Organic electroluminescent material containing b-n fused ring and application thereof

Abstract

The application discloses a series of B-N fused ring organic electroluminescent materials, the structure of which is shown as formula (I). The B-N fused ring organic electroluminescent material has 100% internal quantum efficiency based on the TADF principle, has a narrow half-wave width by utilizing the multiple resonance effect between B and N, and has good color purity. The indole (3,2,1-JK) carbazole is introduced, the multiple resonance effect is strengthened in one step, and the luminous efficiency and color purity are significantly improved. The compound has good thermal stability and meets the requirements of an OLED panel on a light-emitting material. The application further provides an organic electroluminescent device, wherein at least one layer of an organic layer in the device contains the compound shown as formula (I).

Description

TECHNICAL FIELD

[0001] The present application relates to the field of light-emitting materials, in particular to an organic light-emitting material containing a B-N fused ring and its application in an organic light-emitting diode. BACKGROUND

[0002] Organic light-emitting diode (OLED) devices have been widely used in display and lighting industries, especially in mobile phone display. The latest mobile phone products of mobile phone manufacturers such as Apple, Samsung, Huawei and Xiaomi all use OLED screens, which is mainly due to the excellent characteristics of OLED, such as self-luminescence, wide viewing angle, high contrast, fast response speed and flexible device preparation.

[0003] The current commercialized OLED device is a multi-layer sandwich structure, including an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer and a cathode. The anode generates holes, which enter the light-emitting layer through the hole injection layer and the transport layer, while the electrons move from the cathode to the light-emitting layer through the electron injection layer and the transport layer. The holes and electrons recombine in the light-emitting layer to generate excitons. These excitons transition from the excited state to the ground state, thereby emitting visible light. In order to achieve color display, the OLED device uses the additive color principle, i.e. the light-emitting layer is divided into a blue light-emitting layer, a green light-emitting layer and a red light-emitting layer, and different light-emitting layers use different light-emitting colors of organic materials.

[0004] When OLED devices are applied to display, they are required to have low driving voltage, high luminous efficiency and long service life. Therefore, in the process of gradually improving display performance, organic materials have undergone development from fluorescent materials to phosphorescent materials, and then to thermally activated delayed fluorescence materials (TADF). Currently, green and red light materials are phosphorescent materials, which can utilize both singlet and triplet excitons for light emission, so the internal quantum efficiency can reach 100%. However, phosphorescent materials contain heavy metals, which have problems such as high price and poor material stability. Blue light materials are fluorescent materials, which can only use singlet excitons for light emission. Although the theory efficiency is 40% with the use of TTA (two triplet excitons transform into one singlet exciton) principle, it is far lower than the market demand. TADF materials utilize small singlet-triplet energy level difference (△EST), so triplet excitons can be converted into singlet excitons through reverse intersystem crossing, thus achieving 100% internal quantum efficiency. However, TADF materials have strong charge transfer characteristics (CT), and the spectral half-width is too wide, which is not conducive to high color purity display. SUMMARY

[0005] To address the existing problems of the aforementioned organic materials, this invention provides a class of BN fused-ring organic light-emitting materials and their applications in organic light-emitting devices. Based on the TADF mechanism, this material achieves multiple resonance effects through its BN fused-ring structure. Furthermore, the introduction of indole (3,2,1-JK)carbazole and its derivatives further enhances these multiple resonance effects. The resulting molecules possess a large rigid plane, effectively suppressing intramolecular vibrations, thus yielding highly efficient organic light-emitting materials with narrow half-wavelengths.

[0006] This invention also provides a class of organic electroluminescent materials containing a BN fused ring structure, the structure of which is shown in general formula (I):

[0007]

[0008] in:

[0009] Ar1 to Ar4 are each independently selected from substituted or unsubstituted aryl groups having 6-30 carbon atoms, or substituted or unsubstituted heteroaryl groups having 5-30 carbon atoms;

[0010] Ar5 and Ar6 are each independently selected from substituted or unsubstituted C1-C60 alkyl, substituted or unsubstituted C2-C60 alkenyl, substituted or unsubstituted C2-C60 alkynyl, substituted or unsubstituted C1-C60 alkoxy, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 heterocyclic alkyl, substituted or unsubstituted C3-C10 cycloalkenyl, substituted or unsubstituted C1-C10 heterocyclic alkenyl, substituted or unsubstituted C6 -C60 aryl, substituted or unsubstituted C6-C60 aryloxy, substituted or unsubstituted C6-C60 arylthio, substituted or unsubstituted C1-C60 heteroaryl, substituted or unsubstituted non-aromatic fused polycyclic, or substituted or unsubstituted non-aromatic fused heterocyclic; or one or more selected from Ar1 to Ar6 respectively bonded to adjacent groups Ar1 and Ar2 by a single bond, -CC-, -C=C-, -C=N-, -C=P-, -C≡C-, -CC-, -C=C-, -C≡C-, -CC-, -C=C-, -C=P-, -C≡C-, Any one or more bonds in the structure are linked together to form a ring structure;

[0011] Among them, at least one pair of Ar1 and Ar2, and Ar5 and Ar6 cannot be the same;

[0012] the substituent is one or more selected from the group consisting of deuterium, cyano, nitro, halogen, hydroxyl, alkylthio group having 1 to 4 carbon atoms, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 1 to 20 carbon atoms, aryloxy group having 6 to 30 carbon atoms, alkoxy group having 1 to 30 carbon atoms, alkylamino group having 1 to 30 carbon atoms, arylamino group having 6 to 30 carbon atoms, aralkylamino group having 6 to 30 carbon atoms, heteroarylamino group having 2 to 24 carbon atoms, alkylsilyl group having 1 to 30 carbon atoms, arylsilyl group having 6 to 30 carbon atoms, alkyl group having 1 to 30 carbon atoms, alkenyl group having 2 to 30 carbon atoms, alkynyl group having 2 to 24 carbon atoms, aralkyl group having 7 to 30 carbon atoms, aryl group having 6 to 30 carbon atoms, heteroaryl group having 5 to 60 carbon atoms, heteroarylalkyl group having 6 to 30 carbon atoms,

[0013] the heteroatom in the heterocycloalkyl group, heterocycloalkenyl group or heteroaryl group is one or more selected from the group consisting of N, S, O, P, B, Si.

