Patent Application
20250031570
The present application relates to the technical field of display, in particular to an organic electroluminescent material composition and an application thereof.
An organic light emitting device (OLED) converts electrical energy into light by applying electricity to an organic electroluminescent material, and typically includes an anode, a cathode, and an organic layer formed between these two electrodes. The organic layer of the organic EL device may contain a hole injection layer, a hole transport layer, a hole auxiliary layer, a light emitting auxiliary layer, an electron blocking layer, a light emitting layer (containing a host material and a dopant material), an electron buffer layer, a hole blocking layer, an electron transport layer, an electron injection layer, etc. The materials used in the organic layer can be divided into hole injection materials, hole transport materials, hole auxiliary materials, light emitting auxiliary materials, electron blocking materials, light emitting materials, electron buffer materials, hole blocking materials, electron transport materials, electron injection materials, etc. depending on their functions. In the organic EL device, holes from the anode and electrons from the cathode are injected into the light emitting layer by applying voltages, and high-energy excitons are produced by the recombination of the holes and the electrons. Organic light emitting compounds move to an excited state through energy and the organic light emitting compounds emit light through energy when the organic light emitting compounds return to a ground state from the excited state.
At present, due to the low stability and unbalanced carrier mobility of organic functional materials, etc., resulting in problems such as high driving voltage, and short lifespan of organic light-emitting diodes, thereby severely limiting the application of organic light-emitting diodes.
The purpose of the present application is to overcome the defects of high driving voltage and short lifespan of organic light-emitting diodes caused by low stability and unbalanced carrier mobility of organic electroluminescent materials, and then provide an organic electroluminescent material composition and an application thereof.
In the present application, the definitions of substituent terms are as follows.
As used in the present application, the term “halogen” may include fluorine, chlorine, bromine or iodine.
As used in the present application, the term “C1-C30 alkyl” refers to a univalent substituent derived from linear or branched saturated hydrocarbon with 1 to 30 carbon atoms, and its examples include but are not limited to methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl and hexyl.
As used in the present application, the term “C3-C30 cycloalkyl” refers to monocyclic hydrocarbon or polycyclic hydrocarbon with 1 to 30 cycle main chain carbon atoms, and the C3-C30 cycloalkyl may include cyclopropyl, cyclobutyl, adamantyl, etc.
The aryl and arylenyl in the present application include monocyclic, polycyclic or fused-ring aryls, and rings may be separated by short non-aromatic units and may contain spiro structures, the aryl includes but not limited to phenyl, biphenyl, triphenyl, naphthyl, phenanthryl, anthryl, fluorenyl, spirodifluorenyl, etc. The arylenyl includes but not limited to phenylenyl, biphenylidenyl, tribiphenylidenyl, naphthenyl, phenanthrylenyl, anthrylenyl, fluorenylidenyl, spirodifluorenylidenyl, etc.
The heteroaryl and heteroarylenyl in the present application include monocyclic, polycyclic or fused-ring heteroaryls, rings may be separated by short non-aromatic units, and heteroatoms include nitrogen, oxygen and sulfur. The heteroaryl include but are not limited to furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuryl, benzothienyl, isobenzofuryl, dibenzofuryl, dibenzothienyl, benzimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenothiazinyl, phenanthridinyl, benzodioxolyl, dihydroacridinyl, and derivatives thereof, etc. The heteroarylenyl includes but are not limited to furylenyl, thienylenyl, pyrrolylenyl, imidazolylenyl, pyrazolylenyl, thiazolylenyl, thiadiazolylenyl, isothiazolylenyl, isoxazolylenyl, oxazolylenyl, oxadiazolylenyl, triazinylenyl, tetrazinylenyl, triazolylenyl, tetrazolylenyl, furazanylenyl, pyridylenyl, pyrazinylenyl, pyrimidinylenyl, pyridazinylenyl, benzofurylenyl, benzothienylenyl, isobenzofurylenyl, dibenzofurylenyl, dibenzothienylenyl, benzimidazolylenyl, benzothiazolylenyl, benzoisothiazolylenyl, benzoisoxazolylenyl, benzoxazolylenyl, isoindolylenyl, indolylenyl, indazolylenyl, benzothiadiazolylenyl, quinolylenyl, isoquinolylenyl, cinnolinylenyl, quinazolinylenyl, quinoxalinylenyl, carbazolylenyl, phenoxazinylenyl, phenothiazinylenyl, phenanthridinylenyl, benzodioxolylenyl, dihydroacridinylenyl, and derivatives thereof.
