[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

WO2017028460A1 - 一类九元稠环衍生物及其合成方法与应用 - Google Patents

一类九元稠环衍生物及其合成方法与应用 Download PDF

Info

Publication number
WO2017028460A1
WO2017028460A1 PCT/CN2015/100035 CN2015100035W WO2017028460A1 WO 2017028460 A1 WO2017028460 A1 WO 2017028460A1 CN 2015100035 W CN2015100035 W CN 2015100035W WO 2017028460 A1 WO2017028460 A1 WO 2017028460A1
Authority
WO
WIPO (PCT)
Prior art keywords
fused ring
membered fused
alkyl group
effect transistor
reaction
Prior art date
Application number
PCT/CN2015/100035
Other languages
English (en)
French (fr)
Inventor
张斌
杨勇
杨伟
曹镛
Original Assignee
华南理工大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 华南理工大学 filed Critical 华南理工大学
Publication of WO2017028460A1 publication Critical patent/WO2017028460A1/zh

Links

Images

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains four or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
    • C07F7/0816—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring comprising Si as a ring atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
    • C07F7/0827—Syntheses with formation of a Si-C bond
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene

Definitions

  • the invention belongs to the field of organic photoelectric technology, and particularly relates to a class of nine-membered fused ring derivatives and a synthesis method and application thereof.
  • the object of the present invention is to synthesize a small-molecular organic semiconductor material having a large conjugate plane of a nine-membered ring structure, which has a high mobility and is suitable for use in an organic field effect transistor.
  • the nine-membered fused ring derivative of the present invention is obtained by a ring closure reaction and an oxidation reaction.
  • a class of nine-membered fused ring derivatives of the present invention having the following chemical structural formula:
  • the nine-membered fused ring forms a large conjugate plane structure
  • R 1 is a C 1 -C 30 linear or branched alkyl group
  • R 2 is H, a C 1 to C 30 linear or branched alkyl group, or a linear or branched alkyl group of OC 1 to OC 30 ;
  • R 3 , R 4 , R 5 and R 6 are the same or different and are H, C 1 -C 30 linear or branched alkyl, OC 1 -OC 30 linear or branched alkyl, F, CF 3 or (wherein R 7 is H, a linear or branched alkyl group of C 1 to C 30 , a linear or branched alkyl group of OC 1 to OC 30 , F or CF 3 );
  • Z O, S, Se, N, P, C, Si, Ge or Sn.
  • both compound 4 and compound 5 are the nine-membered fused ring derivatives
  • the nine-membered fused ring derivatives have high and stable hole mobility with a mobility of from 0.1 to 5.0 square centimeters per volt per second. It can be used as an active layer in an organic field effect transistor device; the active layer of an organic field effect transistor device has a thickness of 20-1000 nm; and the active layer of the organic field effect transistor device is realized by solution processing, including rotation Coating, brushing, spraying, dip coating, roll coating, screen printing, printing or ink jet printing methods; wherein the solvent used is an organic solvent; and the active layer of the organic field effect transistor device is prepared in air.
  • a method for synthesizing a large fused-ring aromatic compound is provided; since the introduction of the fused ring increases the rigidity and planarity of the molecule, the conjugate of the molecule is increased, thereby not only improving the thermal stability of the material but also improving the thermal stability of the material.
  • the material conducts holes.
  • most of the organic field effect transistor materials are prepared in an inert gas-protected glove box.
  • the large fused-ring aromatic compounds synthesized by the present invention can be used to prepare an organic field-effect transistor device in air. Layer, and exhibits good hole transport properties and stability.
  • Figure 1 is a differential scanning calorimetry graph of Compound 4.
  • Figure 2 is a graph of thermogravimetric analysis of Compound 4.
  • Figure 3 is a graph showing the absorption spectrum of the compound 4 solution.
  • Figure 4 is a graph showing the absorption spectrum of a compound 4 film.
