Hexa-membered heterocyclic organic light-emitting compound, preparation method thereof and photoelectric device

文档序号：1038414 发布日期：2020-10-30 浏览：38次中文

阅读说明：本技术 一种六元杂环类有机发光化合物及其制备方法和光电器件 (Hexa-membered heterocyclic organic light-emitting compound, preparation method thereof and photoelectric device ) 是由马晓宇王进政张鹤赵贺陈明李明崔建勇于 2020-07-28 设计创作，主要内容包括：本发明公开了一种六元杂环类有机发光化合物及其制备方法和光电器件,属于发光材料技术领域,该有机发光化合物的结构通式为：<Image he="373" wi="383" file="DDA0002604854500000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>式中,R1、R2和R3独立地为氢、氘、卤素、氰基、硝基、三氟甲基、羟基、磺酸基、磷酸基、酰基、取代或非取代的C1～C20的烷基、取代或非取代的C6～C30的芳基、取代或非取代的3元～10元的杂芳基中的至少一种。本发明提供的有机发光化合物,可用于有机电致发光器件等光电器件的制备,将其作为有机电致发光器件等光电器件的空穴注入层材料,可显著降低光电器件的驱动电压明,以及显著提高光电器件的发光效率以及使用寿命。(The invention discloses a hexabasic heterocyclic organic luminescent compound, a preparation method thereof and a photoelectric device, belonging to the technical field of luminescent materials, wherein the organic luminescent compound has a structural general formula as follows: in the formula, R 1 、R 2 And R 3 Independently hydrogen, deuterium, halogen, cyano, nitro, trifluoromethyl, hydroxyl, sulfonic group, phosphoric group, acyl, substituted or unsubstituted alkyl of C1-C20, substituted or unsubstitutedAt least one of substituted C6-C30 aryl and substituted or unsubstituted 3-to 10-membered heteroaryl. The organic luminescent compound provided by the invention can be used for preparing photoelectric devices such as organic electroluminescent devices and the like, and can be used as a hole injection layer material of the photoelectric devices such as the organic electroluminescent devices and the like, so that the driving voltage of the photoelectric devices can be obviously reduced, the luminous efficiency of the photoelectric devices can be obviously improved, and the service life of the photoelectric devices can be obviously prolonged.)

1. A six-membered heterocyclic organic light-emitting compound is characterized in that the structural general formula of the organic light-emitting compound is shown as formula I:

in the formula, R₁、R₂And R₃Independently at least one of hydrogen, deuterium, halogen, cyano, nitro, trifluoromethyl, hydroxyl, sulfonic group, phosphoric group, acyl, substituted or unsubstituted alkyl of C1-C20, substituted or unsubstituted aryl of C6-C30, and substituted or unsubstituted heteroaryl of 3-to 10-membered.

2. A six-membered heterocyclic organic light emitting compound according to claim 1, wherein said halogen is one of fluorine, chlorine, bromine and iodine.

3. A six-membered heterocyclic organic light-emitting compound according to claim 2, wherein said halogen is fluorine or chlorine.

4. A six-membered heterocyclic organic light-emitting compound according to claim 1, wherein substituted means substituted with a substituent; the substituent is at least one of deuterium, halogen, nitrile group, hydroxyl, carbonyl and nitro.

5. A six-membered heterocyclic organic light-emitting compound according to claim 1, wherein R is₁、R₂And R₃Independently one of fluorine, trifluoromethyl and nitrile groups.

6. A six-membered heterocyclic organic light-emitting compound according to claim 1, wherein said organic light-emitting compound has any one of the following chemical structural formulas L01-L31:

7. a method for producing an organic light-emitting compound according to any one of claims 1 to 6, comprising the steps of:

reacting the raw material A, n-butyllithium and the raw material B to obtain an intermediate C;

reacting the intermediate C with bromosuccinimide to obtain an intermediate D;

reacting the intermediate D, the raw material E and a palladium catalyst to obtain an intermediate F;

reacting the intermediate F with [ bis (trifluoroacetoxy) iodine ] benzene to obtain the organic light-emitting compound;

the structural general formula of the raw material A is shown as a formula A, the structural general formula of the raw material B is shown as a formula B, the structural general formula of the intermediate C is shown as a formula C, the structural general formula of the intermediate D is shown as a formula D, the structural general formula of the raw material E is shown as a formula E, and the structural general formula of the intermediate F is shown as a formula F:

8. the method according to claim 7, wherein the palladium catalyst is palladium tetrakistriphenylphosphine.

