WO2023179275A1 - Unité cyclique fusionnée à base d'un dérivé de quinoxaline, petite molécule la contenant, polymère, procédés de préparation et utilisation - Google Patents

Unité cyclique fusionnée à base d'un dérivé de quinoxaline, petite molécule la contenant, polymère, procédés de préparation et utilisation Download PDF

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WO2023179275A1
WO2023179275A1 PCT/CN2023/077359 CN2023077359W WO2023179275A1 WO 2023179275 A1 WO2023179275 A1 WO 2023179275A1 CN 2023077359 W CN2023077359 W CN 2023077359W WO 2023179275 A1 WO2023179275 A1 WO 2023179275A1
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carbon atoms
polymer
fused ring
quinoxaline
organic
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彭沣
张天阳
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华南协同创新研究院
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Definitions

  • the invention belongs to the technical field of polymer optoelectronic materials, and specifically relates to fused ring units based on quinoxaline derivatives, small molecules containing the units, polymers, preparation methods and applications.
  • organic optoelectronic devices As a new type of thin-film photovoltaic cell technology, organic optoelectronic devices have outstanding advantages such as all-solid state, wide adjustable range of photovoltaic material properties, translucency, flexible cells, and large-area low-cost preparation potential.
  • the photovoltaic performance of organic materials has a wide adjustable range, and chemical means can be used to effectively regulate the energy level, carrier mobility, absorption and other properties of the material.
  • Organic/polymer photovoltaic devices can be processed by methods such as printing and printing. Large-area, flexible thin-film photovoltaic devices can be manufactured through roll-to-roll processing using traditional plastic processing techniques. This production process can effectively reduce the cost of photovoltaic cells. manufacturing cost.
  • Organic photovoltaic devices are almost not subject to environmental and site restrictions.
  • optoelectronic materials containing quinoxaline and its derivatives have been widely used in materials such as organic electroluminescence, organic solar cells, chemical and biological sensors, and organic field-effect transistors.
  • materials such as organic electroluminescence, organic solar cells, chemical and biological sensors, and organic field-effect transistors.
  • quinoxaline and its derivatives after fused cyclization of quinoxaline and its derivatives, it has a structure in which two quinoxalines are connected. Therefore, it not only has the basic advantages of quinoxaline and its derivatives, but also It has a larger rigid plane and stronger electron deficiency.
  • quinoxaline and its derivatives also have some special properties after fused cyclization.
  • the present invention designs and synthesizes a series of fused ring units containing quinoxaline derivatives, and uses them in organic optoelectronic devices, showing good carrier mobility and device efficiency.
  • the object of the present invention is to provide a class of quinoxaline derivative-based Fused ring units and small molecules and polymers containing them.
  • the fused ring unit based on quinoxaline derivatives has a large conjugation plane and strong electron attraction.
  • Another object of the present invention is to provide small molecules containing the above-mentioned fused ring units based on quinoxaline derivatives; small molecules and polymers based on this monomer have narrower band gaps and wider absorption spectra, and the spectra are easy to pass through The structure is adjusted; at the same time, this type of small molecules and polymers also have high carrier mobility, which is beneficial to improving the external quantum efficiency of the polymer.
  • Another object of the present invention is to provide a polymer containing the above-mentioned fused ring unit based on the quinoxaline derivative.
  • Another object of the present invention is to provide a method for preparing the above-mentioned fused ring unit based on quinoxaline derivatives.
  • Another object of the present invention is to provide a method for preparing the above-mentioned small molecule containing a fused ring unit based on a quinoxaline derivative.
  • Another object of the present invention is to provide a method for preparing the above-mentioned polymer containing fused ring units based on quinoxaline derivatives.
  • Another object of the present invention is to provide the application of the above-mentioned small molecules and polymers containing fused ring units based on quinoxaline derivatives in organic/polymer electronic devices.
  • X and Y are each one of O, S, and Se;
  • R is an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms, or an aromatic heterocyclic group having 3 to 60 carbon atoms.
  • R is an alkyl group with 5 to 20 carbon atoms, a cycloalkyl group with 8 to 20 carbon atoms, an aromatic hydrocarbon group with 10 to 40 carbon atoms, or an aromatic heterocyclic ring with 10 to 40 carbon atoms. base.