As used in the present application, the term “substituted” refers to the substitution of a hydrogen atom in a compound by another substituent. The position is not limited to a specific position, as long as hydrogen(s) at that position can be substituted by substituent(s). When two or more substituents appear, they can be the same or different.
As used in the present application, unless otherwise specified, hydrogen atoms include protium, deuterium, and tritium.
In the present application, in the limitation of the groups, the range of carbon atom number is limited, which is any integer within the limited range, for example, C6-C30 aryl represents that the carbon atom number of aryl may be any integer within the range of 6-30, such as 6, 8, 10, 13, 15, 17, 20, 22, 25, or 30, etc.
The solution adopted by the present application is as follows:
The present application provides an organic electroluminescent material composition, wherein the organic electroluminescent material composition comprise compound N and compound M, compound N and compound M are compounds represented by Formula (1):
It can be understood that compound N has the following structure:
It can be understood that compound M has the following structure:
It can be understood, in the present application, R can be substituted on ring B or on ring C; ring A and ring B are connected through La.
Preferably, in formula (1). X1-X14 are all selected from CR8, R8 is selected from hydrogen or deuterium;
Preferably, the compound N has a structure as shown in any one of Formula 1-1 to Formula 1-64:
Preferably, in Formula 1-A, Ar2 is selected from the following groups:
Wherein, Ar5 is defined the same as above.
Preferably, the compound N has a structure as shown in any one of Formula 1-a to Formula 1-h:
Preferably, the compound N has a structure as shown in any one of Formula 1-i to Formula 1-ii:
Preferably, in Formula 1-i or Formula 1-ii, R1-R2 are each independently selected from a C3-C15 cycloalkyl and a C6-C15 aryl;
Preferably, the compound N has a structure as shown in any one of the following Formula N-i-1 to Formula N-i-72:
Preferably, the compound N has the structure as shown in any one of the following N-1 to N-549:
Preferably, the compound M has the structure as shown in any one of Formula 2-1 to Formula 2-28:
Preferably, the structure of compound M is shown in any one of M-1 to M-619:
Preferably, the mass ratio of compound N to compound M is from 1:9 to 9:1;
The present application also provides an application of the organic electroluminescent material composition described above in the preparation of optical devices.
Preferably, the optical devices comprise any one of organic electroluminescent devices, organic field-effect transistors, organic thin-film transistors, organic light emitting transistors, organic integrated circuits, organic solar cells, organic field quenching devices, luminescent electrochemical cells, organic laser diodes, and organic photoreceptors.
The present application also provides an organic electroluminescent device, the organic electroluminescent device comprises an anode, a cathode, and an organic layer arranged between the anode and the cathode; the organic layer comprises the organic electroluminescent material composition described above, preferably, an light emitting layer of the organic layer the comprises the organic electroluminescent material composition described above.
Preferably, the organic layer comprises a hole injection layer, a hole transport layer, an electron barrier layer, a light emitting layer, a hole barrier layer, an electron transport layer, and an electron injection layer sequentially arranged from the anode side to the cathode side;
Preferably, the guest material comprises a phosphorescent dopant, and the phosphorescent dopant comprises a complex containing transition metals.
The present application also provides an organic electroluminescent equipment, the organic electroluminescent equipment comprises the organic electroluminescent device above.
