Boron-nitrogen compound with polynary fused ring, OLED (Organic Light Emitting Diode) with compound and organic light emitting device

Abstract

The invention relates to the technical field of preparation of organic photoelectric materials, in particular to a boron-nitrogen compound with a polynary fused ring, an OLED (Organic Light Emitting Diode) with the compound and an organic light-emitting device with the compound. According to the boron-nitrogen compound disclosed by the invention, through matching of a fused heterocyclic structure and limited groups such as tertiary butyl and naphthenic base, the thermal stability of the compound can be improved, and the boron-nitrogen compound has an excellent luminescence characteristic; the boron-nitrogen compound provided by the invention is used as a light-emitting layer material, so that the organic light-emitting device can effectively have lower driving voltage and maintain the stability of the voltage, and the light-emitting efficiency is improved.

Description

Technical Field

[0001] The invention relates to the technical field of preparation of organic photoelectric materials, and in particular to a boron nitrogen compound with a polynary condensed ring, an OLED and an organic light-emitting device having the compound. Background Art

[0002] Organic light-emitting diodes (OLEDs), also known as organic electroluminescent devices, are a technology that applies voltage to organic electroluminescent elements to inject holes from the anode and electrons from the cathode into the light-emitting layer respectively. The injected holes and electrons recombine to form excitons, resulting in luminescence. It can convert electrical energy into light energy through organic light-emitting materials.

[0003] The light-emitting layer in OLED devices mostly uses a host-guest light-emitting system, that is, doping guest materials in the host material. Currently, the research hotspot of green light doping materials is mostly boron nitrogen condensed ring molecules, but the types and quantities of existing materials are still relatively small, which makes the study of structure-activity relationship more difficult; and in its application, the display technology still has the problems of high driving voltage and short display life, which seriously affects the further practical application of this technology.

[0004] Therefore, continuous efforts are needed to develop organic light-emitting devices with low voltage drive, high brightness and long life. Finding suitable OLED optoelectronic functional materials for OLED devices to solve the above problems is a long-term need in the field. Summary of the invention

[0005] In order to solve the above technical problems, the present invention provides a boron nitrogen compound with a polycyclic condensed ring, an OLED and a display or lighting device having the compound. The boron nitrogen compound can improve the luminous efficiency and thermal stability by combining a boron nitrogen condensed heterocycle with a limiting group, and the molecular structure is easy to modify. The boron nitrogen compound provided by the present invention is used as a light-emitting layer material, which can effectively make the organic light-emitting device have a lower driving voltage and maintain voltage stability, and the luminous efficiency is improved.

[0006] The boron nitrogen compound with a polynary condensed ring provided by the present invention is realized by the following technical scheme: A boron-nitrogen compound having a polycyclic condensed ring, Represented by the structure of formula I: ; In Formula I, X is selected from C or Si; Y1 and Y3 represent absence or presence; when Y1 and / or Y3 represent presence, Y1 and Y3 are each independently selected from a single bond, O, S, C(CH3)2, Si(CH3)2; Ring M1 and Ring M2 each independently represent one or more of C3-C20 cycloalkyl, C6-C30 aromatic ring, and C5-C36 heteroaromatic ring; R1-R4, R6, R7 represent unsubstituted, monosubstituted or polysubstituted; R1-R4, R 4' Each of the substituents is identically or differently selected from one or more of hydrogen, deuterium, C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C30 aryl, and any two adjacent substituents may form a saturated or unsaturated C3-C12-membered ring; R5 is selected from hydrogen or deuterium. 5' R5 is independently selected from one or more of deuterium, substituted C6-C30 aryl, substituted or unsubstituted C5-C36 heteroaryl, and C6-C36 arylsilyl; or R5 is selected from deuterium, C1-C20 alkyl, C6-C30 aryl, and R 5' With R 4' Bonded into a ring; or R5, R 5' Also selected from deuterium; R6-R7 are each the same or different and are selected from hydrogen, deuterium, C1-C20 alkyl, C1-C20 alkylamino, C6-C36 arylamino; When R1-R7, R 4' , R 5' When there is substitution, the substitution is selected from one or more of deuterium, C1-C20 alkyl, C3-C20 cycloalkyl, and C6-C18 aryl.

[0007] Optionally, any two adjacent substituents may form a saturated or unsaturated C3-C12 membered ring.

[0008] The hydrogen atoms in the compounds of formula I of the present invention may be replaced by deuterium, tritium, cyano or halogen atoms.