[0014] the structure is selected from one of the structures represented by general formulae (II-1) to (II-10):

[0015]

[0016] wherein X1to X 16 independently represent a nitrogen atom or CR1, R1is independently selected from the group consisting of a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a phosphoric acid or a salt thereof, a linear or branched C1-20alkyl group, a linear or branched C1-20alkyl group-substituted silyl group, a C6-30substituted or unsubstituted aryl group, or a C5-30substituted or unsubstituted heteroaryl group, or two or more R1s are combined with each other to form an alkyl ring, a heteroalkyl ring, an aromatic ring or a heteroaromatic ring, and

[0017] Y1to Y3, Y4to Y6, Y7to Y9, Y 10 -Y 12 independently represent an oxygen atom, a sulfur atom, N-R2, R3-C-R4, C=O, C=S, R5-Si-R6, P-R7, P=O or O=P=O, and the remaining independently represent a nitrogen atom or C-R8, R2to R8are independently selected from the group consisting of a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a phosphoric acid or a salt thereof, a linear or branched C1-20alkyl group, a linear or branched C1-20alkyl group-substituted silyl group, a C6-30substituted or unsubstituted aryl group, or a C5-30substituted or unsubstituted heteroaryl group, or two or more R2to R8are combined with each other to form an alkyl ring, a heteroalkyl ring, an aromatic ring or a heteroaromatic ring, or R2to R8are independently or combined with each other by a single bond, -C-C-, -C=C-, -C=N-, -C=P-, any one or more of the bonds in the above formulae are linked to form a ring structure;

[0018] Ar5, Ar6are each independently selected from the group consisting of substituted or unsubstituted C1-C60alkyl, substituted or unsubstituted C2-C60alkenyl, substituted or unsubstituted C2-C60alkynyl, substituted or unsubstituted C1-C60alkoxy, substituted or unsubstituted C3-C10cycloalkyl, substituted or unsubstituted C1-C10heterocycloalkyl, substituted or unsubstituted C3-C10cycloalkenyl, substituted or unsubstituted C1-C10heterocycloalkenyl, substituted or unsubstituted C6-C60aryl, substituted or unsubstituted C6-C60aryloxy, substituted or unsubstituted C6-C60arylthio, substituted or unsubstituted C1-C60heteroaryl, substituted or unsubstituted non-aromatic fused polycyclic ring, or substituted or unsubstituted non-aromatic fused heteropolycyclic ring; and one or more of Ar5, Ar6are selected to be linked together with any one or more of Ar1, Ar2, respectively, with a single bond, -C-C-, -C=C-, -C=N-, -C=P-, -C≡C-, a ring formed by linking any one or more of them together;

[0019] the substituents are selected from one or more of deuterium, cyano, nitro, halogen group, hydroxyl group, alkylthio group of 1 to 4 carbon atoms, substituted or unsubstituted alkyl group of 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group of 1 to 20 carbon atoms, aryloxy group of 6 to 30 carbon atoms, alkoxy group of 1 to 30 carbon atoms, alkylamino group of 1 to 30 carbon atoms, arylamino group of 6 to 30 carbon atoms, aralkylamino group of 6 to 30 carbon atoms, heteroarylamino group of 2 to 24 carbon atoms, alkylsilyl group of 1 to 30 carbon atoms, arylsilyl group of 6 to 30 carbon atoms, alkyl group of 1 to 30 carbon atoms, alkenyl group of 2 to 30 carbon atoms, alkynyl group of 2 to 24 carbon atoms, aralkyl group of 7 to 30 carbon atoms, aryl group of 6 to 30 carbon atoms, heteroaryl group of 5 to 60 carbon atoms, or heteroarylalkyl group of 6 to 30 carbon atoms;

[0020] the heteroatom in the heteroaryl, heteroalkyl ring, or heteroaromatic ring is selected from one or more of N, O, S, or Si.

[0021] wherein at least one of X1and X8, X2and X7, X3and X6, X4and X5, Y1and Y6, Y2and Y5, Y3and Y4, Ar5and Ar6is not the same.

[0022] wherein X1-X 16each independently represents a nitrogen atom or CR1, R1is the same or different and is independently selected from one of a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a linear or branched C1-C8alkyl group, a C6-C20substituted or unsubstituted aryl group, or a C5-C20substituted or unsubstituted heteroaryl group, or two or more R1s are combined with each other to form an alkyl ring, a heteroalkyl ring, an aromatic ring, or a heteroaromatic ring;

[0023] Y1-Y3, Y4-Y6, Y7-Y9, Y 10 -Y 12 each independently has one of a representation of an oxygen atom, a sulfur atom, N-R2, or R3-C-R4, and the rest are independently selected from a nitrogen atom or C-R8, R2to R8are the same or different and are independently selected from one of a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, a linear or branched C1-C20alkyl group, a C6-C30substituted or unsubstituted aryl group, or a C5-C30substituted or unsubstituted heteroaryl group, or R2to R8are independently or combined with each other by a single bond, -C-C-, -C=C-, -C=N-, -C≡C-, any one or more of the bonds in the above are linked together to form an alkyl ring, a heteroalkyl ring, an aromatic ring, or a heteroaromatic ring;

