An organic compound and its application

Abstract

An organic compound, characterized in that it has a structure as shown in (I): wherein m and n are each independently an integer of 0 to 10, and 1≤m+n≤10; L 1 and L 2 Each is independently selected from a single bond, a substituted or unsubstituted C6-C30 arylene group or a substituted or unsubstituted C3-C30 heteroarylene group; Ar 1 and Ar 2 are each independently selected from substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, and Ar 1 and Ar 2 At least one of them has a structure as shown in (II): wherein A, B, C and D are each independently a substituted or unsubstituted aromatic ring, and any connecting position on the ring of A, B, C or D is connected to L 1 or L 2 When the aforementioned organic compound of the present invention is used as a light-emitting host material in an organic electroluminescent device, it is beneficial to improve the device efficiency and reduce the driving voltage.

Description

Technical Field

[0001] The invention relates to the technical field of organic electroluminescence, and in particular to an organic compound containing a large conjugated condensed ring and application thereof. Background Art

[0002] Organic light emitting diodes (OLED) devices are a type of device with a sandwich-like structure, including positive and negative electrode film layers and organic functional material layers sandwiched between the electrode film layers. When voltage is applied to the electrodes of the OLED device, positive charges are injected from the positive electrode and negative charges are injected from the negative electrode. Under the action of the electric field, the positive and negative charges migrate in the organic layer and meet to combine and emit light. Due to the advantages of high brightness, fast response, wide viewing angle, simple process, and flexibility, OLED devices have attracted much attention in the fields of new display technology and new lighting technology. At present, this technology has been widely used in display panels of new lighting fixtures, smart phones, tablet computers and other products, and will further expand to the application fields of large-size display products such as televisions. It is a new display technology with fast development and high technical requirements.

[0003] As OLED continues to advance in the two major fields of lighting and display, people are paying more attention to the research on its core materials. This is because an OLED device with good efficiency and long life is usually the result of an optimized combination of device structure and various organic materials, which provides great opportunities and challenges for chemists to design and develop functional materials of various structures. Common functional organic materials include: hole injection materials, hole transport materials, hole blocking materials, electron injection materials, electron transport materials, electron blocking materials, luminescent host materials and luminescent guests (dyes), etc.

[0004] In order to prepare OLED light-emitting devices with lower driving voltage, better luminous efficiency and longer device life, and to continuously improve the performance of OLED devices, it is necessary not only to innovate the structure and manufacturing process of OLED devices, but also to continuously study and innovate the optoelectronic functional materials in OLED devices to prepare functional materials with higher performance. Based on this, the OLED material industry has been committed to developing new organic electroluminescent materials to achieve low driving voltage, high luminous efficiency and better device life. Summary of the invention

[0005] Problem that the invention aims to solve

[0006] In order to further meet the ever-increasing demand for the optoelectronic performance of OLED devices and the energy-saving needs of mobile electronic devices, it is necessary to continuously develop new and efficient OLED materials, among which the development of new blue light hosts with low driving voltage, high efficiency and long life is of great significance.

[0007] Solutions to the problem

[0008] In order to solve the above-mentioned problems in the prior art, the inventors have conducted intensive research and found that by using anthracene as the parent structure and introducing a large conjugated group, the molecule has good planar conjugation and improves the carrier transfer efficiency. Secondly, this large conjugated group has a relatively high singlet energy level and a low triplet energy level, so that the organic electroluminescent device using the compound containing this group exhibits better efficiency and life in the blue fluorescent system.

[0009] Specifically, the present invention provides an organic compound, characterized in that it has a structure as shown in (1):

[0010]

[0011] wherein m and n are each independently an integer of 0 to 10, and 1≤m+n≤10, preferably 2≤m+n≤4, more preferably 2 or 3, and most preferably 2; L 1 and L 2 Each is independently selected from a single bond, a substituted or unsubstituted C6-C30 arylene group or a substituted or unsubstituted C3-C30 heteroarylene group; Ar 1 and Ar 2 are each independently selected from substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, and Ar 1 and Ar 2 At least one of them has the structure shown in (II):

[0012]

[0013] Wherein, A, B, C and D are each independently a substituted or unsubstituted aromatic ring, and any connectable position on the ring of A, B, C or D is connected to L 1 or L 2 connection; when the above-mentioned substituted or unsubstituted group has a substituent, the substituent is selected from any one of deuterium, C1~C10 alkyl, C3~C10 cycloalkyl, C1~C10 alkoxy, C3~C10 cycloalkoxy, halogen, cyano, nitro, hydroxyl, silanyl, amino and C6~C30 aryl, C6~C30 arylamino, C3~C30 heteroarylamino and C3~C30 heteroaryl, or a combination of two or more thereof.

