Phenanthrofuran compound and application thereof

Abstract

The invention provides a phenanthrofuran compound and application thereof, and relates to the technical field of organic photoelectric materials. The phenanthrofuran compound is used as an electron transport layer material in the organic electroluminescent device, so that the driving voltage of the organic electroluminescent device can be effectively reduced, the current efficiency of the organic electroluminescent device is improved, and the service life of the organic electroluminescent device is prolonged.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic optoelectronic materials, and particularly relates to a phenanthrofuran compound and its application. Background Art

[0002] Organic Light-Emitting Diode (hereinafter simply referred to as OLED) has the advantages of light weight, small size, wide viewing angle, fast response, wide operating temperature range, low energy consumption, high efficiency, good color purity, high definition, good flexibility, etc., and can meet the new demands of consumers for display technology, and has good application prospects in the fields of lighting and display.

[0003] An organic electroluminescent element is a self-luminous element that utilizes the following principle: by applying an electric field, the recombination of holes injected from the anode and electrons injected from the cathode can cause a fluorescent substance to emit light. It has the following structure: an anode, a cathode, and an organic layer therebetween. In order to improve the efficiency and stability of the organic electroluminescent element, the organic layer usually includes a plurality of functional layers with different materials, such as a hole injection layer HIL, a hole transport layer HTL, a light-emitting layer, an electron transport layer ETL, and an electron injection layer EIL. In such an organic light-emitting element, when a voltage is applied between the anode and the cathode, holes from the anode and electrons from the cathode are injected into the organic material layer, and the generated excitons emit light with a specific wavelength when migrating to the ground state.

[0004] Currently, the research on organic electroluminescent materials has been widely carried out in the academic and industrial fields. Designing and finding a compound as a new material for OLED to overcome the deficiencies that occur in the actual application process is the focus and future research and development trend in the research work of OLED materials. Summary of the Invention

[0005] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a phenanthrofuran compound and its application.

[0006] To achieve this purpose, the present invention adopts the following technical solutions:

[0007] In the first aspect, the present invention provides a phenanthrofuran compound, and the phenanthrofuran compound has the structure shown in the following formula I:

[0008]

[0009] In formula I, the R 1 , R 2 each independently selected from C 1 ~C 12 alkyl, substituted or unsubstituted C 6 ~C 30Aryl, substituted or unsubstituted C 3 ~C 30 any one of heteroaryl;

[0010] The substituents of the substitution are selected from C 1 ~C 12 alkyl, C 6 ~C 30 aryl, C 3 ~C 30 any one of heteroaryl.

[0011] The phenanthrofuran compounds provided by the present invention have a specific molecular structure and spatial configuration, endowing them with excellent electron transport properties and film-forming properties, making the electron transport layer more closely arranged, facilitating the transport of carriers, reducing the driving voltage of the device, promoting the improvement of the device efficiency, prolonging the service life of the device, and comprehensively improving the comprehensive performance of the organic electroluminescent device.

[0012] Preferably, the C 1 ~C 12 alkyl is selected from methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, pivalyl, n-hexyl or cyclohexyl.

[0013] Preferably, the C 6 ~C 30 aryl is selected from phenyl, biphenyl, terphenyl, naphthyl, anthryl, indenyl, fluorenyl, perylenyl, phenanthryl, pyrenyl, fluoranthenyl or benzophenanthryl.

[0014] Preferably, the heteroatom in the C 3 ~C 30 heteroaryl is selected from an oxygen atom, a sulfur atom or a nitrogen atom.

[0015] Preferably, the C 3 ~C 30 heteroaryl is selected from benzofuranyl, benzothiophenyl, pyridyl, dibenzofuranyl, pyrimidinyl, dibenzothiophenyl, carbazolyl, N-phenylcarbazolyl, diarylamino, benzofuranocarbazolyl, benzofuranothiophenyl or triazinyl.