[0024] Ar5, Ar6are each independently selected from a substituted or unsubstituted C1-C8alkyl group, a substituted or unsubstituted C2-C10alkenyl group, a substituted or unsubstituted C2-C10alkynyl group, a substituted or unsubstituted C1-C80alkoxy group, a substituted or unsubstituted C3-C10cycloalkyl group, a substituted or unsubstituted C1-C8heterocycloalkyl group, a substituted or unsubstituted C3-C10cycloalkenyl group, a substituted or unsubstituted C1-C10heterocycloalkenyl group, a substituted or unsubstituted C6-C20aryl group, a substituted or unsubstituted C6-C20aryloxy group, a substituted or unsubstituted C6-C20arylthio group, a substituted or unsubstituted C1-C20heteroaryl group, a substituted or unsubstituted non-aromatic fused polycyclic ring, or a substituted or unsubstituted non-aromatic fused heteropolycyclic ring; and one or more of Ar5, Ar6are selected to be linked together with adjacent groups Ar1, Ar2by any one or more of a single bond, -C-C-, -C=C-, -C=N-, -C≡C-,

[0025] ​the substituent is selected from one or more of deuterium, cyano, nitro, halogen, hydroxy, alkylthio group having 1 to 4 carbon atoms, substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, aryloxy group having 6 to 20 carbon atoms, alkoxy group having 1 to 10 carbon atoms, alkylamino group having 1 to 10 carbon atoms, arylamino group having 6 to 20 carbon atoms, aralkylamino group having 6 to 20 carbon atoms, heteroarylamino group having 2 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, alkynyl group having 2 to 10 carbon atoms, aralkyl group having 7 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, heteroaryl group having 5 to 20 carbon atoms, or heteroarylalkyl group having 6 to 20 carbon atoms,

[0026] the heteroatom in the heteroaryl, heteroalkyl ring or heteroaromatic ring is selected from one or more of N, O, S or Si.

[0027] wherein, X1-X 16 independently represent a nitrogen atom or CR1, R1 is selected from one or more of hydrogen atom, linear or branched C1-C8 alkyl group, C6-C20 substituted or unsubstituted aryl group, or C5-C20 substituted or unsubstituted heteroaryl group, or two or more R1s combine with each other to form an alkyl ring, heteroalkyl ring, aromatic ring or heteroaromatic ring;

[0028] Y1-Y3, Y4-Y6, Y7-Y9, Y 10 -Y 12 independently represent one of oxygen atom, sulfur atom or N-R2; the rest are independently selected from nitrogen atom or C-R8, R2, R8 is selected from one or more of hydrogen atom, linear or branched C1-C20 alkyl group, C6-C20 substituted or unsubstituted aryl group, or C5-C20 substituted or unsubstituted heteroaryl group, or R2, R8 independently or combine with each other to form an alkyl ring, heteroalkyl ring, aromatic ring or heteroaromatic ring by single bond, -C-C-, -C=C-, -C=N-, independently represent one of oxygen atom, sulfur atom or N-R2; the rest are independently selected from nitrogen atom or C-R8, R2, R8 is selected from one or more of hydrogen atom, linear or branched C1-C20 alkyl group, C6-C20 substituted or unsubstituted aryl group, or C5-C20 substituted or unsubstituted heteroaryl group, or R2, R8 independently or combine with each other to form an alkyl ring, heteroalkyl ring, aromatic ring or heteroaromatic ring by single bond, -C-C-, -C=C-, -C=N-,

[0029] Ar5 and Ar6 are each independently selected from substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C1-C80 alkoxy, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C8 heterocyclic alkyl, substituted or unsubstituted C3-C10 cycloalkenyl, substituted or unsubstituted C1-C10 heterocyclic alkenyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C6-C20 aryloxy, substituted or unsubstituted C6-C20 arylthio, substituted or unsubstituted C1-C20 heteroaryl, substituted or unsubstituted non-aromatic fused polycyclic, or substituted or unsubstituted non-aromatic fused heteropolycyclic; or one or more selected from Ar5 and Ar6 are respectively connected to the adjacent groups Ar1 and Ar2 by a single bond, -CC-, -C=C-, -C=N-. Any one or more of them can be connected together to form a ring;

[0030] The substitution is made by one or more substituents selected from the group consisting of deuterium, alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 20 carbon atoms, heteroaryl groups having 5 to 20 carbon atoms, or heteroarylalkyl groups having 6 to 20 carbon atoms.

[0031] The heteroatom in the heteroaryl, heteroalkyl, or heteroaromatic ring is selected from one or more of N, O, or S.

[0032] The structure is selected from one of the general formulas (II-1)-(II-3), wherein X1-X 16 Each is independently represented as a nitrogen atom or CR1, where R1 is independently selected from one of the following: a hydrogen atom, a straight-chain or branched C1-C8 alkyl group, or a substituted or unsubstituted aryl group of C6-C20;

[0033] Y1-Y3, Y4-Y6, Y7-Y9, Y 10 -Y 12 Each of the following is independently represented as an oxygen atom, a sulfur atom, or N-R2; the remaining ones are independently selected from C-R8, wherein the R2 and R8 are the same or different and are independently selected from one of hydrogen atoms, straight-chain or branched C1-C20 alkyl groups, or substituted or unsubstituted aryl groups of C6-C20, or R8 are connected to each other by any one or more of single bonds, -CC-, -C=C- to form an alkyl ring or a six-membered aromatic ring;

[0034] Ar5, Ar6are each independently selected from the group consisting of substituted or unsubstituted C1-C8alkyl, substituted or unsubstituted C6-C20aryl, substituted or unsubstituted C1-C20heteroaryl, substituted or unsubstituted non-aromatic fused polycyclic, or substituted or unsubstituted non-aromatic fused heteropolycyclic; or selected one of Ar5, Ar6is linked together with adjacent group Ar1, Ar2, respectively, with any one or more of single bond, -C-C- to form a ring;

[0035] the substitution is substituted with one or more substituents selected from the group consisting of deuterium, alkyl group of 1 to 8 carbon atoms, cycloalkyl group of 1 to 10 carbon atoms, aryl group of 6 to 10 carbon atoms,

[0036] the heteroatom in the heteroaryl is selected from one or more of N, O, S or Si.