[0009] Preferably, the present invention provides a boron nitrogen compound having a polycyclic condensed ring, represented by the structure of Formula II: ; In formula II, X and X1 are selected from C or Si; Y3 is selected from a single bond, O, S, C(CH3)2, Si(CH3)2; Y4 is selected from a single bond, O, S; ring M1, ring M2, ring M3, and ring M4 each independently represent one or more of a C6-C30 aromatic ring and a C3-C20 cycloalkyl; when X and X1 are both selected from Si, at least one of rings M1 to M4 is a C6-C30 aromatic ring substituted by a C3-C20 cycloalkyl condensation; R1-R4 represent unsubstituted, monosubstituted or polysubstituted; R1-R4 are each the same or different and are selected from one or more of hydrogen, deuterium, C1-C20 alkyl, C1-C20 alkyl substituted or unsubstituted C3-C20 cycloalkyl, and any two adjacent substituents may form a saturated or unsaturated C3-C12 membered ring; R5 is selected from hydrogen, deuterium, C1-C20 alkyl, C6-C30 aryl; R6-R7 are each the same or different and are selected from hydrogen, deuterium, C1-C20 alkyl, C1-C20 alkylamine, C6-C36 arylamine; R8 and R9 are each the same or different and are selected from one or more of hydrogen, deuterium, C1-C20 alkyl.

[0010] Preferably, the ring M1, ring M2, ring M3 and ring M4 in Formula I or Formula II each independently represent phenyl, naphthyl or tetrahydronaphthyl.

[0011] Preferably, R1-R4 in Formula I or Formula II are each the same or different and are selected from hydrogen, deuterium, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, adamantyl, methyl-substituted fused cyclopentyl, methyl-substituted fused cyclohexyl, tert-butyl-substituted or unsubstituted phenyl.

[0012] Preferably, in Formula I, R5 is selected from hydrogen or deuterium and R 5' Independently selected from one or more of deuterium, deuterated phenyl, tert-butylphenyl, terphenyl, triphenylsilyl, tetraphenylsilyl, biphenyl, tert-butyl substituted biphenyl, carbazole, and N-phenylcarbazole; in Formula II, R5 is independently selected from one or more of hydrogen, deuterium, tert-butyl, and phenyl.

[0013] Preferably, R6-R7 are each independently selected from hydrogen, deuterium, methyl, ethyl, propyl, tert-butyl, dimethylamino, and diphenylamino.

[0014] Preferably, the structure of formula I is selected from any one of the following formulas I-1 to I-2: ; In Formula I-1 to Formula I-2, Ring M1, Ring M2, X, Y3, R1-R7, R 4' , R 5' The substitution range is the same as defined in the above formula I.

[0015] According to one or more embodiments, the present invention provides a boron nitrogen compound having a polycyclic condensed ring, wherein the compound is selected from any one of the chemical structures shown below, wherein "tBu" represents a tert-butyl group, "Ph" represents a phenyl group, and "Ad" represents an adamantyl group: .

[0016] The present invention also provides a use of the boron nitrogen compound having a polycyclic condensed ring as described above in the preparation of an organic electroluminescent device.

[0017] The present invention also provides an organic electroluminescent device, the organic electroluminescent device comprising: substrate layer; a first electrode, the first electrode being on the substrate; An organic light-emitting functional layer, the organic light-emitting functional layer is on the first electrode; A second electrode, the second electrode being on the organic light-emitting functional layer; The organic light-emitting functional layer comprises a light-emitting layer; the light-emitting layer comprises the boron-nitrogen compound having a polycyclic condensed ring as described above.

[0018] The present invention also provides a composition, which comprises the boron nitrogen compound having a polycyclic condensed ring as described in Formula I.

[0019] The present invention also provides a preparation, the preparation comprising a boron nitrogen compound with a polycyclic condensed ring structure as shown in the above formula I or the composition as described above and at least one solvent. The solvent is not particularly limited, and can be used, for example, unsaturated hydrocarbon solvents, halogenated saturated hydrocarbon solvents, halogenated unsaturated hydrocarbon solvents, ether solvents or ester solvents well known to those skilled in the art; wherein the unsaturated hydrocarbon solvent is toluene, xylene, mesitylene, tetralin, n-butylbenzene, sec-butylbenzene or tert-butylbenzene; the halogenated saturated hydrocarbon solvent is carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, hexyl chloride, bromohexane, chlorocyclohexane or bromocyclohexane; the halogenated unsaturated hydrocarbon solvent is chlorobenzene, dichlorobenzene or trichlorobenzene; the ether solvent is tetrahydrofuran or tetrahydropyran; the ester solvent is alkyl benzoate.

