阅读说明：本技术 一类不对称取代的蒽衍生物及其制备方法与应用 (Asymmetric substituted anthracene derivatives, and preparation method and application thereof ) 是由 江浪 刘洁 石燕君 师晓松 于 2021-01-14 设计创作，主要内容包括：本发明公开了一类不对称取代的蒽衍生物及其制备方法与应用。该类化合物结构如式I所示。本发明的优点在于：1、此反应路线具有简单高效、环境友好、原料价格廉价、合成成本低的优点；方法普适性高,重复性好；2、为不对称高性能有机半导体材料提供了一个新的选择。(The invention discloses an asymmetric substituted anthracene derivative and a preparation method and application thereof. The structure of the compound is shown as a formula I. The invention has the advantages that: 1. the reaction route has the advantages of simplicity, high efficiency, environmental friendliness, low price of raw materials and low synthesis cost; the method has high universality and good repeatability; 2. provides a new choice for asymmetric high-performance organic semiconductor materials.)

1. A compound of the formula I, wherein,

in the formula I, R₀Any one selected from the following groups:

r and R' are both selected from any one of H, C1-C24 alkyl and substituted C1-C24 alkyl;

in the alkyl group containing the substituent, the substituent is selected from any one of S, O, N, an ester group and an amide group.

2. The compound of claim 1, wherein: the compound shown in the formula I is any one of the following compounds:

the definitions of R and R' are the same as in claim 1.

3. A process for the preparation of a compound of formula I as claimed in any one of claims 1 or 2, comprising:

mixing and refluxing 2-bromoanthracene, an aryl compound and a palladium catalyst for reaction, and obtaining the catalyst after the reaction is finished;

the aryl compound is aryl boron ester or substituted aryl boron ester, aryl vinyl boron ester or substituted aryl vinyl boron ester, aryne or substituted aryne;

in the substituted arylboronic ester, substituted arylvinylboronic ester and substituted arylalkynyl group, the definition of the substituent is the same as that of R described in claim 1.

4. The method of claim 3, wherein: the palladium catalyst is at least one of tetratriphenylphosphine palladium and dichloroditriphenylphosphine palladium.

5. The method according to claim 3 or 4, characterized in that: the feeding molar ratio of the 2-bromoanthracene to the aryl compound to the palladium catalyst is 1:1: 0.05;

the reflux reaction step is carried out for 3-12 hours or 3-5 hours;

the reaction is carried out in an inert atmosphere; the inert atmosphere is nitrogen or argon atmosphere.

6. Use of a compound of formula I according to any one of claims 1 or 2 for the preparation of at least one of an organic field effect transistor device, an organic light emitting device and an organic light emitting field effect transistor device.

7. At least one of an organic semiconductor field effect transistor device, an organic light emitting device and an organic light emitting field effect transistor device comprising a compound of formula I according to any one of claims 1 or 2.

Technical Field

The invention belongs to the field of materials, and relates to an asymmetrically substituted anthracene derivative, and a preparation method and application thereof.

Background

Field Effect Transistors (FETs) are an important component of microelectronics, and their principle was proposed as early as 1930. In 1945, Bell laboratories began working on field effect transistors, and in 1960, Kahng and Atalla of the laboratories succeeded in developing the first silicon-based metal/oxide/semiconductor field effect transistor. The basic operating principle of a field effect transistor is that a charge accumulation layer is formed at the interface of a semiconductor/insulating layer by means of a strong electric field, thereby forming a conduction channel, and a current is formed under the action of an applied electric field. The concept of organic semiconductor field effect transistors was proposed in the 70 s of the 20 th century, the first with better field effectOrganic transistors of energy were introduced in the mid 80's, when the organic semiconductor material used was polythiophene, and subsequently a great deal of research was undertaken on field effect transistors based on polythiophene materials. To date, thousands of materials have been reported to have field effect properties, and a variety of new fabrication techniques (e.g., spin coating, dip coating, ink jet printing, etc.) have been invented or applied in the fabrication of field effect transistors. The mobility of a plurality of organic semiconductor materials can reach 1cm²V^{- 1}s^-1Above that, it can be compared with amorphous silicon, even close to polysilicon>10cm²V^-1s^-1). The highest mobility of the small molecular film of vacuum evaporation currently reported reaches 17.2cm²V^-1s^-1The solution processed small molecule is more than 30cm²V^-1s^-1Even polymers can reach 20cm²V^-1s^-1The mobility of the field effect transistor based on the organic single crystal is more than 40cm²V^-1s^-1. These will further promote the industrialization and related applications of organic semiconductor materials. Through years of research and development, the organic field effect transistor has been developed greatly, and some products are put into the market, but still there are still many problems to be solved: the environmental stability of the material needs to be further improved, the performance distribution of the device is wider, and the like.