  • Figure 5 is a graph showing the emission spectrum of the compound 4 solution.
  • Figure 6 is a graph showing the emission spectrum of the compound 4.
  • Figure 7 is a graph showing the cyclic volt-ampere characteristics of Compound 4.
  • Figure 8 is a graph showing the transfer characteristics of Compound 4.
  • 3,9-Dibromocarbazole (1.0 g, 2.4 mmol) was dissolved in a 250 mL three-necked flask containing 40 mL of dimethyl sulfoxide, and a 50% potassium hydroxide solution (1.4 mL) was added. Tetrabutylammonium bromide (77 mg, 0.24 mmol) was stirred under a nitrogen atmosphere for 30 min then cetyl bromide (2.2 g, 7.2 mmol). The reaction was warmed to 65 ° C and reacted for 4 h. The reaction was then cooled to room temperature and poured into 300 mL of methanol and stirred. After suction filtration and washing with N,N-dimethylformamide, methanol and acetone for 1-3 times, finally, 1.5 g of a pale yellow powdery solid was obtained, yield 72%.
  • FIG. 2 FIG. 3, FIG. 4, FIG. 5, FIG. 6, FIG. 7, and FIG. 8 are respectively a differential scanning calorimetry curve, a thermogravimetric analysis curve, a solution absorption spectrum, and a film absorption of the compound 4.
  • compound 4 has relatively high thermal stability and the thermal decomposition temperature is close to 400 ° C.
  • the optical performance characterization indicates that compound 4 is a comparative wide band gap macromolecule and is a polar compound in a polar solvent. Weak solvent polarization effect; electrochemical characterization of surface compound 4 has a minimum non-occupied orbital energy level close to -5.0 eV; characterized by organic field effect transistor, the hole mobility of the compound exceeds 0.1 cm 2 ⁇ per volt per second .
  • the indole (254 mg, 1.0 mmol) was added to a 150 mL three-necked flask and dissolved in 60 mL of anhydrous tetrahydrofuran. At this time, the temperature of the reaction solution was lowered to -78 ° C, and the temperature was stabilized and then slowly added 2.4 M n- BuLi (4.2 mL, 10 mmol) was then incubated for 2 h, then 1-bromooctane (2.9 g, 15 mmol) was added in one portion and allowed to react overnight. The reaction was stopped, and the reaction solution was concentrated, then extracted with dichloromethane and washed with water 2-3 times. The column was passed through a column. The eluent was in the form of petroleum ether/dichloromethane (5:1 by volume), followed by ethanol. Recrystallization gave a white solid (390 mg, 0.56 mmol).
  • the field effect transistor was prepared and the field effect properties of the compound were measured.
  • the device was top-touch type, with gold as the source and drain, and the specific device structure was Al/AlO x :Nd/PMMA/ICzBT/Au.
  • a layer of aluminum is sputtered on the surface of the glass as a gate electrode, and at the same time, an aluminum oxide is plated as a gate insulating layer in the performance of aluminum (the preparation of the above substrate is completed by a manufacturer and can be directly purchased commercially). Due to the rough surface of the alumina, it is not conducive to the film formation of the compound.
  • a layer of polymethyl methacrylate (PMMA is prepared on the surface of the gate insulating layer, and a n-butyl acetate solution of 3% by mass is prepared.
  • the rotation speed is 2000 rpm
  • the film thickness is 130 nm
  • the annealing is performed at 220 ° C for 30 min in a nitrogen glove box.
  • the interfacial contact is improved, and the compound is formulated into a toluene solution having a mass fraction of 0.7%, and the film is deposited on the PMMA at 2000 rpm (film thickness: 30 to 40 nm) in the air.
  • MoO 3 molybdenum oxide
  • Gold plating is used as the source and drain of the device.
  • the device was tested in an atmosphere with a humidity of approximately 70% without encapsulation.
  • the prepared transistor device has a long-to-wide channel ratio (W/L) of 500/70 ⁇ m.
  • the photoelectric performance of the transistor was tested on a semiconductor parameter analyzer (Aglient 4155C) and a step meter with a test atmosphere at room temperature.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Thin Film Transistor (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

