A naphthofuran compound and an organic electroluminescent device
Patent Information
- Application Number
- CN202610750752.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-05-28
- Publication Date
- 2026-08-18
AI Technical Summary
[0036]本发明通过对化合物的结构进行设计，得到的萘并呋喃类化合物具有优异的成膜性和热稳定性，可用于制备有机电致发光器件，可以作为空穴传输层、电子阻挡层、发光层、空穴阻挡层的构成材料。特别地，本发明的萘并呋喃类化合物具有优异的传输性能和发光性能，在作为发光层主体材料，尤其是蓝光发光层的主体材料时，能够降低有机电致发光器件的驱动电压，提高器件的效率以及延长器件寿命。
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of organic electroluminescent materials technology, specifically relating to a naphthofuran compound and an organic electroluminescent device. Background Technology
[0002] Organic electroluminescent devices, as a novel display technology, possess unique advantages such as self-illumination, wide viewing angle, low energy consumption, high efficiency, thinness, rich colors, fast response speed, wide applicable temperature range, low driving voltage, the ability to manufacture flexible, bendable, and transparent display panels, and environmental friendliness. They can be applied to flat panel displays and next-generation lighting, and can also serve as backlights for LCDs.
[0003] Currently, organic electroluminescence has become the mainstream display technology. Correspondingly, various novel materials have been developed to prepare organic thin film layers. However, with social and technological advancements, higher demands are being placed on the performance of organic electroluminescent devices, particularly in terms of efficiency, lifetime, and voltage. Therefore, there is an urgent need in this field to develop more diverse and higher-performance organic thin film layer materials to meet these higher requirements for organic electroluminescent devices. Summary of the Invention
[0004] To address the shortcomings of existing technologies, the present invention aims to provide a naphthofuran compound and an organic electroluminescent device. The naphthofuran compound provided by the present invention, used as the main material of the light-emitting layer, enables the organic electroluminescent device to exhibit lower driving voltage, higher current efficiency, and longer lifespan.
[0005] To achieve this objective, the present invention adopts the following technical solution:
[0006] In a first aspect, the present invention provides a naphthofuran compound having the structure shown in Formula I:
[0007]
[0008] Formula I;
[0009] Ring A is naphthyl;
[0010] R1 is selected from any one of -H and C6~C40 aryl groups;
[0011] R2 is selected from any one of the groups shown in a~e below:
[0012]
[0013] abcde;
[0014] In the groups shown in a~e above, sp2 hybridized carbon atoms participate in the bonding.
[0015] This invention, through the design of compound structures, yields naphthofuran compounds with excellent film-forming properties and thermal stability, which can be used to prepare organic electroluminescent devices. These compounds can serve as constituent materials for hole transport layers, electron blocking layers, luminescent layers, and hole blocking layers. In particular, the naphthofuran compounds of this invention exhibit excellent transport and luminescence properties. When used as the main material for the luminescent layer, especially the blue luminescent layer, they can reduce the driving voltage of organic electroluminescent devices, improve device efficiency, and extend device lifespan.
[0016] Preferably, the C6-C40 aryl group is selected from any one of phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthrene, fluorenyl, benzo[a]fluorenyl, dibenzo[a]fluorenyl, naphthyl, pyrene, perylene, spirofluorenyl, triphenylene, fluoranyl, hydrogenated benzo[a]anthrayl, ind[a]fluorenyl, benzo[a]ind[a]fluorenyl, dibenzo[a]ind[a]fluorenyl, naphthyl, or benzo[a]naphthyl.
[0017] Preferably, the naphthofuran compound has a structure as shown in Formula I-1 to Formula I-3:
[0018]
[0019] Formula I-1, Formula I-2, Formula I-3;
[0020] In Equations I-1 to I-3, R1 and R2 have the same limited range as in Equation I.
[0021] Preferably, the naphthofuran compound is selected from any one of the following compounds:
[0022] .
[0023] Preferably, the naphthofuran compound is selected from any one of the following compounds 1 to 16:
[0024] .
[0025] In a second aspect, the present invention provides an organic electroluminescent device, the organic electroluminescent device comprising the naphthofuran compounds as described in the first aspect.
[0026] Preferably, the organic electroluminescent device includes an anode, a cathode, and an organic layer disposed between the anode and the cathode, the organic layer comprising the aforementioned naphthofuran compound.
[0027] Preferably, the organic layer comprises at least one of a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, and an electron transport layer. The naphthofuran compounds provided by this invention can be used as materials for the hole transport layer, electron blocking layer, light-emitting layer, hole blocking layer, and electron transport layer.
[0028] Preferably, the organic layer includes a light-emitting layer, which contains the aforementioned naphthofuran compound.
