Boron-containing compound and organic electroluminescent device using the same

Abstract

The present invention relates to a novel organic compound having the structure of the following formula (1): Rings A, B, C, D, and E independently represent aromatic rings or heteroaromatic rings, and two adjacent rings can be fused to form a ring containing X 1 or X 2 A five-membered ring or a six-membered ring; X 1 and X 2 are independently selected from one of O, S, N, C, and Si; m and n are independently 0, 1 or 2, and R 1 To R 5 They are independently selected from hydrogen, C1-C10 chain alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, halogen, cyano, nitro, hydroxyl, ester, silyl, amino, arylamino, heteroarylamino, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, and at least one of them is of formula (2). When the compound of the present invention is used as a light-emitting layer material in an OLED device, it exhibits excellent device performance and stability. The present invention also protects an organic electroluminescent device using the compound of the above general formula.

Description

Technical Field

[0001] The invention relates to a boron-containing organic material, belonging to the technical field of organic luminescent materials. The invention also relates to the application of the compound in an organic electroluminescent device. Background Art

[0002] Optoelectronic devices using organic materials are becoming increasingly popular for a number of reasons. Many of the materials used to make such devices are relatively cheap, and optoelectronic devices have potential cost advantages over inorganic devices. In the structure of organic electroluminescent devices in the display and lighting fields, blue fluorescence is generally used in combination with red and green phosphorescent materials. Recently, a literature has reported an ultra-pure blue fluorescent dye BN compound based on TADF (Thermally Activated Delayed Fluorescence). This type of compound is based on triphenylboron and contains two nitrogen atoms, forming a rigid polycyclic aromatic skeleton. The nitrogen atom has an opposite resonance effect to the boron atom, and the opposite resonance effect is enhanced at its para position. Therefore, this effect can clearly separate the HOMO and LUMO orbitals. The calculated molecular orbitals of DABNA-1 show that the LUMO orbital is distributed on the boron atom and the ortho and para positions of the boron atom, and the HOMO orbital is distributed on the nitrogen atom and the meta position of the boron atom.

[0003]

[0004] BN compounds, based on triphenylborane, contain two nitrogen atoms, forming a rigid polycyclic aromatic skeleton. The nitrogen atom has an opposite resonance effect to the boron atom, and the opposite resonance effect is enhanced at its para position. Summary of the invention

[0005] In order to solve the above technical problems, the present invention provides a new type of compound, which belongs to the thermally activated delayed fluorescence material. Alkyl aromatic groups are introduced into the structure of this series of compounds to increase the molecular distance, inhibit molecular stacking and Dexter energy transfer, and thus improve the efficiency roll-off problem of organic electroluminescent devices using this type of compound.

[0006] The present invention provides a new type of boron-based organic compound, the structure of which is shown in the general formula (1):

[0007]

[0008] In the general formula (1):

[0009] Rings A, B, C, D, and E independently represent aromatic rings or heteroaromatic rings, and two adjacent rings may be fused to form a ring containing X 1 or X2 A five-membered ring or a six-membered ring;

[0010] Preferably, ring A is fused with ring C to form a 1 or, ring B and ring D are fused to form a five-membered ring or a six-membered ring containing X 2 or, ring A and ring C are fused to form a five-membered ring or a six-membered ring containing X 1 At the same time, ring B and ring D are fused to form a five-membered ring or a six-membered ring containing X 2 A five-membered ring or a six-membered ring;

[0011] X 1 and X 2 Each independently selected from one of O, S, N, C, and Si;

[0012] m is 0, 1 or 2. 1 When selected from O or S, m is 0; n is 0, 1 or 2, when X 2 When selected from O or S, n is 0;

[0013] R 1 , R 2 , R 3 , R 4 , R 5 Each independently represents a monosubstituted to maximum permissible substituent, and each independently is selected from hydrogen, C1-C12 chain alkyl, C3-C12 cycloalkyl, C1-C12 alkoxy, halogen, cyano, nitro, hydroxyl, ester, silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, R 1 , R 2 , R 3 , R 4 and R 5 At least one of them is represented by formula (2);

[0014] In formula (2): Z 1 Selected from C or Si, Z 2 Selected from CR 6 R 7 NR 8 、O、S、SiR 9 R 10 One of the following, a is 0 or 1. When a is 0, it indicates a single bond;

[0015] R 6 , R 7 , R 8 , R 9 , R 10Each of the following is independently selected from a substituted or unsubstituted C1-C12 chain alkyl group, a substituted or unsubstituted C3-C12 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C3-C30 heteroaryl group;

[0016] R A1 One selected from C1-C12 chain alkyl, C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl;

[0017] R B1 and R C1 Each independently represents a monosubstituted to maximum permissible substituent, and each independently is selected from one of hydrogen, C1-C12 chain alkyl, C3-C12 cycloalkyl, C1-C12 alkoxy, halogen, cyano, nitro, hydroxyl, ester, silane, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl;

[0018] When the above-mentioned groups have substituents, the substituents are selected from one or a combination of at least two of halogen, cyano, carbonyl, C1-C12 alkyl, C3-C12 cycloalkyl, C2-C10 alkenyl, C1-C6 alkoxy or thioalkoxy, C6-C30 monocyclic aromatic or condensed aromatic, C3-C30 monocyclic heteroaryl or condensed heteroaryl.