9. An optoelectronic device comprising a first electrode, a second electrode and at least one organic layer disposed between said first electrode and said second electrode, wherein said organic layer comprises an organic light-emitting compound according to any one of claims 1 to 6.

10. The optoelectronic device according to claim 9, wherein the organic layer comprises a hole injection layer; the hole injection layer partially or entirely contains the organic light-emitting compound.

Technical Field

The invention relates to the technical field of luminescent materials, in particular to a hexabasic heterocyclic organic luminescent compound, a preparation method thereof and a photoelectric device.

Background

An organic electroluminescent device refers to a photoelectric device that utilizes the light emitting property of a material when excited by an electric current. Due to the advantages of self-emission, fast response, high brightness, flexibility and rollability, optoelectronic devices such as organic electroluminescent devices have attracted attention in the fields of new-generation large-area flat panel displays and semiconductor solid-state illumination light sources.

It is now well known that organic electroluminescent devices are characterized by high luminance, high efficiency, low driving voltage, variable color, low cost, and the like. However, in order to have such characteristics, each layer (e.g., a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer) forming an organic film in a device must be formed of a more stable and efficient material.

The hole injection material is a major obstacle to the overall practical application of the OLED technology, and directly limits the luminous efficiency, the service life, the operating voltage and the like of the device. However, the conventional hole injection material still has the problems of short service life, low efficiency, high driving voltage and the like.

Therefore, it is also crucial to find efficient and long-lived hole injection materials in organic electroluminescent devices.

Disclosure of Invention

An embodiment of the present invention is directed to providing a six-membered heterocyclic organic light emitting compound to solve the problems set forth in the background art.

In order to achieve the above purpose, the embodiments of the present invention provide the following technical solutions:

a six-membered heterocyclic organic luminescent compound has a structural general formula as formula I:

Preferably, the halogen is one of fluorine, chlorine, bromine and iodine.

Preferably, the halogen is fluorine or chlorine.

Preferably, substituted means substituted with a substituent; the substituent is at least one of deuterium, halogen, nitrile group, hydroxyl, carbonyl and nitro.

Preferably, R₁、R₂And R₃Independently one of fluorine, trifluoromethyl and nitrile groups.

Preferably, the chemical structural formula of the organic light-emitting compound is any one of formula L01 to formula L31:

it should be noted that, only some specific structural forms are listed above, but the series of compounds are not limited to the above molecular structures, and any simple group, substituted group and substituted position can be simply transformed to obtain other specific molecular structures, which are not described in detail herein.

Another object of an embodiment of the present invention is to provide a method for preparing the organic light emitting compound, including the following steps:

reacting the raw material A, n-butyllithium and the raw material B to obtain an intermediate C;

reacting the intermediate C with bromosuccinimide to obtain an intermediate D;

reacting the intermediate D, the raw material E and a palladium catalyst to obtain an intermediate F;

reacting the intermediate F with [ bis (trifluoroacetoxy) iodine ] benzene to obtain the organic light-emitting compound;

preferably, the palladium catalyst is tetratriphenylphosphine palladium, but is not limited thereto, and other palladium catalysts, such as palladium acetate, diphenylphosphine ferrocene palladium dichloride and the like, can be selected according to requirements.

Specifically, the preparation method specifically comprises the following steps:

s1, dissolving the raw material A in Tetrahydrofuran (THF), cooling to-80-75 ℃, dropwise adding n-butyl lithium while stirring, stirring at-80-75 ℃, slowly heating the reaction temperature to room temperature, and keeping the temperature at the room temperature for 10-20 minutes. And cooling the reaction liquid to-80 to-75 ℃ again and keeping the temperature for 20 to 40 minutes. The THF solution of the raw material B containing iodine is cooled to-80 to-75 ℃ in advance, added into the reaction solution, removed from the cold bath after the addition is finished and stirred overnight. The reaction was quenched with saturated ammonium chloride solution, the aqueous layer was extracted with Dichloromethane (DCM), the organic phases were combined and washed successively with aqueous sodium thiosulfate solution and sodium chloride solution and dried over magnesium sulfate. And (3) concentrating the solvent to a small amount, dripping the concentrated solvent into cold ethanol while stirring, and carrying out suction filtration, washing and drying on the precipitated solid to obtain an intermediate C.

