CN110627602A - Organic photoelectric semiconductor material and synthesis method and application thereof - Google Patents

Organic photoelectric semiconductor material and synthesis method and application thereof Download PDF

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CN110627602A
CN110627602A CN201810653830.2A CN201810653830A CN110627602A CN 110627602 A CN110627602 A CN 110627602A CN 201810653830 A CN201810653830 A CN 201810653830A CN 110627602 A CN110627602 A CN 110627602A
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naphthalene
semiconductor material
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胡文平
李金峰
郑磊
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Tianjin University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/20—Polycyclic condensed hydrocarbons
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    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
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    • C07F7/0803—Compounds with Si-C or Si-Si linkages
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    • C07F7/083—Syntheses without formation of a Si-C bond
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • 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
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
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    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
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Abstract

The invention discloses an organic photoelectric semiconductor material and a synthesis method and application thereof. The organic photoelectric semiconductor material is 2, 7-dianthracene naphthalene, 2, 7-bis (9, 10-triisopropylsilylethynyl anthracene group) naphthalene or 2, 7-bis (6-sunflower anthracene group) naphthalene. The synthesis method of the organic photoelectric semiconductor material comprises the following steps: in an inert gas environment, uniformly mixing a reactant A, a reactant B, palladium tetrakis (triphenylphosphine) as a catalyst, toluene and a potassium carbonate aqueous solution, heating to 90-100 ℃ after mixing, reacting for 24-96 hours, filtering to obtain filter residues, and washing the filter residues with a detergent to obtain the organic photoelectric semiconductor material, wherein the preparation reaction route provided by the invention has the advantages of simplicity, high efficiency, environmental friendliness, low raw material price and low synthesis cost; the method has high universality and good repeatability; the invention provides a new choice for high-performance organic semiconductor materials.

Description

Organic photoelectric semiconductor material and synthesis method and application thereof
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to an organic photoelectric semiconductor material, and a synthesis method and application thereof.
Background
Organic semiconductor devices such as organic solar cells (OPVs), Organic Light Emitting Diodes (OLEDs), Organic Electrochromism (OECs), and Organic Thin Film Transistors (OTFTs) have been developed and applied in many fields. In all these organic photoelectric fields, organic photoelectric materials are key. The organic semiconductor material which is designed and synthesized and has simple process, lower cost, stable material performance and long service life so as to achieve the purpose of commercialization has wide application prospect.
The condensed ring acene material is an organic material with good photoelectric property. For example, the single crystal mobility of pentacene has reached 15-40cm2V-1s-1. Anthracene is the smallest member of the acene family with transistor properties and has better luminescence and device performance. In general, increasing conjugation can increase the combination of transfer integration and decreasing recombination energy resulting in higher charge carrier mobility. Therefore, naphthalene ring is added in the middle of the anthracene ring, so that conjugation is increased, and luminescence of anthracene is maintained.
Although a large number of organic semiconductor materials have been designed and synthesized, there are not many materials that have high fluorescence quantum efficiency and high mobility. However, such materials are critical in the preparation of OLETs and OLEDs. The preparation of such materials is of great importance.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide an organic photoelectric semiconductor material.
The invention also aims to provide a synthesis method of the organic photoelectric semiconductor material.
The invention also aims to provide application of the synthesis method in synthesis of organic photoelectric semiconductor materials.
The purpose of the invention is realized by the following technical scheme.
An organic photoelectric semiconductor material has a structural general formula as follows:
wherein R is1Is hydrogen or sunflower radical, R2The material is hydrogen or triisopropyl silyl acetylene, and the organic photoelectric semiconductor material is 2, 7-dianthranylnaphthalene, 2, 7-bis (9, 10-triisopropyl silyl ethynyl anthracenyl) naphthalene or 2, 7-bis (6-sunflower anthracenyl) naphthalene.