[0029] Preferably, the light-emitting layer comprises a host material and a dopant material, wherein the host material contains the aforementioned naphthofuran compound.
[0030] In this invention, the main material of the light-emitting layer can be a single compound or a mixture formed by two or more compounds.
[0031] In this invention, the volume percentage of the main material in the light-emitting layer is 60% to 99.9% (for example, it can be 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98% or 99.9%), preferably 70% to 99.5%, and more preferably 88% to 98%.
[0032] Preferably, the light-emitting layer is a blue light-emitting layer.
[0033] Preferably, the organic electroluminescent device is a blue organic electroluminescent device.
[0034] Thirdly, the present invention provides a display device comprising the organic electroluminescent device as described in the second aspect.
[0035] Compared with the prior art, the present invention has the following beneficial effects:
[0036] This invention, through the design of compound structures, yields naphthofuran compounds with excellent film-forming properties and thermal stability, which can be used to prepare organic electroluminescent devices. These compounds can serve as constituent materials for hole transport layers, electron blocking layers, luminescent layers, and hole blocking layers. In particular, the naphthofuran compounds of this invention exhibit excellent transport and luminescence properties. When used as the main material for the luminescent layer, especially the blue luminescent layer, they can reduce the driving voltage of organic electroluminescent devices, improve device efficiency, and extend device lifespan. Detailed Implementation
[0037] To facilitate understanding of the present invention, the following embodiments are provided. Those skilled in the art should understand that these embodiments are merely illustrative and should not be construed as limiting the scope of the invention.
[0038] Example 1 of intermediate preparation
[0039] This example of intermediate preparation provides a method for synthesizing intermediate 1, and the specific synthesis steps are as follows:
[0040]
[0041] (1) Synthesis of intermediate MI
[0042] Under nitrogen protection, 150 mL of toluene, 80 mL of ethanol, and 80 mL of water were added sequentially to a 500 mL three-necked flask. Then, raw material A-1 (60.0 mmol), raw material A-2 (72.0 mmol), potassium carbonate (90.0 mmol), and tetraphenylphosphine palladium (0.6 mmol) were added. The mixture was slowly heated to reflux and reacted for 8 hours. After the reaction was completed, the mixture was cooled to room temperature and diluted with water. The aqueous phase was extracted once with toluene, and the organic phases were combined. The organic phase was washed with water, dried with magnesium sulfate, filtered to remove magnesium sulfate, and the solvent was removed under reduced pressure. The mixture was separated by silica gel column chromatography and eluted with petroleum ether to obtain intermediate MI.
[0043] The intermediate MI was analyzed by mass spectrometry, and the mass-to-charge ratio (m / z) was 244.09.
[0044] (2) Synthesis of intermediate M-II
[0045] Under nitrogen protection, 200 mL of THF was added to a 1000 mL three-necked flask, followed by intermediate MI (60.0 mmol). The mixture was cooled to -78 °C and stirred until dissolved. 2.5 mol / L n-butyllithium (60.0 mmol) was added dropwise and stirred at low temperature for 1 h. N-bromosuccinimide (60.0 mmol) was added, and the mixture was slowly heated to 25 °C and reacted for 4 h. 100 mL of 1 mol / L hydrochloric acid was added and stirred for 1 h. 200 mL of water was then added, and a large amount of solid precipitated. The solid was filtered, and the filter cake was washed twice with 500 mL of water, dried, and purified by column chromatography to obtain intermediate M-II.
[0046] The intermediate M-II was analyzed by mass spectrometry, and the mass-to-charge ratio (m / z) was 322.00.
[0047] (3) Synthesis of intermediate M-III
[0048] Under nitrogen protection, 200 mL of toluene, 100 mL of ethanol, and 100 mL of water were added sequentially to a 1000 mL three-necked flask. Then, intermediate M-II (60.0 mmol), A-3 (72.0 mmol), potassium carbonate (90.0 mmol), and dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine palladium(II) (0.12 mmol) were added. The mixture was slowly heated to reflux and reacted for 6 hours. After the reaction was completed, the mixture was cooled to room temperature, 100 mL of ethanol was added, and the mixture was stirred in a water bath. The mixture was then filtered, and the filter cake was washed twice with water and once with ethanol to obtain intermediate M-III.
[0049] The intermediate M-Ⅲ was analyzed by mass spectrometry, and the mass-to-charge ratio (m / z) was 420.15.
[0050] (4) Synthesis of intermediate M-Ⅳ
[0051] Under nitrogen protection, 300 mL of DMF was added to a 1500 mL three-necked flask, followed by intermediate M-III (70.0 mmol) and N-bromosuccinimide (105.0 mmol). The reaction was carried out at 25 °C for 6 h. After the reaction was completed, 500 mL of water was added, and the mixture was stirred for 30 min. The mixture was then filtered, and the filter cake was recrystallized from the filter cake using a mixed solvent of toluene and ethanol to obtain intermediate M-IV.