本发明涉及一类九元稠环衍生物及其合成方法与应用。本发明通过将五元环单元偶联亚砜基苯单元，并且进行并环反应，获得一类具有九元大环结构的芳香化合物。此类九元稠环化合物具有高热稳定性和高空穴迁移率，能作为活性层应用在有机场效应晶体管器件中，获得高性能和高稳定性的有机场效应晶体管。

Description

一类九元稠环衍生物及其合成方法与应用 技术领域
本发明属于有机光电技术领域，具体涉及一类九元稠环衍生物及其合成方法与应用。
背景技术
有机场效应晶体管的报道最早可以追溯到上世纪80年代，1986年Ando等人用电化学的方法合成了基于聚噻吩单元的p-型半导体材料，但在当时，材料的空穴迁移率只有10-5cm2V-1s-1,电流开关比也只有100(Appl.Phys.Lett.,1986,49(18),1210-1212)。到后来并五苯小分子的出现使得OFET材料的发展有了很大程度的飞跃，Jackson等人在1997年制备出堆砌结构规整的并五苯小分子OFET器件，得到了高达1.5cm2V-1s-1的空穴迁移率和108的开关电流比(IEEE Electr.Device L.,1997,18(12),606-608)。但是，此后更高迁移率的OFET材料的报道比较少见，OFET材料在阈值电压和稳定性方面的报道更加鲜见，因此在提高迁移率，降低阈值电压，增加器件的稳定性方面还有很大的发掘空间。
发明内容
本发明的目的在于针对现有技术的不足，合成了有九元环结构的大共轭平面的小分子有机半导体材料，此类材料具有较高的迁移率，适用于有机场效应晶体管中。
本发明的目的在于提供一种高迁移率的九元稠环类衍生物结构小分子。
本发明的九元稠环衍生物通过闭环反应和氧化反应得到。
本发明的一类九元稠环衍生物，化学结构式如下：
Figure PCTCN2015100035-appb-000001
其中九元稠环形成大共轭平面结构
R1为C1～C30的直链或者支链烷基；
R2为H、C1～C30的直链或者支链烷基、OC1～OC30的直链或者支链烷基；
R3、R4、R5、R6相同或不同，为H、C1～C30的直链或者支链烷基、OC1～OC30的直链或 者支链烷基、F、CF3或
Figure PCTCN2015100035-appb-000002
(其中R7为H、C1～C30的直链或者支链烷基、OC1～OC30的直链或者支链烷基、F或CF3)；
X、Y包括如下组合：X＝S,Y＝O；或者X＝S,Y不含任何元素；
Z＝O、S、Se、N、P、C、Si、Ge或Sn。
所述的一类九元稠环衍生物，合成路线如下：
Figure PCTCN2015100035-appb-000003
其中化合物4和化合物5均为所述九元稠环衍生物；
所述的一类九元稠环衍生物的合成步骤如下：
(1)1摩尔当量烷基化的3,9-二溴五元稠环化合物溶解在二氧六环中，惰性气体环境中加入2～5摩尔当量双频哪醇硼酸酯与5～10摩尔当量的醋酸钾，搅拌，升高温度至50～120℃时加入0.01-0.055摩尔当量的1,1'-双二苯基膦二茂铁二氯化钯反应5～24小时，反应结束后冷却到室温并抽滤，滤液经柱层析提纯后得到产物2；
(2)将1摩尔当量产物2溶于甲苯中，加入2～4摩尔当量的2-溴(甲亚磺酰基)苯，0.05～0.2摩尔当量的四丁基溴化铵以及0.02-0.1摩尔当量的四(三苯基膦)钯，加热回流反应2～24小时，反应结束后，冷却到室温，萃取，干燥，柱层析提纯得到产物3；
(3)将1摩尔当量产物3加入到三氟甲磺酸或者三氟乙酸中，同时加入1.5-4.0摩尔当量的五氧化二磷，密闭条件下室温反应5～24小时，反应结束后将反应液滴加到水中并抽滤，滤渣晾干后在吡啶中加热回流2～12小时，反应结束后萃取、柱层析提纯、重结晶，得到产物4；
(4)将1摩尔当量产物4溶于二氯甲烷中，加入4～30摩尔当量的3-氯过氧苯甲酸，冰浴下反应5～10小时，反应结束后用碱水洗涤，萃取、干燥、柱层析提纯、重结晶，得到九元稠环衍生物小分子产物5。
该类九元稠环衍生物具有高的和稳定的空穴迁移率，其迁移率介于0.1～5.0平方厘米·每伏特·每秒。可以作为活性层在有机场效应晶体管器件中的应用；有机场效应晶体管器件的活性层的厚度为20-1000纳米；所述的有机场效应晶体管器件的活性层是通过溶液加工法实现，包括旋涂、刷涂、喷涂、浸涂、辊涂、丝网印刷、印刷或喷墨打印方法；其中所用溶剂为有机溶剂；所述有机场效应晶体管器件的活性层的制备是在空气中进行。
与现有技术相比，本发明具有的优点与技术效果如下：
提供了一种大稠环类芳香化合物的合成方法；由于并环的引入，增大了分子的刚性和平面性，使分子的共轭性增加，从而不仅可以提高材料的热稳定性也可以提高材料传导空穴能力。目前，绝大多数的有机场效应晶体管材料都是在惰性气体保护的手套箱中制备而得，然而本发明所合成的大稠环类芳香化合物可以在空气中进行制备有机场效应晶体管器件的活性层，而且表现出良好的空穴迁移性能和稳定性。通过本发明的实施，为未来设计和合成高迁移率、低成本和高稳定性的有机场效应管材料提供了一定的指导基础。
