7-bis(4-octylthien-2-yl)-fluoren-9-one | 612531-87-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: 2,7-bis(4-octylthien-2-yl)-fluoren-9-one
• 英文别名: 2,7-bis(4-octylthien-2-yl)fluoren-9-one；2,7-Bis(4-octylthiophen-2-yl)-9H-fluoren-9-one；2,7-bis(4-octylthiophen-2-yl)fluoren-9-one
• CAS: 612531-87-0
• 化学式: C₃₇H₄₄OS₂
• 分子量: 568.888
• InChiKey: VUFCBEGJTZQYCB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  13.8
• 重原子数：
  40
• 可旋转键数：
  16
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  73.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2,7-bis(4-octylthien-2-yl)-fluoren-9-one 在 N-碘代丁二酰亚胺 、 溶剂黄146 作用下， 以 氯仿 为溶剂， 以86.6%的产率得到2,7-bis(5-iodo-4-octylthien-2-yl)fluoren-9-one
  参考文献：
  名称：

  Conjugated alternating copolymer of dialkylquaterthiophene and fluorenone: synthesis, characterisation and photovoltaic properties

  摘要：

  我们合成了含有噻吩和芴酮单元的新型π共轭交替共聚物，即聚[(5,5‴-二辛基-[2,2′;5′,2″;5″,2‴]季噻吩)-alt-(2,7-芴-9-酮)]（PQTF8）及其不含芴酮基团的类似物（PQT8）。在溶液和薄膜中进行的吸收研究表明，与 PQT8 相比，PQTF8 中芴酮发色团的存在使其在可见光范围内的吸收光谱显著扩展。这两种聚合物的氧化还原特性，特别是它们的 LUMO 和 HOMO 水平，已通过循环伏安法进行了表征，并发现这些系统适用于有机太阳能电池的潜在用途。最后，我们还测试了这些材料在使用 PCBM 作为电子受体的体外异质结型光伏电池中作为供体元件的性能。我们证明，聚合物的分子量对电池的关键参数（如短路电流密度 Jsc）有很大影响，因此对电池的整体效率也有很大影响。这种影响对于基于 PQTF8 的电池尤为明显，最高分子量的电池的功率转换效率可达 1.5%。

  DOI：

  10.1039/b708372f
• 作为产物：
  描述：

  3-辛基噻吩 在 potassium phosphate 、 四(三苯基膦)钯 、 正丁基锂 、 硼酸三丁酯 作用下， 以 四氢呋喃 、 正己烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 16.0h， 生成 2,7-bis(4-octylthien-2-yl)-fluoren-9-one
  参考文献：
  名称：

  Regiochemically Well-Defined Fluorenone−Alkylthiophene Copolymers:  Synthesis, Spectroscopic Characterization, and Their Postfunctionalization with Oligoaniline

  摘要：

  A new solution processable, regioregular, alternate copolymer of fluorenone and dialkyl-bithiophene, namely poly [(5,5'-(3,3'-di-n-octyl-2,2'-bithiophene))-alt-(2,7-fluoren-9-one)] (abbreviated as PDOBTF), was synthesized by three different preparation methods: chemical or electrochemical oxidation of 2,7-bis(4-octylthien-2-yl)-fluoren-9-one or polycondensation of 2,7-bis(5-bromo-4-octylthien-2-yl)-fluoren-9-one in the presence of Ni(0) reagent. Independent of the preparation method, the crude product is a mixture of high molecular weight fractions and short oligomers. It can be however easily fractionated into fractions differing in their molecular weight by sequential extractions with a series of solvents. The principal absorption band registered for the undoped polymer (lambda(max) = 384 nm for the THF solution and 389 nm for the solid state) originates from the pi-->pi* transition of the conjugated backbone and is blue-shifted because of the chain torsion effects caused by steric hindrance. This band is accompanied by a peak of smaller intensity (lambda(max) = 476 nm for the THF solution and 485 nm for the solid state) attributed to the n-pi* transition in the carbonyl group of the fluoren-9-one subunit. Preliminary photoluminescence studies show that PDOBTF exhibits a very large Stokes shift and emits red light (lambda(max) = 631 nm in THF solution and 643 nm in the solid state). Upon chemical p-type doping with FeCl4-, the polymer reaches the conductivity of sigma(dc) = 0.05 S cm(-1). Mossbauer spectroscopy studies of the doping process show that both structural subunits, i.e., the bithiophene subunit and the fluoren-9-one one, participate in the doping. PDOBTF can be relatively easily postfunctionalized by grafting aniline oligomers as pendant groups via the carbonyl groups of the fluoren-9-one subunit. By consequence, the spectrum of the modified polymer can be precisely tuned in the visible region by changing the grafting level.

