An organic electroluminescent material containing a double-host compound, a preparation method therefor, and use thereof

Abstract

The application relates to the technical field of organic photoelectric materials, in particular to an organic electroluminescent material containing a double-host compound, a preparation method and application thereof. The application provides an organic electroluminescent material containing a double-host compound, which comprises a first host compound with a structure shown in formula I and a second host compound with a structure shown in formula II; and groups involved in the formula are limited. By using the double-host material, triplet excitons can be dispersed on two hosts, so that triplet-triplet annihilation (TTA) is reduced, the efficiency roll-off of the organic electroluminescent device is reduced, the efficiency and the service life of the organic electroluminescent device are improved while the voltage is reduced.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic photoelectric materials, in particular to an organic electroluminescent material containing a double-host compound, a preparation method and application thereof. BACKGROUND

[0002] Organic light emission device (OLED) can be used to manufacture new display products, and can also be used to manufacture new lighting products, which is gradually replacing the existing liquid crystal display and fluorescent lamp lighting, and has a very wide market application prospect. The structure of OLED is like a sandwich, which includes electrode material film layers and organic functional materials sandwiched between different electrode film layers, which together form OLED by mutual superposition according to different purposes. As a current device, when a voltage is applied to the two electrodes of OLED, positive and negative charges in the organic layer functional material film layer are generated by the action of electric field, and the positive and negative charges are further recombined in the light-emitting layer, that is, OLED electroluminescence is generated.

[0003] At present, in the field of smart phones, tablet computers and the like, OLED display technology has been applied, and the continuous expansion to large-size application fields such as television is the next goal. However, compared with the actual product application requirements, the performance of OLED such as luminous efficiency and service life needs to be further improved.

[0004] The efficiency of OLED is improved by doping in the light-emitting layer, which is because the radiation transition of most organic molecular triplets is forbidden, and the contribution to electroluminescence is small. By doping platinum, iridium, osmium and other organic metal complexes, the triplet excitons of organic molecules can be transferred to the triplet state of the metal complex, thereby greatly improving the efficiency of the organic light-emitting device. However, triplet excitons will produce triplet-triplet annihilation (TTA) in the transfer process, thereby causing energy loss and making the organic light-emitting device produce efficiency roll-off. SUMMARY

[0005] Therefore, the technical problem to be solved by the present application is to provide an organic electroluminescent material containing a double-host compound and a preparation method and application thereof. By using a double-host compound, triplet excitons can be dispersed on two hosts, thereby reducing triplet-triplet annihilation (TTA) and reducing the efficiency roll-off of the organic electroluminescent device, so as to improve the efficiency and service life of the organic electroluminescent device while reducing the voltage.

[0006] The present application provides an organic electroluminescent material containing a double-host compound, which comprises a first host compound having a structure shown in formula I and a second host compound having a structure shown in formula II.

[0007]

[0008] wherein Ar1and Ar2are independently selected from substituted or unsubstituted C6-C60aryl, substituted or unsubstituted C3-C60heteroaryl, substituted or unsubstituted 3-60 membered non-aromatic ring system;

[0009] R1, R2, and R3are independently selected from hydrogen, deuterium, silyl, cyano, isocyano, hydroxyl, nitro, amine, -CF3, halogen, substituted or unsubstituted C1-C20alkyl, substituted or unsubstituted C1-C20linear alkoxy, substituted or unsubstituted C3-C20branched alkoxy, substituted or unsubstituted C3-C30cycloalkyl, substituted or unsubstituted C3-C20cycloalkoxy, substituted or unsubstituted C1-C20keto, substituted or unsubstituted C2-C20alkenyl, substituted or unsubstituted 6-60 membered ring aryl, substituted or unsubstituted 3-30 membered ring heteroaryl.

[0010] In some embodiments of the present application, Ar1and Ar2are independently selected from substituted or unsubstituted 6-30 membered ring aryl, substituted or unsubstituted 3-60 membered ring heteroaryl.

[0011] In some embodiments of the present application, Ar1and Ar2are independently selected from substituted or unsubstituted 6-14 membered ring aryl, substituted or unsubstituted 6-14 membered ring heteroaryl.

[0012] In some embodiments of the present application, R1, R2, and R3are independently selected from hydrogen, deuterium, cyano, isocyano, nitro, -Cl, -Br, -F, -I, substituted or unsubstituted C1-C10alkyl, substituted or unsubstituted C3-C10cycloalkyl, substituted or unsubstituted 6-30 membered ring aryl, substituted or unsubstituted 5-20 membered ring heteroaryl.

[0013] In some embodiments of the present application, substituted or unsubstituted C1-C10alkyl is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, or t-amyl; substituted or unsubstituted C3-C10cycloalkyl is selected from cyclopropyl, cyclopentyl, cyclohexyl, or adamantyl; substituted or unsubstituted 6-30 membered ring aryl is selected from substituted or unsubstituted 6-12 membered ring aryl, specifically phenyl; substituted or unsubstituted 5-20 membered ring heteroaryl is selected from substituted or unsubstituted 6-10 membered ring heteroaryl.

