WO2017028460A1 - Dérivé à cycle condensé à neuf chaînons, procédé de synthèse associé, et application associée - Google Patents

Dérivé à cycle condensé à neuf chaînons, procédé de synthèse associé, et application associée Download PDF

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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
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Prior art keywords
fused ring
membered fused
alkyl group
effect transistor
reaction
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PCT/CN2015/100035
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English (en)
Chinese (zh)
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张斌
杨勇
杨伟
曹镛
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华南理工大学
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    • 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.

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  • 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

La présente invention concerne un dérivé à cycle condensé à neuf chaînons, un procédé de synthèse associé, et son application. Selon la présente invention, une unité cycle à cinq chaînons est couplée à une unité phényl sulfoxyde pour une réaction de condensation de cycles, de manière à obtenir un composé aromatique avec la structure macrocyclique à neuf chaînons. Le dérivé à cycle condensé à neuf chaînons a une stabilité thermique élevée et une mobilité de trous élevée, et peut servir de couche active appliquée sur un transistor organique à effet de champ, de telle sorte qu'un transistor organique à effet de champ présentant une excellente performance et une stabilité élevée est obtenu.
PCT/CN2015/100035 2015-08-15 2015-12-31 Dérivé à cycle condensé à neuf chaînons, procédé de synthèse associé, et application associée WO2017028460A1 (fr)

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CN201510504626.0 2015-08-15
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

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Cited By (1)

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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)

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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 (fr) * 2016-10-05 2022-09-07 Raynergy Tek Inc. Composés semi-conducteurs organiques
CN110582502A (zh) * 2016-12-06 2019-12-17 巴斯夫欧洲公司 噻吩并-茚并-单体和聚合物
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

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