Based on the development of the OLED and the OFET, Seggern et al in germany in 2003 reports for the first time that a device combining the functions of the OLED and the OFET has the same structure as the OFET, but has the function of regulating the current by an electric field and the function of regulating the light emission by the electric field. Unipolar and bipolar OLETs are classified according to the polarity of the organic layer. The unipolar field effect light emitting tube is mainly p-type. At present, the main problems faced by organic light-emitting transistors are that the mobility ratio of organic materials is low, bipolar materials are too few, carrier injection is unbalanced, and the like, so that the field effect performance and the light-emitting performance of the manufactured device cannot meet the requirements of application.

In the invention, a series of asymmetric benzothiophene, bithiophene or other aryl substituted anthracene derivatives, namely 2-aryl anthracene and substituted 2-aryl anthracene derivatives are designed, and optical and electrochemical tests prove that the compound has good stability. By using the physical vapor transport technology, single crystals of the material are prepared, and in-situ transistor devices and light-emitting transistor devices are constructed.

Disclosure of Invention

The invention aims to provide an asymmetric substituted anthracene derivative and a preparation method and application thereof.

The asymmetrically substituted anthracene derivatives claimed by the present invention, i.e. the compounds of formula I,

in the formula I, R₀Any one selected from the following groups:

r and R' are both selected from any one of H, C1-C24 alkyl and substituted C1-C24 alkyl; in the C1-C24 alkyl, the number of the alkyl can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23 or 24 or 1-10 or 1-9;

in the alkyl group containing the substituent, the substituent is selected from any one of S, O, N, an ester group and an amide group. The ester group is C1-C10 (such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10), such as methyl ester group, ethyl ester group, boron ester group, etc.

Specifically, the compound shown in the formula I is any one of the following compounds:

the definitions of R and R' are the same as those in formula I above.

The invention provides a method for preparing the compound shown in the formula I, which comprises the following steps:

mixing and refluxing 2-bromoanthracene, an aryl compound and a palladium catalyst for reaction, and obtaining the catalyst after the reaction is finished;

the aryl compound is aryl boron ester or substituted aryl boron ester, aryl vinyl boron ester or substituted aryl vinyl boron ester, aryne or substituted aryne;

in the substituted aryl boron ester, the substituted aryl vinyl boron ester and the substituted aryl alkynyl, the definition of the substituent is the same as that of R in the formula I.

In the above method, the palladium catalyst is at least one selected from the group consisting of tetratriphenylphosphine palladium and dichloroditriphenylphosphine palladium.

The feeding molar ratio of the 2-bromoanthracene to the aryl compound to the palladium catalyst is 1:1: 0.05;

the reflux reaction step is carried out for 3-12 hours or 3-5 hours;

the reaction is carried out in an inert atmosphere; the inert atmosphere is nitrogen or argon atmosphere;

the reflux reaction is carried out in a solvent; the solvent is specifically selected from at least one of toluene, ethanol, water and tetrahydrofuran.