The beneficial effects of the present application:
The organic electroluminescent material composition of the present application, based on Formula (1), compound N and compound M cooperate with each other to facilitate the matching of HOMO and LUMO energy levels with adjacent energy levels, resulting in relatively high stability and balanced carrier mobility of the organic electroluminescent compound, thereby enabling the organic electroluminescent device containing the material to have a better lifespan, lower driving voltage and higher efficiency at the same time.
In order to illustrate the technical solutions in the specific embodiments of the present application or in the prior art more clearly, the drawings to be used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings in the following description show some of the embodiments of the present application, and those of ordinary skill in the art may still obtain other drawings from these drawings without creative efforts.
The following examples are provided for a better further understanding of the present application and are not limited to the best embodiments, not limiting the content and scope of protection of the present application, and any product that is the same as or similar to that of the present application obtained by anyone under the inspiration of the present application or by combining the features of the present application with that of other prior art falls within the scope of protection of the present application.
If specific experimental steps or conditions are not specified in the examples, the operation or conditions of conventional experimental steps described in the literature in this field can be carried out. The adopted reagents or instruments which are not specified with the manufacturer are conventional commercially-available reagent products.
The present example provides a method for preparing a compound with M-17 structure in an organic electroluminescent material composition, comprising the following steps:
A 50 mL double-neck round-bottom flask was taken, a stirrer and an upwards-connected return pipe were placed in the flask, the flask was filled with nitrogen after being dried, compounds M17-A (19.8 mmol, CAS: 1884145-03-2), M17-B (20.75 mmol, CAS: 1883265-32-4), tetrakis(triphenylphosphine)palladium (0.396 mmol), potassium carbonate (39.6 mmol), 35 mL of toluene, 15 mL of ethanol and 15 mL of distilled water were added respectively, and the mixture was stirred at 90 degrees Celsius for 8 hours. After the reaction was completed, the mixture was added into methanol dropwise, and the obtained solid was filtered. The obtained solid was purified through column chromatography to obtain compound M-17 (8.5 g, yield: 75%).
Elemental analysis: C41H25N3O; theoretical value: C, 85.54; H, 4.38; N, 7.30; 0, 2.78; measured value: C, 85.52; H, 4.38; N, 7.32; HRMS (ESI) m/z (M+): theoretical value: 575.20; measured value: 576.34.
The present example provides a method for preparing a compound with M-296 structure in an organic electroluminescent material composition, comprising the following steps:
(I) Synthesis of an intermediate M296-A, with a synthetic route being as follows:
An intermediate M296-1 (2-bromoquinoline, CAS: 2005-43-8, 20 g) and 200 mL of anhydrous tetrahydrofuran were added into a 250 mL three-necked flask equipped with a thermometer and a magnetic stirrer, the temperature was reduced to −78° C. under a nitrogen protection condition, n-butyl lithium (1.6 M, 45.2 mL) was added dropwise with the temperature controlled, stirring was conducted for 1 h after dropwise adding, triisopropyl borate (19.52 g) was added dropwise with the temperature controlled at −78° C., the mixture was transferred to the room temperature after dropwise adding to react for 12 h, a hydrochloric acid solution (6.5 mL of 36% hydrochloric acid+24 mL of water) was added dropwise, 50 mL of ethyl acetate and 25 mL of water were added into the reaction liquid for extraction and liquid separation, the organic phase was spin-dried and then 50 mL of n-hexane was added, reflux was conducted for 1 h to produce a slurry, filtering was conducted at the room temperature, and 15 g of an intermediate M296-2 was obtained after drying.
The intermediate M296-2 (15 g), an intermediate 7-bromo-1-chloronaphthalene (21.9 g), potassium carbonate (16.6 g) and tetrakis(triphenylphosphine)palladium (2.0 g) were added into a 250 mL three-necked flask equipped with a thermometer and a magnetic stirrer, toluene (80 mL), ethanol (35 mL) and water (35 mL) were added, under a nitrogen protection condition, the temperature was raised to 85° C. to react for 6 h, 50 mL of ethyl acetate and 25 mL of water were added into the reaction liquid for extraction and liquid separation, the organic phase was prepared into sample and subjected column chromatography, and 15 g of an intermediate M296-3 was obtained.
