3,3'-bis(hexylthio)-2,2'-bithiophene | 1309469-56-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 双噻吩和低聚噻吩
• 英文名称: 3,3'-bis(hexylthio)-2,2'-bithiophene
• 英文别名: 3-Hexylsulfanyl-2-(3-hexylsulfanylthiophen-2-yl)thiophene；3-hexylsulfanyl-2-(3-hexylsulfanylthiophen-2-yl)thiophene
• CAS: 1309469-56-4
• 化学式: C₂₀H₃₀S₄
• 分子量: 398.722
• InChiKey: IHSIADWGHGJEMH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.7
• 重原子数：
  24
• 可旋转键数：
  13
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  107
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3,3'-bis(hexylthio)-2,2'-bithiophene 在 N-溴代丁二酰亚胺(NBS) 、 1,1'-双(二苯膦基)二茂铁二氯化钯(II)二氯甲烷复合物 、 碳酸氢钠 、 频那醇硼烷 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 为溶剂， 生成 3,3',3''',4''-tetrakis(hexylsulphanyl)quaterthiophene
  参考文献：
  名称：

  Synthesis and Photovoltaic Properties of Regioregular Head-to-Head Substituted Thiophene Hexadecamers

  摘要：

  We describe the expedient synthesis of regioregular thiophene hexadecamers head-to-head (hh) substituted with hexyl and hexylthio grous. The synthesis was carried out by means of a sequence of ultrasound-assisted selective monobrominations and microwave-assisted Suzuki reactions using 4,4,5,5-tetramethyl-1,3,2-dioxaborolane in THF:water. The hexadecamers, which are very soluble in organic solvents, were investigated in solution and thin film by a variety of techniques (UV, PL, CV, X-ray diffraction, FET charge mobility, SKFM) with the aim of elucidating the effect of the sulfur spacer on morphology and functional properties. We show that the sulfur spacer compensates for the decrease in pi-pi conjugation caused by the hh regiochemistry and that the lambda(max) value and redox potentials of the S-alkyl-substituted hexadecamer are similar to those of head-to-tail substituted poly(3-hexylthiophene). Measurements in field effect transistor devices showed that the alkylthio-substituted hexadecamer is a p-type semiconductor while the alkyl-substituted counterpart in the same conditions is not electroactive. Scanning Kelvin force microscopy measurements showed that a blend of the alkylthio-substituted hexadecamer with PCBM displays photovoltaic behavior under illumination. In agreement with this, a bulk heterojunction cell fabricated employing the same blend displayed near 1.5% conversion efficiency without addition of additives or device optimization.

  DOI：

  10.1021/ma301678g
• 作为产物：
  描述：

  3-(hexylthio)thiophene 在 N-溴代丁二酰亚胺(NBS) 、 (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride 、 碳酸氢钠 、 联硼酸频那醇酯 作用下， 以 四氢呋喃 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 0.7h， 生成 3,3'-bis(hexylthio)-2,2'-bithiophene
  参考文献：
  名称：

  A Successful Chemical Strategy To Induce Oligothiophene Self-Assembly into Fibers with Tunable Shape and Function

  摘要：

  Functional supramolecular architectures for bottom-up organic nano- and microtechnology are a high priority research topic. We discovered a new recognition algorithm, resulting from the combination of thioalkyl substituents and head-to-head regiochemistry of substitution, to induce the spontaneous self-assembly of sulfur overrich octathiophenes into supramolecular crystalline fibers combining high charge mobility and intense fluorescence. The fibers were grown on various types of surfaces either as superhelices or straight rods depending on molecular structure. Helical fibers directly grown on a field effect transistor displayed efficient charge mobility and intrinsic 'memory effect'. Despite the fact that the oligomers did not have chirality centers, one type of hand-helicity was always predominant in helical fibers, due to the interplay of molecular atropisomerism and sup ramolecular helicity induced by terminal substituents. Finally, we found that the new sulfur overrich oligothiophenes can easily be prepared in high yields through ultrasound and microwave assistance in green conditions.

  DOI：

  10.1021/ja2014949

文献信息

• Intramolecular Locked Dithioalkylbithiophene‐Based Semiconductors for High‐Performance Organic Field‐Effect Transistors
  作者：Sureshraju Vegiraju、Bo‐Chin Chang、Pragya Priyanka、Deng‐Yi Huang、Kuan‐Yi Wu、Long‐Huan Li、Wei‐Chieh Chang、Yi‐Yo Lai、Shao‐Huan Hong、Bo‐Chun Yu、Chien‐Lung Wang、Wen‐Jung Chang、Cheng‐Liang Liu、Ming‐Chou Chen、Antonio Facchetti