[0052] The intermediate M-Ⅳ was analyzed by mass spectrometry, and the mass-to-charge ratio (m / z) was 498.06.
[0053] The NMR spectra of intermediate M-Ⅳ were measured, and the data are as follows: 1H-NMR (Bruker, Switzerland, Avance II 400MHz NMR spectrometer, CDCl3), δ8.31 (m, 2H), δ8.22 (m, 2H), δ7.80 (m, 2H), δ7.63 (d, 1H), δ7.60~7.42 (m, 11H), δ7.22 (m, 1H).
[0054] (5) Synthesis of intermediate 1
[0055] Under nitrogen protection, 250 mL of toluene was added to a 500 mL round-bottom flask, followed by intermediate M-Ⅳ (60.0 mmol), pinacol diborate (90.0 mmol), potassium acetate (180.0 mmol), and palladium dichloride bis(triphenylphosphine) (0.3 mmol). The mixture was slowly heated to reflux for 6 h. After the reaction was completed, the mixture was cooled to room temperature, and water was added to separate the phases. The aqueous phase was extracted once with toluene, and the organic phases were combined. After washing the organic phase with water, the mixture was concentrated to 100 mL, and 200 mL of ethanol was added. The mixture was stirred at room temperature for 30 min and then filtered to obtain intermediate 1.
[0056] Intermediate 1 was analyzed by mass spectrometry, and the mass-to-charge ratio (m / z) was 546.24.
[0057] Examples of intermediate preparation 2-8
[0058] Examples 2-8 of intermediate preparation provide an intermediate, and the synthesis method is the same as that of intermediate 1. The only difference is that the raw material A-1 in step (1) of intermediate preparation example 1 is replaced with the corresponding equal amount of raw material 1, and the raw material A-2 is replaced with the corresponding equal amount of raw material 2 (see Table 1 for details). Other conditions are the same as the synthesis method of intermediate 1. The intermediate is detected by mass spectrometry, and the test data are shown in Table 1 below.
[0059] Table 1
[0060]
[0061]
[0062]
[0063] Synthesis Example 1
[0064] This synthetic example provides a method for synthesizing compound 1, comprising the following steps:
[0065]
[0066] Under nitrogen protection, 150 mL of toluene, 80 mL of water, and 80 mL of ethanol were added sequentially to a 500 mL three-necked flask. Then, compound A-4 (10.0 mmol), intermediate 1 (12.0 mmol), potassium carbonate (15.0 mmol), and tetraphenylphosphine palladium (0.3 mmol) were added. The mixture was slowly heated to reflux and reacted for 12 h. After the reaction was completed, the mixture was cooled to room temperature, and 150 mL of ethanol was added. The mixture was stirred in a water bath and then filtered. The filter cake was crystallized using a mixed solvent of toluene and ethanol to obtain compound 1.
[0067] The mass-to-charge ratio (m / z) of compound 1 was 702.26.
[0068] Synthesis Examples 2-16
[0069] Synthesis Examples 2-16 provide compounds 2-16 respectively. The synthesis method is the same as that of compound 1, except that compound A-4 is replaced with an equal amount of brominated compound (see Table 2), and intermediate 1 is replaced with an equal amount of other intermediates (see Table 2). Other conditions are the same as those of compound 1. The synthesized compounds were detected by mass spectrometry, and the test data are shown in Table 2.
[0070] Table 2
[0071]
[0072]
[0073]
[0074]
[0075] For other compounds whose specific synthesis methods are not listed, they can be synthesized by referring to the above examples and combining them with common knowledge in the field.
[0076] The specific structures of some of the substances used in the following application examples and comparative examples are as follows:
[0077] .
[0078] Application Example 1
[0079] This application example provides an organic electroluminescent device, using compound 1 provided in synthesis example 1 of the present invention as the main material of the light-emitting layer;
[0080] The structure of the organic electroluminescent device is: ITO / HT (40nm) / light-emitting layer main material: BD-2 3% (30nm) / TPBI (30nm) / LiF (0.5nm) / Al (150nm).
[0081] The fabrication method of the above-mentioned organic electroluminescent device is as follows:
[0082] The glass substrate coated with an ITO transparent conductive layer (as the anode) was ultrasonically treated in a cleaning agent, then rinsed in deionized water, then ultrasonically degreased in a mixed solvent of acetone and ethanol, then baked in a clean environment until completely dehydrated, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam to improve the surface properties and enhance the bonding ability with the hole layer.