[0020] The organic electroluminescent device of the present invention can be used in OLED lighting or display devices. Preferably, the organic electroluminescent device prepared by the present invention is used in smart phones, tablet computers, smart wearable devices, televisions, VR, micro-display fields, and automobile central control screens or automobile taillights.

[0021] The present invention also provides a display or lighting device, which comprises one or more of the organic electroluminescent devices described above.

[0022] In summary, compared with the prior art, the present invention has the following beneficial effects: The present invention combines a boron-nitrogen fused heterocyclic structure with a spirocyclic fragment to give the boron-nitrogen compound a large conjugated system, and modifies it with an alkyl group or a cycloalkyl group, thereby increasing the spatial stereoscopic property of the structure. The structure as a whole has good thermal stability and film-forming properties, exhibits good hole and electron transmission capabilities, and can effectively improve the energy transmission performance between the subject and the guest. After the boron-nitrogen compound provided by the present invention is prepared into an organic light-emitting device, the organic light-emitting device can effectively have a lower driving voltage and maintain voltage stability, and the luminous efficiency is improved, and the working life of the device can also be better. DETAILED DESCRIPTION

[0023] The following will be described clearly and completely in conjunction with the technical solutions of the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative work are within the scope of protection of the present invention.

[0024] The term "alkyl" refers to and includes straight and branched chain alkyl groups. Preferred alkyl groups are those containing 1 to 20 carbon atoms and include methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, etc. In addition, the alkyl group may be optionally substituted.

[0025] The term "cycloalkyl" refers to and includes monocyclic, polycyclic and spiroalkyl groups. Preferred cycloalkyl groups are those containing 3 to 20 ring carbon atoms, more preferred cycloalkyl groups are those containing 3 to 12 ring carbon atoms, and particularly preferred are those containing 3 to 6 ring carbon atoms, and include cyclopropyl, cyclopentyl, cyclohexyl, bicyclo[3.1.1]heptyl, spiro[4.5]decyl, spiro[5.5]undecyl, adamantyl, etc. In addition, the cycloalkyl group may be optionally substituted.

[0026] The term "aryl" refers to and includes monocyclic aromatic hydrocarbon groups and polycyclic aromatic ring systems. Polycyclic rings may have two or more rings in which two carbons are shared by two adjacent rings (the rings are "fused"), wherein at least one of the rings is an aromatic hydrocarbon group, for example, the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocycle and / or heteroaryl. Preferred aryl groups are aryl groups containing six to thirty carbon atoms, more preferably six to twelve carbon atoms. Particularly preferred are aryl groups with six carbons, ten carbons or twelve carbons. Suitable aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenanthrene, fluorene, pyrene, perylene and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorene and naphthalene. In addition, aryl groups may be optionally substituted.

[0027] The heteroaryl group refers to a general term for a group in which one or more aromatic carbon atoms in an aromatic group are replaced by heteroatoms, wherein the heteroatoms include but are not limited to oxygen, sulfur, silicon or nitrogen atoms, and the heteroaryl group may be a monocyclic heteroaryl group or a condensed ring heteroaryl group, and may be a heteroaryl group having 5 to 36 carbon atoms, preferably a heteroaryl group having 6 to 20 carbon atoms. Examples may include pyridyl, pyrrolyl, pyridyl, thienyl, furanyl, indolyl, quinolyl, isoquinolyl, benzothienyl, benzofuranyl, dibenzofuranyl, dibenzothienyl, carbazolyl, etc., but are not limited thereto.

[0028] In the present invention, the terms "optionally" and "optionally" mean that the event or environment described subsequently may or may not occur. For example, "optionally, any two adjacent..." means that the two substituents may or may not form a ring, that is, including: the scenario where two adjacent substituents form a ring and the scenario where two adjacent substituents do not form a ring. "Any two adjacent" may include two substituents on the same atom, and may also include two adjacent atoms each having one substituent; wherein, when there are two substituents on the same atom, the two substituents may form a saturated or unsaturated spiro ring with the atom to which they are connected; when there is one substituent on two adjacent atoms each, the two substituents may be fused into a ring.

[0029] Throughout the specification, unless explicitly described to the contrary, "comprising" any component will be understood to imply the inclusion of other elements, rather than excluding any other elements. In addition, it should be understood that throughout the specification, when an element such as a layer, film, region or substrate is referred to as being "on" or "above" another element, it can be "directly on" another element, or there may be intervening elements. In addition, "on..." or "above..." means being located above the target portion, and does not necessarily mean being located above according to the direction of gravity.