  • the small molecule containing the fused ring unit based on the quinoxaline derivative has the following general formula:
  • Ar 1 and Ar 2 are each H, D, F, CN, alkenyl, alkynyl, amine, nitro, acyl, alkoxy, carbonyl, aromatic hydrocarbon group with 6 to 100 carbon atoms or carbon atoms.
  • aromatic heterocyclic groups with a number of 3 to 100.
  • the definitions of X, Y and R are the same as above.
  • the polymer containing the fused ring unit based on the quinoxaline derivative has a chemical structural formula that satisfies the following general formula:
  • x and y are the mole fractions of each unit, where 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1; n is the number of repeating units, n is an integer in the range of 2 to 1000; the definitions of X, Y and R are as follows: Same as above.
  • Ar 3 is an aromatic hydrocarbon group having 6 to 100 carbon atoms or an aromatic heterocyclic group having 3 to 100 carbon atoms.
  • fused ring unit based on quinoxaline derivatives is preferably the following structure or a halogenated, deuterated or alkyl substituted derivative of the following structure:
  • R is the same as above.
  • the Ar 1 and Ar 2 units are preferably the following structures or the halogenated, deuterated, or alkyl substituted derivatives of the following structures. one or more:
  • R 1 is an alkyl group with 1 to 30 carbon atoms, a cycloalkyl group with 3 to 30 carbon atoms, an aromatic hydrocarbon group with 6 to 60 carbon atoms, or an aromatic heterocyclic group with 3 to 60 carbon atoms.
  • R 1 is an alkyl group with 5 to 20 carbon atoms, a cycloalkyl group with 8 to 20 carbon atoms, an aromatic hydrocarbon group with 10 to 40 carbon atoms, or an aromatic hetero group with 10 to 40 carbon atoms.
  • ring base is an alkyl group with 1 to 30 carbon atoms, a cycloalkyl group with 3 to 30 carbon atoms, an aromatic hydrocarbon group with 6 to 60 carbon atoms, or an aromatic heterocyclic group with 3 to 60 carbon atoms.
  • R 1 is an alkyl group with 5 to 20 carbon atoms, a cycloalkyl group with 8 to 20 carbon atoms, an aromatic hydrocarbon group with 10 to 40 carbon atoms, or an aromatic hetero group
  • the Ar 3 unit is preferably one of the following structure or a halogenated, deuterated, or alkyl substituted derivative of the following structure or Various:
  • R 1 is an alkyl group with 1 to 30 carbon atoms, a cycloalkyl group with 3 to 30 carbon atoms, an aromatic hydrocarbon group with 6 to 60 carbon atoms, or an aromatic heterocyclic group with 3 to 60 carbon atoms.
  • R 1 is an alkyl group with 5 to 20 carbon atoms, a cycloalkyl group with 8 to 20 carbon atoms, an aromatic hydrocarbon group with 10 to 40 carbon atoms, or an aromatic hetero group with 10 to 40 carbon atoms.
  • ring base is an alkyl group with 1 to 30 carbon atoms, a cycloalkyl group with 3 to 30 carbon atoms, an aromatic hydrocarbon group with 6 to 60 carbon atoms, or an aromatic heterocyclic group with 3 to 60 carbon atoms.
  • R 1 is an alkyl group with 5 to 20 carbon atoms, a cycloalkyl group with 8 to 20 carbon atoms, an aromatic hydrocarbon group with 10 to 40 carbon atoms, or an aromatic hetero group
  • the present invention also provides a method for preparing the above-mentioned fused ring unit based on quinoxaline derivatives, including the following steps:
  • the carboxyl-containing quinoxaline is acid chlorinated to obtain a quinoxaline intermediate containing an acid chloride group; then the quinoxaline intermediate containing an acid chloride group is catalyzed by aluminum trichloride.
  • An electrophilic substitution reaction occurs with aromatic compounds to form fused ring units based on quinoxaline derivatives.
  • the invention also provides a method for preparing small molecules containing fused ring units based on quinoxaline derivatives, which includes the following steps: under the protection of inert gas, combine brominated fused ring unit monomers based on quinoxaline derivatives with alkane Tin-substituted Ar 1 and Ar 2 undergo Stille coupling under the conditions of catalyst tetrakis(triphenylphosphine)palladium and/or tris(dibenzylideneacetone)dipalladium/tris(o-methylphenylphosphine) The reaction yields small molecules containing fused ring units based on quinoxaline derivatives.