[0019] It should be noted that, in the present invention, the maximum permissible substituents refer to the maximum number of substituents under the premise that the substituted groups meet the bonding requirements.

[0020] In the present specification, the expression of Ca to Cb represents that the number of carbon atoms in the group is a to b. Unless otherwise specified, the number of carbon atoms generally does not include the number of carbon atoms in the substituent.

[0021] In the present specification, the expression of a ring structure crossed by “—” indicates that the connection site is any position on the ring structure that can form a bond.

[0022] In the present specification, the substituted or unsubstituted C6-C30 aryl group is preferably a C6-C20 aryl group, more preferably a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, an indenyl group, a fluorenyl group and its derivatives, a fluoranthenyl group, a triphenylene group, a pyrenyl group, a peryl group, A group consisting of a tetraphenyl group and a naphthyl group. 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 and 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 fluorenyl derivative is selected from 9,9'-dimethylfluorene, 9,9'-spirobifluorene and benzofluorene; the pyrenyl group is selected from 1-pyrenyl, 2-pyrenyl and 4-pyrenyl; the tetraphenyl group is selected from 1-tetraphenyl, 2-tetraphenyl and 9-tetraphenyl.

[0023] The heteroatom described in the present invention generally refers to an atom or an atom group selected from N, O, S, P, Si and Se, preferably selected from N, O and S. The atom names described in the present invention include their corresponding isotopes. For example, hydrogen (H) includes 1 H (protium or H), 2 H (deuterium or D), etc.; Carbon (C) includes 12 C. 13 C, etc.

[0024] In the present specification, the substituted or unsubstituted C3~C30 heteroaryl group is preferably a C4~C20 heteroaryl group, and more preferably a nitrogen-containing heteroaryl group, an oxygen-containing heteroaryl group, a sulfur-containing heteroaryl group, etc. Specific examples include: furyl, thienyl, pyrrolyl, benzofuranyl, benzothienyl, isobenzofuranyl, indolyl, dibenzofuranyl, dibenzothienyl, carbazole and derivatives thereof, wherein the carbazole derivative is preferably 9-phenylcarbazole, 9-naphthylcarbazole, benzocarbazole, dibenzocarbazole, or indolecarbazole.

[0025] In the present specification, the C1-C20 chain alkyl group is preferably a C1-C10 chain alkyl group, and more preferably a C1-C6 chain alkyl group, examples of which include methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, isopropyl, isobutyl, and tert-butyl.

[0026] In the present specification, the C3-C12 cycloalkyl group includes a monocyclic alkyl group and a polycyclic alkyl group, and preferably a C1-C10 alkyl group and a C3-C10 cycloalkyl group.

[0027] Furthermore, in the general formula compounds of the present invention, the rings A, B, C, D, and E are independently selected from 5- to 8-membered aryl rings or 5- to 8-membered heteroaryl rings; preferably, the rings A, B, C, D, and E are independently selected from 6-membered aryl rings or 5-membered heteroaryl rings.

[0028] Furthermore, in the general formula compound described in the present invention, the rings A, B, C, D, and E are independently selected from one of substituted or unsubstituted C6-C30 aromatic groups and substituted or unsubstituted C3-C30 heteroaromatic groups; preferably, the rings A, B, C, D, and E are independently selected from the following substituted or unsubstituted groups: benzene ring, furan ring, thiophene ring, naphthalene ring, phenanthrene ring or carbazole ring.

[0029] Further, formula (2) is shown in formula (2-1) or formula (2-2):

[0030]

[0031] Where Z 1 , Z 2 , R A1 , R B1 and R C1 The definition of is the same as that in formula (2).

[0032] Furthermore, R A1 is selected from one of C1-C12 chain alkyl, C3-C12 cycloalkyl, substituted or unsubstituted C6-C12 aryl, substituted or unsubstituted C5-C12 heteroaryl; preferably, R A1 One selected from methyl, ethyl or phenyl;

[0033] R B1 and R C1 are independently selected from one of hydrogen, C1-C12 chain alkyl, C3-C12 cycloalkyl, substituted or unsubstituted C6-C12 aryl, substituted or unsubstituted C5-C12 heteroaryl; preferably, R B1 and R C1 Each is independently selected from hydrogen, phenyl or one of the following alkyl groups:

[0034]

[0035] Furthermore, the general compound of the present invention is selected from the following formula (1-2):

[0036]

[0037] In formula (1-2), ring C, D, R 1 , R 2 , R 3 , R 4 , R 5 The definitions of m and n are the same as those in the general formula (1), wherein X 1 and X 2 are independently selected from one of O, S, N, C, and Si, and X 1 and X 2At least one of them is N.