附图说明
图1为化合物4差示扫描量热曲线图。
图2为化合物4热重分析曲线图。
图3为化合物4溶液吸收光谱图。
图4为化合物4薄膜的吸收光谱图。
图5为化合物4溶液发射光谱图。
图6为化合物4薄膜发射光谱图。
图7为化合物4循环伏安特性曲线图。
图8为化合物4转移特性曲线图。
具体实施方式
下面结合实施例对本发明所提出的各组分单体进行说明，本发明并不限于此例。
实施例1  3,9-二溴-5,11-双十六烷基吲哚咔唑(1)的合成
Figure PCTCN2015100035-appb-000004
将3,9-二溴吲哚咔唑(1.0g,2.4mmol)溶解在盛有40mL二甲基亚砜的250mL三口烧瓶中，同时加入质量分数为50％的氢氧化钾溶液(1.4mL)和四丁基溴化铵(77mg,0.24mmol)，氮气气氛中搅拌30min之后加入十六烷基溴(2.2g,7.2mmol)。反应升温到65℃并反应4h。之后将反应冷却到室温倒入到300mL甲醇中搅拌。抽滤并用N,N-二甲基甲酰胺、甲醇和丙酮洗涤1-3次，最终得到淡黄色粉末状固体1.5g，产率72％。
实施例2  3,9-双(4,4,5,5-四甲基-1,3,2-二氧硼戊环-2-基)-5,11-双十六烷基吲哚咔唑(2)的合成
Figure PCTCN2015100035-appb-000005
将3,9-二溴-5,11-双十六烷基吲哚咔唑(1.0g,1.1mmol)，醋酸钾(1.08g，11mmol)和双频哪醇硼酸酯(0.9g,3.5mmol)溶解在装有50mL二氧六环的100mL三口圆底烧瓶中并在氮气气氛中搅拌。温度升至80℃时快速加入1,1'-双二苯基膦二茂铁二氯化钯(40mg,0.055mmol)。反应进行24h之后冷却到室温并抽滤。滤液初产物用硅胶/二氯甲烷柱层析得到黄色针状晶体0.7g，产率63％。
实施例3  3,9-二(2-甲亚磺酰苯基)-5,11-双十六烷基吲哚咔唑(3)的合成
Figure PCTCN2015100035-appb-000006
将10mL 2M的K2CO3溶液，3,9-双(4,4,5,5-四甲基-1,3,2-二氧硼戊环-2-基)-5,11-双十六烷基吲哚咔唑(2.0g,2.1mmol)和2-溴(甲亚磺酰基)苯(1.42g,6.5mmol)溶解于100mL甲苯溶液中，同时加入四(三苯基膦)钯(100mg)和四丁基溴化铵(60mg)，反应加热回流24h。之后将反应冷却到室温并用二氯甲烷萃取。有机相干燥，减压蒸馏并用硅胶，乙酸乙酯 /石油醚(体积比为1:2)为流动相进行柱层析，得到黄色粘稠油状液体(1.25g，61％)。
实施例4  5,11-双十六烷基二[2-b,3；8-b,9]苯并[d]噻吩吲哚[3,2-b]咔唑(4)的合成
Figure PCTCN2015100035-appb-000007
3,9-二(2-甲亚磺酰苯基)-5,11-双十六烷基吲哚咔唑(2.1g,2.2mmol)加入到15mL三氟甲磺酸，并加入1.0g五氧化二磷。反应室温下搅拌24h，之后将反应液缓慢滴加到冰水中，抽滤并干燥滤渣得到淡黄色粉末固体。将淡黄色粉末溶解到100mL吡啶中，氮气气氛中加热回流12h脱甲基。之后将反应冷却到室温，用盐酸中和并用二氯甲烷萃取，粗产物用硅胶，石油醚/二氯甲烷(体积比为2:1)为流动相进行层析柱，再用乙酸乙酯重结晶得到黄色粉末状固体(0.8g，40％)。图1、图2、图3、图4、图5、图6、图7、图8分别为化合物4的差示扫描量热曲线图、热重分析曲线图、溶液吸收光谱图、薄膜的吸收光谱图、溶液发射光谱图、薄膜发射光谱图、循环伏安特性曲线图和转移特性曲线图。通过测试可以得知，化合物4具有比较高的热稳定性，热分解温度接近400摄氏度；光学性能表征表明化合物4为比较宽带隙大分子，并且为若极性化合物，在极性溶剂中具有比较弱的溶剂极化效应；电化学表征表面化合物4的最低非占有轨道能级接近于-5.0电子伏特；通过有机场效应晶体管表征，化合物的空穴迁移率超过0.1平方厘米·每伏特·每秒。
实施例5  5,11-双十六烷基二[2-b,3；8-b,9]苯并[d]-S,S-二氧噻吩吲哚[3,2-b]咔唑(5)的合成
Figure PCTCN2015100035-appb-000008
将5,11-双十六烷基二[2-b,3；8-b,9]苯并[d]噻吩吲哚[3,2-b]咔唑(156mg,0.17mmol)和3-氯过氧苯甲酸(570mg,3.3mmol)溶解于10mL二氯甲烷中并在冰浴条件下搅拌10h。之后将反应液倒入冷的10％质量浓度的氢氧化钠水溶液中搅拌30min，萃取、干燥。有机层用水洗(150mL×3)，浓缩并过层析柱，洗脱剂极性为二氯甲烷/四氢呋喃(体积比为10:1)，之后用 乙醇重结晶得到淡黄色粉末(117mg,70％)。