The intermediate M296-3 (15 g), bis(pinacolato)diboron (15.8 g), potassium acetate (10 g) and Pd(dppf)Cl2 (0.64 g) were added into a 250 mL three-necked flask equipped with a thermometer and a magnetic stirrer, 1,4-dioxane (150 mL) was added, under a nitrogen protection condition, the temperature was raised to 110° C. to react for 4 h, 100 mL of toluene and 100 mL of water were added into the reaction liquid for extraction and liquid separation, the organic phase was prepared into sample and subjected column chromatography, and 16 g of the intermediate M296-A was obtained.
(II) Synthesis of the compound M-296, with a synthetic route being as follows:
The intermediate M296-A (16 g), an intermediate M296-B (2-chloro-4,6-diphenyl-1,3,5-triazine, CAS: 3842-55-5, 11.2 g), potassium carbonate (11.6 g) and tetrakis(triphenylphosphine)palladium (1.3 g) were added into a 250 mL three-necked flask equipped with a thermometer and a magnetic stirrer, toluene (110 mL), ethanol (50 mL) and water (50 mL) were added, under a nitrogen protection condition, the temperature was raised to 85° C. to react for 6 h, water and ethanol were added into the reaction liquid at the room temperature for filtration, and 16 g of the product M-296 was obtained after drying (yield 78%).
Elemental analysis: C34H22N4; theoretical value: C, 83.93; H, 4.56; N, 11.51; measured value: C, 83.95; H, 4.56; N, 11.49; HRMS (ESI) m/z (M+): theoretical value: 486.18; measured value: 487.12.
The present example provides a method for preparing a compound with M-381 structure in an organic electroluminescent material composition, comprising the following steps:
(I) Synthesis of an intermediate M381-B, with a synthetic route being as follows:
An intermediate M381-1 (CAS: 5332-25-2, 20 g) and 200 mL of anhydrous tetrahydrofuran were added into a 250 mL three-necked flask equipped with a thermometer and a magnetic stirrer, the temperature was reduced to −78° C. under a nitrogen protection condition, n-butyl lithium (1.6 M, 45.2 mL) was added dropwise with the temperature controlled, stirring was conducted for 1 h after dropwise adding, triisopropyl borate (19.52 g) was added dropwise with the temperature controlled at −78° C., the mixture was transferred to the room temperature after dropwise adding to react for 12 h, a hydrochloric acid solution (6.5 mL of 36% hydrochloric acid+24 mL of water) was added dropwise, 50 mL of ethyl acetate and 25 mL of water were added into the reaction liquid for extraction and liquid separation, the organic phase was spin-dried and then 50 mL of n-hexane was added, reflux was conducted for 1 h to produce a slurry, filtering was conducted at the room temperature, and 15 g of an intermediate M381-2 was obtained after drying.
The intermediate M381-2 (15 g), a raw material M367-a (CAS: 99455-15-9, 21 g), potassium carbonate (16.6 g) and tetrakis(triphenylphosphine)palladium (2.0 g) were added into a 250 mL three-necked flask equipped with a thermometer and a magnetic stirrer, toluene (80 mL), ethanol (35 mL) and water (35 mL) were added, under a nitrogen protection condition, the temperature was raised to 85° C. to react for 6 h, 50 mL of ethyl acetate and 25 mL of water were added into the reaction liquid for extraction and liquid separation, the organic phase was prepared into sample and subjected column chromatography, and 13 g of an intermediate M381-3 was obtained.