The synthesis method of the organic photoelectric semiconductor material comprises the following steps:
uniformly mixing a reactant A, a reactant B, tetrakis (triphenylphosphine) palladium as a catalyst, toluene and a potassium carbonate aqueous solution in an inert gas environment, heating to 90-100 ℃ after mixing, reacting for 24-96 hours, filtering to obtain filter residue, and washing the filter residue with a detergent to obtain the organic photoelectric semiconductor material, wherein the mass ratio of the reactant A to the reactant B is (2.1-2.5): 1, the ratio of the volume parts of the toluene, the mass parts of the potassium carbonate in the potassium carbonate aqueous solution and the mass parts of the reactant B is (9-18): (4-15): 1;
when the organic photoelectric semiconductor material is 2, 7-dianthracene naphthalene, the reactant A is 2-anthracene borate, and the reactant B is 2, 7-dibromo naphthalene;
when the organic photoelectric semiconductor material is 2, 7-bis (9, 10-triisopropylsilylethynyl anthracene base) naphthalene, the reactant A is 2-bromo-9, 10-triisopropylsilylethynyl anthracene, and the reactant B is 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) naphthalene;
when the organic photoelectric semiconductor material is 2, 7-bis (6-sunflower anthryl) naphthalene, the reactant A is 2-sunflower-6 trifluoromethanesulfonate anthracene, and the reactant B is 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) naphthalene.
In the above technical scheme, the concentration of potassium carbonate in the potassium carbonate aqueous solution is 2M.
In the above technical solution, the ratio of the reactant B to the tetrakis (triphenylphosphine) palladium is 1: (0.048-0.1).
In the above technical scheme, the inert gas is argon or nitrogen.
In the above technical solution, when the organic photoelectric semiconductor material is 2, 7-dianthracene naphthalene, the ratio of the reactant a to the reactant B is (2.1-2.2): 1.
when the organic photoelectric semiconductor material is 2, 7-bis (9, 10-triisopropylsilylethynyl anthracenyl) naphthalene, the ratio of the reactant A to the reactant B is (2.2-2.4) by mass: 1.
when the organic photoelectric semiconductor material is 2, 7-bis (6-sunflower anthryl) naphthalene, the ratio of the reactant A to the reactant B is (2.1-2.2) by mass: 1.
in the technical scheme, the unit of volume parts is mL, and the unit of mass parts is mmol.
The synthesis method is applied to synthesis of the organic photoelectric semiconductor material.
In the technical scheme, the yield of the synthesis method is 79-83%.
Compared with the prior art, the invention has the following beneficial effects:
the preparation reaction route provided by the invention has the advantages of simplicity, high efficiency, environmental friendliness, low raw material price and low synthesis cost; the method has high universality and good repeatability;
the invention provides a new choice for high-performance organic semiconductor materials.
Drawings
FIG. 1 is a graph showing the UV-VIS absorption spectrum of 2, 7-dianthracene naphthalene of the present invention in a solid state;
FIG. 2 is a UPS plot of 2, 7-dianthracene naphthalene according to the present invention;
FIG. 3 is a TGA curve of 2, 7-dianthracene naphthalene of the present invention;
FIG. 4 is a schematic structural diagram of an organic field effect transistor;
FIG. 5(a) is a typical transfer curve for OFETs prepared from 2, 7-dianthracene naphthalene of the present invention;
FIG. 5(b) is a graph showing a typical output curve for OFETs prepared from 2, 7-dianthracene naphthalene of the present invention;
FIG. 6 shows the single crystal structure of 2, 7-dianthracene naphthalene of the present invention.
Detailed Description
The following characterizations relate to the instruments and models as follows:
nuclear magnetism: BRUKER AVANCE III
Mass spectrum: APEX II type Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR-MS)
Elemental analysis: FLASH EA1112 element analyzer
Ultraviolet: UV2600 ultraviolet visible spectrophotometer
UPS test: ESCLAb 250Xi multifunctional X-ray photoelectron spectrometer
And (3) thermogravimetric testing: thermal Analysis Excellence TGA 2
And (3) testing a device: keithley 4200-scs
Crystal resolution: XtalaBmini, Inc. of society
The technical scheme of the invention is further explained by combining specific examples.