More specifically, the compound of formula IV belonging to formula I can be prepared as follows:

reacting 2-bromoanthracene, aryl boron ester or substituted aryl boron ester shown in formula I', tetratriphenylphosphine palladium and K₂CO₃Putting into a three-neck flask, vacuumizing and filling argon for three times, adding bubbling toluene, ethanol and water, heating, refluxing and stirring overnight to obtain the single-bond substituted asymmetric anthracene derivative (formula IV). In the substituted aryl boron ester, the definition of the substituent is the same as that of R in the formula I;

in the formula I', R is defined as the same as R in the formula I.

The formula I' can be prepared according to the following method: bromoaryl or substituted bromoaryl, pinacol borate, palladium acetate and X-phos are mixed and added into a three-neck flask, vacuumizing and argon introducing are carried out for three times, DMF is added, the mixture is heated to 80 ℃, and the mixture is stirred overnight. Cooling to room temperature, adding a large amount of water, extracting the water phase with dichloromethane, collecting the organic phase, washing with water and saturated saline in sequence, drying, mixing with silica gel powder, spin-drying, and passing through silica gel column. In the substituted bromoaryl, the definition of the substituent is the same as that of R in the formula I;

the feeding molar ratio of the bromoaryl or substituted bromoaryl, pinacol borate, dichloroditriphenylphosphine palladium and X-phos is 1:1.5:0.03: 0.06.

The reaction is carried out in an inert atmosphere, which is nitrogen or argon.

The compounds of formula V belonging to formula I can be prepared as follows:

2-bromoanthracene, aryl vinyl boron ester or substituted aryl vinyl boron ester shown in formula III', tetratriphenyl phosphorus palladium and K₂CO₃Putting into a three-neck flask, vacuumizing and filling argon for three times, adding bubbling toluene, ethanol and water, heating, refluxing and stirring overnight to obtain the product.

Wherein, the aryl vinyl boron ester or the substituted aryl vinyl boron ester shown in the formula III' is prepared according to the following method:

the pinacolboronic ester, the sodium hydroxide, the triphenylphosphine and the copper bromide are placed in a three-neck flask, the flask is vacuumized and filled with argon three times, and dried THF is added. Then adding aryne or substituted aryne shown in the formula II' and ethanol, and stirring at room temperature. Removing solvent, adding n-hexane, filtering, mixing the filtrate with silica gel powder, and passing through column. In the substituted aryl vinyl boron ester, the definition of a substituent is the same as that of R in the formula I;

the charging molar ratio of the aryne or substituted aryne shown in the formula II', the pinacol boron ester, the sodium hydroxide, the triphenylphosphine and the copper bromide is 1:1:0.1:0.3: 0.2.

The reaction is carried out in an inert atmosphere, which is nitrogen or argon.

The compounds of formula VI belonging to formula I can be prepared as follows:

adding 2-bromoanthracene, aryne or substituted aryne shown in the formula II', dichloroditriphenylphosphine palladium and cuprous iodide into a three-neck flask at one time, vacuumizing and introducing argon for three times, injecting tetrahydrofuran and triethylamine, heating, refluxing and stirring overnight to obtain the acetylene bond substituted asymmetric anthracene derivative (formula VI).

Wherein, the aryl alkynyl or substituted aryl alkynyl shown in the formula II' is prepared according to the following method:

mixing bromoaryl or substituted bromoaryl, trimethylsilylacetylene, dichlorodiphenylpalladium phosphate and cuprous iodide, adding into a three-neck flask, vacuumizing, introducing argon for three times, adding THF (tetrahydrofuran), heating to 80 ℃, and stirring overnight. Cooling to room temperature, mixing with silica gel powder, spin drying, and passing through silica gel column to obtain intermediate product (aryltrimethylsilylacetylene or substituted aryltrimethylsilylacetylene). And then putting the intermediate product and NaOH into a two-neck flask, adding methanol, stirring overnight at room temperature, filtering, washing filter residue with dichloromethane, and spin-drying the organic solvent to obtain the intermediate product. In the substituted bromoaryl, the definition of the substituent is the same as that of R in the formula I;

the feeding molar ratio of the bromoaryl or substituted bromoaryl, the trimethylsilylacetylene, the dichlorodiphenylene palladium and the cuprous iodide is 1:1.2:0.03: 0.06.