S2, dissolving the intermediate C and bromosuccinimide (NBS) in DMF, heating to 95-105 ℃, reacting, concentrating the reaction solution to a small amount, and performing chromatographic purification by using a mixed solution of dichloromethane and petroleum ether to obtain an intermediate D.

S3, dissolving the intermediate D in THF, fully cooling to-5 ℃ under the protection of nitrogen, slowly adding sodium hydride in batches under stirring, and reacting at-5 ℃. Adding the raw material E and the palladium tetratriphenylphosphine in a nitrogen atmosphere, heating the mixture to 65-75 ℃ after 0.3-0.7 hours, and reacting for 8-12 hours. Removing the solvent, adding hydrochloric acid, filtering the precipitated solid, washing with water and ethanol, and drying to obtain an intermediate F.

S4, intermediate F was added to DCM, followed by addition of [ bis (trifluoroacetoxy) iodo ] benzene (PIFA) and stirring at room temperature. And concentrating the solvent to a small amount by vacuum evaporation, dripping the solvent into cold ethanol while stirring, and carrying out suction filtration, washing and drying on the precipitated solid to obtain the organic luminescent compound.

The chemical synthesis route of the preparation method is as follows:

it is another object of an embodiment of the present invention to provide an optoelectronic device, which includes a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, the organic layer including the organic light emitting compound described above.

Preferably, the organic layer includes a hole injection layer; the hole injection layer partially or entirely contains the organic light-emitting compound.

The hole injection layer may further include N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB), and the mass ratio of the NPB to the organic light emitting compound is (90-97): 3-10). The thickness of the hole injection layer is preferably 10 to 500 nm.

The first electrode is an anode, and the kind thereof is not particularly limited, and may be a conventional anode known to those skilled in the art, and is more preferably one of ITO (indium tin oxide), tin oxide, zinc oxide, and indium oxide. The thickness of the anode is preferably 10-500 nm. The second electrode is a cathode, and the kind thereof is not particularly limited, and may be a conventional cathode known to those skilled in the art, and more preferably one of Al, Li, Na, K, Mg, Ca, Au, Ag, and Pb.

The organic layer may further include other functional layers, and the other functional layers may be specifically selected from one or more of the following functional layers: the organic light emitting diode comprises an organic light emitting layer, a Hole Transport Layer (HTL), a hole injection-hole transport functional layer (namely, the organic light emitting layer has both the hole injection function and the hole transport function), an Electron Blocking Layer (EBL), a Hole Blocking Layer (HBL), an Electron Transport Layer (ETL), an Electron Injection Layer (EIL) and an electron transport-electron injection functional layer (namely, the organic light emitting layer has both the electron transport function and the electron injection function).

The kind of each functional layer is not particularly limited, and may be a conventional functional layer known to those skilled in the art. Preferably: the hole transport layer is [ di- [4- (N, N-xylyl-amino) -phenyl group]Cyclohexane (TAPC), TPD (i.e., N '-diphenyl-N, N' - (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine), PAPB (i.e., N '-bis (phenanthren-9-yl) -N, N' -diphenylbenzidine), arylamine carbazole compounds, indolocarbazole compounds; the thickness of the hole transport layer is preferably 10-500 nm; the thickness of the electron blocking layer is preferably 10-500 nm. The hole blocking layer is one of BAlq, BCP and BPhen; the thickness of the hole blocking layer is preferably 10-500 nm. The electron transport layer is one of Alq3, coumarin No. 6, triazole derivatives, azole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives and anthrone derivatives; the thickness of the electron transport layer is preferably 10-500 nm. The electron injection layer is LiF, CsF or Li₂O、Al₂O₃MgO; the thickness of the electron injection layer is preferably 0.1-10 nm. The organic light-emitting layer is 10nm thick and may comprise 90% of 4,4' -bis (carbazol-9-yl) -biphenyl, CBP) as the light-emitting host material and 10% of bis (1-phenyl-isoquinoline) (acetylacetone) iridium (III) (Ir (ppy)₂(acac)), but not limited thereto; the thickness of the electron transmission-electron injection functional layer is preferably 10-500 nm. The inventionIn the above, the light-emitting layer and other various functional layers may be formed by vapor deposition.

In addition, the optoelectronic device may include an Organic Light Emitting Device (OLED), an Organic Solar Cell (OSC), an electronic paper (e-paper), an Organic Photoreceptor (OPC), or an Organic Thin Film Transistor (OTFT), but is not limited thereto.