[0014] The specific reason why the compound of the general formula (I) of the present invention has excellent performance as a light-emitting layer material in an organic electroluminescent device is not clear, but it is speculated that the following reasons may be the reason: the compound of the general formula of the present invention introduces a 7-membered conjugated aromatic ring structure on anthracene, which has great conjugation, is conducive to improving the singlet S1 energy level and reducing the triplet energy level T1, which is conducive to the transfer of carriers in blue fluorescent devices, and the structure of the 7-membered conjugated aromatic ring makes the molecule have good rigidity, thus having good stability and a high glass transition temperature Tg. Combining the above two characteristics, the molecule as a whole can show good luminous efficiency and a long service life.

[0015] It should be noted that in this specification, the expression of Ca to Cb represents that the number of carbon atoms in the group is a to b, and unless otherwise specified, the number of carbon atoms generally does not include the number of carbon atoms in the substituent. In the present invention, the expression of chemical elements includes the concept of isotopes with the same chemical properties, for example, the expression of "hydrogen" also includes the concept of "deuterium" and "tritium" with the same chemical properties.

[0016] In the present specification, the expression of a ring structure crossed by a “-” indicates that the connection site is at any position on the ring structure that can form a bond.

[0017] In this specification, the definition of "aromatic ring" includes aromatic ring and aromatic heterocycle, wherein the aromatic ring is a hydrocarbon compound with a conjugated planar ring formed by alternating single and double bonds, and the aromatic heterocycle is a compound containing at least one heteroatom such as N, O, S, etc. in the conjugated planar ring. The "aromatic ring" is preferably an aromatic ring.

[0018] In the present specification, the C6-C60 aryl group is a group selected from the group consisting of phenyl, naphthyl, anthracenyl, benzanthryl, phenanthryl, triphenylenyl, pyrene, chrysene, peryl, fluoranthene, tetraphenyl, pentacene, benzopyrene, biphenyl, isophenyl, terphenyl, triphenyl, tetraphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthryl, dihydropyrenyl, tetrahydropyrenyl, cis- or trans-indenofluorenyl, trimerized indenyl, isotrimerized indenyl, spirotrimerized indenyl and spiroisotrimerized indenyl. Specifically, the biphenyl group is selected from 2-biphenyl, 3-biphenyl and 4-biphenyl; the terphenyl group includes p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl and m-terphenyl-2-yl; the naphthyl group includes 1-naphthyl or 2-naphthyl; the anthracenyl group is selected from 1-anthracenyl, 2-anthracenyl and 9-anthracenyl; the fluorenyl group is selected from 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl; the pyrenyl group is selected from 1-pyrenyl, 2-pyrenyl and 4-pyrenyl; the naphthyl group is selected from 1-naphthyl, 2-naphthyl and 9-naphthyl. The C6-C30 arylene group is similar to the C6-C60 aryl group, as long as the above-mentioned groups satisfying the carbon number are changed to the corresponding subunits.

[0019] The heteroatom in the present invention generally refers to an atom or an atom group selected from B, N, O, S, P, P(=O), Si and Se, and is preferably selected from N, O and S. In the present specification, examples of C3-C60 heteroaryl groups include nitrogen-containing heteroaryl groups, oxygen-containing heteroaryl groups, sulfur-containing heteroaryl groups, and specific examples include furyl, thienyl, pyrrolyl, pyridyl, benzofuranyl, benzothienyl, isobenzofuranyl, isobenzothienyl, indolyl, isoindolyl, dibenzofuranyl, dibenzothienyl, carbazolyl and its derivatives, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo-5,6-quinolyl, benzo-6,7-quinolyl. yl, benzo-7,8-quinolyl, phenothiazinyl, phenazinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazoimidazolyl, quinoxalinoimidazolyl, oxazolyl, benzoxazolyl, naphthoxazolyl, anthrazolyl, phenanthroxazolyl, 1,2-thiazolyl, 1,3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1,5-diazaanthryl, 2,7-diaza pyrenyl, 2,3-diazapyrenyl, 1,6-diazapyrenyl, 1,8-diazapyrenyl, 4,5-diazapyrenyl, 4,5,9,10-tetraazaperyl, pyrazinyl, phenazinyl, phenothiazinyl, naphthyridinyl, azacarbazolyl, benzocarbolinyl, phenanthrolinyl, 1,2,3-triazolyl, 1,2,4-triazolyl, benzotriazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,3-oxadiazolyl ...3-oxadiazolyl, 1,2,3-oxadiazolyl, 1,2,3-oxadiazolyl, 1,2,3-oxadiazolyl, 1,2,3-oxadiazolyl, 1,2,3-oxadi 2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, tetrazolyl, 1,2,4,5-tetrazinyl, 1,2,3,4-tetrazinyl, 1,2,3,5-tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazole, etc., wherein the carbazolyl derivative is preferably 9-phenylcarbazole, 9-naphthylcarbazole, benzocarbazole, dibenzocarbazole, or indolecarbazole. C3-C30 heteroaryl is similar to C3-C60 heteroaryl, as long as the above-mentioned groups satisfying the carbon number are replaced with corresponding subunits.