The intermediate M381-3 (13 g) and 200 mL of anhydrous tetrahydrofuran were added into a 250 mL three-necked flask equipped with a thermometer and a magnetic stirrer, the temperature was reduced to −78° C. under a nitrogen protection condition, n-butyl lithium (1.6 M, 40 mL) was added dropwise with the temperature controlled, stirring was conducted for 1 h after dropwise adding, triisopropyl borate (17 g) was added dropwise with the temperature controlled at −78° C., the mixture was transferred to the room temperature after dropwise adding to react for 12 h, a hydrochloric acid solution (6.5 mL of 36% hydrochloric acid+24 mL of water) was added dropwise, 50 mL of ethyl acetate and 25 mL of water were added into the reaction liquid for extraction and liquid separation, the organic phase was spin-dried and 50 mL of n-hexane was added, reflux was conducted for 1 h to produce a slurry, filtering was conducted at the room temperature, and 12 g of an intermediate M381-4 was obtained after drying.
The intermediate M381-4 (12 g), a raw material M381-b (CAS: 112719-97-8, 11 g), potassium carbonate (11 g) and tetrakis(triphenylphosphine)palladium (1.2 g) were added into a 250 mL three-necked flask equipped with a thermometer and a magnetic stirrer, toluene (80 mL), ethanol (35 mL) and water (35 mL) were added, under a nitrogen protection condition, the temperature was raised to 85° C. to react for 6 h, 50 mL of ethyl acetate and 25 mL of water were added into the reaction liquid for extraction and liquid separation, the organic phase was prepared into sample and subjected column chromatography, and 16 g of the intermediate M381-B was obtained.
(II) Synthesis of the compound M-381, with a synthetic route being as follows:
The intermediate M381-B (16 g), a raw material M381-A (6.85 g, CAS: 395087-89-5), potassium carbonate (9 g) and tetrakis(triphenylphosphine)palladium (1.0 g) were added into a 250 mL three-necked flask equipped with a thermometer and a magnetic stirrer, toluene (80 mL), ethanol (35 mL) and water (35 mL) were added, under a nitrogen protection condition, the temperature was raised to 85° C. to react for 6 h, 50 mL of ethyl acetate and 25 mL of water were added into the reaction liquid for extraction and liquid separation, the organic phase was prepared into sample and subjected column chromatography, and 15 g of the final product M-381 was obtained (yield 74%).
Elemental analysis: C43H25N50; theoretical value: C, 82.28; H, 4.01; N, 11.16; O, 2.55; measured value: C, 82.30; H, 4.01; N, 11.14; HRMS (ESI) m/z (M+): theoretical value: 627.21; measured value: 628.13.
Examples 4-31 provides the method for preparing Compounds M-76, M-108, M-145, M-253, M-394, M-412, M-423, M-442, M-450, M-460, M-461, M-480, M-502, M-520, M-526, M-537, M-548, M-562, M-572, M-579, M-584, M-589, M-599, M-610, M-611, M-308, M-365 or M-371. The specific preparation method is as follows:
The structures of the raw material Mn-B, the raw material Mn-A and the product as well as the yields were shown in Table 1 below. The elemental analysis results of the prepared compounds were shown in Table 2. The dosage of the materials and experimental parameters are the same as those in Example 1.