实施例6  6,6’,12,12’-四辛基茚并芴(6)的合成
Figure PCTCN2015100035-appb-000009
将茚并芴(254mg,1.0mmol)加入到150mL三口长颈瓶中，并加入60mL无水四氢呋喃溶解，此时将反应液的温度降到-78℃，温度稳定后缓慢滴加2.4M n-BuLi(4.2mL,10mmol)，之后保温2h，一次性加入1-溴辛烷(2.9g,15mmol)并反应过夜。停止反应，将反应液浓缩，之后用二氯甲烷萃取并用水洗2-3次，过层析柱，洗脱剂极性为石油醚/二氯甲烷(体积比为5:1)，之后用乙醇重结晶得到白色固体(390mg,0.56mmol)，产率56％。
实施例7  2,8-二溴-6,6’,12,12’-四辛基茚并芴(7)的合成
Figure PCTCN2015100035-appb-000010
将溴化铜(10g,44.8mmol)稀释在100mL水中，并加入中兴氧化铝粉末(20g)，搅拌均匀后将水分减压蒸馏，最终可以得到棕色粉末备用。将6,6’,12,12’-四辛基茚并芴(0.7g,1mmol)溶解于30mL四氯化碳溶液中，并加入制备好的棕色粉末3g，加热回流10h即可。之后停止反应并冷却到室温，将反应液抽滤并用四氯化碳萃取滤液，过层析柱，洗脱剂极性石油醚/二氯甲烷(体积比为6:1)，最终得到白色粉末(516mg,60％)。
实施例8  2,8-二(4,4,5,5-四甲基-1,3,2-二氧硼戊环-2-基)-6,6’,12,12’-四辛基茚并芴(8)的合成
Figure PCTCN2015100035-appb-000011
将2,8-二溴-6,6’,12,12’-四辛基茚并芴(0.86g,1.0mmol)，醋酸钾(0.93g,10mmol)和双频哪醇硼酸酯(0.9g,3.5mmol)溶解在装有50mL二氧六环的100mL三口圆底烧瓶中并在氮气气氛中搅拌。温度升至80℃时快速加入1,1'-双二苯基膦二茂铁二氯化钯(40mg,0.055 mmol)。反应进行24h之后冷却到室温并抽滤。滤液初产物用硅胶/二氯甲烷柱层析，之后用甲醇重结晶得到白色固体(477mg,50％)。
实施例9  2,8-二(2-甲亚磺酰苯基)-6,6’,12,12’-四辛基茚并芴(9)的合成
Figure PCTCN2015100035-appb-000012
将10mL 2M的K2CO3溶液，2,8-二(4,4,5,5-四甲基-1,3,2-二氧硼戊环-2-基)-6,6’,12,12’-四辛基茚并芴(0.96g,1.0mmol)和2-溴(甲亚磺酰基)苯(660mg,3.0mmol)溶解于100mL甲苯溶液中，同时加入四(三苯基膦)钯(70mg)和四丁基溴化铵(40mg)，反应加热回流24h。之后将反应冷却到室温并用二氯甲烷萃取。有机相干燥，减压蒸馏并用硅胶，乙酸乙酯/石油醚(体积比为1:2)为流动相进行柱层析得到黄色固体(0.6g，61％)。
实施例10  6,6’,12,12’-四辛基二[2,3-b；8,9-b]苯并[d]噻吩茚并芴(10)的合成
Figure PCTCN2015100035-appb-000013
2,8-二(2-甲亚磺酰苯基)-6,6’,12,12’-四辛基茚并芴(0.98g,1.0mmol)加入到5mL三氟甲磺酸，并加入0.5g五氧化二磷。反应室温下搅拌24h，之后将反应液缓慢滴加到冰水中，抽滤并干燥滤渣得到淡黄色粉末固体。将淡黄色粉末溶解到50mL吡啶中，氮气气氛中加热回流12h脱甲基。之后将反应冷却到室温，用盐酸中和并用二氯甲烷萃取，有机相粗产物过层析柱，洗脱剂极性石油醚/二氯甲烷(体积比为3:1)，再用乙醇重结晶得到白色粉末状固体(0.36g,40％)。
实施例11  6,6’,12,12’-四辛基二[2,3-b；8,9-b]苯并[d]-S,S-二氧噻吩茚并芴(11)的合成
Figure PCTCN2015100035-appb-000014
将6,6’,12,12’-四辛基二[2,3-b；8,9-b]苯并[d]噻吩茚并芴(0.92g,1.0mmol)和3-氯过氧苯甲酸(3.46g,20mmol)溶解于100mL二氯甲烷中并在冰浴条件下搅拌10h。之后将反应液倒入冷的10％质量浓度的氢氧化钠水溶液中搅拌30min。有机层用水洗(150mL×3)，浓缩并过层析柱，洗脱剂极性为二氯甲烷/四氢呋喃(体积比为10:1)，之后用乙醇重结晶得到淡黄色粉末(0.69g,70％)。
实施例12  5,5’,7,7’-四甲基苯并[b][1]苯并噻咯[3,2-f][1]苯并噻咯(12)的合成
Figure PCTCN2015100035-appb-000015