[0014] In the present application, the "substituted or unsubstituted" means that the group can be not substituted, or substituted with one or more substituents selected from deuterium, a cyano group, an isocyano group, a nitro group, a halogen, an alkyl group having C1-C20, a heterocyclic group having 3-20-membered ring, an aryl group having 6-20-membered ring, a heteroaryl group having 3-20-membered ring, or a combination of these groups; further, the substituent is selected from deuterium, a cyano group, an isocyano group, a nitro group, -Cl, -Br, -F, -I, an alkyl group having C1-C10, a heterocyclic group having 3-10-membered ring, an aryl group having 6-10-membered ring, a heteroaryl group having 3-10-membered ring, or a combination of these groups.

[0015] It is to be noted that the "substituted" described above means that the hydrogen atom bonded to the carbon atom of the compound is changed into another substituent, and the position of substitution is not limited as long as it is the position where the hydrogen atom is substituted, i.e., the position where the substituent can be substituted, and when two or more substituents are substituted, the two or more substituents can be the same as or different from each other.

[0016] The heteroaryl group is a monocyclic aromatic group containing at least one heteroatom and / or a polycyclic aromatic ring group containing at least one heteroatom, and the heteroatom includes, but is not limited to, O, S, N, P, B, Si, and Se.

[0017] In some embodiments of the present application, the Ar1 is selected from at least one of a phenyl group, a naphthyl group, an anthryl group, a pyridyl group, a biphenyl group, and a 1,3-dimethyl-substituted phenyl group.

[0018] In some embodiments of the present application, the Ar2 is selected from at least one of a phenyl group, a naphthyl group, an anthryl group, a pyridyl group, a biphenyl group, and a 1,3-dimethyl-substituted phenyl group.

[0019] In some embodiments of the present application, the R1, R2, and R3 are independently selected from at least one of hydrogen, a phenyl group, a methyl group, an ethyl group, a propyl group, a tert-butyl group, a 1,1-dimethylpropyl group, and a cyano group.

[0020] In some embodiments of the present application, the first host compound having the structure represented by Formula I has a structure represented by Formula (Z001) to Formula (Z136):

[0021]

[0022]

[0023]

[0024]

[0025]

[0026]

[0027]

[0028]

[0029]

[0030]

[0031] In some embodiments of the present application, the second host compound having the structure shown in Formula II has the structure shown in Formula (T001) to Formula (T160):

[0032]

[0033]

[0034]

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

[0041]

[0042] In some embodiments of the present application, the mass ratio of the first host compound having the structure shown in Formula I and the second host compound having the structure shown in Formula II is 1-50: 1-50; preferably 1-10: 1-10, more preferably 6:4.

[0043] In some embodiments of the present application, the preparation method of the first host compound having the structure shown in Formula I comprises the following steps:

[0044] The compound having the structure shown in Formula III-1, the compound having the structure shown in Formula IV-1, sodium tert-butoxide, toluene, Pd2(dba)3 and P(t-Bu)3 are mixed under the condition of protective gas, and then refluxed at 80-90°C to obtain the first host compound having the structure shown in Formula I;

[0045]

[0046] wherein Ar1 is selected from substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, substituted or unsubstituted 3-60 membered non-aromatic ring system;

[0047] R1 and R2 are independently selected from hydrogen, deuterium, silyl, cyano, isocyano, hydroxyl, nitro, amine, -CF3, halogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 linear alkoxy, substituted or unsubstituted C3-C20 branched alkoxy, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C20 cycloalkoxy, substituted or unsubstituted C1-C20 ketone, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted 6-60 membered aryl, substituted or unsubstituted 3-30 membered heteroaryl;

[0048] X is selected from halogen, such as fluorine, chlorine, bromine or iodine, preferably chlorine.

[0049] In the preparation method provided by the present application, the groups of Ar1, R1 and R2 can be selected as above, which will not be repeated here.

[0050] The protective gas is nitrogen.

[0051] The reflux reaction time is 18-24 h.

[0052] After the reaction, the method further comprises the following steps: cooling to 25-28℃, mixing with pure water, stirring and then standing to separate layers, separating the layers, column chromatography, to obtain the first host compound having the structure shown in Formula I. Pure water is added for desalination.

[0053] In some embodiments of the present application, the preparation method of the second host compound having the structure shown in Formula II comprises the following steps:

[0054] The compound having the structure shown in Formula III-2, the compound having the structure shown in Formula IV-2, sodium tert-butoxide, toluene, Pd2(dba)3 and P(t-Bu)3 are mixed under the condition of protective gas, and then reflux reaction is carried out at 80-90℃ to obtain the second host compound having the structure shown in Formula II.