Example 1
The organic photoelectric semiconductor material of the embodiment is 2, 7-dianthracene naphthalene, and the structural formula is as follows:
the synthesis method of the organic photoelectric semiconductor material comprises the following steps:
7.69mmol of 2-boronic acid anthracene (2.34g), 3.5mmol of 2, 7-dibromonaphthalene (1g) and 0.175mmol of tetrakis (triphenylphosphine) palladium (202mg) as a catalyst were placed in a 250mL three-necked flask, vacuum-pumping and argon-charging were carried out three times, 50mL of toluene and 25mL of a 2M aqueous solution of potassium carbonate were added, and then the temperature of the reaction system was raised to 100 ℃ to carry out Suzuki coupling reaction for 96 hours. And filtering the reaction system, washing filter residues with triethylamine and dichloromethane in sequence to obtain a crude product, sublimating and purifying to obtain 1.4g of yellow solid, namely the organic photoelectric semiconductor material, wherein the yield is 83%.
The specific synthetic process is as follows:
the structural confirmation data for this product are shown below:
mass spectrum: EI-MS: 480;
elemental analysis: carbon: 94.84%, hydrogen: 4.89 percent.
As can be seen from the above, the yellow solid product has a correct structure and is 2, 7-dianthracene naphthalene.
The spectral properties, UPS test and thermodynamic properties of the organic photoelectric semiconductor material obtained in example 1, and the properties of the organic field effect transistor were determined as follows:
1) spectral properties of the 2, 7-dianthracene naphthalenes of the invention
As can be seen from fig. 1, the peak of the maximum absorption side band of 2, 7-dianthracene naphthalene in the solid state is 456nm, and the corresponding optical band gap is 2.72eV (the optical band gap is calculated according to the formula Eg 1240/λ, where Eg is the optical band gap and λ is the boundary value of the uv absorption curve).
2) UPS testing of 2, 7-dianthracene naphthalene of the present invention
The UV light source used was non-monochromatized He I, the energy of the He I light source used was 21.22eV, and the base vacuum of the analysis chamber during the UPS analysis test of the apparatus was 3.0X10-8Torr, the bias applied during the test was-9V. The sample was evaporated under vacuum to a thickness of about 15nm onto a silicon wafer of about 10mm by 10mm (1cm by 1 cm).
From FIG. 2, it can be calculated that the ionization potential of 2, 7-dianthracene naphthalene is-5.48 eV, that is, the HOMO value with respect to the vacuum level is-5.48 eV. The 2, 7-dianthracene naphthalene is shown to have high oxidation stability and good hole injection capability.
3) Thermodynamic properties of organic 2, 7-dianthracene naphthalene
As can be seen from FIG. 3, the compound 2, 7-dianthracene naphthalene shows excellent thermal stability and the decomposition temperature of thermal weight loss is 450 ℃.
4) Field effect transistor properties of organic 2, 7-dianthracene naphthalene
As shown in FIG. 4, 1 is Si/SiO2Substrate with Si as gate electrode and 2 of OTS (octadecyltrichlorosilane) modified SiO2As an insulating layer, 3 is a semiconductor micro-nano crystal layer of 2, 7-dianthracene naphthalene, and 4 and 5 are Au source and drain electrodes. The whole device adopts a bottom gate top contact configuration, namely the structure of the device is Si (500 mu m)/SiO2(300nm)/OTS (monomolecular layer)/2, 7-dianthranthracene micro-nano crystal/Au.
The transition curve (fig. 5(a)) and the output curve (fig. 5(b)) of the 2, 7-dianthracene naphthalene micro-nano single crystal field effect transistor are shown in fig. 5. Equation (i) is calculated using the following saturation region, and the mobility μ is calculated:
from FIG. 5 and the above saturation equation (I), it can be seen that: at VG<In the range of +3V, the linear field effect transistor device is operated in the saturation region, ISDThere is little change; when V isG>At +3V, the linear field effect transistor device operates in the linear region, ISDLinearly changing. The mobility of the 2, 7-dianthracene naphthalene is calculated to be 20cm2V-1s-1。
(the calculation method of the mobility is described in detail in organic field-effect transistor in chapter 2, section 2, which is a basic introduction of organic field-effect transistor, the author: Huwenping, Press: scientific Press, ISBN 9787030320629.)