  DOI：10.1002/adma.201702414

  日期：2017.9

  resulting SBT systems are planar (torsional angle <1°) and highly π‐conjugated. Charge transport is investigated for solution‐sheared films in field‐effect transistors demonstrating that SBT can enable good semiconducting materials with hole mobilities ranging from ≈0.03 to 1.7 cm2 V−1 s−1. Transport difference within this family is rationalized by film morphology, as accessed by grazing incidence X‐ray

  通过用二噻吩并噻吩-2-基单元进行封端或共聚，合成了新的基于3,3'-二硫代烷基-2,2'-联噻吩（SBT）的小分子和聚合物半导体。单晶，分子轨道计算以及光学/电化学数据表明，SBT核是完全平面的，可能是通过S（烷基）⋯S（噻吩）分子内锁。因此，与基于常规3,3'-二烷基-2,2'-联噻吩的半导体相比，所得的SBT系统是平面的（扭转角<1°）且高度π共轭。研究了场效应晶体管中溶液剪切薄膜的电荷传输，证明了SBT可以使空穴迁移率在≈0.03至1.7 cm 2 V -1 s -1之间的良好半导体材料成为可能。通过掠射入射X射线衍射实验可以通过薄膜形态来合理化该家族中的运输差异。
• Synthesis and Photovoltaic Properties of Regioregular Head-to-Head Substituted Thiophene Hexadecamers
  作者：Francesca Di Maria、Massimo Gazzano、Alberto Zanelli、Giuseppe Gigli、Anna Loiudice、Aurora Rizzo、Mariano Biasiucci、Elisabetta Salatelli、Pasquale D’ Angelo、Giovanna Barbarella

  DOI：10.1021/ma301678g

  日期：2012.10.23

  We describe the expedient synthesis of regioregular thiophene hexadecamers head-to-head (hh) substituted with hexyl and hexylthio grous. The synthesis was carried out by means of a sequence of ultrasound-assisted selective monobrominations and microwave-assisted Suzuki reactions using 4,4,5,5-tetramethyl-1,3,2-dioxaborolane in THF:water. The hexadecamers, which are very soluble in organic solvents, were investigated in solution and thin film by a variety of techniques (UV, PL, CV, X-ray diffraction, FET charge mobility, SKFM) with the aim of elucidating the effect of the sulfur spacer on morphology and functional properties. We show that the sulfur spacer compensates for the decrease in pi-pi conjugation caused by the hh regiochemistry and that the lambda(max) value and redox potentials of the S-alkyl-substituted hexadecamer are similar to those of head-to-tail substituted poly(3-hexylthiophene). Measurements in field effect transistor devices showed that the alkylthio-substituted hexadecamer is a p-type semiconductor while the alkyl-substituted counterpart in the same conditions is not electroactive. Scanning Kelvin force microscopy measurements showed that a blend of the alkylthio-substituted hexadecamer with PCBM displays photovoltaic behavior under illumination. In agreement with this, a bulk heterojunction cell fabricated employing the same blend displayed near 1.5% conversion efficiency without addition of additives or device optimization.
• Facilitated synthesis of functional oligothiophenes for application in thin film devices and live cell imaging
  作者：Francesca DiMaria、Giovanna Barbarella

  DOI：10.1080/17415993.2013.807810

  日期：2013.12.1

  This paper describes recent developments in the synthesis of ultrapure functional oligothiophene-based materials taking advantage of enabling techniques such as microwave/ultrasound irradiation and chitosan-supported palladium catalysts. Examples showing how ultrapure oligothiophenes self-organize in order to optimize charge transport in thin film devices and fluorescence emission inside living cells are reported.[GRAPHICS].
• A Successful Chemical Strategy To Induce Oligothiophene Self-Assembly into Fibers with Tunable Shape and Function
  作者：Francesca Di Maria、Pasquale Olivelli、Massimo Gazzano、Alberto Zanelli、Mariano Biasiucci、Giuseppe Gigli、Denis Gentili、Pasquale D’Angelo、Massimiliano Cavallini、Giovanna Barbarella

  DOI：10.1021/ja2014949

  日期：2011.6.8

  Functional supramolecular architectures for bottom-up organic nano- and microtechnology are a high priority research topic. We discovered a new recognition algorithm, resulting from the combination of thioalkyl substituents and head-to-head regiochemistry of substitution, to induce the spontaneous self-assembly of sulfur overrich octathiophenes into supramolecular crystalline fibers combining high charge mobility and intense fluorescence. The fibers were grown on various types of surfaces either as superhelices or straight rods depending on molecular structure. Helical fibers directly grown on a field effect transistor displayed efficient charge mobility and intrinsic 'memory effect'. Despite the fact that the oligomers did not have chirality centers, one type of hand-helicity was always predominant in helical fibers, due to the interplay of molecular atropisomerism and sup ramolecular helicity induced by terminal substituents. Finally, we found that the new sulfur overrich oligothiophenes can easily be prepared in high yields through ultrasound and microwave assistance in green conditions.