Compared with the prior art, the embodiment of the invention has the beneficial effects that:

the hexabasic heterocyclic organic luminescent compound provided by the embodiment of the invention can be used for preparing photoelectric devices such as organic electroluminescent devices, can be used as a hole injection layer material of the photoelectric devices such as the organic electroluminescent devices, can obviously reduce the driving voltage of the photoelectric devices, and can obviously improve the luminous efficiency and service life of the photoelectric devices. In addition, the preparation method of the organic luminescent compound provided by the embodiment of the invention has the characteristics of simple synthesis steps, easiness in product purification, high purity, high yield and the like.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.

Compound example 1

The embodiment of the compound provides a six-membered heterocyclic organic luminescent compound, the chemical structural formula of which is shown as formula L01 in the invention, and the reaction route of the preparation method of the organic luminescent compound is as follows:

the specific preparation method comprises the following steps:

s1, raw material A-1(100mmol) was dissolved in THF (500mL), cooled to-78 ℃, 132mL of n-butyllithium (2.5M) was added dropwise with stirring, and after stirring at-78 ℃ for 1 hour, the reaction temperature was gradually raised to room temperature and maintained at room temperature for 15 minutes. The reaction solution was cooled to-78 ℃ again and held for 30 minutes. A THF solution (50ml) of the iodine-containing starting material B-1(300mmol) was cooled to-78 deg.C, added to the reaction solution, and after the addition was complete the cold bath was removed and stirred overnight. The reaction was quenched with saturated ammonium chloride solution, the aqueous layer was extracted with DCM, the organic phases were combined and washed successively with aqueous sodium thiosulfate solution and sodium chloride solution and dried over magnesium sulfate. The solvent was concentrated to a small amount (50ml), and the mixture was dropped into cold ethanol (500ml) with stirring, and the precipitated solid was suction-filtered, washed and dried to give intermediate C-1(24.37g, yield 84%, MS: 290.10).

S2, intermediate C-1(80mmol) and bromosuccinimide (NBS 264mmol) were dissolved in DMF (200ml), heated to 100 ℃ and reacted for 10 hours, the reaction solution was concentrated to a small amount (30ml), and purified by chromatography using a mixed solution of dichloromethane and petroleum ether to give intermediate D-1(37.71g, yield 90%, MS: 523.80).

S3, dissolving intermediate D-1(70mmol) in THF (350ml), cooling to 0 ℃ with nitrogen protection, adding sodium hydride (210mmol) slowly in portions while stirring, and reacting at 0 ℃ for 1 h. E-1(210mmol) and tetrakistriphenylphosphine palladium (10.5mmol) were added under nitrogen and after half an hour the mixture was heated to 70 ℃ for 10 h. The solvent was removed and hydrochloric acid (2N) was added to adjust the pH to 1, and the precipitated solid was filtered off with suction, washed with water and ethanol, and dried to give intermediate F-1(26.67g, yield 79%, MS: 482.15).

S4, intermediate F-1(55mmol) was added to DCM (200ml) followed by the addition of [ bis (trifluoroacetoxy) iodo ] benzene (PIFA, 247.5mmol) and stirring at room temperature for 10 h. The solvent was concentrated to a small amount (30mmol) by vacuum evaporation, the reaction solution was concentrated to a small amount (30ml), and the reaction solution was purified by chromatography using a mixed solution of dichloromethane and petroleum ether to obtain an organic luminescent compound represented by the formula L01 (23.83, yield 91%, MS: 476.10).

Compound example 2

The embodiment of the compound provides a six-membered heterocyclic organic luminescent compound, the chemical structural formula of which is shown as formula L06 in the invention, and the reaction route of the preparation method of the organic luminescent compound is as follows:

the specific preparation method comprises the following steps:

s1, step 1: the starting material A-6(100mmol) was dissolved in THF (500ml), cooled to-78 deg.C, 132ml of n-butyllithium (2.5M) was added dropwise with stirring, and after stirring at-78 deg.C for 1 hour, the reaction temperature was slowly raised to room temperature and kept at room temperature for 15 minutes. The reaction solution was cooled to-78 ℃ again and held for 30 minutes. A THF solution (50ml) of the iodine-containing starting material B-6(300mmol) was cooled to-78 deg.C, added to the reaction solution, and after the addition was complete the cold bath was removed and stirred overnight. The reaction was quenched with saturated ammonium chloride solution, the aqueous layer was extracted with DCM, the organic phases were combined and washed successively with aqueous sodium thiosulfate solution and sodium chloride solution and dried over magnesium sulfate. The solvent was concentrated to a small amount (50ml), and the mixture was dropped into cold ethanol (500ml) with stirring, and the precipitated solid was suction-filtered, washed and dried to obtain intermediate C-6(24.05g, yield 82.9%, MS: 290.10).