[0055]

[0056] wherein Ar2 is selected from substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, substituted or unsubstituted 3-60 membered non-aromatic ring system;

[0057] R3 is selected from hydrogen, deuterium, silyl, cyano, isocyano, hydroxyl, nitro, amine, -CF3, halogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 linear alkoxy, substituted or unsubstituted C3-C20 branched alkoxy, substituted or unsubstituted C3-C30 cyclic alkyl, substituted or unsubstituted C3-C20 cyclic alkoxy, substituted or unsubstituted C1-C20 ketone, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted 6-60-membered cyclic aryl, substituted or unsubstituted 3-30-membered cyclic heteroaryl.

[0058] X is selected from halogen, such as fluorine, chlorine, bromine or iodine, preferably chlorine.

[0059] In the preparation method provided by the present application, the optional groups of Ar2 and R3 are the same as above, and will not be repeated here.

[0060] The protective gas is nitrogen.

[0061] The reflux reaction time is 18-24 h.

[0062] After the reaction, the method further comprises cooling to 25-28℃, mixing with pure water, stirring, standing and separating, column chromatography, to obtain the second host compound with the structure shown in formula II. Pure water is added for desalination.

[0063] The present application also provides a preparation method of the organic electroluminescent material containing the double-host compound.

[0064] The first host compound with the structure shown in formula I and the second host compound with the structure shown in formula II are mixed to obtain the organic electroluminescent material containing the double-host compound.

[0065] The preparation methods of the first host compound with the structure shown in formula I and the second host compound with the structure shown in formula II are the same as above, and will not be repeated here.

[0066] The organic electroluminescent material containing the double-host compound provided by the present application can be used as the light-emitting layer material of the organic electroluminescent device. Thus, the application of the organic electroluminescent compound as the light-emitting layer material of the organic electroluminescent device is claimed.

[0067] The present application also provides an organic electroluminescent device and products thereof, comprising the organic electroluminescent material containing the double-host compound described above or the organic electroluminescent material containing the double-host compound prepared by the preparation method described above. The organic electroluminescent device product can be an organic solar cell, electronic paper, organic photoreceptor or organic thin film transistor.

[0068] In certain embodiments of the present application, the organic electroluminescent device comprises a first electrode, a second electrode, and one or more organic compound layers disposed between the two electrodes, at least one of the organic compound layers comprising the organic electroluminescent material comprising the bis-host compound described above.

[0069] In certain embodiments of the present application, at least one or more layers selected from a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting auxiliary layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a capping layer are disposed between the first electrode and the second electrode. In certain embodiments, a hole injection layer, a hole transport layer, a light-emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer are sequentially disposed between the first electrode and the second electrode.

[0070] In certain embodiments of the present application, the first electrode is an anode.

[0071] As an anode material, a material having a large work function is generally preferred in order to enable smooth injection of holes into the organic layer. Specific examples of the anode material that can be used in the present application include: metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), or indium zinc oxide (IZO); combinations of metals and oxides such as ZnO / Al or SnO2 / Sb; conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylenedioxy)thiophene] (PEDOT), polypyrrole, or polyaniline; but are not limited thereto. In certain embodiments of the present application, the anode is an ITO anode.

[0072] The hole injection layer material is a material that receives holes from the anode at low voltage, and the highest occupied molecular orbital (HOMO) of the hole injection layer material is preferably between the work function of the anode material and the HOMO of the surrounding organic material layer. In certain embodiments of the present application, the hole injection material includes metalloporphyrin, oligothiophene, arylamine-based organic material, hexacyno-hexaazatriphenylene-based organic material, quinacridone-based organic material, perylene-based organic material, anthraquinone, and polyaniline- and polythiophene-based conductive polymers, etc. In certain embodiments of the present application, the hole injection layer material is 4,4',4"-tris(N-3-methylphenyl-N-phenylamino)triphenylamine (m-MTDATA).

[0073] The hole transport layer material is a material capable of receiving holes from the anode or hole injection layer and transporting the holes to the light emitting layer, and having a high hole mobility. In certain embodiments of the present application, the hole transport layer material includes an arylamine-based organic material, a conductive polymer, a block copolymer having both a conjugated portion and a non-conjugated portion, etc., but is not limited thereto. In certain embodiments of the present application, the hole transport layer material is NPB (i.e., N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine).

[0074] In the present application, the light emitting layer includes a dopant material and the organic electroluminescent material including the dual-host compound described above;

[0075] The mass ratio of the organic electroluminescent material including the dual-host compound and the dopant material is 90 to 99.5: 0.5 to 10; preferably 50: 0.5 to 10; more preferably 50: 5.

[0076] In certain embodiments of the present application, the molecular structure of the dopant material is as shown in C1.