[0030] An object of the present invention is to provide an organic electroluminescent device, which includes: a substrate layer; a first electrode, which is on the substrate; an organic light-emitting functional layer, which is on the first electrode; a second electrode, which is on the organic light-emitting functional layer; the organic light-emitting functional layer includes a light-emitting layer, and the light-emitting layer includes a boron nitrogen compound with a polycyclic fused heterocyclic fragment.

[0031] In one embodiment of the present invention, the light-emitting layer in the organic electroluminescent (OLED) device comprises one or more of the compounds represented by the above general formula I as light-emitting doping materials.

[0032] In a preferred embodiment of the present invention, an OLED is provided, which includes a substrate, an anode, a cathode, and an organic light-emitting functional layer, wherein the organic light-emitting functional layer may include a light-emitting layer, a hole transport layer, a hole injection layer, an electron transport layer, an electron injection layer, etc., or may only include a light-emitting layer and one or more other layers; wherein the light-emitting layer includes a light-emitting doping material composed of one or more of the compounds represented by the above general formula (I). Optionally, there is also a covering layer, a protective layer and / or an encapsulation layer on the organic light-emitting functional layer.

[0033] The substrate of the present invention can be any substrate used in a typical organic light-emitting device. It can be a glass or transparent plastic substrate, or a substrate of an opaque material such as silicon or stainless steel, or a flexible PI film. Different substrates have different mechanical strengths, thermal stability, transparency, surface smoothness, and waterproofness. Depending on the properties of the substrate, the use direction is different.

[0034] In a preferred embodiment of the present invention, the OLED device comprises a hole injection layer, and the P-type doping material in the hole injection layer can be selected from known or unknown materials, and is particularly preferably selected from the following structures, but it does not mean that the present invention is limited to the following structures: .

[0035] In a preferred embodiment of the present invention, the OLED device comprises a hole transport layer, and the hole transport layer can be selected from known or unknown materials, and is particularly preferably selected from the following structures, but it does not mean that the present invention is limited to the following structures: .

[0036] In a preferred embodiment of the present invention, the OLED device comprises an electron transport layer, and the electron transport layer can be selected from known or unknown materials, and is particularly preferably selected from the following structures, but it does not mean that the present invention is limited to the following structures:

[0037] As a host material capable of producing green fluorescence, it is not only required to have a very high fluorescence quantum luminescence efficiency, but also to have an appropriate energy level to effectively cooperate with the guest material to excite and emit light. The host material can be selected from known or unknown materials.

[0038] The present invention is described in detail below in conjunction with specific examples. Synthesis Examples All raw materials and solvents are commercially available unless otherwise specified, and the solvents are used directly without further treatment.

[0039] Example Example 1: Synthesis of Compound 15 Synthesis route: ; 1) Compound SM1 (1 mmoL) and CsCO3 (2 mmoL) were dissolved in 50 ml of anhydrous DMF solution and stirred for 20 min. Compound SM2 (1 mmoL) was added under nitrogen atmosphere, and the temperature was raised to 120°C and heated for 15 hours, then cooled to room temperature. The solvent was removed by rotary evaporation, and the residue was extracted with dichloromethane (3×100 mL). The organic phase was washed with water and dried with sodium sulfate. The solvent was removed by vacuum distillation, and the resulting crude product was separated and purified by silica gel chromatography, with the eluent being dichloromethane: petroleum ether = 1:4, and the intermediate product S1; 2) Dissolve the intermediate product S1 (1 mmol) in 50 mL THF solution, add n-butyl lithium (2 mmol) solution under nitrogen and low temperature conditions, stir and dissolve, then slowly add compound SM3 (1 mmol) THF solution. Continue to stir the reaction solution at room temperature for 12 hours. After the reaction is completed, add 0.5 mol / L HCl solution, H2O, and EA, and then extract with EA several times. After the organic phase is washed with anhydrous DMF, it is dried with sodium sulfate and evaporated through a column to obtain the intermediate product S2; 3) The intermediate products S3 (1 mmoL) and S2 (1 mmoL) were dissolved in 50 mL toluene solution. Under nitrogen atmosphere, sodium tert-butoxide (2 mmoL), palladium acetate (0.05 mmoL), and tri-tert-butylphosphine tetrafluoroborate (0.5 mmoL) were added. After the reaction system was refluxed for 72 hours, it was cooled to room temperature. The solvent was removed by rotary evaporation, and the residue was extracted with dichloromethane (3×100 mL). The organic phase was washed with water and dried with sodium sulfate. The solvent was removed by vacuum distillation, and the obtained crude product was separated and purified by silica gel chromatography, and the eluent was dichloromethane: petroleum ether = 1:4 to obtain the intermediate product S4; 4) The intermediate product S4 (1 mmoL) was dissolved in 60 mL of anhydrous tert-butylbenzene. The reaction system was cooled to -78°C, and BuLi (1 mL, 2 mmoL, 2M in hexane) was slowly added. After reacting at -78°C for 4 hours, BBr3 (247 mg, 1 mmoL) was slowly added. After reacting at -50°C for 1 hour, the mixture was warmed to room temperature, and then N,N-diisopropylethylamine (387 mg, 3 mmoL) was added, followed by heating to 120°C for 12 hours. After cooling to room temperature, 5 mL of sodium acetate aqueous solution (1 M) was added. The solvent was removed by rotary evaporation, and the residue was extracted with dichloromethane (3×100 mL). The organic phase was washed with water and dried over sodium sulfate. The solvent was removed by distillation under reduced pressure, and the resulting crude product was separated and purified by silica gel chromatography, with the eluent being dichloromethane: petroleum ether = 1:8, to obtain the final product, compound 15; The structure of the test target product compound 15: LC-MS (m / z) was obtained by liquid chromatography-mass spectrometry analysis: the theoretical value was 994.63, and the test value was 995.25.

