CN113121560A - Benzothienobenzo five-membered heterocyclic material and preparation method and application thereof - Google Patents

Benzothienobenzo five-membered heterocyclic material and preparation method and application thereof Download PDF

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CN113121560A
CN113121560A CN202110332520.2A CN202110332520A CN113121560A CN 113121560 A CN113121560 A CN 113121560A CN 202110332520 A CN202110332520 A CN 202110332520A CN 113121560 A CN113121560 A CN 113121560A
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membered heterocyclic
benzothienobenzo
benzothiophene
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孟鸿
王胧佩
张鑫康
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Peking University Shenzhen Graduate School
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Abstract

The invention discloses a benzothiophene acene five-membered heterocyclic material and a preparation method and application thereof, wherein the material has the following structural general formula:
Figure DDA0002996741520000011
wherein, aromatic ring Ar1And Ar2Each independently selected from substituted or unsubstituted aryl or heteroaryl, R1‑R8Each independently selected from hydrogen, aromatic substituents or aliphatic substituents, and X is selected from oxygen, sulfur, selenium and substituted heteroatom rings as described above. The accumulation of materials can be effectively improved by introducing the benzo five-membered heterocycle, and the compound adopts a plane rigid structure, thereby being beneficial to showing high electron mobility and improving stability. Proper electron-withdrawing groups are used as peripheral groups to adjust the energy levels of HOMO and LUMO, so that the injection energy barrier is reduced, and the starting voltage is reduced; the asymmetric modification is beneficial to increasing dipole moment, improving molecular triplet state energy level, blocking excitons and reducing quenching of effective excitons in a transmission layer, and has the advantages of high carrier mobility, excellent device performance, good stability and the like when being used as an electron transmission material of an organic electroluminescent device.

Description

Benzothienobenzo five-membered heterocyclic material and preparation method and application thereof
Technical Field
The invention relates to the field of organic display, in particular to a benzothiophene acene five-membered heterocyclic material and a preparation method and application thereof.
Background
The electroluminescence of organic materials can be traced back to 1963 for the first time, and Pope et al found that a single-layer anthracene (anthracene) crystal emits weak blue light as an electron transport layer, but the single-layer anthracene crystal is not developed because the driving voltage is as high as 100V or more. Organic Light Emitting Diodes (OLEDs), which were prepared by c.w. tang et al, Kodak, usa, using aluminum 8-hydroxyquinoline (AlQ3) as an electron transport layer, had a low Light-on voltage of up to several volts and a luminance of up to 1000cd/m, until 19872Organic light emitting devices have made great progress.
The electron transport material is a key material of the OLED, and needs to have good electron accepting capability, and can effectively transfer electrons under a certain forward bias (see the introduction of organic electroluminescent materials and devices, Huangchunhui, Likui, Huangwei, page 143) to ensure smooth injection and transport of electrons and carrier balance in the light emitting device. This makes the electron transport material required to have the following properties: (1) reversible electrochemical reduction and sufficiently high reduction potential; (2) a suitable Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO); (3) higher electron mobility; (4) high glass transition temperature (Tg); (5) non-crystalline thin films (see OLED organic electroluminescent materials and devices, chenjinxin, huangxianzhu, page 52).
However, the current electron transport materials still have to be further improved and developed in performance.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a benzothienobenzo five-membered heterocyclic material, and a preparation method and application thereof, and aims to improve the accumulation of materials, promote the electron transfer rate, and improve the stability and the service life of a device by introducing the benzo five-membered heterocyclic.
The technical scheme of the invention is as follows:
a benzothienobenzo five-membered heterocyclic material, wherein the structural formula is as follows:
Figure BDA0002996741500000011
wherein, aromatic ring Ar1And Ar2Each independently selected from substituted or unsubstituted aryl or heteroaryl, R1-R8Each independently selected from hydrogen, aromatic substituents or aliphatic substituents, and X is selected from one of an oxygen or oxygen substituted heteroatom ring, a sulfur or sulfur substituted heteroatom ring, selenium or selenium substituted heteroatom ring.
The substituted or unsubstituted aryl or heteroaryl includes, but is not limited to, benzene, thiophene, furan, pyridine.