The reaction is carried out in an inert atmosphere, which is nitrogen or argon.

In addition, the application of the compound shown in the formula I in the preparation of at least one of an organic field effect transistor device, an organic light-emitting device and an organic light-emitting field effect transistor device, and at least one of an organic semiconductor field effect transistor device, an organic light-emitting device and an organic light-emitting field effect transistor device containing the compound shown in the formula I also belong to the protection scope of the invention.

The reaction schemes described above for the preparation of formulae I ', II ', III ', IV, V and VI are shown below:

the invention has the advantages that:

1. the reaction route has the advantages of simplicity, high efficiency, environmental friendliness, low price of raw materials and low synthesis cost; the method has high universality and good repeatability;

2. provides a new choice for asymmetric high-performance organic semiconductor materials.

Drawings

FIG. 1 shows UV-visible absorption spectra of six compounds in dichloromethane.

FIG. 2 is a cyclic voltammogram of six compounds.

Figure 3 is a TGA plot of six compounds of material.

Fig. 4 is a schematic structural view of an organic field effect transistor.

Fig. 5 is a graph showing transfer and output curves of the organic field effect transistor prepared.

Detailed Description

The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.

Example 1 preparation of 5-benzothiopheneboronic acid ester.

In a 50mL three-necked flask, 5-bromobenzothiophene (1mmol), pinacol boronate (1.5mmol), palladium acetate (0.03mmol), and X-phos (0.06mmol) were added, evacuated and argon-purged three times, and 10mL of DMF was added. Heating the reaction system to 80 ℃, reacting overnight, cooling to room temperature, adding a large amount of water, extracting a water phase by dichloromethane, collecting an organic phase, washing by water and saturated saline water in sequence, drying, stirring with silica gel powder, spin-drying, and passing through a silica gel column. 220mg of a white solid was obtained (yield 85%).

The structural confirmation data for this product are shown below:

mass spectrum: EI: M⁺:260.

Nuclear magnetic hydrogen spectrum:¹H NMR(300MHz,CDCl₃)δ(ppm):7.90(d,1H),7.52(s,1H),7.44(d,1H),7.33(d,1H),6.23(d,1H),1.33(s,12H).

from the above, the compound has a correct structure and is represented by the formula I.

Example 2 preparation of 5-benzothiopheneneyne.

In a 50mL three-necked flask, 5-bromobenzothiophene (1mmol), dichlorodiphenylpalladium (0.03mmol), and cuprous iodide (0.06mmol) were added, vacuum was applied to argon three times, THF (10mL) and triethylamine (2mL) were added, the mixture was heated to 80 ℃ and stirred overnight. Cooling to room temperature, stirring with silica gel powder, spin-drying, and passing through silica gel column to obtain 5-trimethylsilylethynyl benzothiophene. And then placing the intermediate product and NaOH in a two-neck flask, adding methanol, stirring at room temperature overnight, filtering, washing filter residue with dichloromethane, and spin-drying the organic solvent to obtain the 5-benzothiophenyne.

The structural confirmation data for this product are shown below:

mass spectrum: EI: M⁺:158.

Nuclear magnetic hydrogen spectrum:¹H NMR(300MHz,Chloroform-d)δ7.98(d,J＝1.6Hz,1H),7.82(d,J＝8.3Hz,1H),7.51–7.44(m,2H),7.31(d,J＝5.2Hz,1H),3.09(s,1H).

from the above, the compound has a correct structure and is represented by formula II.

Example 3 preparation of 5-benzothiophene-vinylboron ester.