[0040] Example 2: Synthesis of Compound 23 Referring to the synthesis steps and reaction conditions of Example 1, compound 23 was synthesized, and LC-MS (m / z) was obtained by liquid chromatography-mass spectrometry analysis: the theoretical value was 974.61, and the test value was 975.23.

[0041] Example 3: Synthesis of Compound 46 Referring to the synthesis steps and reaction conditions of Example 1, compound 46 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 1402.82 and the test value was 1403.78.

[0042] Example 4: Synthesis of Compound 47 Referring to the synthesis steps and reaction conditions of Example 1, compound 47 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 1222.73 and the test value was 1223.51.

[0043] Example 5: Synthesis of Compound 55 Referring to the synthesis steps and reaction conditions of Example 1, compound 55 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 1048.63 and the test value was 1049.35.

[0044] Example 6: Synthesis of Compound 61 Referring to the synthesis steps and reaction conditions of Example 1, compound 61 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 1142.66 and the test value was 1143.40.

[0045] Example 7: Synthesis of Compound 65 Referring to the synthesis steps and reaction conditions of Example 1, compound 65 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 1122.70 and the test value was 1123.32.

[0046] Example 8: Synthesis of Compound 68 Referring to the synthesis steps and reaction conditions of Example 1, compound 68 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 1280.75 and the test value was 1281.67.

[0047] Example 9: Synthesis of Compound 69 Referring to the synthesis steps and reaction conditions of Example 1, compound 69 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 1179.76 and the test value was 1180.50.

[0048] Example 10: Synthesis of Compound 70 Referring to the synthesis steps and reaction conditions of Example 1, compound 70 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 1248.69 and the test value was 1249.57.

[0049] Example 11: Synthesis of Compound 72 Referring to the synthesis steps and reaction conditions of Example 1, compound 72 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 1103.73 and the test value was 1104.41.

[0050] Example 12: Synthesis of Compound 75 Referring to the synthesis steps and reaction conditions of Example 1, compound 75 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 1202.76 and the test value was 1203.50.

[0051] Example 13: Synthesis of Compound 77 Referring to the synthesis steps and reaction conditions of Example 1, compound 77 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 966.60 and the test value was 967.12.

[0052] Example 14: Synthesis of Compound 94 Referring to the synthesis steps and reaction conditions of Example 1, compound 94 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 1076.66 and the test value was 1077.38.

[0053] Example 15: Synthesis of Compound 97 Compound 97 was synthesized by referring to the synthesis steps and reaction conditions of Example 1. The LC-MS (m / z) was obtained by liquid chromatography-mass spectrometry analysis: the theoretical value was 1134.71 and the test value was 1135.47.

[0054] Example 16: Synthesis of Compound 98 Compound 98 was synthesized by referring to the synthesis steps and reaction conditions of Example 1. The LC-MS (m / z) was obtained by liquid chromatography-mass spectrometry analysis: the theoretical value was 1382.77 and the test value was 1383.65.