[0038] Furthermore, the general formula compound of the present invention is selected from one of the following formulas (I), (II), (III), (IV), (V), (VI), (VII) or (VIII):

[0039]

[0040]

[0041] Most preferably, the general compound of the present invention is selected from the following formula (I), (II) or (III):

[0042]

[0043] More preferably, R 1 , R 2 , R 3 , R 4 , R 5 are independently selected from hydrogen or are independently selected from one of the following groups, R 1 , R 2 , R 3 , R 4 and R 5 At least one of them is shown in formula (2):

[0044]

[0045] As preferred structures of the compounds of the present invention, the following specific compounds S1-S292 can be cited, but are not limited to these compounds:

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059] As another aspect of the present invention, there is also provided an application of the compound as described above in an organic electroluminescent device. Specifically, it is preferably used as a light-emitting layer material in an organic electroluminescent device, and more preferably used as a material in the light-emitting layer in the organic electroluminescent device, and specifically can be used as a luminescent dye.

[0060] As another aspect of the present invention, an organic electroluminescent device is provided, comprising a first electrode, a second electrode and one or more organic layers inserted between the first electrode and the second electrode, wherein the organic layer contains a compound of the general formula (1) as described above, or contains a compound having the structure shown in S1-S292 as described above.

[0061] Specifically, one embodiment of the present invention provides an organic electroluminescent device, comprising a substrate, and a first electrode, a plurality of light-emitting functional layers and a second electrode sequentially formed on the substrate; the light-emitting functional layers comprise a hole injection layer, a hole transport layer, a light-emitting layer and an electron transport layer, the hole injection layer is formed on the anode layer, the hole transport layer is formed on the hole injection layer, the cathode layer is formed on the electron transport layer, and a light-emitting layer is provided between the hole transport layer and the electron transport layer; wherein the light-emitting layer contains the general formula compound of the present invention represented by the above formula (1).

[0062] The present invention further discloses a display screen or a display panel, wherein the organic electroluminescent device as described above is adopted in the display screen or the display panel; preferably, the display screen or the display panel is an OLED display.

[0063] The present invention also discloses an electronic device, wherein the electronic device has a display screen or a display panel, and the display screen or the display panel adopts the organic electroluminescent device as described above.

[0064] The OLED device prepared by using the compound of the present invention has low starting voltage, high luminous efficiency and better service life, and can meet the requirements of current panel manufacturing companies for high-performance materials.

[0065] The specific reason why the above-mentioned compound of the present invention has excellent performance as a luminescent dye in the luminescent layer of an organic electroluminescent device is not clear, but it is speculated that the following reasons may be the reason:

[0066] 1. The boron atom contained in the compound of the present invention has a resonance effect with the nitrogen atom in the same ring, and the opposite resonance effect is enhanced at the para position. Therefore, this effect can clearly separate the HOMO and LUMO orbitals, thereby having thermally activated delayed fluorescence properties.

[0067] 2. The introduction of the group formula (2) used in the compound of the present invention helps to adjust the energy level of the compound so that it is more compatible with the energy levels of the host material and other functional layer materials, which is beneficial to the injection of carriers into the light-emitting layer;

[0068] 3. The introduction of the non-conjugated group formula (2) used in the compound of the present invention helps to protect the active site of the compound, prevent exciton quenching, and prevent the red shift of luminescence caused by increased conjugation, thereby improving the efficiency and life of the device, making it match the main material in the light-emitting layer, and facilitating its use as a dye;

[0069] 4. When the compound of the present invention is used as a dye, compared with the comparative example compound, its voltage is reduced, and its efficiency and life are improved, showing excellent device performance; this is because the group represented by formula (2) does not form a conjugated relationship with the A, B, C, D, and E rings connected thereto, while suppressing exciton quenching, it ensures that the compound emits light in the deep blue light region, thereby improving the efficiency and life of the device. This is conducive to the practical application of the compound of the present invention.

[0070] 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

[0071] The specific preparation method of the above-mentioned novel compound of the present invention will be described in detail below by taking a plurality of synthesis examples as examples, but the preparation method of the present invention is not limited to these synthesis examples.

[0072] It should be noted that obtaining the compound is not limited to the synthesis method and raw materials used in the present invention, and those skilled in the art may also select other methods or routes to obtain the compound proposed in the present invention. The compounds of the synthesis method not mentioned in the present invention are raw materials obtained through commercial channels, or are prepared by these raw materials according to known methods.

[0073] The solvents and reagents used in the synthesis examples of the present invention, such as dichloromethane, petroleum ether, ethanol, tetrahydrofuran, N, N-dimethylacetamide, anhydrous magnesium sulfate, carbazole, benzimidazole and the like chemical reagents, can be purchased from the domestic chemical product market, such as Sinopharm Group Reagent Company, TCI Company, Shanghai Bid Pharmaceutical Company, Bailingwei Reagent Company, etc. In addition, those skilled in the art can also synthesize by known methods.

[0074] The analysis and detection of the intermediates and compounds in the synthesis examples were performed using an ABSCIEX mass spectrometer (4000QTRAP).

[0075] The synthesis method of the compound of the present invention is briefly described below.