In a 50mL three-necked flask, pinacolboronic ester (1mmol), sodium hydroxide (0.1mmol), triphenylphosphine (0.3mmol) and copper bromide (0.2mmol) were added, and then evacuated under argon for three times, THF (10mL) was added and the mixture was stirred at room temperature for 30 min. 1mmol of 5-benzothiophenyne and 2mL of ethanol were added, and the mixture was stirred at room temperature for 2 hours. The solvent was removed by evaporation, n-hexane was added, the mixture was filtered, and the filtrate was mixed with silica gel powder and passed through a column to obtain 229mg of a white solid (yield 80%).

The structural confirmation data for this product are shown below:

mass spectrum: EI: M⁺:286.

Nuclear magnetic hydrogen spectrum:¹H NMR(300MHz,Chloroform-d)δ7.90–7.79(m,2H),7.57–7.46(m,2H),7.44(d,J＝5.5Hz,1H),7.33(d,J＝5.5Hz,1H),6.23(d,J＝18.4Hz,1H),1.33(s,12H).

from the above, the compound has a correct structure and is represented by the formula III.

Example 4 preparation of 5-Benzothienylanthracene

Placing 5-benzothiophene borate ester (1mmol), 2-bromoanthracene (1mmol) and tetrakis (triphenylphosphine) palladium (0.05mmol) in a 50mL three-neck flask, vacuumizing and filling argon for three times, adding toluene (10mL) and ethanol (2mL), raising the temperature of a reaction system to 90 ℃, and then adding 2M K₂CO₃The solution was 2mL and reacted at 90 ℃ for 3 h. And filtering the reaction system, washing filter residues by triethylamine and dichloromethane in sequence, and sublimating and purifying a crude product to obtain a yellow solid 220mg with the yield of 70%.

The structural confirmation data for this product are shown below:

mass spectrum: EI: M⁺:310.

Nuclear magnetic hydrogen spectrum:¹H NMR(300MHz,Chloroform-d)δ8.48(d,J＝11.0Hz,2H),8.24(d,J＝16.4Hz,2H),8.12(d,J＝8.8Hz,1H),8.02(dd,J＝8.6,5.1Hz,3H),7.81(ddd,J＝15.1,8.6,2.0Hz,2H),7.53–7.42(m,5H).

example 5 preparation of 5-benzothiophenylethynyl anthracene

2-bromoanthracene (1mmol), 5-benzothiophenylacetylene (1mmol), dichlorodiphenylphosphorodiamidinium palladium (0.03mmol) and cuprous iodide (0.06mmol) are added into a three-neck flask at a time, vacuum pumping is carried out, argon is introduced for three times, tetrahydrofuran (10mL) and triethylamine (2mL) are injected, and heating, refluxing and stirring are carried out for 3 hours. Cooling to room temperature, filtering, sublimating filter residue and purifying to obtain 216mg (65%) of 5-benzothiophene ethynyl anthracene.

The structural confirmation data for this product are shown below:

mass spectrum: EI: M⁺:334.

Nuclear magnetic hydrogen spectrum: 1H NMR (300MHz, Chloroform-d) δ 8.41(s,2H),8.25(s,1H),8.08(s,1H),7.99(d, J ═ 9.0Hz,3H),7.88(d, J ═ 8.3Hz,1H),7.52(dd, J ═ 23.1,7.7Hz,5H),7.36(d, J ═ 5.5Hz,1H).

Example 6 preparation of 5-benzothiophene vinyl Anthracene

Placing 5-benzothiophene vinyl borate (1mmol), 2-bromoanthracene (1mmol) and tetrakis (triphenylphosphine) palladium (0.05mmol) in a 50mL three-neck flask, vacuumizing and filling argon for three times, adding toluene (10mL) and ethanol (2mL), raising the temperature of a reaction system to 90 ℃, and then adding 2M K₂CO₃The solution was 2mL and reacted at 90 ℃ for 3 h. And filtering the reaction system, washing filter residues by triethylamine and dichloromethane in sequence, and sublimating and purifying a crude product to obtain a yellow solid 233mg with the yield of 70%.