FIG. 6 shows the single crystal structure of 2, 7-dianthracene naphthalene as an organic substance, which belongs to the orthorhombic system and has the following unit cell parameters: 6.06608(18), 23.9018(6), 50.470(3), 90.00 α, 90.00 β, 90.00 γ.
Example 2
The organic photoelectric semiconductor material of the embodiment is 2, 7-bis (9, 10-triisopropylsilylethynyl anthracenyl) naphthalene 3, and the structural formula of the organic photoelectric semiconductor material is as follows:
the synthesis process of 2, 7-bis (9, 10-triisopropylsilylethynyl anthryl) naphthalene includes the following steps:
2.63mmol of 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) naphthalene (1g), 6.05mmol of 2-bromo-9, 10-triisopropylsilylethynylanthracene (3.74g) and 0.1315mmol of tetrakis (triphenylphosphine) palladium (152mg) as a catalyst were placed in a 100mL three-necked flask, evacuated three times with argon, and 24mL of toluene and 6mL of a 2M aqueous solution of potassium carbonate were added. Then, the temperature of the reaction system is raised to 90 ℃, and the Suzuki coupling reaction is carried out for 24 hours. Filtering the reaction system, washing filter residue with dichloromethane to obtain a crude product, recrystallizing and purifying with toluene to obtain 2.6g of bright yellow solid as the organic photoelectric semiconductor material, wherein the yield is 82%.
The structural confirmation data for this product are shown below:
nuclear magnetic hydrogen spectrum (CDCl)3)：9.10(2H,d)，8.78(2H,d)，8.65(4H,dt)，8.38(2H,s)，8.11(2H,dd)，8.04(4H,s)，7.63(4H,m)，1.31(84H,m)；
ESI-MS:m/z＝1200。
The specific synthetic process is as follows:
wherein, in the process of preparing 2, 7-bis (9, 10-triisopropylsilylethynyl anthracenyl) naphthalene 3 in example 2, two reactants are respectively 2-bromo-9, 10-triisopropylsilylethynyl anthracene 1 and 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) naphthalene 2, which are prepared respectively as follows:
the preparation method of the 2-bromo-9, 10-triisopropylsilylethynyl anthracene 1 comprises the following steps:
to a three-necked flask equipped with a stirrer were added 1.5mL of anhydrous tetrahydrofuran and triisopropylsilylacetylene (0.52mL, 2.31mmol) under a nitrogen blanket and cooled to-78 deg.C, and 3.14mmol (1.90mL) of butyllithium (a 1.65M solution of butyllithium in hexane) was added and stirred for 2 hours to obtain solution A. 2-Bromoanthraquinone (2.30g, 8.03mmol) was dissolved in anhydrous tetrahydrofuran (15ml) and added to solution A, followed by stirring at-78 ℃ for 1.5 hours and then warming to room temperature 20-25 ℃. The reaction was allowed to proceed at room temperature for 21 hours, then quenched with water, the resulting intermediate was extracted with chloroform, and the organic layer was washed with water, dried over anhydrous sodium sulfate, and concentrated in vacuo. The concentrated intermediate was dissolved in 35mL of tetrahydrofuran and a mixed solution of stannous chloride (4.54g, 24mmol) dissolved in water (20mL) and glacial acetic acid (3.60mL, 62.9mmol) (i.e., a mixed solution of water containing stannous chloride and glacial acetic acid was added dropwise) and stirred at room temperature for 12 hours. After pouring into water, the solid obtained by filtration was washed with ethyl acetate. The filtrate was transferred to a separatory funnel, and the organic layer was separated. The aqueous layer was extracted with ethyl acetate. The combined organic layers were washed with water, dried over anhydrous sodium sulfate, and concentrated in vacuo. Purification by silica gel column chromatography (petroleum ether as eluent) gave 2-bromo-9, 10-triisopropylsilylethynyl anthracene 1(3.98g, 6.45mmol) as a green solid in 80% yield.