[0055] Example 17: Synthesis of Compound 99 Referring to the synthesis steps and reaction conditions of Example 1, compound 99 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 1183.69 and the test value was 1184.41.

[0056] Example 18: Synthesis of Compound 103 Referring to the synthesis steps and reaction conditions of Example 1, compound 103 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 1309.74 and the test value was 1310.60.

[0057] Example 19: Synthesis of Compound 107 Referring to the synthesis steps and reaction conditions of Example 1, compound 107 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 1164.56 and the test value was 1165.28.

[0058] Example 20: Synthesis of Compound 108 Referring to the synthesis steps and reaction conditions of Example 1, compound 108 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 1012.49 and the test value was 1013.11.

[0059] Example 21: Synthesis of Compound 111 Referring to the synthesis steps and reaction conditions of Example 1, compound 111 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 1180.68 and the test value was 1181.42.

[0060] Example 22: Synthesis of Compound 112 Referring to the synthesis steps and reaction conditions of Example 1, compound 112 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 1460.99 and the test value was 1461.97.

[0061] Example 23: Synthesis of Compound 116 Referring to the synthesis steps and reaction conditions of Example 1, compound 116 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 1040.52 and the test value was 1041.14.

[0062] Example 24: Synthesis of Compound 119 Referring to the synthesis steps and reaction conditions of Example 1, compound 119 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 1188.74 and the test value was 1189.26.

[0063] Example 25: Synthesis of Compound 120 Referring to the synthesis steps and reaction conditions of Example 1, compound 120 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 1032.63 and the test value was 1033.21.

[0064] Example 26: Synthesis of Compound 124 Referring to the synthesis steps and reaction conditions of Example 1, compound 124 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 1014.51 and the test value was 1015.11.

[0065] Example 27: Synthesis of Compound 127 Referring to the synthesis steps and reaction conditions of Example 1, compound 127 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 996.48 and the test value was 997.02.

[0066] Example 28: Synthesis of Compound 128 Referring to the synthesis steps and reaction conditions of Example 1, compound 128 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 1028.44 and the test value was 1029.18.

[0067] Example 29: Synthesis of Compound 130 Referring to the synthesis steps and reaction conditions of Example 1, compound 130 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 1007.55 and the test value was 1008.13.

[0068] Example 30: Synthesis of Compound 131 Referring to the synthesis steps and reaction conditions of Example 1, compound 131 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 1031.51 and the test value was 1032.15.

[0069] Example 31: Synthesis of Compound 132 Referring to the synthesis steps and reaction conditions of Example 1, compound 132 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 1023.52 and the test value was 1024.16.

[0070] Example 32: Synthesis of Compound 133 Referring to the synthesis steps and reaction conditions of Example 1, compound 133 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 1184.71 and the test value was 1185.35.

[0071] Example 33: Synthesis of Compound 138 Referring to the synthesis steps and reaction conditions of Example 1, compound 138 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 1404.93 and the test value was 1405.87.

[0072] Example 34: Synthesis of Compound 141 Referring to the synthesis steps and reaction conditions of Example 1, compound 141 was synthesized and analyzed by liquid chromatography-mass spectrometry to obtain LC-MS (m / z): the theoretical value was 1436.88 and the test value was 1438.00.

[0073] Several examples of the boron nitrogen compounds of the present invention being applied to OLED devices are listed below to further illustrate the beneficial effects of the compounds of the present invention. The materials used in the examples are purchased commercially or synthesized by themselves.

[0074] Fabrication of OLED devices:

[0075] As a reference preparation method for a device embodiment, the present invention evaporates 50-500nm ITO / Ag / ITO on an alkali-free glass substrate as an anode, evaporates a hole injection layer (5nm-20nm), a hole transport layer (50-120nm), a light-emitting auxiliary layer (5-120nm), a light-emitting layer (20-50nm), a hole blocking layer (5-20nm), an electron transport layer (20-80nm), and an electron injection layer (1-10nm) on the anode, and then co-evaporates Mg and Ag (weight ratio 1:9, 100-150nm) to make a semi-transparent cathode, and then evaporates a cover layer compound. Finally, the light-emitting device is encapsulated using an epoxy resin adhesive in a nitrogen atmosphere.