S2, intermediate C-6(80mmol) and bromosuccinimide (NBS, 264mmol) were dissolved in DMF (200ml), heated to 100 ℃ for reaction for 10 hours, the reaction solution was concentrated to a small volume (30ml), and purified by chromatography using a mixed solution of dichloromethane and petroleum ether to give intermediate D-6(37.80g, yield 90.2%, MS: 523.85).

S3, dissolving intermediate D-6(70mmol) in THF (350ml), cooling to 0 ℃ with nitrogen protection, adding sodium hydride (210mmol) slowly in portions while stirring, and reacting at 0 ℃ for 1 h. E-6(210mmol) and tetrakistriphenylphosphine palladium (10.5mmol) were added under nitrogen and after half an hour the mixture was heated to 70 ℃ for 10 h. The solvent was removed and hydrochloric acid (2N) was added to adjust the pH to 1, and the precipitated solid was filtered off with suction, washed with water and ethanol, and dried to give intermediate F-6(50.30g, yield 79.4%, MS: 905.10).

S4, intermediate F-6(55mmol) was added to DCM (200ml) followed by the addition of [ bis (trifluoroacetoxy) iodo ] benzene (PIFA 247.5mmol) and stirring at room temperature for 10 h. The solvent was concentrated to a small amount (30mmol) by vacuum evaporation, the reaction solution was concentrated to a small amount (30ml), and the reaction solution was purified by chromatography using a mixed solution of dichloromethane and petroleum ether to give an organic luminescent compound represented by the formula L06 (40.1g, yield 81.2%, MS: 899.05).

Compound example 3

The embodiment of the compound provides a six-membered heterocyclic organic luminescent compound, the chemical structural formula of which is shown as formula L12 in the invention, and the reaction route of the preparation method of the organic luminescent compound is as follows:

the specific preparation method comprises the following steps:

s1, the raw material A-12(100mmol) was dissolved in THF (500ml), cooled to-78 ℃, 132ml of n-butyllithium (2.5M) was added dropwise with stirring, and after stirring at-78 ℃ for 1 hour, the reaction temperature was gradually raised to room temperature and kept at room temperature for 15 minutes. The reaction solution was cooled to-78 ℃ again and held for 30 minutes. A THF solution (50ml) of the iodine-containing starting material B-12(300mmol) was cooled to-78 deg.C, added to the reaction solution, and after the addition was complete the cold bath was removed and stirred overnight. The reaction was quenched with saturated ammonium chloride solution, the aqueous layer was extracted with DCM, the organic phases were combined and washed successively with aqueous sodium thiosulfate solution and sodium chloride solution and dried over magnesium sulfate. The solvent was concentrated to a small amount (50ml), and the mixture was dropped into cold ethanol (500ml) with stirring, and the precipitated solid was suction-filtered, washed and dried to obtain intermediate C-12(25.05g, yield 86.4%, MS: 209.05).

Step 2: intermediate C-12(85mmol) and bromosuccinimide (NBS 260mmol) were dissolved in DMF (200ml), heated to 100 ℃ for 10 hours, the reaction mixture was concentrated to a small amount (30ml), and purified by chromatography using a mixed solution of dichloromethane and petroleum ether to give intermediate D-12(40.1g, yield 95.7%, MS: 523.80).

And step 3: intermediate D-12(75mmol) was dissolved in THF (350ml), cooled well to 0 ℃ under nitrogen blanket, and sodium hydride (210mmol) was added slowly in portions with stirring and reacted at 0 ℃ for 1 h. E-12(210mmol) and tetrakistriphenylphosphine palladium (10.5mmol) were added under nitrogen and after half an hour the mixture was heated to 70 ℃ for 10 h. The solvent was removed and hydrochloric acid (2N) was added to adjust the pH to 1, and the precipitated solid was filtered off with suction, washed with water and ethanol, and dried to give intermediate F-12(45.5g, yield 80.7%, MS: 752.11).