The structural confirmation data for this product are shown below:
nuclear magnetic hydrogen spectrum (CDCl)3):δ8.86(d,1H),8.60–8.63(m,2H),8.51(d,1H),7.62–7.68(m,3H),1.25–1.33(m,42H,TIPS)ppm；
Nuclear magnetic carbon spectrum (CDCl)3):δ133.5，132.9，132.7，130.9，129.7，129.3，127.7，127.6，127.5，127.4，121.9，119.3，118.1，105.9，105.8，103.0，19.1，11.7，11.7ppm；
High resolution mass spectrometry (ESI-MS) with m/z 617.2606.
A process for the preparation of 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) naphthalene 2 comprising the steps of:
2, 7-dibromonaphthalene (0.3g, 1.05mmol), pinacol diboron (0.6g, 2.5mmol), [1, 1' -bis (diphenylphosphino) ferrocene ] dichloropalladium (II) dichloromethane adduct (0.15g, 0.18mmol) and potassium acetate (0.6g, 6.1mmol) were mixed in a 100mL two-necked flask and pre-degassed 1, 4-dioxane (10mL) was added under a nitrogen atmosphere. The flask was sealed and held at 80 ℃ for 12 hours. The reaction was quenched by the addition of water (25ml) and the organics extracted 2 times with ethyl acetate (20ml each). The organic layer was separated, dried (magnesium sulfate) and concentrated. The crude product was purified by column and eluted with 10-30% ethyl acetate in hexane. The desired product, 2, 6-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) naphthalene, was isolated in 0.3g as a white solid in 75% yield.
The structural confirmation data for this product are shown below:
nuclear magnetic hydrogen spectrum (CDCl)3)：8.42(s,2H)，7.87(d,2H)，7.80(d,2H)，1.39(s,24H)；
Nuclear magnetic carbon spectrum (CDCl)3)：137.27，136.75，132.38，131.68，126.93，84.02，25.08ppm；
ESI-MS:m/z＝380.2336。
Example 3
The organic photoelectric semiconductor material of the embodiment is 2, 7-bis (6-sunflower anthryl) naphthalene 5, and the structural formula of the organic photoelectric semiconductor material is as follows:
the synthesis method of 2, 7-bis (6-sunflower anthryl) naphthalene comprises the following steps:
115.76. mu. mol of 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) naphthalene (44mg), 254.67. mu. mol of 2-decyl-6-trifluoromethanesulfonylanthracene (118.82mg) and 5.79. mu. mol of tetrakis (triphenylphosphine) palladium (6.69mg) as catalyst were placed in a 25mL reaction tube, evacuated and filled with argon three times, 2mL of toluene and 0.5mL of a 2M aqueous solution of potassium carbonate were added. Then, the temperature of the reaction system is raised to 90 ℃, and the Suzuki coupling reaction is carried out for 36 hours. Filtering the reaction system, washing the filter residue with dichloromethane to obtain a crude product, recrystallizing and purifying with toluene to obtain 70mg of light green solid as the organic photoelectric semiconductor material, wherein the yield is 79.45%.
The structural confirmation data for this product are shown below:
ESI-MS:m/z＝761。
wherein, the reactants involved in the synthesis of 2, 7-bis (6-sunflower anthryl) naphthalene are 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) naphthalene 1 and 2-sunflower-6 trifluoromethanesulfonyl anthracene 4, and the preparation methods are respectively as follows:
a process for the preparation of 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) naphthalene 1 comprising the steps of:
2, 7-dibromonaphthalene (0.3g, 1.05mmol), pinacol diboron (0.6g, 2.5mmol), [1, 1' -bis (diphenylphosphino) ferrocene ] dichloropalladium (II) dichloromethane adduct (0.15g, 0.18mmol) and potassium acetate (0.6g, 6.1mmol) were mixed in a 100mL two-necked flask and pre-degassed 1, 4-dioxane (10mL) was added under a nitrogen atmosphere. The flask was sealed and held at 80 ℃ for 12 hours. The reaction was quenched by the addition of water (25ml) and the organics extracted 2 times with ethyl acetate (20ml each). The organic layer was separated, dried (magnesium sulfate) and concentrated. The crude product was purified by column and eluted with 10-30% ethyl acetate in hexane. The desired product, 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) naphthalene, was isolated as a light brown solid in 0.3g yield at 75%.