[0020] In this specification, the C1-C10 chain alkyl includes straight chain alkyl and branched chain alkyl, and specific examples include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, preferably methyl. The C1-C10 chain alkoxy is similar to the C1-C10 chain alkyl, except that the groups have an additional -O-.

[0021] In the present specification, examples of C3-C10 cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc., preferably cyclopropyl. C3-C10 cycloalkoxy and C3-C10 cycloalkyl are different in that one -O- is added to the group.

[0022] In the present specification, examples of halogen include fluorine, chlorine, bromine, iodine and the like, and fluorine is preferred.

[0023] The compound of the general formula (I) of the present invention preferably has a structure as shown in (I-1) or (I-2):

[0024]

[0025] The reason why the above preferred structure has better performance as a light-emitting layer material is not yet clear. It is speculated that the connection of a 7-membered conjugated aromatic ring or aromatic heterocycle at a specific position of anthracene is beneficial to further improve the singlet energy level S1 of the molecule. Furthermore, this large conjugated group has a good planar structure, which is beneficial to the transmission of carriers, thereby making this type of molecule have good photoelectric properties.

[0026] The above-mentioned compound of the general formula of the present invention is preferably Ar 1 and Ar 2 At least one of them has the structure shown in (II-1) or (II-2):

[0027]

[0028] Ar 1 and Ar 2 At least one of them has the structure shown in (II-2-1) or (II-2-2):

[0029]

[0030] Among them, R 1 and R 2 Each independently represents a single substituent to the maximum allowed number of substituents, and each independently is selected from any one of hydrogen, substituted or unsubstituted C1-C10 chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 chain alkoxy, substituted or unsubstituted C3-C10 cycloalkoxy, halogen, cyano, nitro, hydroxyl, silane, amino, and substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, and substituted or unsubstituted C3-C30 heteroaryl; and R 1 and R 2 It can be fused with the connected benzene ring to form a ring. Specifically, when R 1 or R 2When fused with the connected benzene ring to form a ring, R 1 or R 2 It only condenses with one benzene ring connected to it to form a ring, and will not condense with multiple nearby benzene rings to form a ring at the same time.

[0031] The above-mentioned compound of the general formula of the present invention is preferably R 1 and R 2 Each is independently selected from any one of hydrogen, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C1-C10 chain alkyl, substituted or unsubstituted C3-C10 cycloalkyl, preferably R 1 and R 2 Each is hydrogen.

[0032] The above-mentioned compound of the general formula of the present invention is preferably Ar 1 and Ar 2 One of them has the structure shown in (II), and the other is a substituted or unsubstituted C6-C30 aryl group.

[0033] The above-mentioned compound of the general formula of the present invention is preferably L 1 and L 2 Each is independently selected from a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group or a substituted or unsubstituted biphenylene group, and more preferably selected from a single bond or a substituted or unsubstituted phenylene group.

[0034] The above-mentioned general formula compound of the present invention is preferably selected from the structures shown in the following P1 to P136, but these compounds are only representative:

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

[0041]

[0042]

[0043]

[0044]

[0045] The organic compound provided by the present invention is used in an organic electroluminescent device, so that the organic electroluminescent device has the effects of low starting voltage and high luminous efficiency.

[0046] The second object of the present invention is to provide an application of the above organic compound in an organic electroluminescent device, which can be but is not limited to being used as a material of a light-emitting host in an organic electroluminescent device.

[0047] The third object of the present invention is to provide an organic electroluminescent device, the organic electroluminescent device comprising a first electrode, a second electrode and an organic layer located between the first electrode and the second electrode, the organic layer containing at least one organic compound of the present invention. Preferably, the organic layer comprises a light-emitting layer, the light-emitting layer containing any one or a combination of at least two of the above-mentioned organic compounds.

[0048] Effects of the Invention

[0049] The general formula compound of the present invention adopts a 7-membered conjugated aromatic ring structure, which is different from the commonly used benzene, naphthalene, phenanthrene, pyrene or Compared with the structures of the present invention, the structure of the compound of the present invention has greater conjugation, so it has a higher singlet S1 energy level and a lower triplet energy level T1, which is beneficial to the transfer of carriers in blue fluorescent devices. At the same time, the 7-membered conjugated aromatic ring with a large conjugated structure in the compound of the present invention makes the molecule have a good rigid structure, thus having good stability and a high glass transition temperature Tg. The above two structural characteristics can make the molecule as a whole show good luminous efficiency and a long service life.