[0077]

[0078] The present application can form the light emitting layer using the organic electroluminescent material including the dual-host compound by a solution coating method and a vacuum deposition method; here, the solution coating method means spin coating, dip coating, inkjet printing, screen printing, spraying, etc., but is not limited thereto.

[0079] The hole blocking layer is disposed between the light emitting layer and the electron transport layer, and a material known in the art can be used, such as a triazine-based compound. In certain embodiments of the present application, the hole blocking layer material is bis(2-methyl-8-quinolinolato-N1,O8)-(1,1'-biphenyl-4-ylolato)aluminum.

[0080] The electron transport layer functions to facilitate electron transport, and the electron transport layer material is a material for receiving electrons from the cathode and transporting the electrons to the light emitting layer, having a high electron mobility. This includes an 8-hydroxyquinoline Al complex; a complex containing Alq3; an organic radical compound; a hydroxyflavone-metal complex, etc., but is not limited thereto. The thickness of the electron transport layer is set to 1 nm to 50 nm, which can prevent a decrease in electron transport characteristics, and prevent an increase in driving voltage due to the electron transport layer being too thick. In certain embodiments of the present application, the electron transport layer material is aluminum 8-hydroxyquinolate.

[0081] The electron injection layer can promote electron injection, and the electron injection material preferably has the ability to transport electrons, exhibiting an electron injection effect from the cathode, and demonstrating excellent electron injection effect on the light-emitting layer or light-emitting material. It prevents excitons generated in the light-emitting layer from migrating to the hole injection layer, and also possesses excellent thin film forming ability. Specific examples include fluorenone, anthraquinone dimethane, biphenylquinone, thiamethane dioxide, azoles, diazoles, triazoles, imidazoles, perylenetetracarboxylic acid, fluorenemethane, anthrone, and their derivatives, metal complexes, nitrogen-containing five-membered ring derivatives, etc., but are not limited thereto. In some embodiments of the present invention, the electron injection layer material is LiF.

[0082] In some embodiments of the present invention, the second electrode is a cathode.

[0083] As a cathode material, a material with a low work function is generally preferred to facilitate the injection of electrons into the organic layer. Specific examples of cathode materials include: metals, such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, and other metals or alloys thereof; multilayer materials, such as LiF / Al or LiO2 / Al; but are not limited thereto. In some embodiments of the present invention, the cathode material is aluminum.

[0084] Depending on the materials used, the organic electroluminescent device can be a top-emitting, bottom-emitting, or bilaterally emitting type.

[0085] The present invention does not impose any special restrictions on the source of the raw materials used above, and they can be commercially available.

[0086] Experimental results show that organic electroluminescent devices made from the organic electroluminescent materials containing dual host compounds of the present invention have lower driving voltage, higher luminous efficiency, and longer lifetime. Detailed Implementation

[0087] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0088] Example 1

[0089] Preparation of compound L004 having the structure shown in Formula III-1:

[0090] 1) Under nitrogen protection system, take (1.0 eq) 7-methoxy-2-naphthalenedione (CAS: 4133-34-0), add (1.5 eq) phenylhydrazine, reduce the temperature of the system to 0-10°C, slowly add HCl (mass concentration is 37%) under constant temperature, continue to react at 0-10°C for 1.5 h, gradually change to yellow and precipitate in the system, filter and dry, then add DDQ (2,3-dichloro-5,6-dicyanoquinone) and toluene into the bottle, continue to react at 110°C for 3 h, confirm the complete reaction of the raw material by TLC, reduce the temperature of the system to 25°C, add potassium carbonate aqueous solution, stir for 30 min, then stand and separate the layers, separate the liquid, column chromatography, and recrystallize from toluene to finally obtain compound L004-1 (CAS 23681-97-2).

[0091] 2) Under nitrogen protection system, take (1.0 eq) L004-1, add (3 eq) copper chloride, add acetonitrile, reduce the temperature of the system to -40°C, slowly add benzylamine under constant temperature, the color of the system changes to brown, continue to react at -40°C for 4 h, gradually change to black, increase to room temperature, add water, control the internal temperature at 10-15°C, filter, column chromatography, and recrystallize from tetrahydrofuran to finally obtain the compound L004 (MW: 334.68).

[0092] L004 nuclear magnetic resonance hydrogen spectrum data: 1 H-NMR (500 MHz, Chloroform-d) δ 8.90-8.83 (m, 1H), 8.16-8.06 (m, 2H), 8.03-7.96 (m, 1H), 7.88-7.76 (m, 2H), 7.53-7.41 (m, 6H), 7.41-7.34 (m, 1H), 7.26 (td, 1H).