[0076] In a preferred specific embodiment, the structure of the OLED device provided by the present invention is as follows: first, an alkali-free glass substrate is cleaned with isopropyl alcohol using an ultrasonic cleaner for 15 minutes, and then a UV ozone cleaning treatment is performed in air for 30 minutes. The processed substrate was vacuum-deposited with ITO / Ag / ITO 100nm as the anode, and then a hole injection layer (HT:PD, 10nm, 2%), a hole transport layer (HT, 130nm), a light-emitting auxiliary layer (GP, 5nm), a green light-emitting layer (host material: doping material = compound GHN01: GHP01: compound GD1: compound 1 (weight ratio 66:30:3:1, 30nm)), a hole blocking layer (compound HBL, 5nm), an electron transport layer (compound ET: Liq=1:1, 30nm), and an electron injection layer (Yb, 1nm) were sequentially stacked and evaporated, and Mg and Ag (weight ratio 1:9, 130nm) were co-evaporated to make a semi-transparent cathode, and then compound CPL (65nm) was evaporated as a cover layer. Finally, the light-emitting device was encapsulated with an epoxy resin adhesive in a nitrogen atmosphere, which was recorded as Application Example 1. The molecular structural formula of the relevant materials is as follows (particularly preferably selected from the following structures, but it does not mean that the present invention is limited to the following structures): .

[0077] Application Examples 2 to 34 and Comparative Examples 1-4 were prepared by referring to the method provided in Application Example 1, except that the compounds listed in Table 1 were used as doping materials to replace Compound 1 in Application Example 1. The doping materials in Comparative Examples 1-4 are as follows:

[0078] Performance evaluation of OLED devices:

[0079] The current of the OLED device at different voltages was tested using a Keithley 2365A digital nanovoltmeter, and the current was then divided by the luminous area to obtain the current density of the OLED device at different voltages. The brightness and radiant energy flux density of the OLED device at different voltages were tested using a Konicaminolta CS-2000 spectroradiometer. Based on the current density and brightness of the OLED device at different voltages, the current density (10 mA / cm 2 ) working voltage Volt and current efficiency. The test data are shown in Table 1, and the data of Comparative Example 1 is used as a benchmark for comparison.

[0080] Table 1 Organic electroluminescent devices and electronic luminescence characteristics

[0081] As can be seen from Table 1, compared with Comparative Examples 1-4, Application Examples 1 to Application Examples 34 have a comparable operating voltage, higher BI luminous efficiency and longer service life. Compared with Application Examples 1-2, when only Y3 exists, the compound has better application performance in the device by replacing R1-R4 on the boron nitrogen parent nucleus. Compared with Application Examples 3-34, a symmetrical fused structure is formed on both sides above the boron nitrogen parent nucleus, and then R1-R5 and the selection of rings M1-M4 are matched, and the application performance of the obtained compound, especially in terms of luminous efficiency, can be further improved. The improvement in the performance of each application example is based on the fact that the present invention uses different multi-component fused heterocyclic structures with limiting groups such as tert-butyl and cycloalkyl groups to make the boron nitrogen compound material have better luminous efficiency, and the compatibility of the doping material of the present invention is good, which can make the light-emitting layer better realize the balance of electron and hole transmission and exciton conversion rate, reduce the power consumption of the device, and improve the service life.

[0082] This specific embodiment is merely an explanation of the present invention and is not a limitation of the present invention. After reading this specification, those skilled in the art may make non-creative modifications to the present embodiment as needed. However, as long as they are within the scope of the claims of the present invention, they are protected by the patent law.

Claims

1. A boron-nitrogen compound having a polycyclic condensed ring, characterized in that: Represented by the structure of formula I: ； In Formula I, X is selected from C or Si; Y1 and Y3 represent absence or presence; when Y1 and / or Y3 represent presence, Y1 and Y3 are each independently selected from a single bond, O, S, C(CH3)2, Si(CH3)2; Ring M1 and Ring M2 each independently represent one or more of C3-C20 cycloalkyl, C6-C30 aromatic ring, and C5-C36 heteroaromatic ring; R1-R4, R6, R7 represent unsubstituted, monosubstituted or polysubstituted; R1-R4, R 4' Each of the substituents is identically or differently selected from one or more of hydrogen, deuterium, C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C30 aryl, and any two adjacent substituents may form a saturated or unsaturated C3-C12-membered ring; R5 is selected from hydrogen or deuterium while R 5' R5 is independently selected from one or more of deuterium, substituted C6-C30 aryl, substituted or unsubstituted C5-C36 heteroaryl, and C6-C36 arylsilyl; or R5 is selected from deuterium, C1-C20 alkyl, C6-C30 aryl, and R 5' With R 4' Bonded into a ring; or R5, R 5' Also selected from deuterium; R6-R7 are each the same or different and are selected from hydrogen, deuterium, C1-C20 alkyl, C1-C20 alkylamino, C6-C36 arylamino; When R1-R7, R 4' , R 5' When there is substitution, the substitution is selected from one or more of deuterium, C1-C20 alkyl, C3-C20 cycloalkyl, and C6-C18 aryl.