The structural confirmation data for this product are shown below:
nuclear magnetic hydrogen spectrum (CDCl)3)：8.42(s,2H)，7.87(d,2H)，7.80(d,2H)，1.39(s,24H)；
Nuclear magnetic carbon spectrum (CDCl)3)：137.27，136.75，132.38，131.68，126.93，84.02，25.08ppm；
ESI-MS:m/z＝380.2336。
The preparation method of the 2-decyl-6 trifluoromethanesulfonate anthracene 4 comprises the following steps:
a stirrer was placed in a 100ml two-necked flask, and a condenser tube was connected to the stirrer and then replaced with argon gas. 2, 6-bis (trifluoromethanesulfonate) anthracene (2g, 4.22mmol), [1, 1' -bis (diphenylphosphino) ferrocene ] dichloropalladium (II) dichloromethane adduct (0.13g) and tert-butyl methyl ether (25ml) were added. A1M solution of decyl magnesium bromide in diethyl ether (0.52g, 2.11mmol) was added dropwise at 30 ℃ and refluxed for 3 hours. After the reaction, 20ml of each of water and 2M diluted hydrochloric acid was added, and the mixture was extracted with ethyl acetate. The organic phase was dried over anhydrous magnesium sulfate and the solvent was evaporated under reduced pressure. Purification on silica gel column (petroleum ether) afforded the product (120mg, 6.1%).
Nuclear magnetic hydrogen spectrum (CDCl)3)：8.39(d,2H)，8.05(d,1H)，7.94(d,1H)，7.88(d,1H)，7.76(s,1H)，7.40(dd,1H)，7.32(dd,1H)，2.82(t,2H)，1.28(d,19H)；
ESI-MS:m/z＝466。
Among the above preparation methods, the preparation method of 2, 6-bis (trifluoromethanesulfonate) anthracene 3 includes the steps of:
2, 6-dihydroxyanthraquinone (2.28g) was added to a 100ml three-necked flask equipped with a stirrer, and then 3 times of argon gas was introduced under vacuum. Anhydrous dichloromethane (25ml) and triethylamine (53.04mmol, 7.38ml) were injected into the system. Cooled to-30 ℃ and trifluoromethanesulfonic anhydride (26.6mmol, 4.48ml) was added dropwise via syringe, stirred at-30 ℃ for 2 h and then warmed to room temperature. Dichloromethane (40mL) was added and washed 3 times with brine (100 mL each time, brine as a saturated sodium chloride solution). The organic phase was separated, dried over anhydrous magnesium sulfate and the solvent was evaporated under reduced pressure. The crude product was purified by column chromatography to give a pale yellow solid (2.2g, 43.6%).
The structural confirmation data for this product are shown below:
nuclear magnetic hydrogen spectrum (CDCl)3)：8.41(s,2H)，8.03(d,2H)，7.89(d,2H)，7.40(dd,2H)；
ESI-MS:m/z＝474。
In the above production method, the production method of 2, 6-dihydroxyanthracene 2 includes the steps of:
to a 1L single neck round bottom flask was added a stirrer, sodium borohydride (14.25g, 375mmol) and 1M sodium carbonate solution (300ml), cooled at 0 deg.C, added 2, 6-dihydroxyanthracene-9, 10-dione (6g, 25mmol) in small portions, with evolution of colorless gas during the addition, and when gas evolution ceased, the reaction mixture was allowed to return to room temperature and stirred for 12 hours. Thereafter, the reaction was heated to 80 ℃ and held for 30 minutes. After the reaction was complete, the mixture was poured into a 1L beaker, stirred at 0 ℃ with a stirrer and acidified slowly with 3M dilute hydrochloric acid until no bubbles emerged, and the solid obtained by filtration was dried at 110 ℃ for 6 hours. Drying, placing into a suction filter funnel, washing with acetone to obtain filtrate, evaporating to dryness to obtain brown solid 2.4g, and directly preparing the 2, 6-bis (trifluoromethanesulfonate) anthracene without purification.