[0093] The specific synthesis route is as follows:

[0094]

[0095] Preparation of compound L003 with the structure shown in formula III-2:

[0096] 1) Under nitrogen protection system, take 1.0 eq 5-chloroquinoline (CAS: 635-27-8), 1.5 eq pinacol boryl, and 2.0 eq potassium acetate into the reaction system, add 1,4-dioxane, 0.02 eq catalyst Pd2(dba)3 under nitrogen protection, and reflux at 110°C under nitrogen protection for 16-18 h, then cool to 25°C, add pure water, stir for 30 min, then stand and separate the layers, separate the liquid, column chromatography, and obtain compound L003-1.

[0097] 2) Under the protection of nitrogen system, take (1.0 eq) L003-1, 1.3 eq of reactant 2-chloro-1-naphthylamine (CAS: 13711-39-2), 2.0 eq of sodium tert-butoxide into the reaction system, add toluene, under the protection of nitrogen, 0.02 eq of catalyst Pd2(dba)3 and 0.04 eq of 50% P(t-Bu)3, under the protection of nitrogen, reflux at 80-90°C for 16-18h, then cool to 25°C, add pure water, stir for 30 min, then stand to separate layers, separate, column chromatography to obtain the indicated compound L003-2;

[0098] 3) Under the protection of nitrogen system, take (1.0 eq) L003-2, add (0.4 eq) sodium nitrite, reduce the temperature of the system to 0-10°C, slowly add HCl (mass concentration is 37%) dropwise, continue to react at 0°C for 1.5h, gradually change to yellow and precipitate in the system, filter, dry, and then put into a bottle with 1,2-dichlorobenzene, heat the system to 180°C and continue to react for 3h, confirm the complete reaction of the raw material by TLC, cool the system to 25°C, add potassium carbonate aqueous solution, stir for 30 min, then stand to separate layers, separate, column chromatography, toluene recrystallization, finally obtain the indicated compound L003 (MW: 268.62).

[0099] L003 nuclear magnetic resonance hydrogen spectrum data: 1 H-NMR (500 MHz, Chloroform-d) δ 8.88 (dd, 1H), 8.24-8.17 (m, 1H), 7.99-7.91 (m, 3H), 7.83 (dd, 2H), 7.77 (d, 1H), 7.69 (dt, 1H), 7.52 (td, 1H), 7.47-7.34 (m, 2H).

[0100] The specific synthesis route is as follows:

[0101]

[0102] Example 1

[0103] Preparation of compound Z001:

[0104]

[0105] Under the protection of nitrogen system, take L004 (59.81 mmol), reactant M001 (cas: 108-90-7) (59.81 mmol), C4H9NaO (119.63 mol) into the reaction system, add 200 mL of toluene, under the protection of nitrogen, catalyst C 51 H 42 O3Pd2 (1.79 mmol) and C12 H 27 P(2.39mmol), under nitrogen protection, 90°C reflux for 24h, then cooled to 25°C, added 250mL pure water, stirred for 30min, then separated the layers, column chromatography, to obtain the compound shown in formula Z001 (MW: 410.65, 18g, yield 73.31%), HPLC purity greater than 99%.

[0106] Nuclear magnetic resonance hydrogen spectrum data: 1 H-NMR (500MHz, Chloroform-d) δ 8.90 (dd, 1H), 8.14 (dd, 1H), 8.12-8.03 (m, 2H), 8.00-7.89 (m, 4H), 7.72 (d, 1H), 7.67 (dd, 1H), 7.60 (t, 2H), 7.55 (td, 1H), 7.48-7.40 (m, 3H), 7.37 (td, 1H), 7.29 (tt, 1H).

[0107] Example 2

[0108] Preparation of compound Z013:

[0109]

[0110] Under the nitrogen protection system, L004 (59.81mmol) was weighed, and the reactant M002 (cas: 90-13-1) (59.81mmol) and C4H9NaO (119.63mol) were placed into the reaction system, 200mL of toluene was added, and the catalyst C 51 H 42 O3Pd2 (1.79mmol) and C 12 H 27 P (2.39mmol), under nitrogen protection, 90°C reflux for 24h, then cooled to 25°C, added 250mL pure water, stirred for 30min, then separated the layers, column chromatography, to obtain the compound shown in formula Z013 (MW: 460.69, 17.1g, yield 62%), HPLC purity greater than 99%.

[0111] Nuclear magnetic resonance hydrogen spectrum data: 1 H-NMR (500MHz, Chloroform-d) δ 8.93 (dd, 1H), 8.28 (dd, 1H), 8.08 (ddt, 4H), 8.04-7.96 (m, 2H), 7.91 (dd, 1H), 7.85 (t, 1H), 7.78 (d, 1H), 7.72 (d, 1H), 7.63 (dd, 1H), 7.57 (qd, 2H), 7.50-7.29 (m, 5H).