Ar is1And Ar2Each independently selected from the group consisting of substituted or unsubstituted phenyl, naphthyl, (9, 9-dialkyl) fluorenyl, (9, 9-disubstituted or unsubstituted aryl) fluorenyl, 9-spirofluorenyl, purinyl, diphenylphosphinyloxy, pyridine group, imidazole derivative group, pyrimidinyl, pyridazinyl, imidazopyrimidinyl, pyrazinyl, triazinyl, and triazinbiphenyl, but not limited thereto.
The benzothiophenobenzene five-membered heterocyclic material, wherein Ar1And Ar2Each having one of the following structures:
Figure BDA0002996741500000021
Figure BDA0002996741500000031
wherein the content of the first and second substances,
Figure BDA0002996741500000032
indicates the attachment site.
The benzothiophenacene five-membered heterocyclic material, wherein X can be selected from oxygen, sulfur, selenium, and substituted heteroatom rings as described above.
The benzothiophenacene five-membered heterocyclic material has one of the following structures:
Figure BDA0002996741500000033
Figure BDA0002996741500000041
Figure BDA0002996741500000051
Figure BDA0002996741500000061
Figure BDA0002996741500000071
Figure BDA0002996741500000081
Figure BDA0002996741500000091
Figure BDA0002996741500000101
Figure BDA0002996741500000111
Figure BDA0002996741500000121
Figure BDA0002996741500000131
Figure BDA0002996741500000141
Figure BDA0002996741500000151
Figure BDA0002996741500000161
Figure BDA0002996741500000171
Figure BDA0002996741500000181
Figure BDA0002996741500000191
Figure BDA0002996741500000201
Figure BDA0002996741500000211
Figure BDA0002996741500000221
Figure BDA0002996741500000231
Figure BDA0002996741500000241
a preparation method of benzothienobenzo five-membered heterocyclic material comprises the following steps:
s01, providing a bromo-benzothiophene derivative raw material, adding the bromo-benzothiophene derivative raw material into a first solvent in which a benzene derivative is dissolved, cooling and filtering the mixture in a saturated ammonium chloride solution, and reacting to obtain a first intermediate product;
s02, dissolving the first intermediate product in a second solvent, adding N-bromosuccinimide, filtering after reaction to obtain a white precipitate, dissolving the white precipitate in dichloromethane, and obtaining a second intermediate product after reaction;
s03, dissolving the second intermediate product in a third solvent, adding triphenyl palladium dichloride, 2 equivalents of potassium acetate and diboron acid pinacol ester in a nitrogen atmosphere, and reacting to obtain a benzothiophene acene five-membered heterocyclic borate product;
s04, dissolving the benzothiophenacene five-membered heterocycle borate product and a bromo-modified group in a fourth solvent, adding tetrakis (triphenylphosphine) palladium, a potassium carbonate aqueous solution and a tetrahydrofuran solution in a nitrogen atmosphere, and reacting to obtain the material taking the benzothiophene acene five-membered heterocycle as a core.
In some embodiments, the bromobenzothiophene derivative has one of the following structures:
Figure BDA0002996741500000251
in some embodiments, the benzene derivative includes one or more of o-chlorobenzaldehyde, 2-methoxyphenylthiol, 2-methoxyphenol, 2-methoxyphenylselenol, but is not limited thereto.
In this step, the benzene derivative mainly functions to change one of the reaction substrates under the condition that the reaction substrates are the same (also 3-bromobenzothiophene), so that the formation of the benzothieno-benzo five-membered heterocycle is facilitated, and therefore, the derivative which is beneficial to the formation of the benzothieno-benzo five-membered heterocycle can be selected.
In some embodiments, the first solvent comprises one or more of N, N-dimethylformamide, N-methylpyrrolidone, o-xylene, dimethylsulfoxide, the second solvent comprises one or more of propylene carbonate, ethylene carbonate, diethyl carbonate, the third solvent comprises one or more of benzene, toluene, 1, 4-dioxane, tetrahydrofuran, N-dimethylformamide, and the fourth solvent comprises one or more of benzene, toluene, 1, 4-dioxane, tetrahydrofuran, N-dimethylformamide, but is not limited thereto.
Wherein the first solvent is selected to facilitate the reactant to dissolve the high boiling point solvent, and the second solvent is selected to be an ionic electrolyte.
In some preferred embodiments, the palladium (ll) chloride concentration is 5 mol%, which maximizes the reaction yield on a catalyst-saving basis.