[0037] preferably: X9-X 16 each independently represents CR1, R1is the same or different and is independently selected from one of hydrogen atom, linear or branched C1-C4alkyl group, or C6-C10substituted or unsubstituted aryl group.

[0038] the aryl group is preferably selected from one or more of phenyl, naphthyl, anthryl, binaphthyl, phenanthryl, dihydrophenanthrene, pyryl, perylenyl, naphthacene, pentacene, benzoperylene, benzocyclopentadienyl, spirofluorenyl and fluorenyl; the aryl group is most preferably selected from one or more of phenyl, naphthyl, anthryl, phenanthryl, dihydrophenanthrene, naphthacene, pentacene, benzoperylene, benzocyclopentadienyl, spirofluorenyl and fluorenyl.

[0039] The heteroaryl is preferably selected from one or more of pyrrolyl, imidazolyl, thienyl, furanyl, 1,2-thiazolyl, 1,3-thiazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, thiadiazolyl, selenadiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, pyridyl, pyrazinyl, pyrimidinyl, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, indole, isoindole, benzimidazole, naphthimidazole, phenanthroimidazole, benzotriazole, purine, benzoxazole, naphthoxazole, phenanthroxazole, benzothiadiazolyl, quinolyl, isoquinolyl, benzopyrazinyl, benzothienyl, benzofuranyl, carbazolyl, acridinyl, dibenzothiophenyl, dibenzofuranyl, silafluorenyl, dibenzothiophene-5,5-dioxide, naphthothiadiazolyl, naphthoselenadiazolyl, and 10,15-dihydro-5H-dinaphtho[3,2-a:3',2'-c]carbazolyl; most preferably the heteroaryl is selected from one or more of pyrrolyl, imidazolyl, thienyl, furanyl, 1,2-thiazolyl, 1,3-thiazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, thiadiazolyl, selenadiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, pyridyl, pyrazinyl, pyrimidinyl, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, indole, isoindole, benzimidazole, naphthimidazole, phenanthroimidazole, benzotriazole, purine, benzoxazole, naphthoxazole, phenanthroxazole, benzothiadiazolyl, quinolyl, isoquinolyl, benzopyrazinyl, benzothienyl, benzofuranyl, carbazolyl, acridinyl, dibenzothiophenyl, dibenzofuranyl, dibenzothiophene-5,5-dioxide, naphthothiadiazolyl, naphthoselenadiazolyl, and 10,15-dihydro-5H-dinaphtho[3,2-a:3',2'-c]carbazolyl.

[0040] Preferably, the organic compounds have the following specific structures, but are not limited to the listed structures:

[0041]

[0042]

[0043]

[0044]

[0045]

[0046]

[0047]

[0048] The second application of the application provides an organic electroluminescent device comprising at least one functional layer containing a B-N fused ring organic electroluminescent material;

[0049] Preferably, the B-N fused ring organic electroluminescent material is used as a light-emitting layer material.

[0050] More preferably, the B-N fused ring organic electroluminescent material is used as a doping material of a light-emitting layer.

[0051] The series of B-N fused ring organic electroluminescent materials disclosed in the application have an internal quantum efficiency of 100% based on the TADF principle, have a narrow half-wave width by utilizing the multiple resonance effect between B and N, and exhibit good color purity; the indole (3,2,1-JK) carbazole and derivatives thereof introduced further strengthen the multiple resonance effect, and significantly improve the luminous efficiency and color purity. The compounds have good thermal stability, and meet the requirements of OLED panels for light-emitting materials. BRIEF DESCRIPTION OF DRAWINGS

[0052] Figure 1 The electroluminescent device structure of the application is shown in the figure, wherein 10 represents a glass substrate, 20 represents an anode, 30 represents a hole injection layer, 40 represents a hole transport layer, 50 represents an electron blocking layer, 60 represents a light-emitting layer, 70 represents an electron transport layer, 80 represents an electron injection layer, and 90 represents a cathode. DETAILED DESCRIPTION

[0053] The application does not require a synthesis method for the material, and in order to describe the application in more detail, the following examples are given, but the application is not limited thereto. The raw materials used in the following synthesis are all commercially available products unless otherwise specified.

[0054] Example 1:

[0055] Synthesis of compound structure 7

[0056]

[0057] Synthesis of compound (2):

[0058] A 1L single-neck flask was charged with a magnetic stirrer, compound (1) (5.0g, 24mmol), KI (5.9g, 36mmol), and then 50mL of methanol and 250mL of deionized water were poured in, stirred to dissolve most of the substance, and then KIO3 (3.6g, 16.8mmol) was added, stirred for 0.5h; 40mL of 1.5M HCl solution was added to a dropping funnel, and then added dropwise to the reaction solution, and the temperature was raised to 60 ℃ , and the reaction was carried out for 12h. The temperature was lowered to room temperature, 400mL of deionized water was added, and the filter cake was vacuum dried in an oven at 80 ℃Heated for 10 h; then column separation using PE:DCM=50:1, white powdery solid 10.54 g, yield 95%. ESI-MS (m / z): 460 (M); 458 (M-1).

[0059] Synthesis of compound (4):

[0060] Take 250 mL single mouth bottle, add magnetic son, weigh compound (2) (1.0 g, 2 mmol), compound (3) (2.3 g, 8 mmol), pd(PPh3)2Cl2(0.15 g, 0.2 mmol), K2CO3(2.4 g, 16 mmol), LiCl (0.1 g, 2 mmol), then replace the air, quickly add toluene 50 mL, deionized water 20 mL, replace the air again three times; nitrogen atmosphere, stirring, heating to 100 ℃ , reaction 4 h; cool to room temperature, extract using DCM, dry the organic phase, mix with silica gel, column separation using PE:DCM=10:1 mixed solvent, white powdery solid 0.47 g, yield 35%. 1 H NMR (400 MHz, Chloroform-d) δ 7.64 (dd, J = 8.4, 1.5 Hz, 2H), 7.34 (m, 2H), 3.61 (d, J = 7.4 Hz, 2H), 1.32 (s, 18H). ESI-MS (m / z): 630 (M+1).