[0112] Example 3

[0113] Preparation of compound Z015:

[0114]

[0115] Under the nitrogen protection system, L004 (59.81 mmol), reactant M003 (cas: 716-53-0) (59.81 mmol), C4H9NaO (119.63 mol) were weighed into the reaction system, 200 mL of toluene was added, and the catalyst C 51 H 42 O3Pd2 (1.79 mmol) and C 12 H 27 P (2.39 mmol) were added under the protection of nitrogen, and refluxed at 90°C for 24h, and then cooled to 25°C. 250 mL of pure water was added, stirred for 30 min, and then separated into layers. After column chromatography, the compound Z015 (MW: 510.86, 18.32 g, yield 60%) was obtained, and the HPLC purity was greater than 99%.

[0116] Nuclear magnetic resonance hydrogen spectrum data: 1 H-NMR (500 MHz, Chloroform-d) δ 8.96 (dd, 1H), 8.64 (d, J = 1.5 Hz, 1H), 8.42 (dd, 2H), 8.17 (dt, 2H), 8.12-8.05 (m, 2H), 7.93 (ddd, 2H), 7.75 (dd, 2H), 7.67-7.49 (m, 6H), 7.47-7.37 (m, 3H), 7.34 (td, 1H).

[0117] Example 4

[0118] Preparation of compound Z017:

[0119]

[0120] Under the nitrogen protection system, L004 (59.81 mmol), reactant M004 (cas: 19264-71-2) (59.81 mmol), C4H9NaO (119.63 mol) were weighed into the reaction system, 200 mL of toluene was added, and the catalyst C 51 H 42 O3Pd2 (1.79 mmol) and C 12 H 27P (2.39 mmol), 90 °C under nitrogen protection for 24 h, then cooled to 25 °C, added 250 mL of pure water, stirred for 30 min, then separated the layers, column chromatography, to obtain the compound shown in formula Z017 (MW: 575.87, 15 g, yield 43.5%), HPLC purity greater than 99%.

[0121] Nuclear magnetic resonance hydrogen spectrum data: 1 H-NMR (500 MHz, Chloroform-d) δ 8.93 (dd, 1H), 8.41 (dd, 1H), 8.35 (dd, 1H), 8.22-8.15 (m, 2H), 8.15-8.06 (m, 3H), 8.06-8.00 (m, 5H), 7.93 (dd, 1H), 7.84 (dd, 1H), 7.76-7.67 (m, 2H), 7.57 (td, 1H), 7.47-7.39 (m, 5H), 7.39-7.31 (m, 3H).

[0122] Example 5

[0123] Preparation of compound T001:

[0124]

[0125] Under the protection of nitrogen, L003 (74.54 mmol) was weighed, and the reaction N001 (cas: 108-90-7) (74.54 mmol) and C4H9NaO (149 mol) were put into the reaction system, 200 mL of toluene was added, and the catalyst C 51 H 42 O3Pd2 (2.24 mmol) and C 12 H 27 P (2.98 mmol), 90 °C under nitrogen protection for 24 h, then cooled to 25 °C, added 250 mL of pure water, stirred for 30 min, then separated the layers, column chromatography, to obtain the compound shown in formula T001 (MW: 344.55, 17.3 g, yield 67.39%), HPLC purity greater than 99%.

[0126] Nuclear magnetic resonance hydrogen spectrum data: 1 H-NMR (500 MHz, Chloroform-d) δ 8.90 (dd, 1H), 8.80 (dd, 1H), 8.46 (d, 1H), 8.38 (dd, 1H), 8.28 (d, 1H), 8.22 (d, 1H), 8.09 (dt, 1H), 7.94–7.87 (m, 2H), 7.75–7.52 (m, 6H), 7.29 (tt, 1H).

[0127] Example 6

[0128] Preparation of compound T002:

[0129]

[0130] Under the protection of nitrogen system, L003 (74.54 mmol), reactant N002 (4-methyl chlorobenzene) (74.54 mmol), C4H9NaO (149 mol) were weighed into the reaction system, 200 mL of toluene was added, and the catalyst C 51 H 42 O3Pd2(2.24 mmol) and C 12 H 27 P (2.98 mmol) were added under the protection of nitrogen, and the reaction was refluxed at 90°C for 24 h, then cooled to 25°C, 250 mL of pure water was added, stirred for 30 min, and then separated by layering. After standing, the liquid was separated by column chromatography to obtain the compound T002 (MW: 358.74, 17.11 g, yield 64%), and the HPLC purity was greater than 99%.

[0131] Nuclear magnetic resonance hydrogen spectrum data: 1 H-NMR (500 MHz, Chloroform-d) δ 8.90 (dd, 1H), 8.80 (dd, 1H), 8.46 (d, 1H), 8.38 (dd, 1H), 8.28 (d, 1H), 8.22 (d, 1H), 8.09 (dt, 1H), 7.84-7.75 (m, 2H), 7.71-7.62 (m, 3H), 7.59 (dd, 1H), 7.43-7.32 (m, 2H), 2.41 (d, 3H).