In some preferred embodiments, the concentration of the palladium tetrakis (triphenylphosphine) is 10 mol%, and the concentration of the potassium carbonate aqueous solution is 2M, so that the catalyst effect can be fully exerted on the basis of saving the catalyst, and the reaction yield can be maximized.
In some preferred embodiments, step S01 specifically includes: under the protection of nitrogen atmosphere, dissolving the raw material bromobenzothiophene derivative in a 0.1M first solvent in which the benzene derivative is dissolved in a Schlenk bottle, cooling in a saturated ammonium chloride solution, and filtering. Heating at 90 deg.C for 15min, distilling the reaction solution under reduced pressure, and separating by chromatographic column to obtain first intermediate product.
In some preferred embodiments, step S02 specifically includes: dissolving the first intermediate product in a second solvent at 90 ℃, adding N-bromosuccinimide, heating and refluxing for 24 hours, pouring the solution into water, filtering to obtain a white precipitate, dissolving the white precipitate in dichloromethane, adding water, washing for a plurality of times, and separating the liquid. Drying with anhydrous sodium sulfate and spin-drying to obtain a second intermediate product.
In some preferred embodiments, step S03 specifically includes: and dissolving the second intermediate product in a third solvent, adding triphenyl palladium dichloride (5 mol%), 2 equivalents of potassium acetate and diboron pinacol ester in a nitrogen atmosphere, heating and refluxing for 24 hours, drying the reaction solution by using anhydrous sodium sulfate, and separating by using a chromatographic column to obtain the benzothiophene acene five-membered heterocyclic borate product.
In some preferred embodiments, step S04 specifically includes: dissolving the benzothiophenacene five-membered heterocycle borate product and the selected bromo-modified group in a fourth solvent, adding tetrakis (triphenylphosphine) palladium (10 mol%), a 2M potassium carbonate aqueous solution and a proper amount of tetrahydrofuran solution in a nitrogen atmosphere, heating and refluxing for 24 hours, extracting and separating the reaction solution by dichloromethane, drying by anhydrous sodium sulfate, and separating by a chromatographic column to obtain the benzothiophene acene five-membered heterocycle core electron transport material.
A method for synthesizing benzothienobenzo five-membered heterocyclic material is provided, wherein the synthetic route includes but is not limited to:
Figure BDA0002996741500000261
or
Figure BDA0002996741500000271
An organic light-emitting device, comprising an electron transport layer, wherein the electron transport layer is made of the benzothiophenacene five-membered heterocyclic material.
The organic light-emitting device comprises a metal cathode, an electron injection layer, an electron transport layer, a light-emitting layer, a hole transport layer, a hole injection layer and an anode which are sequentially stacked.
Has the advantages that: according to the benzothiophene benzo five-membered heterocyclic material provided by the invention, the accumulation of the material can be effectively improved by introducing the benzo five-membered heterocyclic ring, and the planar rigid structure is adopted, so that the material can show high electron mobility, and the stability of a device is improved; proper electron-withdrawing groups are used as peripheral groups to adjust the energy levels of HOMO and LUMO, so that the injection energy barrier is reduced, and the starting voltage is reduced; asymmetric modification facilitates an increase in dipole moment, increases molecular triplet energy levels, blocks excitons and reduces quenching of effective excitons in the transport layer. When the benzothiophene benzo five-membered heterocyclic material provided by the invention is used as an electron transport material of an organic electroluminescent device, the benzothiophene benzo five-membered heterocyclic material has the advantages of high carrier mobility, improved luminous efficiency of the device, good thermal stability and the like.
Drawings
FIG. 1 is a fluorescence spectrum of a benzothiophenacene five-membered heterocyclic material 58 prepared in the examples of the present invention.
FIG. 2 is a graph of the UV absorption spectrum of benzothiophenacene five-membered heterocyclic material 58 prepared in the examples of the present invention.
Fig. 3 is a schematic structural diagram of an organic electroluminescent device prepared based on benzothiophene benzo five-membered heterocyclic ring material as an electron transport layer in the embodiment of the present invention.
Detailed Description
The invention provides a benzothienobenzo five-membered heterocyclic material, a preparation method and application thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and more clear. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
It should be noted that the term "comprises/comprising" when used in this specification and claims and in the accompanying drawings is intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus. It should also be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps or conditions described in the literature in the field. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available. The compounds for which no synthetic process is mentioned in the examples are all starting products obtained commercially.