And 4, step 4: intermediate F-12(60mmol) was added to DCM (200ml) and then [ bis (trifluoroacetoxy) iodo ] benzene (PIFA, 247.5mmol) was added and stirred at room temperature for 10 h. The solvent was concentrated to a small amount (30mmol) by vacuum evaporation, the reaction solution was concentrated to a small amount (30ml), and the reaction solution was purified by chromatography using a mixed solution of dichloromethane and petroleum ether to give an organic luminescent compound represented by the formula L12 (40.5g, yield 90.4%, MS: 746.08).

Compound example 4

The embodiment of the compound provides a six-membered heterocyclic organic luminescent compound, the chemical structural formula of which is shown as formula L31 in the invention, and the reaction route of the preparation method of the organic luminescent compound is as follows:

the specific preparation method comprises the following steps:

s1, the raw material A-31(100mmol) was dissolved in THF (500ml), cooled to-78 ℃, 132ml of n-butyllithium (2.5M) was added dropwise with stirring, and after stirring at-78 ℃ for 1 hour, the reaction temperature was gradually raised to room temperature and kept at room temperature for 15 minutes. The reaction solution was cooled to-78 ℃ again and held for 30 minutes. A THF solution (50ml) of the iodine-containing starting material B-31(300mmol) was cooled to-78 deg.C, added to the reaction solution, and after the addition was complete the cold bath was removed and stirred overnight. The reaction was quenched with saturated ammonium chloride solution, the aqueous layer was extracted with DCM, the organic phases were combined and washed successively with aqueous sodium thiosulfate solution and sodium chloride solution and dried over magnesium sulfate. The solvent was concentrated to a small amount (50ml), and the mixture was dropped into cold ethanol (500ml) while stirring, and the precipitated solid was suction-filtered, washed and dried to obtain intermediate C-31(35.0g, yield 83.5%, MS: 419.06).

Step 2: intermediate C-31(83mmol) and bromosuccinimide (NBS, 260mmol) were dissolved in DMF (200ml), heated to 100 ℃ for 10 hours, the reaction solution was concentrated to a small amount (30ml), and purified by chromatography using a mixed solution of dichloromethane and petroleum ether to give intermediate D-31(48.0g, yield 88.6%, MS: 652.80).

And step 3: intermediate D-31(72mmol) was dissolved in THF (350ml), cooled well to 0 ℃ under nitrogen blanket, and sodium hydride (210mmol) was added slowly in portions with stirring and reacted at 0 ℃ for 1 h. E-31(210mmol) and tetrakistriphenylphosphine palladium (10.5mmol) were added under nitrogen and after half an hour the mixture was heated to 70 ℃ for 10 h. The solvent was removed and hydrochloric acid (2N) was added to adjust the pH to 1, and the precipitated solid was suction-filtered, washed with water and ethanol, and dried to give intermediate F-31(85.0g, yield 84.7%, MS: 1394.40).

And 4, step 4: intermediate F-31(60mmol) was added to DCM (200ml) and then [ bis (trifluoroacetoxy) iodo ] benzene (PIFA, 247.5mmol) was added and stirred at room temperature for 10 h. The solvent was concentrated to a small amount (30mmol) by vacuum evaporation, the reaction solution was concentrated to a small amount (30ml), and the reaction solution was purified by chromatography using a mixed solution of dichloromethane and petroleum ether to give an organic luminescent compound represented by the formula L31 (78.2g, yield 93.9%, MS: 1388.35).

The synthetic routes and principles of the preparation methods of other organic light-emitting compounds with the structural general formula of formula I in the summary of the invention are the same as those of the compound example 1 listed above, so that the invention is not exhaustive, and a plurality of organic light-emitting compounds are selected as the compound examples 5-10, which are specifically as follows.

Examples 5 to 10 of the Compounds

The preparation method of the compound example 1 is followed, and each raw material is replaced by a compound corresponding to the corresponding ligand structure in the target product, so as to obtain a series of organic light-emitting compounds, which are shown in the following table 1.