[0050] In addition, the preparation process of the compound of the present invention is simple and easy, the raw materials are easily available, and it is suitable for mass production and expansion. DETAILED DESCRIPTION

[0051] The technical solution of the present invention is further described below through specific implementation methods. Those skilled in the art should understand that the embodiments are only used to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0052] The various chemicals used in the following synthesis examples, such as ethyl acetate, sodium sulfate, toluene, tetrahydrofuran, dichloromethane, acetic acid, potassium carbonate and other basic chemical raw materials, were purchased from Shanghai Titan Technology Co., Ltd. and Xilong Chemical Co., Ltd. The compounds not mentioned in the synthesis method of the present invention are raw materials obtained through commercial channels. The mass spectrometer used to determine the following compounds was a ZAB-HS mass spectrometer (manufactured by Micromass, UK).

[0053] The synthesis route of the compound of general formula (I) of the present invention is:

[0054]

[0055] Synthesis of intermediates M1-M4:

[0056]

[0057] 1,8-dibromonaphthalene (0.1mol, 1eq), phenylboric acid (0.1mol, 1eq), potassium carbonate (0.2mol, 2eq), tetrakis(triphenylphosphine)palladium (0.001mol, 0.01eq), dioxane (300ml) and water (50ml) were added to a three-necked flask. The oil bath was heated to 90°C for 6 hours, and the reaction was completed by TLC monitoring. The reaction solution was cooled to room temperature and the solvent was removed by vacuum rotary evaporation. The crude product was purified by column chromatography to obtain the intermediate MA.

[0058] MA (0.08 mol, 1 eq), o-aminophenylboronic acid pinacol ester (0.1 mol, 1.2 eq), potassium carbonate (0.12 mol, 1.5 eq), tetrakis(triphenylphosphine)palladium (0.0008 mol, 0.01 eq), dioxane (250 ml) and water (40 ml) were added to a three-necked flask. The oil bath was heated to 110°C for 6 hours, and the reaction was completed after TLC monitoring. The reaction solution was cooled to room temperature, the solvent was removed by vacuum rotary evaporation, and the crude product was purified by column chromatography to obtain the intermediate MB.

[0059] MB (0.05 mol) was added to 200 ml of acetic acid, and sulfuric acid (0.25 mol) was added. After cooling to 10°C, an aqueous solution of sodium nitrite (0.1 mol) was added dropwise. After the addition was complete, the mixture was returned to room temperature and reacted for 4 hours. GC-MS detection confirmed that the reaction was complete, and the intermediate M was purified by column chromatography.

[0060] According to the same method as above, only replacing o-aminophenylboronic acid pinacol ester with an equivalent amount of chloro o-aminophenylboronic acid pinacol ester, we can easily obtain the following intermediate:

[0061]

[0062] Synthesis of intermediate M5:

[0063]

[0064] M (0.05 mol) was added to 200 ml of DMF. After cooling to 0°C, a DMF solution of NBS (0.075 mol) was added dropwise. After the addition was complete, the mixture was returned to room temperature and reacted for 4 hours. GC-MS detection confirmed that the reaction was complete. The intermediate M5 was purified by column chromatography.

[0065] Synthesis of intermediate M6:

[0066]

[0067] Add (0.1 mol) 2-nitro-1-naphthol to 300 ml dichloromethane, add triethylamine (0.15 mol) and cool to 0°C, add 0.2 mol trifluoromethanesulfonic anhydride dropwise, react at room temperature for 2 hours after the addition is complete, monitor the reaction by TLC, slowly add water, separate the organic phase, concentrate to obtain a brown oil, and wash with petroleum ether to obtain a yellow solid.

[0068] M6-A (0.1 mol, 1 eq), 2′-(boronic acid pinacol ester-2-yl)-[1,1′-biphenyl]-2-amine (0.12 mol, 1.2 eq), potassium carbonate (0.15 mol, 1.5 eq), tetrakis(triphenylphosphine)palladium (0.001 mol, 0.01 eq), dioxane (250 ml) and water (40 ml) were added to a three-necked flask. The oil bath was heated to 110° C. for 6 hours, and the reaction was monitored by TLC. The reaction solution was cooled to room temperature, the solvent was removed by vacuum rotary evaporation, and the crude product was purified by column chromatography to obtain the intermediate M6-B.

[0069] M6-B (0.05 mol, 1 eq), sulfuric acid (0.1 mol), acetic acid (200 ml) were added to a three-necked flask. The temperature was lowered to 10°C and sodium nitrite aqueous solution (0.1 mol) was added dropwise. After the addition was completed, the reaction was allowed to react at room temperature for 2 h and the reaction was monitored by TLC. After extraction with water and ethyl acetate, the solvent was removed by rotary evaporation under reduced pressure and the crude product was purified by column chromatography to obtain the intermediate M6-C.