[0061] Synthesis of compound (5):

[0062] Take 250 mL single mouth bottle, add magnetic son, compound (4) (3.3 g, 5.2 mmol), CuI (0.22 g, 1.2 mmol), 8-OQ (0.33 g, 2.2 mmol), K2CO3(3.2 g, 2.3 mmol) and DMF (100 mL), stirring, and replace the air three times, replace with nitrogen, then heating to 80°, reaction 12 h. Lower to room temperature, extract three times using DCM, combine the organic phase and dry, then mix with silica gel, column separation using PE:DCM=50:1 mixed solvent, light brown solid 1.3 g, yield 53%. 1 H NMR (400 MHz, Chloroform-d) δ 8.10 (d, J = 2.5 Hz, 2H), 7.72 (dt, J = 8.7, 3.1 Hz, 2H), 7.61 (dt, J = 8.5, 2.7 Hz, 2H), 1.53 - 1.42 (s, 18H). ESI-MS (m / z): 468 (M), 959 (2M+23).

[0063] Synthesis of compound (7b):

[0064] Take 250 mL single mouth bottle, add magnetic son, compound (5) (0.9 g, 2.0 mmol), (7a) (1.2 g, 4.4 mmol), Cs2CO3 (2.6 g, 8 mmol) and DMF (50 mL), stir and replace with nitrogen, then warm to 140 °, react for 36 h. Reduce to room temperature, extract with DCM three times, combine the organic phase and dry, then mix with silica gel, column separate with PE, get 0.8 g of light green oil, yield 42 %. 1 H NMR (400 MHz, Chloroform-d) δ 8.18 (d, J = 2.0, 2H), 7.45 - 7.37 (m, 4H), 7.28 - 7.20 (m, 8H), 7.08 - 7.01 (m, 8H), 1.52 - 1.39 (s, 18H), 1.39-1.28 (s, 36H). ESI-MS (m / z): 1014 (M+23).

[0065] Synthesis of compound structure (7):

[0066] Take 100 mL three mouth bottle, bake in 100 ° oven for 2 h, immediately after taking out, vacuum for 0.5 h; Under nitrogen atmosphere, add magnetic son, compound (7b) (2.0 g, 2.0 mmol) and 20 mL dry t-butyl benzene, use liquid nitrogen, ethanol and water mixture to cool the reaction bottle to -40 °, drop t-BuLi (2 mL, 5 mmol) drop by drop, stir for 0.5 h, then warm to 70 ° and react for 2 h; Cool to -30 °, drop BBr3 (0.4 mL, 5 mmol) drop by drop, slowly warm to room temperature and react for 0.5 h; Reduce to 0 °, drop diisopropyl ethyl amine (0.9 mL, 5 mmol) drop by drop, then warm to 120 °, react for 18 h; After the reaction is completed, distill t-butyl benzene under reduced pressure, then extract with DCM three times, column separate with PE:EA = 50:1 mixed solvent, get 0.63 g of light yellow powder, yield 34 %. 1 H NMR (400 MHz, Chloroform-d) δ 8.19 (d, J = 2.3 Hz, 2H), 7.40-7.39 (m, 2H), 7.35 (d, J = 2.1 Hz, 2H), 7.33-7.32 (m, 2H), 7.29-7.24 (m, 4H), 7.22 (dd, J = 6.3, 2.1 Hz, 2H), 7.05-7.01 (m, 4H), 7.00 (d, J = 6.3 Hz, 2H), 1.43-1.35 (s, 18H), 1.35-1.26 (d, J = 0.7 Hz, 36H). ESI-MS (m / z): 921 (M+1), 943 (M+23).

[0067] Example 2:

[0068] Synthesis of compound structure 13

[0069]

[0070] Synthesis of compound (6):

[0071] Into a 250 mL flask, add a magnetic stir bar, compound (5) (0.9 g, 2.0 mmol), 7(a) (0.6 g, 2.4 mmol), Cs2C03(1.3 g, 4 mmol) and DMF (50 mL), stir and replace with nitrogen, then warm to 140° for 36 h. Cool to room temperature, extract with DCM three times, combine the organic phases and dry down, then stir with silica gel and column separate with PE to give 0.8 g of a light green oil in 45% yield. 1 H NMR (400 MHz, Chloroform-d) δ 8.21 (dd, J = 19.4, 2.1 Hz, 2H), 7.47 - 7.37 (m, 4H), 7.27 - 7.23 (m, 4H), 7.08 - 7.03 (m, 4H), 1.35 (s, 18H), 1.34 (s, 18H). ESI-MS (m / z): 731 (M+l).

[0072] Synthesis of compound (13b):

[0073] Into a 250 mL flask, add a magnetic stir bar, compound (6) (1.5 g, 2.0 mmol), (13a) (0.6 g, 2.2 mmol), Cs2C03(1.3 g, 4 mmol) and DMF (50 mL), stir and replace with nitrogen, then warm to 100° for 36 h. Cool to room temperature, extract with DCM three times, combine the organic phases and dry down, then stir with silica gel and column separate with PE to give 1.0 g of a light green oil in 52% yield. 1 H NMR (400 MHz, Chloroform-d) δ 8.20 - 8.15 (m, 2H), 7.44 - 7.36 (m, 3H), 7.27 - 7.20 (m, 6H), 7.11 (dd, J = 5.1, 2.2 Hz, 1H), 7.07 - 7.01 (m, 4H), 6.71 (d, J = 5.1 Hz, 1H), 1.46-1.43 (s, 6H), 1.36-1.32 (s, 6H), 1.35 (m, 36H), 1.31-1.28 (s, 9H). ESI-MS (m / z): 942 (M+l).