[0076] Synthesis Example

[0077] Representative synthetic routes:

[0078]

[0079] Synthesis Example 1: Synthesis of S1

[0080]

[0081] Synthesis of intermediate S1-1:

[0082] At room temperature, raw material A1 (50g, 111.5mmol), diphenylamine (41.5g, 245.2mmol), Pd2(dba)3 (4.12g, 4.46mmol), tri-tert-butylphosphine (1.80g, 8.92mmol), sodium tert-butoxide (32.14g, 334.4mmol), and xylene (500ml) were added to a 2L single-mouth bottle, and nitrogen was pumped three times, and heated to 130°C for overnight reaction. The reaction solution was cooled to room temperature, filtered, and the filtrate was mixed with silica gel for concentration. Column chromatography (PE: EA = 100: 1) obtained 70g of crude product, and toluene / ethanol recrystallization obtained 61.3g of white solid, with a yield of 87.96%. The molecular ion mass determined by mass spectrometry was: 625.20 (theoretical value: 625.21).

[0083] Synthesis of compound S1:

[0084] S1-1 (50g, 80.0mmol) was added to a 2000ml three-necked flask, and o-xylene (500ml) was added. The flask was filled with nitrogen three times. In an ice-water bath, n-butyl lithium solution (68ml, 1.6M, 96mmol) was added dropwise to the three-necked flask with a thick needle. The mixture was stirred for 1 hour. Boron tribromide (24.4g, 96mmol) was extracted with a thick needle in an ice-water bath and added to the reaction solution. The mixture was stirred for 30 minutes, heated to 45°C and stirred for 50 minutes. In an ice-water bath, N,N-diisopropylethylamine (20.67g, 160mmol) was extracted and added to the reaction system. The mixture was stirred for 30 minutes, heated to 120°C, and reacted overnight. The heating was stopped, and water (1000ml) was added to quench the mixture after the system cooled to room temperature. The lower organic phase was separated, and the aqueous phase was extracted three times with ethyl acetate (1000ml). The organic phases were combined and dried over anhydrous sodium sulfate. The organic phase was mixed with silica gel and concentrated, column chromatography was performed to obtain 20 g of crude product, and toluene / ethanol was used for recrystallization to obtain 13.11 g of yellow solid, with a yield of 27%. The molecular ion mass determined by mass spectrometry was 588.76 (theoretical value: 587.75).

[0085] Synthesis Example 2: Synthesis of S132

[0086]

[0087] Synthesis of intermediate S132-1:

[0088] At room temperature, raw material A132 (50g, 94.9mmol), di-tert-butylaniline (32.06g, 113.9mmol), Pd2(dba)3 (1.75g, 1.9mmol), tri-tert-butylphosphine (0.77g, 3.8mmol), sodium tert-butoxide (18.25g, 189.9mmol), xylene (500ml) were added to a 2L single-mouth bottle, nitrogen was pumped three times, and the reaction was heated to 130°C overnight. The reaction solution was cooled to room temperature, filtered, and the filtrate was mixed with silica gel and concentrated. Column chromatography (PE: EA = 100: 1) obtained 77g of crude product, and toluene / ethanol recrystallization obtained 68.2g of white solid, with a yield of 98%. The molecular ion mass determined by mass spectrometry was: 728.25 (theoretical value: 727.26).

[0089] Synthesis of intermediate S132-2:

[0090] At room temperature, raw material A132 (60g, 82.5mmol), di-tert-butylcarbazole (27.86g, 99mmol), Pd2(dba)3 (1.52g, 1.65mmol), tri-tert-butylphosphine (0.66g, 3.3mmol), sodium tert-butoxide (15.86g, 165mmol), and xylene (600ml) were added to a 2L single-mouth bottle, and nitrogen was pumped three times, and heated to 130°C for overnight reaction. The reaction solution was cooled to room temperature, filtered, and the filtrate was concentrated by mixing with silica gel, column chromatography (PE:EA=100:1), and toluene / ethanol recrystallization to obtain 70.1g of white solid, with a yield of 92%. The molecular ion mass determined by mass spectrometry was: 925.75 (theoretical value: 925.77).

[0091] Synthesis of compound S132:

[0092] S132-2 (50g, 54mmol) was added to a 2000ml three-necked flask, and o-xylene (500ml) was added. The flask was filled with nitrogen three times. In an ice-water bath, n-butyl lithium solution (46ml, 1.6M, 64.8mmol) was added dropwise to the three-necked flask with a thick needle. Stir for 1 hour. Boron tribromide (16.2g, 64.8mmol) was extracted with a thick needle in an ice-water bath and added to the reaction solution. Stir for 30 minutes, heated to 45°C and stirred for 50 minutes. In an ice-water bath, N,N-diisopropylethylamine (13.69g, 108mmol) was extracted and added to the reaction system. Stir for 30 minutes, heated to 120°C, and reacted overnight. Stop heating, wait until the system cools to room temperature, and add water (1000ml) to quench. Separate the liquid, take the lower organic phase, extract the aqueous phase with ethyl acetate (1000ml) three times, combine the organic phases, and dry over anhydrous sodium sulfate. The organic phase was mixed with silica gel and concentrated, column chromatography was performed to obtain 22 g of crude product, and toluene / ethanol was recrystallized to obtain 12.73 g of yellow solid, with a yield of 26%. The molecular ion mass determined by mass spectrometry was 899.11 (theoretical value: 899.12).