将2,2”,4’,6’-四溴-1,1’:3’,1”-邻三联苯(546mg,1.0mmol)加入到250mL长颈瓶中，用无水乙醚(300毫升)溶解，降温到0℃，缓慢滴加2.4M n-BuLi(4.2mL,10mmol),保温2h，将二甲基二氯硅烷(1.94g,15mmol)用10mL正己烷稀释并加入到反应液中，室温下反应12h。停止反应，反应液用二氯甲烷萃取并水洗，以石油醚/二氯甲烷(体积比为1:1)为流动相过层析柱，得到白色固体(137mg,40％)。
实施例13  3,9-二溴-5,5’,7,7’-四甲基苯并[b][1]苯并噻咯[3,2-f][1]苯并噻咯(13)的合成
Figure PCTCN2015100035-appb-000016
将5,5’,7,7’-四甲基苯并[b][1]苯并噻咯[3,2-f][1]苯并噻咯(0.34g,1.0mmol)溶解在50mL四氢呋喃中，冰浴条件下缓慢滴加液溴(0.3mL,5.0mmol)，反应8h后停止反应。将反应液浓缩，用二氯甲烷萃取并水洗，之后用乙醇重结晶得到粗产物(0.25g,50％)。
实施例14  3,9-二(4,4,5,5-四甲基-1,3,2-二氧硼戊环-2-基)-5,5’,7,7’-四甲基苯并[b][1]苯并噻咯[3,2-f][1]苯并噻咯(14)的合成
Figure PCTCN2015100035-appb-000017
将3,9-二溴-5,5’,7,7’-四甲基苯并[b][1]苯并噻咯[3,2-f][1]苯并噻咯(0.5g,1.0mmol)，醋 酸钾(0.93g,10mmol)和双频哪醇硼酸酯(1.02g,4mmol)溶解在装有50mL二氧六环的100mL三口圆底烧瓶中并在氮气气氛中搅拌。温度升至80℃时快速加入1,1'-双二苯基膦二茂铁二氯化钯(40mg,0.055mmol)。反应进行24h之后冷却到室温并抽滤。滤液初产物用硅胶/二氯甲烷柱层析，之后用甲醇重结晶得到淡黄色固体(226mg,38％)。
实施例15  3,9-二(2-甲亚磺酰苯基)-5,5’,7,7’-四甲基苯并[b][1]苯并噻咯[3,2-f][1]苯并噻咯(15)的合成
Figure PCTCN2015100035-appb-000018
将10mL 2M的K2CO3溶液，3,9-二(4,4,5,5-四甲基-1,3,2-二氧硼戊环-2-基)-5,5’,7,7’-四甲基苯并[b][1]苯并噻咯[3,2-f][1]苯并噻咯(1.20g,2.0mmol)和2-溴(甲亚磺酰基)苯(1.31g,6.0mmol)溶解于100mL甲苯溶液中，同时加入四(三苯基膦)钯(100mg)和四丁基溴化铵(50mg)，反应加热回流24h。之后将反应冷却到室温并用二氯甲烷萃取。有机相干燥，减压蒸馏并用硅胶，乙酸乙酯/石油醚(体积比为1:1)为流动相进行柱层析，得到淡黄色固体(0.7g，56％)。
实施例16  5,5’,7,7’-四甲基二[2-b,3；9,10-b]苯并[d]噻吩苯并[b][1]苯并噻咯[3,2-f][1]苯并噻咯(16)的合成
Figure PCTCN2015100035-appb-000019
3,9-二(2-甲亚磺酰苯基)-5,5’,7,7’-四甲基苯并[b][1]苯并噻咯[3,2-f][1]苯并噻咯(1.24g,2.0mmol)加入到8mL三氟甲磺酸，并加入0.5g五氧化二磷。反应室温下搅拌24h，之后将反应液缓慢滴加到冰水中，抽滤并干燥滤渣得到淡黄色粉末固体。将淡黄色粉末溶解到100mL吡啶中，氮气气氛中加热回流8h脱甲基。之后将反应冷却到室温，用盐酸中和并用二氯甲烷萃取，有机相粗产物过层析柱，洗脱剂极性石油醚/二氯甲烷(体积比为1:1)，再用乙醇重结晶得到白色粉末状固体(0.67g,60％)。
实施例17场效应晶体管器件制备
制备场效应晶体管并对化合物的场效应性能进行测定，器件为顶触型，用金作为源极和 漏极，具体器件结构为Al/AlOx:Nd/PMMA/ICzBT/Au。以玻璃作为基板，在玻璃表面溅射一层铝作为栅极，同时在铝的表现镀一层氧化铝作为栅绝缘层(以上基板的制备有厂商完成，可直接商业购买)。由于氧化铝的表面较为粗糙，不利于化合物的成膜，因此在栅绝缘层表面旋涂一层聚甲基丙烯酸甲酯(PMMA，配成质量分数为3％的乙酸正丁酯溶液，甩膜转速2000rpm，膜厚130nm，氮气手套箱中220℃退火处理30min)改善界面接触，将化合物配制成质量分数0.7％的甲苯溶液，2000rpm转速在PMMA上甩膜(膜厚30～40nm)，空气中100℃退火处理10min，之后在3×10-4Pa的真空度中蒸镀一层氧化钼(MoO3，蒸镀速率0.01～0.05nm/s，膜厚约45nm)，然后在同样条件下蒸镀金作为器件的源极和漏极。器件在没有包封情况下在湿度约为70％的大气环境中进行测试。制备的晶体管器件长宽沟道比(W/L)为500/70μm。晶体管的光电性能在半导体参数分析仪(Aglient 4155C)和台阶仪上进行测试，测试环境为室温大气气氛。
本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明权利要求的保护范围之内。