[0074] Synthesis of compound structure (13):

[0075] The same as the synthesis of structure (7), the feeding amount of compound (13b) (1.9 g, 2.0 mmol), t-BuLi (2 mL, 5 mmol), BBr3(0.4 mL, 5 mmol), diisopropylethylamine (0.9 mL, 5 mmol) respectively. Light yellow powder 0.47 g, yield 27%. 1 H NMR (400 MHz, Chloroform-d) δ 8.19 (dt, J = 1.9, 1.0 Hz, 2H), 7.42 - 7.34 (m, 3H), 7.34 - 7.30 (m, 2H), 7.29 - 7.24 (m, 4H), 7.22 (dd, J = 6.3, 2.3 Hz, 1H), 7.05 - 6.97 (m, 3H), 1.45 (s, 6H), 1.40 (s, 6H), 1.36 - 1.32 (m, 45H). ESI-MS (m / z): 871 (M+l).

[0076] Example 3:

[0077] Synthesis of compound structure 41

[0078]

[0079] Synthesis of compound (41b):

[0080] The same as the synthesis of structure (13b), the feeding amount of (6) (1.5 g, 2.0 mmol), (41a) (0.6 g, 2.2 mmol), Cs2CO3(1.3 g, 4 mmol) and DMF (50 mL) respectively, light green oil 1.2 g, yield 61%. 1 H NMR (400 MHz, Chloroform-d) δ 8.22 - 8.17 (m, 2H), 8.06 (d, J = 2.2 Hz, 1H), 7.93 (d, J = 2.4 Hz, 1H), 7.65 (d, J = 7.7 Hz, 1H), 7.44 - 7.35 (m, 5H), 7.30 - 7.22 (m, 6H), 7.08 - 7.02 (m, 4H), 1.35 (m, 54H). ESI-MS (m / z): 990 (M+l).

[0081] Synthesis of compound structure (41):

[0082] The same as the synthesis of structure (7), the feeding amount of compound (13b) (2.0 g, 2.0 mmol), t-BuLi (2 mL, 5 mmol), BBr3(0.4 mL, 5 mmol), diisopropylethylamine (0.9 mL, 5 mmol) respectively. Light yellow powder 0.72 g, yield 39%. 1H NMR (400 MHz, Chloroform-d) δ 8.75 (d, J = 2.3 Hz, 1H), 8.21 (d, J = 1.9 Hz, 2H), 8.11 (d, J = 1.8 Hz, 1H), 7.53 (d, J = 7.7 Hz, 1H), 7.45 - 7.37 (m, 3H), 7.37 - 7.31 (m, 3H), 7.30 - 7.25 (m, 2H), 7.24 - 7.17 (m, 2H), 7.06 - 6.97 (m, 3H), 1.36 - 1.33 (m, 54H). ESI-MS (m / z): 919 (M+1).

[0083] Example 4:

[0084] Synthesis of compound structure 72

[0085]

[0086] Synthesis of compound structure (72) was same as example 3. 1 H NMR (400 MHz, Chloroform-d) δ 8.19 (d, J = 2.1 Hz, 2H), 7.92 (d, J = 4.6 Hz, 1H), 7.39 (dd, J = 7.7, 2.2 Hz, 2H), 7.32 (d, J = 7.7 Hz, 2H), 7.30 - 7.24 (m, 4H), 7.21 (dd, J = 6.2, 2.2 Hz, 1H), 7.19 - 7.15 (m, 1H), 7.06 - 6.97 (m, 4H), 2.27 (d, J = 0.7 Hz, 3H), 2.14 (s, 6H), 1.37 - 1.30 (m, 54H). ESI-MS (m / z): 908 (M+1).

[0087] Example 5:

[0088] Synthesis of compound structure 126

[0089]

[0090] Synthesis of compound structure (126) was same as example 3. 1H NMR (400 MHz, Chloroform-d) δ 8.19 (d, J = 2.1 Hz, 2H), 7.83 (dd, J = 6.9, 1.3 Hz, 1H), 7.75 (dd, J = 6.6, 1.6 Hz, 1H), 7.47 (ddd, J = 7.6, 6.5, 1.2 Hz, 1H), 7.39 (dd, J = 7.8, 2.2 Hz, 3H), 7.36 - 7.31 (m, 3H), 7.29 - 7.24 (m, 4H), 7.22 (dd, J = 6.3, 2.3 Hz, 1H), 7.07 - 6.96 (m, 5H), 1.37 - 1.32 (m, 45H). ESI-MS (m / z): 921 (M+1), 943 (M+23).

[0091] Example 6:

[0092] Synthesis of compound structure 127

[0093]

[0094] The same as the synthesis of example 3, compound structure (127) was obtained. 1 H NMR (400 MHz, Chloroform-d) δ 8.19 (d, J = 2.1 Hz, 2H), 7.83 (dd, J = 6.9, 1.3 Hz, 1H), 7.75 (dd, J = 6.6, 1.6 Hz, 1H), 7.47 (ddd, J = 7.6, 6.5, 1.2 Hz, 1H), 7.39 (dd, J = 7.8, 2.2 Hz, 3H), 7.36 - 7.31 (m, 3H), 7.29 - 7.24 (m, 4H), 7.22 (dd, J = 6.3, 2.3 Hz, 1H), 7.07 - 6.96 (m, 5H), 1.37 - 1.32 (m, 45H). ESI-MS (m / z): 921 (M+1), 943 (M+23).