[0093] Synthesis Example 3: Synthesis of S144

[0094]

[0095] Synthesis of intermediate S144-1:

[0096] At room temperature, raw material A144 (50g, 81.7mmol), diphenylcarbazole (49.8g, 178.4mmol), Pd2(dba)3 (2.99g, 3.25mmol), tri-tert-butylphosphine (1.31g, 6.49mmol), sodium tert-butoxide (23.37g, 243.2mmol), xylene (500ml) were added to a 2L single-mouth bottle, nitrogen was pumped three times, and the reaction was heated to 130°C overnight. The reaction solution was cooled to room temperature, filtered, and the filtrate was mixed with silica gel and concentrated. 90g of crude product was obtained by column chromatography (PE:EA=100:1), and 79.6g of white solid was obtained by recrystallization from toluene / ethanol, with a yield of 89%. The molecular ion mass determined by mass spectrometry was 1093.76 (theoretical value: 1093.77).

[0097] Synthesis of compound S144:

[0098] S144-1 (50 g, 45.7 mmol) was added to a 2000 ml three-necked flask, and o-xylene (500 ml) was added. The flask was filled with nitrogen three times. In an ice-water bath, n-butyl lithium solution (38.8 ml, 1.6 M, 54.9 mmol) was added dropwise to the three-necked flask with a thick needle. The mixture was stirred for 1 hour. Boron tribromide (13.7 g, 54.9 mmol) was extracted with a thick needle in an ice-water bath and added to the reaction solution. The mixture was stirred for 30 minutes, heated to 45°C and stirred for 50 minutes. In an ice-water bath, N,N-diisopropylethylamine (11.82 g, 91.4 mmol) was extracted and added to the reaction system. The mixture was stirred for 30 minutes, heated to 120°C, and reacted overnight. The heating was stopped, and after the system cooled to room temperature, water (1000 ml) was added to quench the mixture. The liquid was separated, and the lower organic phase was taken. The aqueous phase was extracted three times with ethyl acetate (1000 ml), and the organic phases were combined and dried over anhydrous sodium sulfate. The organic phase was mixed with silica gel and concentrated. 21 g of crude product was obtained by column chromatography. 11.44 g of yellow solid was obtained by recrystallization from toluene / ethanol, with a yield of 23%. The molecular ion mass determined by mass spectrometry was 1067.10 (theoretical value: 1067.11).

[0099] Synthesis Example 4: Synthesis of S238

[0100]

[0101] Synthesis of intermediate S238-1:

[0102] At room temperature, raw material A238 (50g, 101mmol), dicyclopentylaniline (37.04g, 121.25mmol), Pd2(dba)3 (1.38g, 1.5mmol), tri-tert-butylphosphine (0.61g, 3.0mmol), sodium tert-butoxide (19.42g, 202.08mmol), xylene (500ml) were added to a 2L single-mouth bottle, nitrogen was pumped three times, and the reaction was heated to 130°C overnight. The reaction solution was cooled to room temperature, filtered, and the filtrate was mixed with silica gel and concentrated. 85g of crude product was obtained by column chromatography (PE:EA=100:1), and 70.1g of white solid was obtained by recrystallization from toluene / ethanol, with a yield of 96%. The molecular ion mass determined by mass spectrometry was 719.42 (theoretical value: 719.42).

[0103] Synthesis of intermediate S238-2:

[0104] At room temperature, the raw material S238-1 (60g, 83.4mmol), cyclopentylphenol (16.24g, 100.1mmol), cesium carbonate (54.35g, 166.8mmol), DMF (600ml) were added to a 2L single-mouth bottle, nitrogen was pumped three times, and the reaction was heated to 80°C overnight. The reaction solution was cooled to room temperature, added to 1000ml of water, filtered, and silica gel column chromatography (PE: EA = 100: 1) was performed to obtain 80g of crude product, which was recrystallized from toluene / ethanol to obtain 69.6g of white solid, with a yield of 97%. The molecular ion mass determined by mass spectrometry was 862.64 (theoretical value: 861.64).

[0105] Synthesis of compound S238:

[0106] S238-2 (50 g, 58.0 mmol) was added to a 2000 ml three-necked flask, and o-xylene (500 ml) was added. The flask was filled with nitrogen three times. In an ice-water bath, n-butyl lithium solution (49.2 ml, 1.6 M, 69.6 mmol) was added dropwise to the three-necked flask with a thick needle. The mixture was stirred for 1 hour. Boron tribromide (17.4 g, 69.6 mmol) was extracted with a thick needle in an ice-water bath and added to the reaction solution. The mixture was stirred for 30 minutes, heated to 45°C and stirred for 50 minutes. In an ice-water bath, N,N-diisopropylethylamine (15.0 g, 116.1 mmol) was extracted and added to the reaction system. The mixture was stirred for 30 minutes, heated to 120°C, and reacted overnight. The heating was stopped, and after the system cooled to room temperature, water (1000 ml) was added to quench the mixture. The liquid was separated, and the lower organic phase was taken. The aqueous phase was extracted three times with ethyl acetate (1000 ml), and the organic phases were combined and dried over anhydrous sodium sulfate. The organic phase was mixed with silica gel and concentrated. 16 g of crude product was obtained by column chromatography. 12.43 g of yellow solid was obtained by recrystallization from toluene / ethanol, with a yield of 25%. The molecular ion mass determined by mass spectrometry was 835.00 (theoretical value: 834.99).

