2,7-bis(5-bromo-4-octylthien-2-yl)-fluoren-9-one | 612531-88-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 芴
• 英文名称: 2,7-bis(5-bromo-4-octylthien-2-yl)-fluoren-9-one
• 英文别名: 2,7-Bis(5-bromo-4-octylthiophen-2-yl)fluoren-9-one
• CAS: 612531-88-1
• 化学式: C₃₇H₄₂Br₂OS₂
• 分子量: 726.68
• InChiKey: VZGUWFFFUUHIOU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  15.9
• 重原子数：
  42
• 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

• 作为产物：
  描述：

  3-辛基噻吩 在 potassium phosphate 、 N-溴代丁二酰亚胺(NBS) 、 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 、 氯仿 、 N,N-二甲基甲酰胺 为溶剂， 反应 16.0h， 生成 2,7-bis(5-bromo-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

• 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。