The following is a further explanation of a benzothienobenzo five-membered heterocyclic material of the present invention, its preparation and use by specific examples:
example 1
This example provides a benzothienobenzo five-membered heterocyclic material, compound 1, whose synthetic route is as follows:
Figure BDA0002996741500000281
the synthesis method of the compound 1 specifically comprises the following steps:
synthesis of intermediate 1: 114g of sodium hydrosulfide was added to 200mL of NMP solution in which 100g of o-chlorobenzaldehyde was dissolved, and stirred for 1 hour, and then heated and stirred at 180 ℃ for 10 hours. After cooling to room temperature, the reaction mixture was poured into 1L of a saturated ammonium chloride solution, cooled in ice bath, and the precipitate was filtered, followed by washing with water and acetone, and purification by silica gel column chromatography using petroleum ether as an eluent to give intermediate 1(102g, yield 72%).
Synthesis of intermediate 2: a500 mL two-necked round-bottom flask was placed in a ball condenser, and intermediate 1(2.38g, 7.5mmol) and Propylene Carbonate (PC) (70mL) were added to the flask and heated to complete dissolution. After cooling to room temperature, N-bromosuccinimide (1.60g) was added and reacted at 90 ℃ for 18 hours. Cool to room temperature, pour solution into water, filter to give a white precipitate, and recrystallize the crude product from ethanol to give intermediate 2(3.57g, 83% yield).
Synthesis of intermediate 3: a100 mL two-necked round-bottomed flask was connected to a spherical condenser, and intermediate 2(1g, 2.51mmol), pinacol diboron diboride (2.54g,10mmol), palladium bis (triphenylphosphine) dichloride (100mg), excess potassium acetate (2.5g) and 50mL of toluene were added, respectively; carrying out oxygen removal operation on the reaction for many times under the nitrogen atmosphere, sealing, mixing the reactants, and stirring for 24 hours at 85 ℃ in a dark place; the toluene was then spun dry, dissolved with a small amount of dichloromethane, washed twice with water, the aqueous phase was back-extracted once with dichloromethane and the operation was repeated twice. Then drying with anhydrous magnesium sulfate, filtering and spin-drying; and this was purified by column chromatography using a mixed solvent (petroleum ether/ethyl acetate, v/v ═ 5:1) as an eluent to give intermediate 3 as a white solid, which was recrystallized from methanol/dichloromethane to give colorless transparent crystals (0.6g, yield 60%).
Synthesis of Compound 1: a50 mL round-bottom flask was connected to a spherical condenser, dried, purged with nitrogen, added with intermediate 3(1.83g, 5mmol), starting material 2(1.49g, 4.16mmol), palladium tetrakistriphenylphosphine (115.6mg, 0.1mmol), 10mL of a 2M aqueous solution of potassium carbonate, 50mL of toluene, and heated under reflux for 24 h. Cooling to room temperature, pouring the solution into water, filtering to give a white precipitate, and isolating the crude product using column chromatography to give compound 1(1.52g, 67% yield).
Example 2
This example provides a benzothienobenzo five-membered heterocyclic material, compound 218, whose synthetic route is shown below:
Figure BDA0002996741500000301
the synthesis method of the compound 218 specifically comprises the following steps:
synthesis of intermediate 4: starting material 3 was dissolved in dry dichloromethane (2.12g,10mmol) in a Schlenk flask under nitrogen at-20 deg.C, 8 equivalents of BF was added3OEt2(12.7g, 0.08 mol). 1.2 equivalents of mCPBA (20.7084g, 0.12mol) were added in three portions over 1.5 h. The progress of the reaction was monitored by TLC until the point of the reaction completely disappeared. Saturated aqueous sodium carbonate and potassium carbonate were added. Filtration through a Buchner funnel loaded with magnesium sulfate and potassium carbonate, followed by washing with dichloromethane and spin-drying afforded the crude product, which was purified by column chromatography over silica gel (EtOAc/CH)2Cl2) Intermediate 4(1.94g, 80% yield) was obtained.
The synthesis method of the intermediate 5 comprises the following steps: a250 mL two-necked round bottom flask was charged with intermediate 4(1.22g, 5mmol) and starting material 4(0.93g, 7.5mmol), cuprous chloride (5 mmol%), cesium carbonate (3.2g, 10mmol), oxygen removed from the system, dissolved in 1, 4-dioxane, and heated to reflux for 22 h. Cooled to room temperature, the solution was poured into water and filtered to give a white precipitate and the crude product was recrystallized from ethanol to give intermediate 5(0.87g, 65% yield).