[0070] M6-C (0.04 mol, 1 eq), iron powder (0.2 mol), and ethanol (200 ml) were added into a three-necked flask and heated under reflux for 24 h. After the reaction was complete, the ethanol was directly dried by spin drying. The residue was washed with dichloromethane and the organic phase was concentrated to obtain a brown oil.

[0071] M6-D (0.04 mol), cuprous bromide (0.1 mol) and hydrochloric acid (0.1 mol) were added to 200 ml of acetonitrile. The temperature was cooled to 0°C and tert-butyl nitrite (0.1 mol) was added dropwise. After the addition was completed, the mixture was reacted at 50°C for 4 h. The reaction was completed under the monitoring of GC-MS. The intermediate M6 was obtained by column chromatography.

[0072] Synthesis Example

[0073] Synthesis Example 1: Synthesis of Compound P3

[0074]

[0075] M5 (0.1 mol, 1 eq), pinacol borate (0.12 mol, 1.2 eq), potassium acetate (0.15 mol, 1.5 eq), [1,1′-bis(diphenylphosphino)ferrocene]palladium dichloride (0.001 mol, 1% eq) were added to a reaction bottle containing dioxane (300 ml), heated under reflux for 4 h, and after the reaction was complete, the reaction solution was directly filtered and concentrated, and washed with methanol and filtered to obtain the intermediate P3-A.

[0076] P3-A (0.05 mol), 9-(naphthalen-2-yl)-10-bromoanthracene (0.05 mol), potassium carbonate (0.075 mol), tetrakis(triphenylphosphine)palladium (0.0005 mol, 0.0leq), dioxane (200 ml) and water (30 ml) were added to a reaction bottle, heated to reflux for 5 h until the reaction was complete, and filtered directly after cooling. The filter cake was purified by column chromatography to obtain compound P3.

[0077] Synthesis Example 2: Synthesis of Compound P7

[0078] Similar to Synthesis Example 1, except that 9-(naphthalene-2-yl)-10-bromoanthracene is replaced with an equivalent amount of 9-bromo-10-(4-(naphthalene-2-yl)phenyl)anthracene to obtain Compound P7.

[0079] Synthesis Example 3: Synthesis of Compound P12

[0080]

[0081] Add p-chlorophenylboric acid (0.1 mol), 9-(naphthalen-1-yl)-10-bromoanthracene (0.1 mol), potassium carbonate (0.12 mol), tetrakis(triphenylphosphine)palladium (0.001 mol, 0.01 eq), dioxane (300 ml) and water (50 ml) into a reaction flask, heat to reflux for 3 h to complete the reaction, add 200 ml of water and dichloromethane after cooling, extract, concentrate the organic phase and purify by column chromatography to obtain compound P12-A.

[0082] P3-A (0.05 mol), P12-A (0.05 mol), potassium phosphate (0.075 mol), tri(dibenzylideneacetone)dipalladium (0.0005 mol, 0.01 eq), 2-dicyclohexylphosphine-2′,6′-dimethoxy-biphenyl (0.1 mol), dioxane (200 ml) and water (30 ml) were added to a reaction bottle, heated to reflux for 8 h until the reaction was complete, filtered after cooling, and the filter cake was purified by column chromatography to obtain compound P12.

[0083] Synthesis Example 4: Synthesis of Compound P16

[0084] Similar to Synthesis Example 3, except that 9-(naphthalene-1-yl)-10-bromoanthracene is replaced with an equivalent amount of 9-bromo-10-(3-phenylnaphthalene-1-yl)anthracene to obtain Compound P16.

[0085] Synthesis Example 5: Synthesis of Compound P22

[0086]

[0087] P3-A (0.1 mol), 9,10-dibromoanthracene (0.05 mol), potassium carbonate (0.12 mol), tetrakis(triphenylphosphine)palladium (0.001 mol, 0.01 eq), dioxane (300 ml) and water (50 ml) were added to a reaction bottle and heated to reflux for 5 h to complete the reaction. After cooling, 200 ml of water and dichloromethane were added for extraction. The organic phase was concentrated and purified by column chromatography to obtain compound P22.

[0088] Synthesis Example 6: Synthesis of Compound P39

[0089]

[0090] 2-(9,10-di(naphthalene-2-yl)anthracene-2-yl)-boric acid pinacol ester (0.05 mol), M6 (0.05 mol), potassium carbonate (0.075 mol), tetrakis(triphenylphosphine)palladium (0.0005 mol, 0.01 eq), dioxane (200 ml) and water (30 ml) were added to a reaction flask and heated to reflux for 5 h to complete the reaction. After cooling, 200 ml of water and dichloromethane were added for extraction. The organic phase was concentrated and purified by column chromatography to obtain compound P39.

[0091] Synthesis Example 7: Synthesis of Compound P56

[0092] Similar to Synthesis Example 1, except that 9-bromo-10-(4-(naphthalen-2-yl)phenyl)anthracene is replaced with an equivalent amount of 9-bromo-10-(4-(naphthalen-2-yl)pentadeuterophenyl)anthracene to obtain Compound P56.