  DOI：

  10.1021/ma030171z

文献信息

• Influence of polymorphism on charge transport properties in isomers of fluorenone-based liquid crystalline semiconductors
  作者：Frédéric Lincker、André-Jean Attias、Fabrice Mathevet、Benoît Heinrich、Bertrand Donnio、Jean-Louis Fave、Patrice Rannou、Renaud Demadrille

  DOI：10.1039/c2cc17276c

  日期：——

  We measured the charge carrier mobilities for two isomers of fluorenone-based liquid crystalline organic semiconductors from their isotropic down to crystalline states through one or two mesophases. Improved charge transport properties of melt-processed crystalline films were obtained for the isomer exhibiting a highly ordered mesophase below its disordered smectic phase.

  我们测量了芴酮基液晶有机半导体的两个异构体从其各向同性到通过一个或两个中间相到结晶态的电荷载流子迁移率。对于在其无序近晶相之下显示出高度有序的中间相的异构体，获得了熔融加工的结晶膜的改进的电荷传输性质。
• Conjugated alternating copolymer of dialkylquaterthiophene and fluorenone: synthesis, characterisation and photovoltaic properties
  作者：Renaud Demadrille、Nicolas Delbosc、Yann Kervella、Muriel Firon、Rémi De Bettignies、Martial Billon、Patrice Rannou、Adam Pron

  DOI：10.1039/b708372f

  日期：——

  New π-conjugated alternating copolymers containing thienylene and fluorenone units, namely poly[(5,5‴-dioctyl-[2,2′;5′,2″;5″,2‴]quaterthiophene)-alt-(2,7-fluoren-9-one)] (PQTF8), as well as its analogue without fluorenone groups (PQT8), have been synthesized. Absorption studies carried out both in solution and in thin films indicate that the presence of fluorenone chromophores in PQTF8 leads to a significant extension of the absorption spectrum in the visible range as compared to PQT8. The redox properties of both polymers, in particular their LUMO and HOMO levels, have been characterized by cyclic voltammetry and have been found suitable for potential use of these systems in organic solar cells. Finally, these materials have been tested as donor components in bulk-heterojunction-type photovoltaic cells using PCBM as an electron acceptor. We demonstrate a strong effect of the polymer's molecular weight on crucial cell parameters, such as the short-circuit current density Jsc, and therefore on the overall cell efficiency. This effect is particularly pronounced for PQTF8-based cells leading to power conversion efficiencies up to 1.5% for the highest molecular weights.

  我们合成了含有噻吩和芴酮单元的新型π共轭交替共聚物，即聚[(5,5‴-二辛基-[2,2′;5′,2″;5″,2‴]季噻吩)-alt-(2,7-芴-9-酮)]（PQTF8）及其不含芴酮基团的类似物（PQT8）。在溶液和薄膜中进行的吸收研究表明，与 PQT8 相比，PQTF8 中芴酮发色团的存在使其在可见光范围内的吸收光谱显著扩展。这两种聚合物的氧化还原特性，特别是它们的 LUMO 和 HOMO 水平，已通过循环伏安法进行了表征，并发现这些系统适用于有机太阳能电池的潜在用途。最后，我们还测试了这些材料在使用 PCBM 作为电子受体的体外异质结型光伏电池中作为供体元件的性能。我们证明，聚合物的分子量对电池的关键参数（如短路电流密度 Jsc）有很大影响，因此对电池的整体效率也有很大影响。这种影响对于基于 PQTF8 的电池尤为明显，最高分子量的电池的功率转换效率可达 1.5%。
• Preparation and spectroelectrochemical behaviour of a new alternate copolymer of 3,3′-di-n-octyl-2,2′-bithiophene and fluoren-9-one
  作者：Renaud Demadrille、Bernadette Divisia-Blohorn、Malgorzata Zagorska、Sophie Quillard、Patrice Rannou、Jean Pierre Travers、Adam Pron

  DOI：10.1039/b304551j

  日期：——

  The synthesis and spectroelectrochemical behaviour of a new solution processible conjugated polymer, namely poly[5,5′-(3,3′-di-n-octyl-2,2′-bithiophene)}-alt-(2,7-fluoren-9-one)] (abbreviated as PDOBTF), are described. PDOBTF can be considered as the first member of a new family of conjugated copolymers—poly(oligothiophene-alt-fluoren-9-one)s—whose properties can be tuned by changing the length of the oligothiophene segments and their regiochemistry. PDOBTF can be obtained by oxidative polymerisation of 2,7-bis(4-octylthien-2-yl)-fluoren-9-one or by condensation polymerisation of 2,7-bis(5-bromo-4-octylthien-2-yl)-fluoren-9-one using a modification of Yamamoto coupling. Both preparation methods lead to a mixture of polymeric and oligomeric species and require post-polymerisation fractionating if high molecular fractions are to be obtained. Oxidative polymerisation gives product of a higher molecular weight (Mn = 41.0 kDa, Mw/Mn = 1.81 for the highest molecular weight fraction) as compared to the one prepared by Yamamoto condensation polymerisation (Mn = 13.3 kDa, Mw/Mn = 1.45 for the highest molecular weight fraction). Electrochemical oxidation of PDOBTF in an nonaqueous electrolyte (0.1 M Bu4NBF4/acetonitrile) gives rise to an anodic peak at E = 835 mV, which can be ascribed to the p-type doping of the copolymer. The extension of the potential to E = 1500 mV results in the oxidative degradation of the copolymer and induces total loss of its electroactivity. UV-Vis-NIR and Raman spectroelectrochemical data are consistent with the oxidative doping. The latter technique enables the monitoring of the doping-induced changes in both structural sub-units of the copolymer: the bithiophene sub-unit and the fluoren-9-one one.