The synthesis method of the intermediate 6 comprises the following steps: a250 mL round-bottom flask is connected with a spherical condenser tube, nitrogen is filled after drying, intermediate 5(3.0g, 12mmol) and DIBAL-H (2.13g, 15mmol) are respectively added to dissolve in dry toluene to prepare a 20% wt solution, and then the solution is heated for 5H at 65 ℃. The solution was cooled to 0 ℃ and quenched by the addition of 2M aqueous sodium hydroxide, the solution was extracted with dichloromethane, washed several times with water until the solution pH was neutral, dried over anhydrous magnesium sulfate, filtered, and the filtrate was spin dried to give a yellow oil (2.31g, 85% yield).
Synthesis of intermediate 7: to 0.9mL of pivalic acid were added intermediate 6(0.048g, 0.18mmol) and Pd (OPiv)2(0.006g, 0.02mmol) and heating at 120 ℃ for 20 h. After cooling, the reaction mixture was chromatographed on silica gel using pure petroleum ether as an eluent to give a colorless solid, which was intermediate 7(0.042g, 0.164mmol, 93% yield).
The synthesis method of the intermediate 8 comprises the following steps: a100 mL Schlenk bottle was taken, intermediate 7(3.44g, 5mmol) and 50mL of tert-butylbenzene were added, respectively, liquid nitrogen was freeze-extracted three times, cooled to-42 deg.C, boron tribromide (0.68mL, 7mmol) was added slowly, and the reaction was continued for 2h by slowly raising the temperature to room temperature. N, N-diisopropylethylamine (1.65mL, 10mmol) was added slowly under ice-water bath and gradually heated to 120 ℃ for 24 h. The reaction solution was cooled to room temperature, washed three times with sodium acetate solution, the organic phase was collected and dried over anhydrous magnesium sulfate, and the crude product was purified by silica gel column chromatography (petroleum ether/ethyl acetate 10/1 (vol.%)) to give intermediate 8(2.98g, 71% yield).
Synthesis of intermediate 9: intermediate 8(0.24g, 1mmol) was dissolved in dichloromethane at-15 deg.C, pyridine (3mmol) was added, and a solution of triflic anhydride (2mmol) in dichloromethane was slowly added dropwise. After 1h of reaction, the reaction was quenched with water and separated, then dried over anhydrous magnesium sulfate and spin-dried, and purified by silica gel column chromatography (ethyl acetate/petroleum ether, v/v ═ 1:9) to give intermediate 9(0.33g, yield 93%).
Synthesis of intermediate 10: the synthesis was identical to that of intermediate 3, except that intermediate 9(3.58g, 5mmol) was used, and intermediate 10(2.76g, 67% yield) was finally obtained.
Synthesis of compound 218: synthesis of compound 1 was performed except that intermediate 10(1.75g, 5mmol) was used to obtain compound 218(0.64g, yield 57%).
Example 3
This example provides a benzothienobenzo five-membered heterocyclic material, compound 3, whose synthetic route is as follows:
Figure BDA0002996741500000321
the synthesis method of the compound 3 specifically comprises the following steps:
synthesis of intermediate 11: to 80mL of N, N-dimethylacetamide with air removed was added raw material 5(2.1g, 40mmol), sodium acetate (6.7g, 80mmol) and PdCl2(PPh3)3(1.4g, 2 mmol). After heating to reflux for 24h, it was quenched with 200mL of 1M aqueous hydrochloric acid. By using BExtraction with ethyl acetate, followed by washing with aqueous sodium chloride solution, followed by drying over anhydrous magnesium sulfate and spin-drying gave the product. Purification by silica gel column chromatography using petroleum ether as the eluent gave pure intermediate 11(1.90g, 74% yield).
Synthesis of intermediate 12: the synthesis was identical to that of intermediate 2, except that intermediate 11(5.65g, 22mmol) was used, and intermediate 12(5.62g, 80% yield) was finally obtained.
Synthesis of intermediate 13: the synthesis was identical to that of intermediate 3, except that intermediate 12(3.51g, 5mmol) was used, and intermediate 13(2.33g, 65% yield) was finally obtained.