[0095] Example 7:

[0096] Synthesis of compound structure 129

[0097]

[0098] The same as the synthesis of example 3, compound structure (129) was obtained. 1H NMR (400 MHz, Chloroform-d) δ 8.19 (d, J = 2.1 Hz, 2H), 7.86 - 7.79 (m, 1H), 7.54 (d, J = 2.2 Hz, 1H), 7.47 - 7.36 (m, 3H), 7.35 - 7.24 (m, 8H), 7.22 (dd, J = 6.3, 2.3 Hz, 1H), 7.06 - 6.98 (m, 5H), 1.38 - 1.31 (m, 45H). ESI-MS (m / z): 905 (M+l).

[0099] The person skilled in the art should know that the above preparation method is only an exemplary example, and the person skilled in the art can obtain other compound structures of the present application by improving it.

[0100] Example 8:

[0101] An organic electroluminescent low-emission device is prepared using the B-N fused ring organic electroluminescent material of the present application, and the device structure is as follows: Figure 1 .

[0102] First, the transparent conductive ITO glass substrate 10 (with an anode 20 on top) is sequentially washed with deionized water, ethanol, acetone, and deionized water, dried at 80°C, and then treated with oxygen plasma for 30 min. Then, 10 nm thick HATCN is evaporated as a hole injection layer 30 in a vacuum <4*10 -4 pa in an evaporation machine, 40 nm thick compound HTL is evaporated to form a hole transport layer 40, 10 nm thick EBL (electron blocking layer) 50 is evaporated on the hole transport layer, then 20 nm thick EML (host material (Host): 3% guest material, light-emitting layer) 60 is evaporated, the light-emitting layer is composed of B-N fused ring organic electroluminescent material and host material doped; 40 nm thick ETL (electron transport layer) 70 is evaporated on the light-emitting layer, the electron transport layer is composed of ETL1 and LiQ two materials. 1 nm of metal ytterbium is evaporated as an electron injection layer 80 and 100 nm of Ag is evaporated as a device cathode 90.

[0103]

[0104] Examples 9-14 and Comparative Examples 1 and 2:

[0105] Examples 9-14 and Comparative Examples 1 and 2 have the same device fabrication as Example 8, except that the guest material in the light-emitting layer is Structure 13, Structure 41, Structure 72, Structure 126, Structure 127, Structure 129 in the present application, and Comparative Example 1 and Comparative Example 2, respectively. The chemical structures of the comparative example materials are as follows:

[0106]

[0107] The electrical and optical properties of the organic electroluminescent devices of Examples 9-14 and Comparative Examples 1 and 2 were measured at 0.4 mA, as shown in Table 1.

[0108] Table 1

[0109] Number Voltage (V) Current efficiency (cd / A) Emission wavelength (nm) Half-wave width (nm) Example 8 3.6 5.1 462 32 Example 9 3.5 5.3 458 28 Example 10 3.6 5.4 468 30 Example 11 3.8 5.9 470 33 Example 12 3.7 5.2 461 28 Example 13 3.7 5.5 461 27 Example 14 3.5 5.1 465 29 Comparative Example 1 3.8 6.5 458 55 Comparative Example 2 3.7 5.1 459 33

[0110] As can be seen from the data in Table 1, under the same conditions, the B-N fused ring organic electroluminescent material of the present application applied to the organic electroluminescent device has a narrow half-wave width, has higher color purity (compared with Comparative Example 1), and achieves a more excellent display effect. Under the same conditions, the B-N fused ring organic electroluminescent material of the present application applied to the organic electroluminescent device has a narrow half-wave width, and compared with Comparative Example 2 which has a more similar structure, the current efficiency is improved, so the performance is also better.

Claims

1. An organic electroluminescent material containing a B-N fused ring structure, having a structure represented by the following general formula (I): ###0001### wherein: Ar1 to Ar4 are each independently selected from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Ar5 is independently selected from a substituted or unsubstituted C1-C60 alkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, or a substituted or unsubstituted C6-C60 aryl group, and Ar5 is bonded to the adjacent group Ar1 with either a single bond, -C-C- to form a cyclic structure; and Ar6 is independently selected from a substituted or unsubstituted C6-C60 aryl group; wherein at least one of Ar1 and Ar2, and Ar5 and Ar6 is not the same; and the substitution is substituted with one or more of deuterium, a cyano group, a halogen, an alkyl group having 1 to 30 carbon atoms, or a cycloalkyl group having 1 to 20 carbon atoms.

2. The organic electroluminescent material according to claim 1, wherein the structure is selected from one of the following general formulae: ###0002### wherein: X1 and X8, X2 and X7, X3 and X6, X4 and X5, Ar5 and Ar6 are not the same; R1 is the same or different and is independently selected from a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, or a straight chain or branched C1-C8 alkyl group; Ar5 is independently selected from a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, or a substituted or unsubstituted C6-C20 aryl group, and Ar6 is independently selected from a substituted or unsubstituted C6-C20 aryl group; and the substitution is substituted with one or more of deuterium, a cyano group, a halogen, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 1 to 10 carbon atoms. R1 is the same or different and is independently selected from a hydrogen atom or a straight chain or branched C1-C8 alkyl group; and the substitution is substituted with one or more of deuterium, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 1 to 10 carbon atoms.

6. The organic electroluminescent material according to claim 5, wherein R1 is the same or different and is independently selected from a hydrogen atom or a straight chain or branched C1-C4 alkyl group.

7. The organic electroluminescent material according to any one of claims 1 to 6, wherein the aryl group is selected from one or more of a phenyl group, a naphthyl group, an anthryl group, a binaphthyl group, a phenanthryl group, a dihydrophenanthryl group, a pyryl group, a perylenyl group, a tetracenyl group, a pentacenyl group, a benzoperylenyl group, a benzocyclopentadienyl group, a spirofluorenyl group, and a fluorenyl group.

8. The organic electroluminescent material according to claim 7, wherein the aryl group is selected from one or more of a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a dihydrophenanthryl group, a tetracenyl group, a pentacenyl group, a benzoperylenyl group, a benzocyclopentadienyl group, a spirofluorenyl group, and a fluorenyl group.