TABLE 1

Examples of the Compounds	Structural formula (I)	Molecular formula	Theoretical value of mass spectrum	Mass spectrometric test values
					Compound example 5	L05	C₂₁F₂₇N₇	862.98	862.55
Compound example 6	L09	C₃₉F₁₂N₁₆	920.03	920.12
					Compound example 7	L13	C₂₇H₆N₂₂	638.11	638.54
Compound example 8	L20	C₃₉N₂₈	860.09	860.15
					Compound example 9	L24	C₇₅N₄₀	1460.12	1460.51
Compound example 10	L29	C₇₂H₄₂N₁₆	1130.38	1130.62

The embodiment of the invention also provides a photoelectric device prepared by using the organic light-emitting compound provided by the embodiment, and particularly, the photoelectric device is an organic electroluminescent device, wherein the organic electroluminescent device comprises a first electrode, a second electrode and at least one organic layer arranged between the first electrode and the second electrode.

The organic layer may include at least one layer selected from a hole injection layer, a hole transport layer, a composite layer of hole injection and hole transport technical layers, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, an electron transport layer, and a composite layer of electron injection technical layers, and at least one layer may or may not include the organic light emitting compound.

Specifically, the hole injection layer may include the organic light emitting compound.

In practical applications, the method for manufacturing the organic electroluminescent device can refer to device example 1 below.

Device example 1

The device embodiment 1 provides an organic electroluminescent device, and a method for manufacturing the organic electroluminescent device includes the steps of:

coating thickness of Fisher company ofThe ITO glass substrate was cleaned in distilled water for 2 times, ultrasonically cleaned for 30 minutes, then repeatedly cleaned with distilled water for 2 times, ultrasonically cleaned for 10 minutes, and after the cleaning with distilled water was completed, ultrasonically cleaned in sequence with isopropyl alcohol, acetone, and methanol, then dried, transferred to a plasma cleaning machine, and the substrate was cleaned for 5 minutes and sent to an evaporation coater. The organic electroluminescent device includes an anode, a hole injection layer, a hole transport layer, an organic light emitting layer, an electron transport layer, and a cathode. Wherein, the anode is indium tin oxide; the hole injection layer is 50nm thick and is formed by mixing and evaporating the organic light-emitting compound L01 provided by the compound example 1 and NPB according to the weight ratio of 5: 95; the hole transport layer is [ di- [4- (N, N-xylyl-amino) -phenyl ] with a thickness of 60nm]Cyclohexane (TAPC); the organic light-emitting layer was 10nm thick and comprised 90% of 4,4' -bis (carbazol-9-yl) -biphenyl, CBP) as the light-emitting host material and doped with 10% bis (1-phenyl-isoquinoline) (acetylacetone) iridium (III) (Ir (ppy)₂(acac)) a light-emitting material; the electron transport layer is a compound Alq3 with the thickness of 40 nm; and the cathode is aluminum with a thickness of 100 nm. Maintaining the vapor deposition speed of each organic material in the above processThe deposition rate of LiF is

The deposition rate of Al is

Device examples 2 to 10

Device examples 2 to 10 were prepared by referring to the preparation method provided in device example 1 above, except that the organic light-emitting compound L01 in device example 1 above was replaced with organic light-emitting compounds L05, L06, L09, L12, L13, L20, L24, L29, and L31, respectively.

Comparative device example 1

An organic electroluminescent device was fabricated as in device example 1, except that the material of the hole injection layer was entirely replaced with HAT-CN. Wherein the structural formula of HAT-CN is as follows:

comparative device example 2

An organic electroluminescent device was fabricated as in device example 1, except that the material of the hole injection layer was entirely replaced with NPB. Wherein the structural formula of NPB is as follows:

comparative device example 3

An organic electroluminescent device was fabricated in the same manner as in device example 1, except that the material of the hole injection layer was entirely replaced with NDP-9. The structural formula of NDP-9 is as follows:

experimental example:

the organic electroluminescent devices obtained in the device examples 1 to 10 and the device comparative examples 1 to 3 were applied with a forward DC bias voltage, and the organic electroluminescent characteristics were measured by PR-650 photometry equipment of Photo Research, and measured at 1000cd/m²The life of T95 was measured using a life measuring device of McScience, and the results are shown in Table 2 below.

TABLE 2

As can be seen from table 2 above, by adding the organic light emitting compound provided in the above example to the hole injection layer, the driving voltage of the photovoltaic device can be significantly reduced, and the light emitting efficiency and the service life of the photovoltaic device can be significantly improved, as compared to when HAT-CN, NPB, or NDP-9 is used as the material of the hole injection layer.

In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.

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Hexa-membered heterocyclic organic light-emitting compound, preparation method thereof and photoelectric device

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