Claims (8)

  1. 一类九元稠环衍生物，其特征在于，该九元稠环衍生物的化学结构式如下：
    Figure PCTCN2015100035-appb-100001
    其中九元稠环形成大共轭平面结构，
    R1为C1～C30的直链烷基或C1～C30的支链烷基；
    R2为H、C1～C30的直链烷基、C1～C30的支链烷基、OC1～OC30的直链烷基或OC1～OC30的支链烷基；
    R3、R4、R5、R6相同或不同，为H、C1～C30的直链烷基、C1～C30的支链烷基、OC1～OC30的直链烷基、OC1～OC30的支链烷基、F、CF3或
    Figure PCTCN2015100035-appb-100002
    其中R7为H、C1～C30的直链烷基、C1～C30的支链烷基、OC1～OC30的直链烷基、OC1～OC30的支链烷基、F或CF3；
    X、Y包括如下组合：X＝S,Y＝O；或者X＝S,Y不含任何元素；
    Z＝O、S、Se、N、P、C、Si、Ge或Sn。
  2. 合成权利要求1所述的一类九元稠环衍生物的方法，其特征在于，合成路线如下：
    Figure PCTCN2015100035-appb-100003
    其中化合物4和化合物5均为所述九元稠环衍生物。
  3. 根据权利要求2所述的合成方法，其特征在于，合成步骤如下：
    (1)1摩尔当量烷基化的3,9-二溴五元稠环化合物溶解在二氧六环中，惰性气体环境中加入2～5摩尔当量双频哪醇硼酸酯与5～10摩尔当量的醋酸钾，搅拌，升高温度至50～120℃时加入0.01-0.055摩尔当量的1,1'-双二苯基膦二茂铁二氯化钯反应5～24小时，反应结束后冷却到室温并抽滤，滤液经柱层析提纯后得到产物2；
    (2)将1摩尔当量产物2溶于甲苯中，加入2～4摩尔当量的2-溴(甲亚磺酰基)苯，0.05～0.2摩尔当量的四丁基溴化铵以及0.02-0.1摩尔当量的四(三苯基膦)钯，加热回流反应2～24小时，反应结束后，冷却到室温，萃取，干燥，柱层析提纯得到产物3；
    (3)将1摩尔当量产物3加入到三氟甲磺酸或者三氟乙酸中，同时加入1.5-4.0摩尔当量的五氧化二磷，密闭条件下室温反应5～24小时，反应结束后将反应液滴加到水中并抽滤，滤渣晾干后在吡啶中加热回流2～12小时，反应结束后萃取、柱层析提纯、重结晶，得到产物4；
    (4)将1摩尔当量产物4溶于二氯甲烷中，加入4～30摩尔当量的3-氯过氧苯甲酸，冰浴下反应5～10小时，反应结束后用碱水洗涤，萃取、干燥、柱层析提纯、重结晶，得到九元稠环衍生物小分子产物5。
  4. 根据权利要求1所述的一类九元稠环衍生物，其特征在于，该类九元稠环衍生物具有高的和稳定的空穴迁移率，其迁移率介于0.1～5.0平方厘米·每伏特·每秒。
  5. 权利要求1所述一类九元稠环衍生物作为活性层在有机场效应晶体管器件中的应用。
  6. 根据权利要求5所述的一类九元稠环衍生物作为活性层在有机场效应晶体管器件中的应用，其特征在于：有机场效应晶体管器件的活性层的厚度为20-1000纳米。
  7. 根据权利要求5所述的一类九元稠环衍生物作为活性层在有机场效应晶体管器件中的应用，其特征在于：所述的有机场效应晶体管器件的活性层是通过溶液加工法实现，包括旋涂、刷涂、喷涂、浸涂、辊涂、丝网印刷、印刷或喷墨打印方法；其中溶液加工所用溶剂为有机溶剂。
  8. 根据权利要求5所述的一类九元稠环衍生物作为活性层在有机场效应晶体管器件中的应用，其特征在于：所述有机场效应晶体管器件的活性层的制备是在空气中进行。
PCT/CN2015/100035 2015-08-15 2015-12-31 一类九元稠环衍生物及其合成方法与应用 WO2017028460A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201510504626.0A CN105061463B (zh) 2015-08-15 2015-08-15 一类九元稠环衍生物及其合成方法与应用
CN201510504626.0 2015-08-15