[0093] Synthesis Example 8: Synthesis of Compound P97

[0094] Similar to Synthesis Example 2, except that 9-bromo-10-(4-(naphthalen-2-yl)phenyl)anthracene is replaced with an equivalent amount of 9-bromo-10-(4-(naphthalen-1-yl)pentadeuterophenyl)anthracene, and M5 is replaced with an equivalent amount of M3 to obtain compound P97.

[0095] Device Embodiment

[0096] OLED includes a first electrode, a second electrode, and an organic material layer between the electrodes. The organic material can be divided into multiple regions. For example, the organic material layer can include a hole transport region, a light emitting layer, and an electron transport region.

[0097] In a specific embodiment, a substrate may be used below the first electrode or above the second electrode. The substrate is a glass or polymer material with excellent mechanical strength, thermal stability, water resistance, and transparency. In addition, a thin film transistor (TFT) may also be provided on the substrate used as a display.

[0098] The first electrode can be formed by sputtering or depositing the material used as the first electrode on the substrate. When the first electrode is used as an anode, an oxide transparent conductive material such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), zinc oxide (ZnO) and any combination thereof can be used. When the first electrode is used as a cathode, a metal or alloy such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag) and any combination thereof can be used.

[0099] The organic material layer can be formed on the electrode by vacuum thermal evaporation, spin coating, printing, etc. The compound used as the organic material layer can be organic small molecules, organic macromolecules and polymers, and combinations thereof.

[0100] The hole transport region is located between the anode and the light-emitting layer. The hole transport region can be a hole transport layer (HTL) of a single-layer structure, including a single-layer hole transport layer containing only one compound and a single-layer hole transport layer containing multiple compounds. The hole transport region can also be a multi-layer structure including at least one layer of a hole injection layer (HIL), a hole transport layer (HTL), and an electron blocking layer (EBL).

[0101] The material of the hole transport region can be selected from, but not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or polymers containing conductive dopants such as polyphenylene ethylene, polyaniline / dodecylbenzenesulfonic acid (Pani / DBSA), poly(3,4-ethylenedioxythiophene) / poly(4-styrenesulfonate) (PEDOT / PSS), polyaniline / camphorsulfonic acid (Pani / CSA), polyaniline / poly(4-styrenesulfonate) (Pani / PSS), aromatic amine derivatives such as the compounds shown in HT-1 to HT-34 below; or any combination thereof.

[0102]

[0103]

[0104]

[0105] The hole injection layer is located between the anode and the hole transport layer. The hole injection layer can be a single compound material or a combination of multiple compounds. For example, the hole injection layer can use one or more compounds of HT-1 to HT-34, or one or more compounds of HI-1 to HI-3 described below; or one or more compounds of HT-1 to HT-34 can be doped with one or more compounds of HI-1 to HI-3 described below.

[0106]

[0107] The light-emitting layer includes a light-emitting dye (i.e., dopant) that can emit light of different wavelength spectra, and may also include a host material (Host). The light-emitting layer may be a monochrome light-emitting layer that emits a single color such as red, green, and blue. A plurality of monochrome light-emitting layers of different colors may be arranged in a plane according to a pixel pattern, or may be stacked together to form a color light-emitting layer. When light-emitting layers of different colors are stacked together, they may be separated from each other or may be connected to each other. The light-emitting layer may also be a single color light-emitting layer that can simultaneously emit different colors such as red, green, and blue.

[0108] According to different technologies, the light-emitting layer material can be made of different materials such as fluorescent electroluminescent materials, phosphorescent electroluminescent materials, and thermally activated delayed fluorescent materials. In an OLED device, a single light-emitting technology can be used, or a combination of multiple different light-emitting technologies can be used. These different light-emitting materials classified by technology can emit light of the same color or different colors.

[0109] In one aspect of the present invention, the light-emitting layer adopts fluorescent electroluminescence technology. The fluorescent dopant of the light-emitting layer can be selected from, but not limited to, one or more combinations of BFD-1 to BFD-12 listed below.

[0110]

[0111]

[0112] The OLED organic material layer may further include an electron transport region between the light emitting layer and the cathode. The electron transport region may be a single-layer electron transport layer (ETL), including a single-layer electron transport layer containing only one compound and a single-layer electron transport layer containing multiple compounds. The electron transport region may also be a multilayer structure including at least one layer of an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL).

[0113] The electron transport region can also be formed by using the compound of the present invention for a multilayer structure including at least one layer of an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL). Of course, the material of the electron transport region can also be a combination of one or more of ET-1 to ET-57 listed below.