[0107] Synthesis Example 5: Synthesis of S243

[0108]

[0109] Synthesis of intermediate S243-1:

[0110] At room temperature, raw material A243 (50g, 139.34mmol), isopropylphenol (22.77g, 167.21mmol), cesium carbonate (90.80g, 278.68mmol), DMF (500ml) were added to a 2L single-mouth bottle, nitrogen was pumped three times, and the reaction was heated to 80°C overnight. The reaction solution was cooled to room temperature, added to 1000ml of water, filtered, and silica gel column chromatography (PE: EA = 100: 1) was performed to obtain 97g of crude product, which was recrystallized from toluene / ethanol to obtain 81.6g of white solid, with a yield of 99%. The molecular ion mass determined by mass spectrometry was 592.21 (theoretical value: 591.21).

[0111] Synthesis of compound S243:

[0112] S243-1 (50 g, 84.6 mmol) was added to a 2000 ml three-necked flask, and o-xylene (500 ml) was added. The flask was filled with nitrogen three times. In an ice-water bath, n-butyl lithium solution (71.7 ml, 1.6 M, 101.5 mmol) was added dropwise to the three-necked flask with a thick needle. The mixture was stirred for 1 hour. Boron tribromide (25.4 g, 101.5 mmol) was extracted with a thick needle in an ice-water bath and added to the reaction solution. The mixture was stirred for 30 minutes, heated to 45°C and stirred for 50 minutes. In an ice-water bath, N,N-diisopropylethylamine (21.9 g, 169.2 mmol) was extracted and added to the reaction system. The mixture was stirred for 30 minutes, heated to 120°C, and reacted overnight. The heating was stopped, and after the system cooled to room temperature, water (1000 ml) was added to quench the mixture. The liquid was separated, and the lower organic phase was taken. The aqueous phase was extracted three times with ethyl acetate (1000 ml), and the organic phases were combined and dried over anhydrous sodium sulfate. The organic phase was mixed with silica gel and concentrated. 14 g of crude product was obtained by column chromatography. 11.78 g of yellow solid was obtained by recrystallization from toluene / ethanol, with a yield of 25%. The molecular ion mass determined by mass spectrometry was 565.57 (theoretical value: 564.55).

[0113] Synthesis Example 6: Synthesis of S257

[0114]

[0115] Synthesis of intermediate S257-1:

[0116] At room temperature, raw material A257 (50g, 104.9mmol), di(3-methylphenyl)amine (45.5g, 230.8mmol), Pd2(dba)3 (3.88g, 4.19mmol), tri-tert-butylphosphine (1.70g, 8.39mmol), sodium tert-butoxide (30.24g, 314.7mmol), xylene (500ml) were added to a 2L single-mouth bottle, nitrogen was pumped three times, and the reaction was heated to 130°C overnight. The reaction solution was cooled to room temperature, filtered, and the filtrate was mixed with silica gel and concentrated. 68g of crude product was obtained by column chromatography (PE:EA=100:1), and 60.4g of white solid was obtained by recrystallization from toluene / ethanol, with a yield of 81.17%. The molecular ion mass determined by mass spectrometry was 709.37 (theoretical value: 709.37).

[0117] Synthesis of compound S257

[0118] S257-1 (50g, 70.5mmol) was added to a 2000ml three-necked flask, and o-xylene (500ml) was added. The flask was filled with nitrogen three times. In an ice-water bath, n-butyl lithium solution (60ml, 1.6M, 85mmol) was added dropwise to the three-necked flask with a thick needle. The mixture was stirred for 1 hour. Boron tribromide (21.2g, 85mmol) was extracted with a thick needle in an ice-water bath and added to the reaction solution. The mixture was stirred for 30 minutes, heated to 45°C and stirred for 50 minutes. In an ice-water bath, N,N-diisopropylethylamine (18.22g, 141mmol) was extracted and added to the reaction system. The mixture was stirred for 30 minutes, heated to 120°C, and reacted overnight. The heating was stopped, and water (1000ml) was added to quench the mixture after the system cooled to room temperature. The lower organic phase was separated, and the aqueous phase was extracted three times with ethyl acetate (1000ml). The organic phases were combined and dried over anhydrous sodium sulfate. The organic phase was mixed with silica gel and concentrated, column chromatography was performed to obtain 23 g of crude product, and toluene / ethanol was recrystallized to obtain 14.51 g of yellow solid, with a yield of 30%. The molecular ion mass determined by mass spectrometry was 682.72 (theoretical value: 682.72).

[0119] Synthesis Example 7: Synthesis of S271

[0120]

[0121] Synthesis of intermediate S271-1:

[0122] At room temperature, raw material A271 (50g, 86.7mmol), di(3-tert-butylphenyl)amine (53.7g, 190.7mmol), Pd2(dba)3 (3.20g, 3.47mmol), tri-tert-butylphosphine (1.40g, 6.93mmol), sodium tert-butoxide (24.99g, 260.1mmol), xylene (500ml) were added to a 2L single-mouth bottle, nitrogen was pumped three times, and the reaction was heated to 130°C overnight. The reaction solution was cooled to room temperature, filtered, and the filtrate was mixed with silica gel and concentrated. 65g of crude product was obtained by column chromatography (PE:EA=100:1), and 57.8g of white solid was obtained by recrystallization from toluene / ethanol, with a yield of 68.19%. The molecular ion mass determined by mass spectrometry was 977.87 (theoretical value: 977.86).