Synthesis of Compound 3: synthesis of compound 1, except using intermediate 13(2.07g, 5mmol) and starting material 2(1.49g, 4.16mmol), yielded compound 3(1.76g, 75% yield) finally.
Example 4
This example provides a benzothienobenzo five-membered heterocyclic material, compound 58, whose synthetic route is shown below:
Figure BDA0002996741500000331
synthesis of compound 58: synthesis of Compound 1, except using starting material 6(1.74g, 6mmol), gave finally Compound 58(1.52g, 60% yield).
The performance test of the benzothienobenzo five-membered heterocyclic material 58 prepared in example 4 is shown in fig. 1 and fig. 2: as can be seen from the fluorescence spectrum of the benzothienobenzo five-membered heterocyclic material 58 in fig. 1, the benzothienobenzo five-membered heterocyclic material has a wide spectrum characteristic, a weak luminescence property and less electron loss in a transmission process; as can be seen from the ultraviolet absorption spectrum of the benzothiophene benzo five-membered heterocyclic material 58 in fig. 2, the peak position is 410nm, the energy level measured by experiments is 3.03eV, the material has a relatively universal energy level, can be matched with a blue light organic light emitting diode device, and has a certain hole and exciton blocking capability.
Example 5
The invention provides an organic light-emitting device based on benzothiophene benzo five-membered heterocyclic materials as an electron transport layer, which comprises a metal cathode 10, an electron injection layer 20, an electron transport layer 30, a light-emitting layer 40, a hole transport layer 50, a hole injection layer 60, an anode 70 and a glass substrate 80 which are sequentially stacked from top to bottom as shown in figure 3.
In the present embodiment, the metal cathode 10 is made of aluminum;
the material of the electron injection layer 20 is lithium fluoride;
the material of the electron transport layer 30 is selected from a compound 58;
the material of the light-emitting layer 40 is formed by co-doping a host material and a guest material, wherein the host material is a compound 2,6-DCzppy with the following structure, the guest material is Firpic with the following structure, and the mass ratio of the host material to the guest material is 80: 20:
Figure BDA0002996741500000341
the material of the hole transport layer 50 is selected from a compound NPB having the following structure:
Figure BDA0002996741500000342
the material of the hole injection layer 60 is selected from a compound HATCN having the following structure:
Figure BDA0002996741500000343
the anode 70 is made of indium tin oxide.
The devices prepared in example 5 were subjected to performance testing, the results of which are shown in table 1:
table 1:
Figure BDA0002996741500000344
as can be seen from table 1, the benzothienobenzo five-membered heterocyclic material 58 provided in the embodiment of the present invention can match with most of the light emitting layers, and has a certain hole blocking capability and exciton blocking capability.
In conclusion, the invention provides a benzothiophene acene five-membered heterocyclic ring material, the accumulation of the materials can be effectively improved by introducing a benzo five-membered heterocyclic ring, and the planar rigid structure is adopted, so that the material can show high electron mobility, and the stability of a device is improved; proper electron-withdrawing groups are used as peripheral groups to adjust the energy levels of HOMO and LUMO, so that the injection energy barrier is reduced, and the starting voltage is reduced; asymmetric modification facilitates an increase in dipole moment, increases molecular triplet energy levels, blocks excitons and reduces quenching of effective excitons in the transport layer. When the benzothiophene benzo five-membered heterocyclic material provided by the invention is used as an electron transport material of an organic electroluminescent device, the benzothiophene benzo five-membered heterocyclic material has the advantages of high carrier mobility, improved luminous efficiency of the device, good thermal stability and the like.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.

Claims (10)

1. A benzothienobenzo five-membered heterocyclic material is characterized by having the following structural general formula:
Figure FDA0002996741490000011
wherein, aromatic ring Ar1And Ar2Each independently selected from substituted or unsubstituted aryl or heteroaryl, R1-R8Each independently selected from hydrogen, aromatic substituents or aliphatic substituents, and X is selected from one of an oxygen or oxygen substituted heteroatom ring, a sulfur or sulfur substituted heteroatom ring, selenium or selenium substituted heteroatom ring.