[0114]

[0115]

[0116]

[0117]

[0118] The device may also include an electron injection layer located between the electron transport layer and the cathode. The electron injection layer material includes but is not limited to one or more combinations of the following: LiQ, LiF, NaCl, CsF, Li2O, Cs2CO3, BaO, Na, Li and / or Ca.

[0119] The technical effects and advantages of the present invention are demonstrated and verified by applying the compound of the present invention to an organic electroluminescent device to test the actual performance.

[0120] Example 1

[0121] This embodiment provides a method for preparing an organic electroluminescent device, which is as follows:

[0122] The glass plate coated with the ITO transparent conductive layer was ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone:ethanol, baked in a clean environment to completely remove the water, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam;

[0123] Place the glass substrate with the anode in a vacuum chamber and evacuate the chamber to a pressure less than 10 -5 Pa, on the anode layer film, HI-3 is vacuum evaporated as a hole injection layer on the anode layer film by a multi-source co-evaporation method, the evaporation rate is 0.1 nm / s, and the evaporation film thickness is 10 mm;

[0124] HT-4 was vacuum-deposited on the hole injection layer as the first hole transport layer of the device, with a deposition rate of 0.1 nm / s and a total deposition thickness of 40 nm;

[0125] Vacuum evaporate HT-14 on the first hole transport layer as the second hole transport layer of the device, the evaporation rate is 0.1nm / s, and the total evaporation film thickness is 10nm;

[0126] The light-emitting layer of the device is vacuum-evaporated on the second hole transport layer. The light-emitting layer includes a main material and a dye material. The evaporation rate of the P3 main material is adjusted to 0.1nm / s by a multi-source co-evaporation method. The evaporation rate of the dye BFD-4 is set at 5% ratio, and the total evaporation film thickness is 20nm.

[0127] ET-17 was vacuum-deposited on the light-emitting layer as the hole blocking layer of the device, with a deposition rate of 0.1 nm / s and a total deposition film thickness of 5 nm;

[0128] An electron transport layer was evaporated on the hole blocking layer by a multi-source co-evaporation method, the evaporation rate of compound ET-46 was adjusted to 0.1 nm / s, and the ratio of the evaporation rate of ET-57 was set to 100%, and the total film thickness of the evaporation was 23 nm;

[0129] LiF with a thickness of 1 nm was vacuum evaporated on the electron transport layer (ETL) as the electron injection layer, and the Al layer with a thickness of 80 nm was used as the cathode of the device.

[0130] Embodiment 2-8

[0131] The preparation process of Examples 2-8 is the same as that of Example 1, except that the compound P3 in the light-emitting layer is replaced by the compounds shown in Table 1.

[0132] Comparative Example 1-2

[0133] The preparation process of Comparative Example 1-2 is the same as that of Example 1, except that the compound P3 of the light-emitting layer is replaced by the existing compound C1 or C2, and the chemical formula is:

[0134]

[0135] The organic electroluminescent device prepared by the above process was subjected to the following performance tests:

[0136] At the same brightness, the driving voltage and current efficiency of the organic electroluminescent devices prepared in Examples 1-8 and Comparative Examples 1-2 were measured using a PR 750 photoradiometer from Photo Research, a ST-86LA luminance meter (from Beijing Normal University Photoelectric Instrument Factory), and a Keithley 4200 test system. Specifically, the voltage was increased at a rate of 0.1 V per second, and the driving voltage and current efficiency of the organic electroluminescent devices were measured when the brightness reached 1000 cd / m 2 The voltage at this time is the driving voltage, and the current density at this time is measured at the same time; the ratio of brightness to current density is the current efficiency; the performance test results are shown in Table 1.

[0137] Table 1

[0138]

[0139] It can be seen from Table 1 that when other materials in the structure of the organic electroluminescent device are the same, the organic electroluminescent devices provided by Examples 1-8 of the present invention have higher current efficiency and lower driving voltage, wherein the current efficiency is 7.05-7.33 cd / A and the driving voltage is 4.11-4.22 V.

[0140] The compounds C1 and C2 in the comparative example are anthracene-based substituents based on naphthalene, and the driving voltage of the device is 4.31V and 4.43V, and the current efficiency is 7.01cd / A and 6.31Vcd / A, which has a large performance gap compared with the device of the embodiment. Its principle is not clear, but the reason is speculated as follows: the main material of Examples 1-8 adopts a 7-membered aromatic ring structure with a larger conjugation compared with the comparative example, and its overall planar conjugation degree is much larger than the comparative example, so its carrier transport capacity is higher than that of the comparative example compound when combined with anthracene. In addition, the compounds of the present invention have a higher Tg than the comparative example, which is beneficial to the thermal stability of the material.