[0016] Preferably, the phenanthrofuran compounds are selected from any one of the following compounds:

[0017]

[0018]

[0019]

[0020]

[0021] Preferably, the phenanthrofurans are selected from any one of the following compounds 1 to 12:

[0022]

[0023] The present invention lists some specific structural forms of the phenanthrofurans, but the phenanthrofurans of the present invention are not limited to these listed chemical structures. Any structure based on the structure shown in Formula I, where R 1 , R 2 meeting the above-defined conditions should be included.

[0024] In a second aspect, the present invention provides an application of the phenanthrofurans as an electron transport material in an organic electroluminescent device.

[0025] In a third aspect, the present invention provides an organic electroluminescent device, which includes the phenanthrofurans.

[0026] Preferably, the organic electroluminescent device includes a first electrode, a second electrode, and an organic layer disposed between the first electrode and the second electrode;

[0027] The organic layer includes the phenanthrofurans.

[0028] Preferably, the organic layer includes an electron transport layer, and the electron transport layer includes the phenanthrofurans.

[0029] In a fourth aspect, the present invention provides a display device, which includes the organic electroluminescent device.

[0030] Compared with the prior art, the present invention has the following beneficial effects:

[0031] As an electron transport layer material in an organic electroluminescent device, the phenanthrofurans of the present invention can effectively reduce the driving voltage of the organic electroluminescent device, improve the current efficiency of the organic electroluminescent device, and improve the lifespan of the organic electroluminescent device. Specific Embodiments

[0032] To facilitate the understanding of the present invention, the following examples are listed. Those skilled in the art should understand that the examples are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.

[0033] Synthesis Example 1

[0034] This example provides a synthesis method for Compound 1, and the synthesis method is as follows:

[0035]

[0036] (1) Synthesis of Intermediate 1-b

[0037] 40 mmol of Compound 1-a, 40 mmol of bis(pinacolato)diboron, 0.4 mmol of tris(dibenzylideneacetone)dipalladium(0), 0.8 mmol of 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl, 60 mmol of potassium acetate, and 300 mL of toluene were added to a reaction flask and heated to reflux for 8 h. The reaction was monitored by TLC until completion. After filtration through diatomaceous earth, the mixture was washed with purified water until neutral. The organic phase was concentrated under reduced pressure, and the resulting solid was recrystallized from a mixed solvent of toluene and ethanol to obtain Intermediate 1-b.

[0038] The mass spectrometry data of Intermediate 1-b was tested, and the measured mass spectrometry m / z was 394.17.

[0039] (2) Synthesis of Compound 1

[0040] 30 mmol of Intermediate 1-b, 30 mmol of 2-chloro-4,6-diphenyl-1,3,5-triazine, 0.3 mmol of dichloro(tert-butyl)bis(4-(dimethylamino)phenyl)phosphine palladium(II), 60 mmol of potassium carbonate, 300 mL of toluene, and 100 mL of water were added to a reaction flask and heated to reflux for 12 h. The reaction was monitored by TLC until completion. After the reaction ended, the temperature was lowered, and the layers were separated. The organic layer was evaporated to dryness, and the resulting solid was recrystallized from a mixed solvent of chloroform and ethanol to obtain Compound 1.

[0041] The mass spectrometry data of Compound 1 was tested, and the measured mass spectrometry m / z was 499.17.

[0042] Synthesis Example 2

[0043] Synthesis of Compound 4:

[0044]

[0045] Referring to the synthesis method of Compound 1, 2-([1,1′-biphenyl]-4-yl)-4-chloro-6-(naphthalen-2-yl)-1,3,5-triazine was used to replace 2-chloro-4,6-diphenyl-1,3,5-triazine in Synthesis Example 1, and other conditions remained unchanged to obtain Compound 4.

[0046] The mass spectrometry data of Compound 4 was tested, and the measured mass spectrometry m / z was 625.22.

[0047] Synthesis Example 3

[0048] Synthesis of Compound 5:

[0049]

[0050] Referring to the synthesis method of Compound 1, replace 2-chloro-4,6-diphenyl-1,3,5-triazine in Synthesis Example 1 with 2-chloro-4-(dibenz[b,d]furan-3-yl)-6-phenyl-1,3,5-triazine, and keep other conditions unchanged to obtain Compound 5.