  • the present invention also provides a method for preparing a polymer containing a fused ring unit based on a quinoxaline derivative, which includes the following steps:
  • the Ar 3 unit monomer containing the dialkyl tin functional group and the dibromo-condensed ring unit monomer based on the quinoxaline derivative are dissolved in the solvent, and then the catalyst is added to perform Stille polymerization to obtain target product.
  • the organic solvent includes but is not limited to at least one of toluene, tetrahydrofuran, xylene, chlorobenzene, and dichlorobenzene;
  • the Stille polymerization catalyst includes but is not limited to at least one of tetrakis(triphenylphosphine)palladium, tris(dibenzylideneacetone)dipalladium/tris(o-methylphenylphosphine).
  • the temperature of the Stille polymerization reaction is 60 to 180°C, and the reaction time is 0.5 to 36 hours.
  • the amount of the Ar 3 unit monomer containing dialkyl tin functional groups and the bis-brominated fused ring unit monomer based on quinoxaline derivatives satisfies the total mole of the monomers containing dialkyl tin functional groups.
  • the amount is equal to the total molar amount of monomers containing dibromo functional groups; the amount of the catalyst is 2 ⁇ 3% of the total molar amount of reaction monomers;
  • the obtained product can be purified, specifically by cooling the obtained reaction liquid to At room temperature, add dropwise to stirring methanol to precipitate, filter, and dry to obtain a crude product.
  • the crude product is extracted with methanol, acetone, dichloromethane, chloroform, and chlorobenzene, concentrated, and precipitated again in a methanol solution, filtered, and dried. , get the target product.
  • alkyl tin thiophene can be added, and the reaction can be continued with insulation for 6 to 12 hours; bromothiophene can then be added to continue the reaction with insulation for 6 to 12 hours;
  • the amount of alkyltin thiophene is 10 to 40% of the total molar amount of reaction monomers, and the amount of bromothiophene is 1 to 20 times the molar amount of alkyltin thiophene.
  • the invention also provides applications of small molecules and polymers containing fused ring units based on quinoxaline derivatives in the preparation of organic/polymer electronic devices, including organic/polymer photodetectors, organic/polymer solar cells, Applications in organic/polymer thin film transistors, organic/polymer light-emitting transistors, organic/polymer phototransistors, and organic/polymer organic light-emitting electrochemical cells.
  • the application of the small molecules and polymers containing fused ring units based on quinoxaline derivatives in the preparation of organic/polymer electronic devices includes the following steps: converting the small molecules and polymers containing fused ring units based on quinoxaline derivatives
  • the small molecules and polymers of fused ring units are dissolved in organic solvents, or mixed with at least one other organic small molecules or polymers and dissolved in organic solvents, and then formed into films by spin coating, inkjet printing or printing to obtain the organic /Active layer of polymer electronic devices.
  • organic solvents include but are not limited to xylene, tetrahydrofuran, chlorobenzene, and dichlorobenzene.
  • the present invention has the following advantages and technical effects:
  • This type of polymer absorbs in a wide spectral range of 300 to 1000 nm, and the absorption spectrum is easily adjusted by the type and content of the polymer unit;
  • This type of polymer has high electron mobility, which is beneficial to the preparation of high-efficiency organic electronic devices, especially organic/polymer photodetectors.
  • Figure 1 shows the absorption spectra of polymer P1, IEICO-4F and P1:IEICO-4F mixed films in the examples.
  • Figure 2 is an example of the external quantum efficiency curve of the polymer photodetector device based on P1:IEICO-4F under 0V bias.
  • the reagents used in the examples can all be purchased from the market unless otherwise specified.
  • compound 4 (10 mmol) and compound 5 (22 mmol) were dissolved in 100 ml of anhydrous dichloromethane.
  • Aluminum trichloride 50 mmol was added to the reaction solution in three batches under an ice-water bath, and the reaction was carried out at room temperature for 2 hours. After the reaction is completed, 500 ml of ice water is slowly poured into the reaction to quench the reaction, the product is extracted with ethyl acetate, and washed three times with saturated aqueous sodium chloride solution.
  • compound 4 (10 mmol) and compound 7 (22 mmol) were dissolved in 100 ml of anhydrous dichloromethane.
  • Aluminum trichloride 50 mmol was added to the reaction solution in three batches under an ice-water bath, and the reaction was carried out at room temperature for 2 hours. After the reaction is completed, 500 ml of ice water is slowly poured into the reaction to quench the reaction, the product is extracted with ethyl acetate, and washed three times with saturated aqueous sodium chloride solution.