[0123] Synthesis of compound S279

[0124] S271-1 (50g, 51.1mmol) was added to a 2000ml three-necked flask, and o-xylene (500ml) was added. The flask was filled with nitrogen three times. In an ice-water bath, n-butyl lithium solution (43ml, 1.6M, 61mmol) was added dropwise to the three-necked flask with a thick needle. Stir for 1 hour. Boron tribromide (15.37g, 61mmol) was extracted with a thick needle in an ice-water bath and added to the reaction solution. Stir for 30 minutes, heated to 45°C and stirred for 50 minutes. In an ice-water bath, N,N-diisopropylethylamine (13.22g, 102mmol) was extracted and added to the reaction system. Stir for 30 minutes, heated to 120°C, and reacted overnight. Stop heating, wait until the system cools to room temperature, and add water (1000ml) to quench. Separate the liquid, take the lower organic phase, extract the aqueous phase with ethyl acetate (1000ml) three times, combine the organic phases, and dry over anhydrous sodium sulfate. The organic phase was mixed with silica gel and concentrated, column chromatography was performed to obtain 25 g of crude product, and toluene / ethanol was recrystallized to obtain 17.26 g of yellow solid, with a yield of 35%. The molecular ion mass determined by mass spectrometry was 951.20 (theoretical value: 951.20).

[0125] Based on the same inventive concept, an embodiment of the present invention further provides an organic electronic light-emitting device comprising the compound of the above embodiment. OLED is used as an organic electronic light-emitting device as an example of a device for illustration below, but it should be understood that the following detailed description is not a limitation of the present invention, and those skilled in the art can extend the following detailed description to other organic electronic light-emitting devices.

[0126] In one embodiment, the OLED includes a first electrode and a second electrode, and a plurality of organic material layers between the electrodes. The organic material layer can be divided into a plurality of regions. For example, the organic material layer can include a hole transport region, a light emitting layer, and an electron transport region.

[0127] In a specific embodiment, a substrate may be used below the first electrode or above the second electrode. The substrate is 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.

[0128] 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.

[0129] 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.

[0130] 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).

[0131] 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.

[0132]

[0133]

[0134]

[0135] 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.

[0136]

[0137] 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.

[0138] 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.

[0139] In one aspect of the present invention, the light-emitting layer adopts fluorescent electroluminescence technology. The fluorescent host material of the light-emitting layer can be selected from, but not limited to, one or more combinations of BFH-1 to BFH-17 listed below.

[0140]

[0141] 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).

[0142] In one aspect of the present invention, the electron transport layer material can be selected from, but not limited to, one or more combinations of ET-1 to ET-57 listed below.

[0143]

[0144]

[0145]

[0146]

[0147] The device may further include an electron injection layer located between the electron transport layer and the cathode. Materials for the electron injection layer include, but are not limited to, one or more combinations of the following.

[0148] LiQ, LiF, NaCl, CsF, Li2O, Cs2CO3, BaO, Na, Li, Ca.

[0149] Device Example 1

[0150] In Example 1, the device structure is as follows:

[0151] The organic electroluminescent device was prepared as follows: a glass plate coated with a transparent conductive layer of ITO (thickness 150 nm) 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 until the water was completely removed, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam;

[0152] Place the glass substrate with the anode in a vacuum chamber and evacuate the chamber to a vacuum of less than 1×10 -5 Pa, HI-2 and HT-4 were vacuum evaporated on the above anode layer as hole injection layer and hole transport layer, respectively, with an evaporation rate of 0.1 nm / s and an evaporation film thickness of 10 nm and 40 nm, respectively;

[0153] "BFH-3: S1 (30nm, 5%wt)" is vacuum evaporated on the hole transport layer as the light-emitting layer of the organic electroluminescent device. The evaporation rate is 0.1nm / s and the total film thickness of the evaporation is 30nm; "5%wt" refers to the doping ratio of the blue light dye, that is, the weight ratio of the main material to S1 is 95:5.

[0154] Vacuum evaporation of ET-46:ET-57 (50% wt:50% wt) on the light-emitting layer as the electron transport layer of the organic electroluminescent device, with an evaporation rate of 0.1 nm / s and a total evaporation film thickness of 25 nm;

[0155] 0.5 nm of LiF as an electron injection layer and 150 nm of Al as a cathode were vacuum-deposited on the electron transport layer.

[0156] The process of the above device embodiment 1 can be briefly summarized as: ITO (150nm) / HI-2 (10nm) / HT-4 (40nm) / BFH-3:S1 (30nm, 5%wt) / ET-46:ET-57 (50%wt:50%wt) (25nm) / LiF (0.5nm) / Al (150nm).