  本文介绍了一种新型溶液可加工共轭聚合物，即聚[5,5â²-(3,3â²-二正辛基-2,2â²-噻吩)}-alt-(2,7-芴-9-酮)]（简称 PDOBTF）的合成和光谱电化学行为。PDOBTF 可被视为新型共轭共聚物--聚（低聚噻吩-alt-芴-9-酮）家族的第一个成员，其特性可通过改变低聚噻吩片段的长度及其区域化学性质来调整。PDOBTF 可通过 2,7-双（4-辛基噻吩-2-基）-芴-9-酮的氧化聚合或通过 2,7-双（5-溴-4-辛基噻吩-2-基）-芴-9-酮的缩合聚合（使用山本偶联的一种改良方法）获得。这两种制备方法都会产生聚合物和低聚物的混合物，如果要获得高分子馏分，则需要进行聚合后分馏。与山本缩合聚合法（Mnâ=â13.3 kDa，最高分子量部分的 Mw/Mnâ=â1.81）相比，氧化聚合法得到的产品分子量更高（Mnâ=â41.0 kDa，最高分子量部分的 Mw/Mnâ=â1.81）。PDOBTF 在非水电解质（0.1 M Bu4NBF4/乙腈）中进行电化学氧化时，在 Eâ=â835 mV 处出现阳极峰，这可归因于共聚物的 p 型掺杂。将电位延长至 Eâ=â1500 mV 时，共聚物会发生氧化降解，从而完全丧失电活性。紫外-可见-近红外光谱和拉曼光谱电化学数据与氧化掺杂一致。后一种技术可以监测掺杂引起的共聚物两个结构亚单位的变化：双噻吩亚单位和芴-9-酮亚单位。
• Regiochemically Well-Defined Fluorenone−Alkylthiophene Copolymers:  Synthesis, Spectroscopic Characterization, and Their Postfunctionalization with Oligoaniline
  作者：Renaud Demadrille、Patrice Rannou、Joël Bleuse、Jean-Louis Oddou、Adam Pron、Malgorzata Zagorska

  DOI：10.1021/ma030171z

  日期：2003.9.1

  A new solution processable, regioregular, alternate copolymer of fluorenone and dialkyl-bithiophene, namely poly [(5,5'-(3,3'-di-n-octyl-2,2'-bithiophene))-alt-(2,7-fluoren-9-one)] (abbreviated as PDOBTF), was synthesized by three different preparation methods: chemical or electrochemical oxidation of 2,7-bis(4-octylthien-2-yl)-fluoren-9-one or polycondensation of 2,7-bis(5-bromo-4-octylthien-2-yl)-fluoren-9-one in the presence of Ni(0) reagent. Independent of the preparation method, the crude product is a mixture of high molecular weight fractions and short oligomers. It can be however easily fractionated into fractions differing in their molecular weight by sequential extractions with a series of solvents. The principal absorption band registered for the undoped polymer (lambda(max) = 384 nm for the THF solution and 389 nm for the solid state) originates from the pi-->pi* transition of the conjugated backbone and is blue-shifted because of the chain torsion effects caused by steric hindrance. This band is accompanied by a peak of smaller intensity (lambda(max) = 476 nm for the THF solution and 485 nm for the solid state) attributed to the n-pi* transition in the carbonyl group of the fluoren-9-one subunit. Preliminary photoluminescence studies show that PDOBTF exhibits a very large Stokes shift and emits red light (lambda(max) = 631 nm in THF solution and 643 nm in the solid state). Upon chemical p-type doping with FeCl4-, the polymer reaches the conductivity of sigma(dc) = 0.05 S cm(-1). Mossbauer spectroscopy studies of the doping process show that both structural subunits, i.e., the bithiophene subunit and the fluoren-9-one one, participate in the doping. PDOBTF can be relatively easily postfunctionalized by grafting aniline oligomers as pendant groups via the carbonyl groups of the fluoren-9-one subunit. By consequence, the spectrum of the modified polymer can be precisely tuned in the visible region by changing the grafting level.