M76-A
M76-B
M-76
M108-A
M108-B
M-108
M145-A
M145-B
M-145
M253-A
M253-B
M-253
M394-A
M394-B
M-394
M412-A
M412-B
M-412
M423-A
M423-B
M-423
M442-A
M442-B
M-442
M450-A
M450-B
M-450
M460-A
M460-B
M-460
M461-A
M461-B
M-461
M480-A
M480-B
M-480
M502-A
M502-B
M-502
M520-A
M520-B
M-520
M526-A
M526-B
M-526
M537-A
M537-B
M-537
M548-A
M548-B
M-548
M562-A
M562-B
M-562
M572-A
M572-B
M-572
M579-A
M579-B
M-579
M584-A
M584-B
M-584
M589-A
M589-B
M-589
M599-A
M599-B
M-599
M610-A
M610-B
M-610
M611-A
M611-B
M-611
M308-A
M308-B CAS:875916-80-6
M-308
M365-A
M365-B
M-365
M371-A
M371-B
M-371
The product characterization data is shown in Table 2:
The present example provides a method for preparing a compound with N-531 structure in an organic electroluminescent material composition, comprising the following steps:
After replacing the air in a three port reaction bottle equipped with mechanical stirrer, thermometer, and condenser tube with nitrogen, intermediate N531-B (10 mmol), intermediate N531-A (11 mmol), and toluene (100 ml) were added sequentially, then heated and refluxed to separate water for 0.5 hours, the temperature was reduced to 70° C. to 80° C., sodium tert butanol (15 mmol), Pd2(dba)3 (0.05 mmol), and s-phos (0.1 mmol) were added slowly, and waited for the system to stabilize before heating to 100° C. to 110° C. and reacted for 3 hours. The temperature was reduced to 25° C. to 30° C., 100 ml of water and 100 ml of toluene were added, stirred to separate the liquid, the aqueous phase was extracted once with 100 ml of toluene, the liquid was separated, and the organic phase was merged, 7 g of anhydrous sodium sulfate was added into the organic phase, stirred, dried and filtered. The organic phase was concentrated (−0.08 MPa to 0.09 MPa, 55° C. to 60° C.) until no liquid flows out. 20 ml of petroleum ether was added under stirring, the temperature was reduced to 0° C. to 5° C., the material was filtered to obtain compound N-531 with a yield of 78%.
Elemental analysis: C44H31N; theoretical value: C, 92.11; H, 5.45; N, 2.44; measured value: C, 92.10; H, 5.45; N, 2.42; IRMS (ESI) m/z (M+): theoretical value: 573.25; measured value: 574.16.
The present example provides a method for preparing a compound with N-532 structure in an organic material composition, comprising the following steps:
After replacing the air in a three port reaction bottle equipped with mechanical stirrer, thermometer, and condenser tube with nitrogen, intermediate N532-B (10 mmol), intermediate N532-A (11 mmol), and toluene (100 ml) were added sequentially, then heated and refluxed to separate water for 0.5 hours, the temperature was reduced to 70° C. to 80° C., sodium tert butanol (15 mmol), Pd2(dba)3 (0.05 mmol), and s-phos (0.1 mmol) were added slowly, and waited for the system to stabilize before heating to 100° C. to 110° C. and reacted for 3 hours. The temperature was reduced to 25° C. to 30° C., 100 ml of water and 100 ml of toluene were added, stirred to separate the liquid, the aqueous phase was extracted once with 100 ml of toluene, the liquid was separated, and the organic phase was merged, 7 g of anhydrous sodium sulfate was added into the organic phase, stirred, dried and filtered. The organic phase was concentrated (−0.08 MPa to 0.09 MPa, 55° C. to 60° C.) until no liquid flows out. 40 ml of n-hexane was added under stirring, the material was filtered at room temperature to obtain compound N-532 with a yield of 71%. m/z=587.1[M+H]+.
Elemental analysis: C44H30N2; theoretical value: C, 90.07; H, 5.15; N, 4.77; measured value: C, 90.10; H, 5.12; N, 4.75; HRMS (ESI) m/z (M+): theoretical value: 586.24; measured value: 587.10.
The present example provides a method for preparing a compound with N-533 structure in an organic electroluminescent material composition, comprising the following steps:
After replacing the air in a three port reaction bottle equipped with mechanical stirrer, thermometer, and condenser tube with nitrogen, intermediate N533-B (10 mmol), intermediate N533-A (11 mmol), and toluene (100 ml) were added sequentially, then heated and refluxed to separate water for 0.5 hours, the temperature was reduced to 70° C. to 80° C., sodium tert butanol (15 mmol), Pd2(dba)3 (0.05 mmol), and s-phos (0.1 mmol) were added slowly, and waited for the system to stabilize before heating to 100° C. to 110° C. and reacted for 3 hours. The temperature was reduced to 25° C. to 30° C., 100 ml of water and 100 ml of toluene were added, stirred to separate the liquid, the aqueous phase was extracted once with 100 ml of toluene, the liquid was separated, and the organic phase was merged, 7 g of anhydrous sodium sulfate was added into the organic phase, stirred, dried and filtered. The organic phase was concentrated (−0.08 MPa to 0.09 MPa, 55° C. to 60° C.) until no liquid flows out. 40 ml of n-hexane was added under stirring, the material was filtered at room temperature to obtain compound N-533 with a yield of 73%.