9. The organic electroluminescent material according to claim 1, having a structure represented by one of the following: ###0003### ###0004### wherein, X1-X8are each independently CR1, X9-X 16 are each independently CR1, R1is the same or different and is independently selected from the group consisting of a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, and a linear or branched C1-20alkyl group.

3. The organic electroluminescent material according to claim 2, wherein 10. An organic electroluminescent material containing a B-N fused ring structure, having a structure represented by the following general formula (I): ###0005### wherein: Ar1 is selected from a substituted or unsubstituted heteroaryl group having 5 to 30 carbon atoms, and Ar2 to Ar4 are each independently selected from a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

4. The organic electroluminescent material according to claim 3, wherein ​ 5. The organic electroluminescent material according to claim 4, wherein ​ ​ ​ ​ ​ ​ ​ ​ Ar5and Ar6are each independently selected from substituted or unsubstituted C6-C60aryl; wherein at least one of Ar1and Ar2, and at least one of Ar5and Ar6are not the same; the substituent is substituted with one or more of deuterium, cyano, halogen, alkyl group having 1 to 30 carbon atoms, and cycloalkyl group having 1 to 20 carbon atoms, the heteroatom in the heteroaryl group is one or more of N, S, and O.

11. The organic electroluminescent material according to claim 10, wherein the structure is selected from one of the structures represented by General Formulae (II-1) to (II-2): wherein, X4represents a nitrogen atom, X1to X3, X5to X7 16 each independently represents a nitrogen atom or CR1, or X2represents a nitrogen atom, X1, X3to X7 16 each independently represents a nitrogen atom or CR1; R1is the same or different and is independently selected from a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, or a linear or branched C1-20alkyl group; Y1-Y3are each independently one of an oxygen atom, a sulfur atom, or N-R2, and the remaining are independently selected from a nitrogen atom or C-R8, R2is independently selected from a hydrogen atom, a deuterium atom, or a linear or branched C1-20alkyl group, and R8is independently selected from a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, or a linear or branched C1-20alkyl group.

12. The organic electroluminescent material according to claim 11, wherein X1and X8, X2and X7, X3and X6, X4and X5, Y1and Y6, Y2and Y5, Y3and Y4, Ar5and Ar6are at least one group that are not the same.

13. The organic electroluminescent material according to claim 12, wherein R1is the same or different and is independently selected from a hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, or a linear or branched C1-C8alkyl group; Ar5and Ar6are each independently selected from substituted or unsubstituted C6-C20aryl; the substituent is substituted with one or more of deuterium, cyano, halogen, alkyl group having 1 to 8 carbon atoms, and cycloalkyl group having 1 to 10 carbon atoms.

14. The organic electroluminescent material according to claim 13, wherein R1is the same or different and is independently selected from a hydrogen atom, or a linear or branched C1-C8alkyl group; R2and R8are the same or different and are independently selected from a hydrogen atom, or a linear or branched C1-C20alkyl group.

15. The organic electroluminescent material according to claim 14, wherein X9to X 16 independently from each other are CR1, and R1is independently selected from the group consisting of a hydrogen atom, or a linear or branched C1-C4alkyl group.

16. The organic electroluminescent material according to any one of claims 10 to 15, wherein the aryl group is selected from one or more of phenyl, naphthyl, anthryl, binaphthyl, phenanthryl, dihydrophenanthrene, pyryl, perylenyl, naphthacene, pentacene, benzoperylenyl, benzocyclopentadienyl, spirofluorenyl, and fluorenyl; and the heteroaryl group is selected from one or more of pyrrolyl, imidazolyl, thienyl, furanyl, 1,2-thiazolyl, 1,3-thiazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, thiadiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, pyridyl, pyrazinyl, pyrimidinyl, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, indolyl, isoindolyl, benzimidazolyl, naphthimidazolyl, phenanthroimidazolyl, benzotriazolyl, purinyl, benzoxazolyl, naphthoxazolyl, phenanthroxazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, benzopyrazinyl, benzothienyl, benzofuranyl, carbazolyl, acridinyl, dibenzothiophenyl, dibenzofuranyl, dibenzothiophene-5,5-dioxy, naphthothiadiazolyl, and 10,15-dihydro-5H-diindolo[3,2-a:3',2'-c]carbazolyl.

17. The organic electroluminescent material according to claim 16, wherein the aryl group is selected from one or more of phenyl, naphthyl, anthryl, phenanthryl, dihydrophenanthryl, naphthacene, pentacene, benzocyclopentadienyl, spirofluorene, and fluorene; and the heteroaryl group is selected from one or more of pyrrolyl, imidazolyl, thienyl, furanyl, 1,2-thiazolyl, 1,3-thiazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, thiadiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, pyridyl, pyrazinyl, pyrimidinyl, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, indolyl, isoindolyl, benzimidazolyl, naphthimidazolyl, phenanthroimidazolyl, benzotriazolyl, purinyl, benzoxazolyl, naphthoxazolyl, phenanthroxazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, benzopyrazinyl, benzothienyl, benzofuranyl, carbazolyl, acridinyl, dibenzothiophenyl, dibenzofuranyl, dibenzothiophene-5,5-dioxide, naphthothiadiazolyl, and 10,15-dihydro-5H-dinaphtho[3,2-a:3',2'-c]carbazolyl.

18. An organic electroluminescent material, the structure of which is shown in one of the following:

19. Use of the organic electroluminescent material according to any one of claims 1 to 18 in an electroluminescent device.

20. An organic electroluminescent device comprising at least one functional layer, the functional layer comprising the organic electroluminescent material according to any one of claims 1 to 18.

21. The organic electroluminescent device according to claim 20, wherein the organic electroluminescent material is used as a dopant material for a light-emitting layer.

22. A lighting or display element characterised in that, 22. An organic electroluminescent device comprising the organic electroluminescent device according to any one of claims 20 to 21.

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