[0132] Example 7

[0133] Preparation of compound T005:

[0134]

[0135] Under the protection of nitrogen system, L003 (74.54 mmol), reactant N003 (cas: 3972-56-3) (74.54 mmol), C4H9NaO (149 mol) were weighed into the reaction system, 200 mL of toluene was added, and the catalyst C 51 H 42 O3Pd2(2.24 mmol) and C 12 H 27P(2.98 mmol), 90 °C under nitrogen protection for 24 h, then cooled to 25 °C, added 250 mL of pure water, stirred for 30 min, then separated, column chromatography, to obtain the compound shown as T005 (MW: 400.73, 16.73 g, yield 56%), HPLC purity greater than 99%.

[0136] Nuclear magnetic resonance hydrogen spectrum data: 1 H-NMR (500 MHz, Chloroform-d) δ 8.90 (dd, 1H), 8.80 (dd, 1H), 8.46 (d, 1H), 8.37 (dd, 1H), 8.28 (d, 1H), 8.22 (d, 1H), 8.09 (dt, 1H), 7.85-7.75 (m, 2H), 7.72-7.56 (m, 4H), 7.53-7.45 (m, 2H), 1.28 (s, 9H).

[0137] Example 8

[0138] Preparation of compound T009:

[0139]

[0140] Under the protection of nitrogen, L003 (74.54 mmol) was weighed, and the reaction N004 (cas: 2051-62-9) (74.54 mmol) and C4H9NaO (149 mol) were put into the reaction system, 200 mL of toluene was added, and the catalyst C 51 H 42 O3Pd2 (2.24 mmol) and C 12 H 27 P (2.98 mmol), 90 °C under nitrogen protection for 24 h, then cooled to 25 °C, added 250 mL of pure water, stirred for 30 min, then separated, column chromatography, to obtain the compound shown as T009 (MW: 420.73, 18.5 g, yield 59%), HPLC purity greater than 99%.

[0141] Nuclear magnetic resonance hydrogen spectrum data: 1 H-NMR (500 MHz, Chloroform-d) δ 8.90 (dd, 1H), 8.80 (dd, 1H), 8.46 (d, 1H), 8.37 (dd, 1H), 8.28 (d, 1H), 8.22 (d, 1H), 8.09 (dt, 1H), 7.85-7.75 (m, 2H), 7.72-7.56 (m, 4H), 7.53-7.45 (m, 2H), 1.28 (s, 9H).

[0142] Examples 9-25

[0143] The synthesis of compounds Z019, Z020, Z025, Z030, Z049, Z050, Z051, Z059, T023, T027, T043, T044, T057, T062, T069, T072, T118 was accomplished according to the preparation methods of Examples 1-8. The mass spectra and molecular formulas of the compounds prepared in Examples 9-25 are listed in Table 1 below.

[0144] Table 1 Mass spectra and elemental analysis of compounds prepared in Examples 9-25

[0145]

[0146]

[0147] In addition, it should be noted that other compounds of the present application can be obtained according to the synthesis methods of the above-listed examples, and therefore, are not listed one by one herein.

[0148] Application Example 1

[0149] Preparation of an organic electroluminescent device:

[0150] An organic electroluminescent device was prepared using compound Z001 and compound T001. Specifically, the preparation method of the organic electroluminescent device was as follows:

[0151] ITO anode: An ITO (indium tin oxide) glass substrate with a coating thickness of 1500 A was cleaned twice in distilled water, ultrasonically washed for 30 min, and then cleaned repeatedly twice in distilled water, ultrasonically washed for 10 min. After washing, the substrate was dried and then transferred to a plasma cleaning machine for washing for 5 min to obtain an ITO anode. HIL (hole injection layer): 4,4',4"-tris(N-3-methylphenyl-N-phenylamino)triphenylamine (m-MTDATA) was vacuum evaporated on the ITO anode in an evaporator to form a hole injection layer.

[0152] The hole injection layer was formed. HTL (hole transport layer): NPB (i.e., N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine) was vacuum evaporated on the hole injection layer to form a hole transport layer.

[0153] The hole transport layer was formed.

[0154] ​Light-emitting layer: The light-emitting layer of the device was vacuum evaporated on the hole-transporting layer, and the light-emitting layer included the organic electroluminescent material containing the dual-host compound (the first host compound Z001 and the second host compound T001, mass ratio 6:4) and the dopant material Cl, and the linear gradient co-evaporation was performed by the method of multi-source co-evaporation The light-emitting layer was formed; wherein the mass ratio of the organic electroluminescent material containing the dual-host compound and the dopant material Cl was 50:5.

[0155] HBL (hole-blocking layer): The bis(2-methyl-8-hydroxyquinoline-N1, O8)-(1, 1'-biphenyl-4-hydroxy) aluminum (BAlq) was vacuum evaporated on the light-emitting layer The hole-blocking layer was formed.