2. According to claim1 the benzothienobenzo five-membered heterocyclic material, wherein Ar is1And Ar2Each independently selected from substituted or unsubstituted phenyl, naphthyl, (9, 9-dialkyl) fluorenyl, (9, 9-disubstituted or unsubstituted aryl) fluorenyl, 9-spirofluorenyl, purinyl, diphenylphosphinyloxy, pyridine group, imidazole derivative group, pyrimidinyl, pyridazinyl, imidazopyrimidinyl, pyrazinyl, triazinyl, triazinbiphenyl group.
3. The benzothienobenzo five-membered heterocyclic material of claim 2, wherein Ar is Ar1And Ar2Each having one of the following structures:
Figure FDA0002996741490000012
Figure FDA0002996741490000021
Figure FDA0002996741490000022
wherein the content of the first and second substances,
Figure FDA0002996741490000023
indicates the attachment site.
4. The benzothienobenzo five-membered heterocyclic material according to claim 1, having one of the following structures:
Figure FDA0002996741490000024
Figure FDA0002996741490000031
Figure FDA0002996741490000041
Figure FDA0002996741490000051
Figure FDA0002996741490000061
Figure FDA0002996741490000071
Figure FDA0002996741490000081
Figure FDA0002996741490000091
Figure FDA0002996741490000101
Figure FDA0002996741490000111
Figure FDA0002996741490000121
Figure FDA0002996741490000131
Figure FDA0002996741490000141
Figure FDA0002996741490000151
Figure FDA0002996741490000161
Figure FDA0002996741490000171
Figure FDA0002996741490000181
Figure FDA0002996741490000191
Figure FDA0002996741490000201
Figure FDA0002996741490000211
Figure FDA0002996741490000221
Figure FDA0002996741490000231
Figure FDA0002996741490000241
5. the preparation method of the benzothienobenzo five-membered heterocyclic material is characterized by comprising the following steps:
providing a bromobenzothiophene derivative raw material, adding the bromobenzothiophene derivative raw material into a first solvent dissolved with a benzene derivative, cooling and filtering the bromobenzothiophene derivative raw material in a saturated ammonium chloride solution, and reacting to obtain a first intermediate product;
dissolving the first intermediate product in a second solvent, adding N-bromosuccinimide, filtering after reaction to obtain a white precipitate, dissolving the white precipitate in dichloromethane, and obtaining a second intermediate product after reaction;
dissolving the second intermediate product in a third solvent, adding triphenyl palladium dichloride, 2 equivalents of potassium acetate and diboron pinacol ester in a nitrogen atmosphere, and reacting to obtain a benzothiophene acene five-membered heterocyclic borate product;
dissolving the benzothiophene acene five-membered heterocycle boric acid ester product and a bromo-modified group in a fourth solvent, adding tetrakis (triphenylphosphine) palladium, a potassium carbonate aqueous solution and a tetrahydrofuran solution in a nitrogen atmosphere, and reacting to obtain the material taking the benzothiophene acene five-membered heterocycle as a core.
6. The method of preparing a benzothiophene acene five-membered heterocyclic material of claim 5, wherein said bromo benzothiophene derivative has one of the following structures:
Figure FDA0002996741490000242
7. the method of claim 5, wherein the benzene derivative comprises one or more of o-chlorobenzaldehyde, 2-methoxythiophenol, 2-methoxyphenol, and 2-methoxyphenylselenol.
8. The method of claim 5, wherein the first solvent comprises one or more of N, N-dimethylformamide, N-methylpyrrolidone, o-xylene, and dimethylsulfoxide, the second solvent comprises one or more of propylene carbonate, ethylene carbonate, and diethyl carbonate, the third solvent comprises one or more of benzene, toluene, 1, 4-dioxane, tetrahydrofuran, and N, N-dimethylformamide, and the fourth solvent comprises one or more of benzene, toluene, 1, 4-dioxane, tetrahydrofuran, and N, N-dimethylformamide.
9. An organic light-emitting device comprising an electron transport layer, wherein the electron transport layer is made of the benzothienoaceno five-membered heterocyclic material according to any one of claims 1 to 4.