[0157] The preparation process of device examples 2-7 and comparative examples 1-2 is the same as that of device example 1, except that dye S1 is replaced with compounds S132, S144, S238, S243, S257, S271 of the present invention and compounds DABAN-1 and DABNA-2 in the prior art.

[0158] The organic electroluminescent device prepared by the above process was subjected to the following performance tests:

[0159] At the same brightness, the driving voltage and current efficiency of the organic electroluminescent devices prepared in Examples 1 to 7 and Comparative Examples 1 to 2, as well as the device life, were measured using a digital source meter and a brightness meter. Specifically, the voltage was increased at a rate of 0.1 V per second, and the brightness of the organic electroluminescent device was measured when it reached 1000 cd / m 2 The voltage at which the light is on 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 life test of LT95 is as follows: use a brightness meter at 1000cd / m 2 At the same brightness, the current is kept constant and the brightness of the organic electroluminescent device is measured to drop to 950cd / m 2 The time is in hours. The life of comparative example 1 is taken as standard 1, and the others are ratios thereto.

[0160] Table 1

[0161]

[0162] As can be seen from Table 1 above, when the compound of the present invention is used as a dye, its voltage is reduced and its efficiency is improved compared with the comparative example compound, showing excellent device performance. This is because the compound of the present invention introduces an electron-withdrawing group at a specific position, which red-shifts the emission spectrum, better matches the host material, and has a higher energy transfer efficiency. At the same time, a rigid group is introduced to improve the luminous efficiency of the material and the carrier mobility, which is conducive to the practical application of the compound of the present invention. .

[0163] The specific embodiments described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

[0164] Although the present invention has been described in conjunction with the embodiments, the present invention is not limited to the above embodiments. It should be understood that under the guidance of the concept of the present invention, those skilled in the art may make various modifications and improvements. The appended claims summarize the scope of the present invention.

Claims

1. A compound of the general formula, as shown in the following formula (1): In the general formula (1): Ring A, Ring B, Ring C, Ring D, and Ring E are independently selected from benzene rings; Ring A and Ring C are not connected or fused to form a ring containing X 1 A five-membered ring or a six-membered ring; And / or, Ring B and Ring D are not connected or fused to form a ring containing X 2 A five-membered ring or a six-membered ring; X 1 and X 2 Each independently selected from one of O, S, and N; m is 0 or 1, when X 1 When selected from O or S, m is 0; n is 0 or 1, when X 2 When selected from O or S, n is 0; R 1 , R 2 , R 3 , R 4 Each independently represents a monosubstituted to maximum permissible substituent, and each independently selected from hydrogen, C1-C12 chain alkyl, C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, R 5 The structure is shown in formula (2); In formula (2): Z 1 Selected from C or Si, Z 2 Selected from NR 8 , O, S, a is 0 or 1; R 8 is selected from substituted or unsubstituted C6-C30 aryl groups; R A1 One selected from methyl, ethyl or phenyl; R B1 and R C1 Each independently represents a single substitution to the maximum permissible substituent, and each independently selected from hydrogen, phenyl or one of the following alkyl groups: When the above-mentioned groups have substituents, the substituents are selected from one of C1-C12 alkyl groups, C3-C12 cycloalkyl groups, and C6-C30 aryl groups.

2. The compound of the general formula according to claim 1, wherein Formula (2) is shown in Formula (2-1) or Formula (2-2): Where Z 1 , Z 2 , R A1 , R B1 and R C1 The definition of is the same as that in formula (2).

3. The compound of the general formula according to claim 1, as shown in the following formula (1-2): In formula (1-2), ring C, D, R 1 , R 2 , R 3 , R 4 , R 5 , m, n, X 1 and X 2 The definition of is the same as that in the general formula (1), and X 1 and X 2 At least one of them is N.

4. The compound of the general formula according to claim 1, selected from one of the following formulas (I), (II), (III), (IV), (V), (VI), (VII) or (VIII): in, R 1 , R 2 , R 3 , R 4 , R 5 The definition of is the same as in the general formula (1).

5. The compound of the general formula according to claim 1, as shown in one of the following formulas (I), (II) or (III): in, R 1 , R 2 , R 3 , R 4 , R 5 The definition of is the same as in the general formula (1).

6. The compound of the general formula according to claim 1, wherein R 1 , R 2 , R 3 , R 4 are independently selected from hydrogen or are independently selected from one of the following groups, R 5 The structure is shown in formula (2):

7. The compound of the general formula according to claim 1 is selected from the following specific structural compounds:

8. Use of the compound according to any one of claims 1 to 7 as a light-emitting layer material in an organic electroluminescent device.

9. An organic electroluminescent device comprising a first electrode, a second electrode and one or more organic layers inserted between the first electrode and the second electrode, characterized in that: The organic layer comprises at least one compound according to any one of claims 1 to 7.

10. The organic electroluminescent device according to claim 9, wherein the organic layer comprises a hole injection layer, a hole transport layer, a light-emitting layer, and an electron transport layer, wherein the hole injection layer is formed on the anode layer, the hole transport layer is formed on the hole injection layer, the cathode layer is formed on the electron transport layer, and the light-emitting layer is between the hole transport layer and the electron transport layer, wherein: The light-emitting layer contains the compound described in any one of claims 1-7.

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