[0083] The material was placed inside a vacuum chamber, and the vacuum was evacuated to 1×10⁻⁶. -5 ~1×10 -6 Pa is sequentially vacuum-deposited onto the cleaned ITO substrate.
[0084] HT-1 (40nm) refers to the hole transport layer, which has a thickness of 40nm.
[0085] The main material of the light-emitting layer: BD-2 3% (30nm) refers to the light-emitting layer. The main material of the light-emitting layer: BD-2 3% means that the volume ratio of the main material to the dopant material BD-2 in the light-emitting layer is 97:3, and the film thickness of the light-emitting layer is 30nm.
[0086] TPBI (30nm) refers to the electron transport layer, which has a film thickness of 30nm.
[0087] LiF (0.5nm) refers to the electron-injected layer, with a film thickness of 0.5nm;
[0088] ITO refers to the anode, and Al (150nm) refers to the cathode.
[0089] Application Examples 2-16
[0090] Application Examples 2-16 provide an organic electroluminescent device, which differs from Application Example 1 only in that the main material of the light-emitting layer is different (see Table 3 for details), while other conditions are the same as in Application Example 1.
[0091] Application Comparative Examples 1-3
[0092] Comparative Examples 1 to 3 each provide an organic electroluminescent device, which differs from Application Example 1 only in that the main material of the light-emitting layer is different (see Table 3 for details), while other conditions are the same as Application Example 1.
[0093] Performance testing
[0094] The driving voltage, current efficiency, and lifetime (LT90) of the OLED devices provided above were tested. LT90 refers to the time required for the brightness to decrease to 90% of its original brightness while maintaining an initial brightness of 1000 nits at a constant current density. Test items included the brightness, driving voltage, and current efficiency of the organic electroluminescent device. The driving voltage, current efficiency, and LT90 data were all based on a brightness of 1000 cd / m². 2 The relative value at that time (based on the test data of Comparative Example 1).
[0095] The performance test results of the organic electroluminescent devices are shown in Table 3.
[0096] Table 3
[0097]
[0098] As shown in Table 3, this invention, through the design of compound structures, yields naphthofuran compounds with specific structures. The naphthofuran compounds provided by this invention can be used as the main material for the light-emitting layer of organic electroluminescent devices, resulting in organic electroluminescent devices exhibiting lower driving voltage, higher current efficiency, and longer lifetime.
[0099] The present invention has been illustrated with the above embodiments to describe 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 improvements to the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.
Claims
1. A naphthofuran compound, characterized by, The naphthofuran compounds have the structure shown in Formula I: Formula I; Ring A is naphthyl; R1 is selected from any one of -H and C6~C40 aryl groups; R2 is selected from any one of the groups shown in a~e below: abcde; In the groups shown in a~e above, sp2 hybridized carbon atoms participate in the bonding.
2. The naphthofuran compound according to claim 1, characterized in that, The C6-C40 aryl group is selected from any one of phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthryl, fluorenyl, benzo[a]fluorenyl, dibenzo[a]fluorenyl, naphthyl, pyrene, perylene, spirofluorenyl, triphenylene, fluoranyl, hydrogenated benzo[a]anthrayl, ind[a]fluorenyl, benzo[a]ind[a]fluorenyl, dibenzo[a]ind[a]fluorenyl, naphthyl, or benzo[a]naphthylfluorenyl.
3. The naphthofuran compound according to claim 1, characterized in that, The naphthofuran compounds have structures as shown in Formulas I-1 to I-3: Formula I-1, Formula I-2, Formula I-3; In Equations I-1 to I-3, R1 and R2 have the same limited range as in Equation I.
4. The naphthofuran compound according to claim 1, characterized in that, The naphthofuran compound is selected from any one of the following compounds: 。 5. The naphthofuran compound according to claim 1, characterized in that, The naphthofuran compound is selected from any one of the following compounds 1 to 16: 。 6. An organic electroluminescent device, characterized in that, The organic electroluminescent device includes the naphthofuran compound as described in any one of claims 1 to 5.
7. The organic electroluminescent device according to claim 6, characterized in that, The organic electroluminescent device includes an anode, a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer contains the aforementioned naphthofuran compound.
8. The organic electroluminescent device according to claim 7, characterized in that, The organic layer includes a light-emitting layer, which contains the aforementioned naphthofuran compound.
9. The organic electroluminescent device according to claim 8, characterized in that, The light-emitting layer includes a host material and a dopant material, wherein the host material comprises the aforementioned naphthofuran compounds.
10. The organic electroluminescent device according to claim 9, characterized in that, The light-emitting layer is a blue light-emitting layer; Preferably, the organic electroluminescent device is a blue organic electroluminescent device.