[0156] ETL (electron-transporting layer): The aluminum 8-hydroxyquinoline (Alq3) was vacuum evaporated on the hole-blocking layer The electron-transporting layer was formed.

[0157] EIL (electron-injecting layer): The The electron-injecting layer was formed.

[0158] Cathode: The Al of was evaporated on the electron-injecting layer to form the cathode, and thus the organic electroluminescent device was obtained.

[0159] Referring to the organic electroluminescent device and the preparation method thereof provided in Application Example 1, the host material of Application Example 1 was replaced to perform evaporation, and the mass ratio of the first host material and the second host material was between 1-50:1-50, preferably between 1-10:1-10, and more preferably 6:4; and the organic electroluminescent device of the corresponding compound was prepared.

[0160] Referring to the organic electroluminescent device and the preparation method thereof provided in Application Example 1, the mass ratio of the total mass of the first host material and the second host material to the mass of the dopant material was 50:0.5-10, specifically 10:1.

[0161] The device manufacturing processes of Application Examples 2-12, Comparative Examples 1-4, and Parallel Example 1 were completely the same as those of Application Example 1, and the same substrate material and electrode material were used, and the film thickness of the electrode material was also kept consistent, and the difference was that the two host materials were not the same, and the specific parameters are shown in Table 2.

[0162] The structure of the comparative example is shown as follows:

[0163]

[0164] Table 2: Parameters used in Application Examples 1-12, Comparative Examples 1-4, and Parallel Example 1

[0165]

[0166]

[0167] Performance test:

[0168] The driving voltage, luminous efficiency, lifetime and efficiency decay coefficient of the organic electroluminescent devices obtained from Comparative Examples 1-4, Application Examples 1-12 and Parallel Example 1 were characterized at a brightness of 3000 (nits), and the test results are shown in Table 3.

[0169] Table 3 Test results of the luminescent properties of the organic electroluminescent devices obtained from Comparative Examples 1-4, Application Examples 1-12 and Parallel Example 1

[0170]

[0171]

[0172] As can be seen from Table 3, compared with Comparative Examples 1-4, the organic electroluminescent devices provided by the Application Examples 1-12 and Parallel Example 1 of the present application have a driving voltage of 3.3-3.7 V, the efficiency decay is significantly smaller than that of Comparative Examples 1-4, the luminous efficiency is higher than that of Comparative Examples 1-4, and the lifetime is significantly improved compared with Comparative Examples 1-4.

[0173] Therefore, compared with the organic electroluminescent devices prepared by using Comparative Compound H2-1 and H2-2 as the double host material of the light-emitting layer, the organic electroluminescent devices prepared by using the organic electroluminescent compound provided by the present application as the light-emitting layer material have a significantly reduced driving voltage, and the luminous efficiency and lifetime are significantly improved.

[0174] The above description of disclosed embodiments enables one of ordinary skill in the art to make or use the application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein can be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. An organic electroluminescent material containing two host compounds, comprising a first host compound having the structure shown in Formula I and a second host compound having the structure shown in Formula II; in, Ar1 and Ar2 are independently selected from aryl groups of 6–14-membered rings, heteroaryl groups of 6–14-membered rings, and phenyl groups substituted with 1,3-dimethyl groups; R1, R2, and R3 are independently selected from hydrogen, deuterium, cyano, isocyano, nitro, -Cl, -Br, -F, -I, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, tert-amyl, 1,1-dimethylpropyl, aryl of 6- to 12-membered rings, and heteroaryl of 6- to 10-membered rings.

2. The organic electroluminescent material containing two host compounds according to claim 1, characterized in that, Ar1 is selected from at least one of phenyl, naphthyl, anthracene, pyridyl, biphenyl, and 1,3-dimethyl-substituted phenyl; Ar2 is selected from at least one of phenyl, naphthyl, anthracene, pyridyl, biphenyl and 1,3-dimethyl-substituted phenyl; R1, R2, and R3 are independently selected from at least one of hydrogen, phenyl, methyl, ethyl, propyl, tert-butyl, 1,1-dimethylpropyl, and cyano.

3. The organic electroluminescent material containing two host compounds according to claim 1, characterized in that, The mass ratio of the first host compound having the structure shown in Formula I to the second host compound having the structure shown in Formula II is 1–50:1–50.

4. An organic electroluminescent material containing two host compounds, comprising a first host compound having the structure shown in Formula I and a second host compound having the structure shown in Formula II; The first host compound having the structure shown in Formula I has structures shown in Formulas (Z001) to (Z136): The second host compound having the structure shown in Formula II has the following structure:

5. The application of the organic electroluminescent material containing dual host compounds as described in any one of claims 1 to 4 as the light-emitting layer material of an organic electroluminescent device.

6. An organic electroluminescent device and its product, comprising the organic electroluminescent material containing a dual host compound as described in any one of claims 1 to 4.

Images