[0051] Test the mass spectrometry data of Compound 5, and the measured mass spectrometry m / z: 589.18.

[0052] Synthesis Example 4

[0053] Synthesis of Compound 7:

[0054]

[0055] Referring to the synthesis method of Compound 1, replace 2-chloro-4,6-diphenyl-1,3,5-triazine in Synthesis Example 1 with 2-chloro-4-naphtho[2,3-b][1]benzofuran-3-yl-6-phenyl-1,3,5-triazine, and keep other conditions unchanged to obtain Compound 7.

[0056] Test the mass spectrometry data of Compound 7, and the measured mass spectrometry m / z: 639.19.

[0057] Synthesis Example 5

[0058] Synthesis of Compound 10:

[0059]

[0060] Referring to the synthesis method of Compound 1, replace 2-chloro-4,6-diphenyl-1,3,5-triazine in Synthesis Example 1 with 2-chloro-4-dibenzofuran-3-yl-6-(4-naphthalen-1-ylphenyl)-1,3,5-triazine, and keep other conditions unchanged to obtain Compound 10.

[0061] Test the mass spectrometry data of Compound 10, and the measured mass spectrometry m / z: 715.23.

[0062] Synthesis Example 6

[0063] Synthesis of Compound 11:

[0064]

[0065] Referring to the synthesis method of Compound 1, replace 2-chloro-4,6-diphenyl-1,3,5-triazine in Synthesis Example 1 with 4-chloro-2-phenyl-6-(3-(9,9-dimethylfluorene))-1,3,5-triazine, and keep other conditions unchanged to obtain Compound 11.

[0066] The mass spectrometry data of Compound 11 was tested, and the measured mass spectrometry m / z was 615.23.

[0067] Synthesis Example 7

[0068] Synthesis of Compound 12:

[0069]

[0070] Referring to the synthesis method of Compound 1, 2-(4-chloro-6-phenyl-1,3,5-triazin-2-yl)-9-phenyl-9H-carbazole was used to replace 2-chloro-4,6-diphenyl-1,3,5-triazine in Synthesis Example 1, and other conditions remained unchanged to obtain Compound 12.

[0071] The mass spectrometry data of Compound 12 was tested, and the measured mass spectrometry m / z was 664.23.

[0072] For compounds without specific synthesis steps listed, they can be prepared by combining the above examples with common general knowledge in the art.

[0073] The specific structures of some compounds used in the following device examples and device comparative examples are shown below:

[0074]

[0075]

[0076] In the device example, the compound of the present application was selected as the electron transport material in the organic electroluminescent device, and in the device comparative example, E1 - E2 were selected as the electron transport material in the organic electroluminescent device.

[0077] Device Example 1

[0078] The structure of the organic electroluminescent device is: ITO / HT(40nm) / BH-1:BD-13%(30nm) / Compound 1(30nm) / LiF(0.5nm) / Al(150nm).

[0079] The preparation method of the above organic electroluminescent device is as follows:

[0080] The glass substrate coated with the ITO transparent conductive layer (as the anode) was ultrasonically treated in a cleaning agent, then rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone and ethanol, baked in a clean environment until completely dehydrated, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam on the surface to improve the surface properties and enhance the bonding ability with the hole injection layer;

[0081] The above glass substrate was placed in a vacuum chamber and evacuated to 1×10 -5~9×10 -3 Pa, vacuum evaporate HT on the anode as the hole transport layer at a evaporation rate of 0.1 nm / s, and the evaporated film thickness is 40 nm;

[0082] Vacuum evaporate the light-emitting layer on the hole transport layer at a evaporation rate of 0.1 nm / s, and the evaporated film thickness is 30 nm. The host material of the light-emitting layer is BH-1, and the doping material is BD-1. 3% refers to the doping ratio of the doping material, that is, the volume ratio of the host material to the doping material in the light-emitting layer is 97:3.

[0083] Vacuum evaporate Compound 1 on the light-emitting layer as the electron transport layer at a evaporation rate of 0.1 nm / s, and the evaporated film thickness is 30 nm; Vacuum evaporate 0.5 nm of LiF and 150 nm of Al on the electron transport layer as the electron injection layer and the cathode. Measure the brightness, driving voltage, current efficiency and lifetime of the prepared organic electroluminescent device.