The structural confirmation data for this product are shown below:
nuclear magnetic hydrogen spectrum (CDCl)3)：9.69(s,2H)，8.19(s,2H)，7.87(d,2H)，7.18(d,2H)，7.12(dd,2H)，；
ESI-MS:m/z＝210。
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.

Claims (10)

1. An organic photoelectric semiconductor material is characterized in that the structural general formula is as follows:
wherein R is1Is hydrogen or sunflower radical, R2The material is hydrogen or triisopropyl silyl acetylene, and the organic photoelectric semiconductor material is 2, 7-dianthranylnaphthalene, 2, 7-bis (9, 10-triisopropyl silyl ethynyl anthracenyl) naphthalene or 2, 7-bis (6-sunflower anthracenyl) naphthalene.
2. A method of synthesis of an organic optoelectronic semiconductor material as claimed in claim 1, comprising the steps of:
uniformly mixing a reactant A, a reactant B, tetrakis (triphenylphosphine) palladium as a catalyst, toluene and a potassium carbonate aqueous solution in an inert gas environment, heating to 90-100 ℃ after mixing, reacting for 24-96 hours, filtering to obtain filter residue, and washing the filter residue with a detergent to obtain the organic photoelectric semiconductor material, wherein the mass ratio of the reactant A to the reactant B is (2.1-2.5): 1, the ratio of the volume parts of the toluene, the mass parts of the potassium carbonate in the potassium carbonate aqueous solution and the mass parts of the reactant B is (9-18): (4-15): 1;
when the organic photoelectric semiconductor material is 2, 7-dianthracene naphthalene, the reactant A is 2-anthracene borate, and the reactant B is 2, 7-dibromo naphthalene;
when the organic photoelectric semiconductor material is 2, 7-bis (9, 10-triisopropylsilylethynyl anthracene base) naphthalene, the reactant A is 2-bromo-9, 10-triisopropylsilylethynyl anthracene, and the reactant B is 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) naphthalene;
when the organic photoelectric semiconductor material is 2, 7-bis (6-sunflower anthryl) naphthalene, the reactant A is 2-sunflower-6 trifluoromethanesulfonate anthracene, and the reactant B is 2, 7-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) naphthalene.
3. The synthesis method according to claim 2, wherein the concentration of potassium carbonate in the aqueous potassium carbonate solution is 2M, the unit of volume fraction is mL, and the unit of mass fraction is mmol.
4. A synthesis method according to claim 3, characterized in that the ratio of reactant B to tetrakis (triphenylphosphine) palladium is 1: (0.048-0.1).
5. The method of synthesis according to claim 4, wherein the inert gas is argon or nitrogen.
6. The synthesis method according to claim 5, wherein when the organic photoelectric semiconductor material is 2, 7-dianthracene naphthalene, the ratio of the reactant A to the reactant B is (2.1-2.2): 1.
7. the synthesis method according to claim 5, wherein when the organic photoelectric semiconductor material is 2, 7-bis (9, 10-triisopropylsilylethynyl anthracenyl) naphthalene, the ratio of the reactant A to the reactant B is (2.2-2.4): 1.
8. the synthesis method according to claim 5, wherein when the organic photoelectric semiconductor material is 2, 7-bis (6-sunflower anthryl) naphthalene, the ratio of the reactant A to the reactant B is (2.1-2.2): 1.
9. use of the synthesis method according to any one of claims 6 to 8 for synthesizing the organic optoelectronic semiconductor material.
10. The use of claim 9, wherein the synthesis method has a yield of 79-83%.
CN201810653830.2A 2018-06-22 2018-06-22 Organic photoelectric semiconductor material and synthesis method and application thereof Pending CN110627602A (en)

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Application publication date: 20191231