The structural confirmation data for this product are shown below:

mass spectrum: EI: M⁺:336.

Nuclear magnetic hydrogen spectrum: 1H NMR (300MHz, Chloroform-d) δ 8.41(s,2H),8.25(s,1H),8.14(s,1H),7.99(d, J ═ 9.2Hz,3H),7.82(d, J ═ 8.2Hz,2H), 7.57-7.47 (m,4H),7.37(s,1H).

The spectral properties, electrochemical properties and thermodynamic properties of the solid product prepared in this example and the properties of the organic field effect transistor were determined as follows:

1) spectral properties of organic 5-benzothiophenylanthracene, 5-benzothiophenylethynyl anthracene, 5-benzothiophenethenylanthracene

FIG. 1 shows the UV-VIS absorption spectrum of a compound in methylene chloride solution. As can be seen from FIG. 1, the peak of the maximum absorption side band of the compound in the dichloromethane solution is about 410nm, and the corresponding optical band gap is 2.9-3.0eV (the optical band gap is according to the formula E)_g1240/λ calculation, where E_gIs the optical band gap, and λ is the boundary value of the ultraviolet absorption curve).

2) Electrochemical Properties of 5-Benzothienylanthracene, 5-benzothiophenylethynyl anthracene, 5-benzothiophenethenylanthracene

FIG. 2 is a cyclic voltammogram of a compoundA wire. And (3) testing by adopting a three-electrode system: the working electrode is a glassy carbon electrode, the platinum wire is a counter electrode, the Ag/AgCl is a reference electrode, and Bu₄NPF₆As a supporting electrolyte. The test conditions were: the scanning range is 0-2.0V (vs. Ag/AgCl), and the scanning speed is 100 mV/s.

Electrochemical tests show that the initial oxidation potential of dP-Ant is about 0.9-1.2 eV, the calculated HOMO (highest occupied orbital level) energy level is-5.3-5.6 eV, and the compound has high oxidation stability and good hole injection capability.

3) Thermo-gravimetric properties of 5-benzothiophenylanthracenes, 5-benzothiophenylethynyl anthracenes, 5-benzothiophenethenylanthracenes

FIG. 3 is a TGA curve of a material, and it can be seen that the compound shows excellent thermal stability and the decomposition temperature of the thermal weight loss is about 280 ℃ to 320 ℃.

4) Field effect transistor properties of the compound 5-benzothiophenylanthracene, 5-benzothiophenylethynyl anthracene, 5-benzothiophenethenylanthracene

FIG. 4 is an optical microscope photograph of a single crystal organic field effect transistor, OTS modified Si/SiO₂As substrate, Si as gate electrode, Au as source and drain as anode electrode, and OTS modified SiO₂As an insulating layer, the asymmetric anthracene derivative is used as a charge transport layer, and the whole device adopts a bottom gate top contact configuration, namely the device structure is Si/SiO₂(300nm)/OTS (SAM)/organic single crystal/Au (100 nm).

Fig. 5 is a typical transfer curve and output curve of the prepared OFETs. The device shows typical p-type characteristics, the turn-on voltage is-2V, and the maximum mobility is 13cm²V^-1s^-1。

All experimental results show that the asymmetric anthracene derivative shown in the formula I provided by the invention is an excellent organic p-type semiconductor material. Good device performance depends on the close molecular packing of the material, which is critical for fast transport of carriers. The invention not only has simple and effective synthesis method, but also obtains the field effect device with higher mobility by changing the details in the device preparation. The method is very helpful for researching the relation between the stacking structure and the performance of the organic semiconductor material, can further guide the design and synthesis of the high-performance polymer material, and provides a certain reference for optimizing the device preparation process according to the characteristics of the material.