[0084] Device Examples 2-7

[0085] Device Examples 2-7 respectively provide an organic electroluminescent device, which is only different from Device Example 1 in that the electron transport material is different (see Table 1 below), and other conditions are the same as those in Device Example 1.

[0086] Device Comparative Examples 1-2

[0087] Device Comparative Examples 1-2 respectively provide an organic electroluminescent device, which is only different from Device Example 1 in that the electron transport material is different (see Table 1 below), and other conditions are the same as those in Device Example 1.

[0088] Performance Test

[0089] Test method: Test the driving voltage, current efficiency and lifetime LT90 of the OLED devices provided above; among them, LT90 refers to the time required for the brightness to drop to 90% of the original brightness while keeping the current density unchanged when the initial brightness is 1000 nit. The test items include the brightness, driving voltage, current efficiency and lifetime LT90 of the organic electroluminescent device. The data of driving voltage, current efficiency and LT90 are all relative values at a brightness of 1000 cd / m 2 (based on Comparative Example 1). The performance test results of the organic electroluminescent device are shown in Table 1 below:

[0090] Table 1

[0091]

[0092]

[0093] As can be seen from the content of Table 1, through molecular design, the present invention has obtained phenanthrofurane-containing compounds, which can be used as electron transport materials for OLED light-emitting devices, enabling the OLED light-emitting devices to have a lower driving voltage, a higher current efficiency, and a longer lifespan.

[0094] The present invention uses the above embodiments to illustrate the detailed process flow of the present invention. However, the present invention is not limited to the above detailed process flow, that is, it does not mean that the present invention must rely on the above detailed process flow to be implemented. Those skilled in the art should understand that any improvement to the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A phenanthrofuran compound, characterized in that: The phenanthrofuran compound has a structure shown in the following formula I: In Formula I, R1 and R2 are each independently selected from C1 to C 12 Alkyl, substituted or unsubstituted C6~C 30 Aryl, substituted or unsubstituted C3~C 30 Any of the heteroaryl groups; The substituted substituent is selected from C1 to C 12 Alkyl, C6~C 30 Aryl, C3~C 30 Any of the heteroaryl groups.

2. The phenanthrofuran compound according to claim 1, characterized in that C1~C 12 The alkyl group is selected from methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, tert-pentyl, n-hexyl or cyclohexyl.

3. The phenanthrofuran compound according to claim 1, characterized in that The C6~C 30 Aryl is selected from phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, indenyl, fluorenyl, perylenyl, phenanthrenyl, pyrenyl, fluoranthenyl or triphenylenyl.

4. The phenanthrofuran compound according to claim 1, characterized in that C3~C 30 The heteroatom in the heteroaryl group is selected from an oxygen atom, a sulfur atom or a nitrogen atom.

5. The phenanthrofuran compound according to claim 1, characterized in that: C3~C 30 The heteroaryl group is selected from benzofuranyl, benzothiophenyl, pyridyl, dibenzofuranyl, pyrimidinyl, dibenzothiophenyl, carbazolyl, N-phenylcarbazolyl, diarylideneamine, benzofuranocarbazolyl, benzofuranothiophenyl or triazine.

6. The phenanthrofuran compound according to claim 1, characterized in that: The phenanthrofuran compound is selected from any one of the following compounds:

7. Use of the phenanthrofuran compound according to any one of claims 1 to 6 as an electron transport material for an organic electroluminescent device.

8. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises the phenanthrofuran compound according to any one of claims 1 to 6.

9. The organic electroluminescent device according to claim 8, characterized in that: The organic electroluminescent device comprises a first electrode, a second electrode and an organic layer disposed between the first electrode and the second electrode; The organic layer includes the phenanthrofuran compound.

10. The organic electroluminescent device according to claim 9, characterized in that: The organic layer includes an electron transport layer, and the electron transport layer includes the phenanthrofuran compound.

Images