Elemental analysis: C42H29N; theoretical value: C, 92.11; H, 5.34; N, 2.56; measured value: C, 92.10; H, 5.35; N, 2.55; HRMS (ESI) m/z (M+): theoretical value: 547.23; measured value: 548.21.
The present example provides a method for preparing a compound with N-534 structure in an organic electroluminescent material composition, comprising the following steps:
After replacing the air in a three port reaction bottle equipped with mechanical stirrer, thermometer, and condenser tube with nitrogen, intermediate N534-B (10 mmol), intermediate N534-A (11 mmol), and toluene (100 ml) were added sequentially, then heated and refluxed to separate water for 0.5 hours, the temperature was reduced to 70° C. to 80° C., sodium tert butanol (15 mmol), Pd2(dba)3 (0.05 mmol), and s-phos (0.1 mmol) were added slowly, and waited for the system to stabilize before heating to 100° C. to 110° C. and reacted for 3 hours. The temperature was reduced to 25° C. to 30° C., 100 ml of water and 100 ml of toluene were added, stirred to separate the liquid, the aqueous phase was extracted once with 100 ml of toluene, the liquid was separated, and the organic phase was merged, 7 g of anhydrous sodium sulfate was added into the organic phase, stirred, dried and filtered. The organic phase was concentrated (−0.08 MPa to 0.09 MPa, 55° C. to 60° C.) until no liquid flows out. 40 ml of n-hexane was added under stirring, the material was filtered at room temperature to obtain compound N-534 with a yield of 58%.
Elemental analysis: C42H29NO; theoretical value: C, 89.49; H, 5.19; N, 2.48; O, 2.84; measured value: C, 89.47; H, 5.18; N, 2.51; HRMS (ESI) m/z (M+): theoretical value: 563.22; measured value: 564.21.
The present example provides a method for preparing a compound with N-535 structure in an organic electroluminescent material composition, comprising the following steps:
After replacing the air in a three port reaction bottle equipped with mechanical stirrer, thermometer, and condenser tube with nitrogen, the raw material N535-B-a (10.5 mmol), the raw material N535-B-b (10 mmol), and toluene (100 ml) were added sequentially, then heated and refluxed to separate water for 0.5 hours, the temperature was reduced to 70° C. to 80° C., sodium tert butanol (15 mmol), Pd2(dba)3 (0.05 mmol), and s-phos (0.1 mmol) were added slowly, and waited for the system to stabilize before heating to 100° C. to 110° C. and reacted for 3 hours. The temperature was reduced to 25° C. to 30° C., 100 ml of water and 100 ml of toluene were added, stirred to separate the liquid, the aqueous phase was extracted once with 100 ml of toluene, the liquid was separated, and the organic phase was merged, 7 g of anhydrous sodium sulfate was added into the organic phase, stirred, dried and filtered. The organic phase was concentrated (−0.08 MPa to 0.09 MPa, 55° C. to 60° C.) until no liquid flows out. 40 ml of n-hexane was added under stirring, the material was filtered at room temperature to obtain intermediate N535-B with a yield of 74%.