  • compound 4 (10 mmol) and compound 7 (22 mmol) were dissolved in 100 ml of anhydrous dichloromethane.
  • Aluminum trichloride 50 mmol was added to the reaction solution in three batches under an ice-water bath, and the reaction was carried out at room temperature for 2 hours. After the reaction is completed, 500 ml of ice water is slowly poured into the reaction to quench the reaction, the product is extracted with ethyl acetate, and washed three times with saturated aqueous sodium chloride solution.
  • the reaction solution is precipitated in methanol, and the polymer obtained by filtration is subjected to Soxhlet extraction with methanol, acetone, methylene chloride, chloroform, and chlorobenzene.
  • the obtained chlorobenzene solution was concentrated, precipitated in methanol again, filtered, and dried to obtain a black fibrous polymer. 1 H NMR and elemental analysis results showed that the obtained The compound is the target product.
  • reaction and purification methods of polymer P2 are similar to those of polymer P1, and a black fibrous polymer is obtained. 1 H NMR and elemental analysis results showed that the obtained compound was the target product.
  • the reaction equation is as follows:
  • compound 18 (0.12mmol), 2,5-bis(trimethyltin)thiophene (0.08mmol), and compound 6 (0.2mmol) were dissolved in 5 mL of anhydrous chlorobenzene, and then tris(dibenzylidene) acetone) dipalladium (3 mg) and tris(o-methylphenyl)phosphorus (6 mg). React at 140°C for 24 hours, and use 2-(tributyltin)thiophene (20 mg) for the first time End-capping, and after reacting for 6 hours, 2-bromothiophene (30 mg) was used for the second end-capping, and the reaction was continued for 6 hours.
  • compound 18 (0.12mmol), compound 14 (0.08mmol), and compound 6 (0.2mmol) were dissolved in 5 mL of anhydrous chlorobenzene, followed by tris(dibenzylideneacetone) dipalladium (3 mg) and tris( o-methylphenyl)phosphorus (6 mg).
  • the reaction was carried out at 140°C for 24 hours, and 2-(tributyltin)thiophene (20 mg) was used for the first blocking. After 6 hours of reaction, 2-bromothiophene (30 mg) was used for the second blocking, and the reaction was continued for 6 hours.
  • reaction solution is precipitated in methanol, and the polymer obtained by filtration is subjected to Soxhlet extraction with methanol, acetone, methylene chloride, chloroform, and chlorobenzene.
  • the obtained chlorobenzene solution was concentrated, precipitated in methanol again, filtered, and dried to obtain a black fibrous polymer. 1 H NMR and elemental analysis results showed that the obtained compound was the target product.
  • the reaction equation is as follows:
  • ITO indium tin oxide
  • PEDOT:PSS polyethoxythiophene film doped with polystyrene sulfonic acid was spin-coated on ITO with a thickness of 40 nm.
  • Figure 2 is the external quantum efficiency curve of the polymer photodetector device based on P1:IEICO-4F under 0V bias. It can be seen from the figure that the device has corresponding response in the wide band range of 300-1000nm and has a high External quantum efficiency.

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Abstract

La présente invention concerne une unité cyclique fusionnée basée sur un dérivé de quinoxaline, une petite molécule la contenant, un polymère, des procédés de préparation associés et une utilisation correspondante. Dans la présente invention, une nouvelle unité aromatique ayant une grande structure cyclique fusionnée est construite sur la base d'un dérivé de quinoxaline ; et une série de petites molécules et de copolymères sont construites au moyen d'une unité cyclique fusionnée sur la base d'un dérivé de quinoxaline, et les petites molécules et polymères préparés ont une large plage d'absorption spectrale et une mobilité de porteurs élevée. Les petites molécules et les polymères qui sont basés sur l'unité cyclique fusionnée sur la base d'un dérivé de quinoxaline peuvent être utilisés en tant que couches actives et utilisés dans des dispositifs électroniques organiques/polymères tels que des détecteurs photoélectriques organiques/polymères et des cellules solaires organiques/polymères.
PCT/CN2023/077359 2022-03-23 2023-02-21 Unité cyclique fusionnée à base d'un dérivé de quinoxaline, petite molécule la contenant, polymère, procédés de préparation et utilisation WO2023179275A1 (fr)

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