10. The organic light-emitting device according to claim 9, comprising a metal cathode, an electron injection layer, an electron transport layer, a light-emitting layer, a hole transport layer, a hole injection layer, and an anode, which are sequentially stacked.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113861172A (en) * 2021-09-23 2021-12-31 北京大学深圳研究生院 Bipolar fluorescent material based on benzo five-membered heterocycle, preparation method thereof and organic electroluminescent device
CN113861143A (en) * 2021-10-12 2021-12-31 北京大学深圳研究生院 Thermal activation delayed fluorescence deep blue light material, preparation method thereof and organic electroluminescent device
CN114163448A (en) * 2021-11-11 2022-03-11 北京大学深圳研究生院 Host material based on naphtho five-membered heterocycle and benzo five-membered heterocycle, preparation method thereof and organic light-emitting device
WO2022262310A1 (en) * 2021-06-17 2022-12-22 广东阿格蕾雅光电材料有限公司 Method for synthesizing btbf aromatic amine derivatives

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012004192A (en) * 2010-06-14 2012-01-05 Yamamoto Chem Inc Organic transistor
CN106866709A (en) * 2017-03-04 2017-06-20 长春海谱润斯科技有限公司 A kind of carbazole meta connects benzothiophene derivative and its organic luminescent device
KR20170086277A (en) * 2016-01-18 2017-07-26 에스에프씨 주식회사 Organic light-emitting compounds and Organic light-emitting device comprising the same
WO2020015029A1 (en) * 2018-07-18 2020-01-23 北京大学深圳研究生院 Semiconductor material, preparation method for same, and application
CN110964007A (en) * 2018-09-30 2020-04-07 江苏三月光电科技有限公司 Compound with quinolinone derivative as core and application of compound in organic electroluminescent device
US20200131202A1 (en) * 2018-10-31 2020-04-30 Adeka Corporation Organic compound, and organic photoelectric device, image sensor, and electronic device including the organic compound
JP2021042138A (en) * 2019-09-06 2021-03-18 日本放送協会 Condensed ring compound, organic electroluminescent element, display device, and illumination device

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012004192A (en) * 2010-06-14 2012-01-05 Yamamoto Chem Inc Organic transistor
KR20170086277A (en) * 2016-01-18 2017-07-26 에스에프씨 주식회사 Organic light-emitting compounds and Organic light-emitting device comprising the same
CN106866709A (en) * 2017-03-04 2017-06-20 长春海谱润斯科技有限公司 A kind of carbazole meta connects benzothiophene derivative and its organic luminescent device
WO2020015029A1 (en) * 2018-07-18 2020-01-23 北京大学深圳研究生院 Semiconductor material, preparation method for same, and application
CN110964007A (en) * 2018-09-30 2020-04-07 江苏三月光电科技有限公司 Compound with quinolinone derivative as core and application of compound in organic electroluminescent device
US20200131202A1 (en) * 2018-10-31 2020-04-30 Adeka Corporation Organic compound, and organic photoelectric device, image sensor, and electronic device including the organic compound
JP2021042138A (en) * 2019-09-06 2021-03-18 日本放送協会 Condensed ring compound, organic electroluminescent element, display device, and illumination device

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
KENTASAITO等: "Palladium-Catalyzed Construction of Heteroatom-Containing p-Conjugated Systems by Intramolecular Oxidative C-H/C-H Coupling Reaction", 《CHEM. EUR.J.》 *
陶友田，杨楚罗著: "《高效有机电致磷光双极主体材料的合成与性能》", 31 May 2015 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022262310A1 (en) * 2021-06-17 2022-12-22 广东阿格蕾雅光电材料有限公司 Method for synthesizing btbf aromatic amine derivatives
CN113861172A (en) * 2021-09-23 2021-12-31 北京大学深圳研究生院 Bipolar fluorescent material based on benzo five-membered heterocycle, preparation method thereof and organic electroluminescent device
CN113861172B (en) * 2021-09-23 2024-04-16 北京大学深圳研究生院 Bipolar fluorescent material based on benzo five-membered heterocycle, preparation method thereof and organic electroluminescent device
CN113861143A (en) * 2021-10-12 2021-12-31 北京大学深圳研究生院 Thermal activation delayed fluorescence deep blue light material, preparation method thereof and organic electroluminescent device
CN113861143B (en) * 2021-10-12 2023-12-12 北京大学深圳研究生院 Thermal-activation delayed fluorescence deep blue light material, preparation method thereof and organic electroluminescent device
CN114163448A (en) * 2021-11-11 2022-03-11 北京大学深圳研究生院 Host material based on naphtho five-membered heterocycle and benzo five-membered heterocycle, preparation method thereof and organic light-emitting device

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