2. The boron-nitrogen compound having a polycyclic condensed ring according to claim 1, characterized in that: Boron nitrogen compounds are represented by the structure of formula II: ； In formula II, X and X1 are selected from C or Si; Y3 is selected from a single bond, O, S, C(CH3)2, Si(CH3)2; Y4 is selected from a single bond, O, S; ring M1, ring M2, ring M3, and ring M4 each independently represent one or more of a C6-C30 aromatic ring and a C3-C20 cycloalkyl; when X and X1 are both selected from Si, at least one of rings M1 to M4 is a C6-C30 aromatic ring substituted by a C3-C20 cycloalkyl condensation; R1-R4 represent unsubstituted, monosubstituted or polysubstituted; R1-R4 are each the same or different and are selected from one or more of hydrogen, deuterium, C1-C20 alkyl, C1-C20 alkyl substituted or unsubstituted C3-C20 cycloalkyl, and any two adjacent substituents may form a saturated or unsaturated C3-C12 membered ring; R5 is selected from hydrogen, deuterium, C1-C20 alkyl, C6-C30 aryl; R6-R7 are each the same or different and are selected from hydrogen, deuterium, C1-C20 alkyl, C1-C20 alkylamine, C6-C36 arylamine; R8 and R9 are each the same or different and are selected from one or more of hydrogen, deuterium, C1-C20 alkyl.

3. The boron-nitrogen compound having a polycyclic condensed ring according to claim 1 or 2, characterized in that: In Formula I or Formula II, ring M1, ring M2, ring M3, and ring M4 each independently represent phenyl, naphthyl, or tetrahydronaphthyl; in Formula I or Formula II, R1-R4 each are the same or different and are selected from hydrogen, deuterium, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, adamantyl, methyl-substituted fused cyclopentyl, methyl-substituted fused cyclohexyl, or tert-butyl-substituted or unsubstituted phenyl.

4. The boron-nitrogen compound having a polycyclic condensed ring according to claim 1, characterized in that: R5 is selected from hydrogen or deuterium, and R5' is independently selected from one or more of deuterium, deuterated phenyl, tert-butylphenyl, terphenyl, triphenylsilyl, tetraphenylsilyl, biphenyl, tert-butyl-substituted biphenyl, carbazolyl, and N-phenylcarbazole.

5. The boron-nitrogen compound having a polycyclic condensed ring according to claim 1, characterized in that: The R6-R7 are each independently selected from hydrogen, deuterium, methyl, ethyl, propyl, tert-butyl, dimethylamino, and diphenylamino.

6. The boron-nitrogen compound having a polycyclic condensed ring according to claim 1, characterized in that: The structure of formula I is selected from any one of the following formulas I-1 to I-2: ； In Formula I-1 to Formula I-2, Ring M1, Ring M2, X, Y3, R1-R7, R 4' , R 5' The substitution scope is the same as that defined in claim 1.

7. The boron-nitrogen compound having a polycyclic condensed ring according to claim 1, characterized in that: Selected from any one of the following chemical structures, "tBu" represents tert-butyl, "Ph" represents phenyl, and "Ad" represents adamantyl: 。 8. Use of the boron nitrogen compound having a polycyclic condensed ring according to any one of claims 1 to 7 in the preparation of an organic electroluminescent device.

9. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises: substrate layer; a first electrode, the first electrode being on the substrate; An organic light-emitting functional layer, the organic light-emitting functional layer is on the first electrode; A second electrode, the second electrode being on the organic light-emitting functional layer; The organic light-emitting functional layer comprises a light-emitting layer; the light-emitting layer comprises a boron-nitrogen compound having a polycyclic condensed ring as described in any one of claims 1 to 7.

10. A composition, characterized in that The composition comprises the boron nitrogen compound having a polycyclic condensed ring as described in any one of claims 1 to 7.

11. A preparation, characterized in that The preparation comprises the boron nitrogen compound having a polycyclic condensed ring as claimed in any one of claims 1 to 7 or the composition as claimed in claim 10 and at least one solvent.

12. A display or lighting device, characterized in that: The device comprises the organic electroluminescent device as claimed in claim 9.

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