Publications (1)

Publication Number Publication Date
WO2017028460A1 true WO2017028460A1 (zh) 2017-02-23

Family

ID=54491023

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2015/100035 WO2017028460A1 (zh) 2015-08-15 2015-12-31 一类九元稠环衍生物及其合成方法与应用

Country Status (2)

Country Link
CN (1) CN105061463B (zh)
WO (1) WO2017028460A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11453680B2 (en) * 2016-11-25 2022-09-27 Merck Patent Gmbh Bisbenzofuran-fused indeno[1,2-B]fluorene derivatives and related compounds as materials for organic electroluminescent devices (OLED)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105061463B (zh) * 2015-08-15 2018-09-14 华南理工大学 一类九元稠环衍生物及其合成方法与应用
EP3306690B1 (en) * 2016-10-05 2022-09-07 Raynergy Tek Inc. Organic semiconducting compounds
JP7078634B2 (ja) 2016-12-06 2022-05-31 ビーエーエスエフ ソシエタス・ヨーロピア チエノ－インデノ－モノマーおよびポリマー
CN106866940A (zh) * 2017-01-17 2017-06-20 华南理工大学 一种基于3,7‑萘并硫氧芴单元的共轭聚合物及其制备方法与应用
CN106916163A (zh) * 2017-02-28 2017-07-04 华南理工大学 基于芳杂环并‑3‑s,s‑二氧二苯并噻吩单元的双极性小分子发光材料及其制法与应用
CN107987255B (zh) * 2017-11-22 2019-12-03 华南协同创新研究院 含9,9,10,10-四氧-噻蒽五元稠环单元聚合物及其制法与应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007019294A (ja) * 2005-07-08 2007-01-25 Konica Minolta Holdings Inc 有機半導体材料、有機半導体膜、有機半導体素子及び有機薄膜トランジスタ
CN105061463A (zh) * 2015-08-15 2015-11-18 华南理工大学 一类九元稠环衍生物及其合成方法与应用

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1627891A1 (en) * 2004-08-11 2006-02-22 Covion Organic Semiconductors GmbH Polymers for use in organic electroluminescent devices
JP5390959B2 (ja) * 2009-06-30 2014-01-15 ウシオケミックス株式会社 スルホン構造を有する有機半導体化合物

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007019294A (ja) * 2005-07-08 2007-01-25 Konica Minolta Holdings Inc 有機半導体材料、有機半導体膜、有機半導体素子及び有機薄膜トランジスタ
CN105061463A (zh) * 2015-08-15 2015-11-18 华南理工大学 一类九元稠环衍生物及其合成方法与应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
NIIMI, KAZUKI ET AL.: "Dianthra [2, 3-b:2', 3'-f] thieno [3, 2-b] thiophene (DATT): Synthesis, Characterization, and FET Characteristics of New pi-Extendd Heteroarene with Eight Fused Aromatic Rings", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 133, no. 22, 30 April 2011 (2011-04-30), pages 8732 - 8739, XP055364065 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11453680B2 (en) * 2016-11-25 2022-09-27 Merck Patent Gmbh Bisbenzofuran-fused indeno[1,2-B]fluorene derivatives and related compounds as materials for organic electroluminescent devices (OLED)

Also Published As

Publication number Publication date
CN105061463A (zh) 2015-11-18
CN105061463B (zh) 2018-09-14

Similar Documents

Publication Publication Date Title
WO2017028460A1 (zh) 一类九元稠环衍生物及其合成方法与应用
TWI363760B (en) Novel condensed polycyclic aromatic compound, production method thereof, and usage thereof
JP5581596B2 (ja) 有機半導体材料
US9761810B2 (en) Organic semiconductor material
Chen et al. Asymmetric fused thiophenes for field-effect transistors: crystal structure–film microstructure–transistor performance correlations
Kim et al. Functionalized dithieno [2, 3-b: 3′, 2′-d] thiophenes (DTTs) for organic thin-film transistors
JP6310173B2 (ja) 半導体組成物
KR101348436B1 (ko) 테트라티아풀바렌 유도체, 유기막 및 유기 트랜지스터
Dai et al. Diacenopentalene dicarboximides as new n-type organic semiconductors for field-effect transistors
Qiao et al. Incorporation of pyrrole to oligothiophene-based quinoids endcapped with dicyanomethylene: a new class of solution processable n-channel organic semiconductors for air-stable organic field-effect transistors
EP2740735A1 (en) Condensed polycyclic aromatic compound, aromatic polymer, and method for synthesizing aromatic compound
WO2020058203A1 (en) Novel fluorescent pyrene derivatives, methods for preparing the same, and uses thereof
Li et al. Facile synthesis of a pyrrole-fused dibenzo [a, e] pentalene and its application as a new extended, ladder-type fused aromatic system
JP5897050B2 (ja) 有機薄膜トランジスタ、有機半導体薄膜および有機半導体材料
KR20150142043A (ko) 파이-연장된 나프탈렌 디이미드의 제조 및 반도체로서의 그의 용도
KR101956970B1 (ko) 티에노[２，３­ｃ]피롤-디온 유도체 및 유기 반도체에 대한 이들의 용도
JP2013119625A (ja) 半導体組成物
EP3434679B1 (en) Organic compound, organic thin film, and electronic device
JP5335379B2 (ja) 有機半導体材料及びこれを使用する有機電子デバイス
Li et al. High-performance electron-transporting hybrid rylenes with low threshold voltage
JP2014133713A (ja) ジナフトフラン化合物とこれを用いた有機半導体デバイス
Liu et al. Dialkylated dibenzotetrathienoacene derivative as semiconductor for organic field effect transistors
EP2920184B1 (en) Organic semiconductor material
JP2011195566A (ja) 新規ビベンゾ［ｂ］フラン化合物、並びに該化合物を含有してなる有機半導体材料及び有機半導体素子
KR100865703B1 (ko) 아릴아세틸렌 구조의 유기반도체 화합물 및 이를 이용한유기박막트랜지스터

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15901660

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15901660

Country of ref document: EP

Kind code of ref document: A1