[0141] The inventors also found that although the device of Example 6 has a lower driving voltage and a higher current efficiency than Comparative Examples 1-2, the above parameters are not as good as those of other embodiments. The difference between Example 6 and other embodiments is mainly that the 7-membered aromatic ring of compound P39 of Example 6 is not located at the 9th or 10th position of anthracene. Although the principle is not clear, it can be inferred that the combination of the 7-membered aromatic ring and the specific position 9 or 10 of anthracene is conducive to reducing the driving voltage and improving the current efficiency.

[0142] The above experimental data show that the novel organic material of the present invention is an organic light-emitting functional material with good performance as a fluorescent light-emitting layer of an organic electroluminescent device, and has broad application prospects. Obviously, the above embodiments are only examples for clear explanation, and are not limitations on the implementation methods. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made on the basis of the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived from this are still within the protection scope of the invention.

Claims

1. An organic compound, characterized in that It has the structure shown in (I): Wherein, m is an integer from 0 to 3, n is an integer from 1 to 3, and 2≤m+n≤4; L 1 is selected from a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group or a substituted or unsubstituted biphenylene group, L 2 is selected from substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene or substituted or unsubstituted biphenylene; Ar 1 is at least one of substituted or unsubstituted phenyl and naphthyl; Ar 2 Having the structure shown in (II-1) or (II-2): Among them, R 1 and R 2 Each independently represents a single substituent to the maximum allowed number of substituents, and each independently is selected from any one of hydrogen, C1~C10 chain alkyl, C1~C10 chain alkoxy, halogen, cyano, nitro, hydroxyl, and amino; When the above-mentioned substituted or unsubstituted group has a substituent, the substituent is selected from any one of deuterium, C1~C10 alkyl, C1~C10 alkoxy, halogen, cyano, nitro, hydroxyl, and amino, or a combination of at least two of them.

2. The organic compound according to claim 1, characterized in that The organic compound has a structure as shown in (I-1), 。 3. The organic compound according to claim 2, characterized in that The organic compound has a structure as shown in (I-2) or (I-1-1): or .

4. The organic compound according to claim 1 or 2, characterized in that Ar 1 and Ar 2 At least one of them has the structure shown in (II-2-2): Among them, R 1 and R 2 Each independently represents a single substituent to the maximum permissible substituent, and is independently selected from hydrogen, C1~C10 chain alkyl, C1~C10 chain alkoxy, halogen, cyano, nitro, hydroxyl, and amino.

5. The organic compound according to claim 1, characterized in that R 1 and R 2 Each is independently selected from any one of hydrogen and C1-C10 chain alkyl.

6. The organic compound according to claim 5, characterized in that R 1 and R 2 Each is hydrogen.

7. An organic compound, characterized in that The organic compound has a structure as shown in (I): Wherein, m is an integer from 0 to 3, and n is 1; L 1 and L 2 is selected from a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group or a substituted or unsubstituted biphenylene group; Ar 1 At least one selected from substituted or unsubstituted phenyl and naphthyl, wherein Ar 1 The substituent is deuterium; Ar 2 Having the structure shown in (II-1) or (II-2): Among them, R 1 and R 2 Each independently represents a single substituent to the maximum allowed number of substituents, and each independently is selected from any one of hydrogen, C1~C10 chain alkyl, C1~C10 chain alkoxy, halogen, cyano, nitro, hydroxyl, and amino; The above L 1 , L 2 When the substituted or unsubstituted group has a substituent, the substituent is selected from any one of deuterium, C1~C10 alkyl, C1~C10 alkoxy, halogen, cyano, nitro, hydroxyl, and amino, or a combination of at least two of them.

8. An organic compound, characterized in that The organic compound has the structure shown in (I): Wherein, m is a positive integer from 0 to 3, n is 1, and 1≤m+n≤4; L 1 and L 2 are each independently selected from a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group or a substituted or unsubstituted biphenylene group; Ar1 is at least one of substituted or unsubstituted phenyl and naphthyl; Ar 2 It has the structure shown in (II-2-1): Among them, R 1 and R 2 Each independently represents a single substituent to the maximum allowed number of substituents, and each independently is selected from any one of hydrogen, C1~C10 chain alkyl, C1~C10 chain alkoxy, halogen, cyano, nitro, hydroxyl, and amino; When the above-mentioned substituted or unsubstituted group has a substituent, the substituent is selected from any one of deuterium, C1~C10 alkyl, C1~C10 alkoxy, halogen, cyano, nitro, hydroxyl, and amino, or a combination of at least two of them.

9. An organic compound, characterized in that The organic compound has a structure shown in any of the following chemical formulas: 。 10. Use of the organic compound according to any one of claims 1 to 9 in an organic electroluminescent device.

11. The use according to claim 10, wherein: The application is application as a light-emitting layer material.

12. An organic electroluminescent device comprising a first electrode, a second electrode and an organic layer located between the first electrode and the second electrode, characterized in that: The organic layer contains at least one organic compound according to any one of claims 1 to 9.

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