After replacing the air in a three port reaction bottle equipped with mechanical stirrer, thermometer, and condenser tube with nitrogen, intermediate N535-B (10 mmol), intermediate N535-A (11 mmol), and toluene (100 ml) were added sequentially, then heated and refluxed to separate water for 0.5 hours, the temperature was reduced to 70° C. to 80° C., sodium tert butanol (15 mmol), Pd2(dba)3 (0.05 mmol), and s-phos (0.1 mmol) were added slowly, and waited for the system to stabilize before heating to 100° C. to 110° C. and reacted for 3 hours. The temperature was reduced to 25° C. to 30° C., 100 ml of water and 100 ml of toluene were added, stirred to separate the liquid, the aqueous phase was extracted once with 100 ml of toluene, the liquid was separated, and the organic phase was merged, 7 g of anhydrous sodium sulfate was added into the organic phase, stirred, dried and filtered. The organic phase was concentrated (−0.08 MPa to 0.09 MPa, 55° C. to 60° C.) until no liquid flows out. 40 ml of n-hexane was added under stirring, the material was filtered at room temperature to obtain compound N-535 with a yield of 65%. m/z=639.28[M+H]+.
Elemental analysis: C48H34N2; theoretical value: C, 90.25; H, 5.36; N, 4.39; measured value: C, 90.26; H, 5.33; N, 4.40; IRMS (ESI) m/z (M+): theoretical value: 638.28; measured value: 639.28.
The present example provides a method for preparing a compound with N-536 structure in an organic electroluminescent material composition, comprising the following steps:
After replacing the air in a three port reaction bottle equipped with mechanical stirrer, thermometer, and condenser tube with nitrogen, intermediate N536-B (10 mmol), intermediate N536-A (11 mmol), and toluene (100 ml) were added sequentially, then heated and refluxed to separate water for 0.5 hours, the temperature was reduced to 70° C. to 80° C., sodium tert butanol (15 mmol), Pd2(dba)3 (0.05 mmol), and s-phos (0.1 mmol) were added slowly, and waited for the system to stabilize before heating to 100° C. to 110° C. and reacted for 3 hours. The temperature was reduced to 25° C. to 30° C., 100 ml of water and 100 ml of toluene were added, stirred to separate the liquid, the aqueous phase was extracted once with 100 ml of toluene, the liquid was separated, and the organic phase was merged, 7 g of anhydrous sodium sulfate was added into the organic phase, stirred, dried and filtered. The organic phase was concentrated (−0.08 MPa to 0.09 MPa, 55° C. to 60° C.) until no liquid flows out. 40 ml of n-hexane was added under stirring, the material was filtered at room temperature to obtain compound N-536 with a yield of 34%.
Elemental analysis: C44H32N2; theoretical value: C, 89.76; H, 5.48; N, 4.76; measured value: C, 89.78; H, 5.46; N, 4.77; IRMS (ESI) m/z (M+): theoretical value: 588.26; measured value: 589.46.
The present example provides a method for preparing a compound with N-537 structure in an organic electroluminescent material composition, comprising the following steps:
After replacing the air in a three port reaction bottle equipped with mechanical stirrer, thermometer, and condenser tube with nitrogen, raw material N537-B-a (10.5 mmol), intermediate N537-B-b (10 mmol), and toluene (100 ml) were added sequentially, then heated and refluxed to separate water for 0.5 hours, the temperature was reduced to 70° C. to 80° C., sodium tert butanol (15 mmol), Pd2(dba)3 (0.05 mmol), and s-phos (0.1 mmol) were added slowly, and waited for the system to stabilize before heating to 100° C. to 110° C. and reacted for 3 hours. The temperature was reduced to 25° C. to 30° C., 100 ml of water and 100 ml of toluene were added, stirred to separate the liquid, the aqueous phase was extracted once with 100 ml of toluene, the liquid was separated, and the organic phase was merged, 7 g of anhydrous sodium sulfate was added into the organic phase, stirred, dried and filtered. The organic phase was concentrated (−0.08 MPa to 0.09 MPa, 55° C. to 60° C.) until no liquid flows out. 40 ml of toluene was added under stirring, the material was filtered at room temperature and the crystallization process was repeated twice to obtain intermediate N537-B with a yield of 46%.
After replacing the air in a three port reaction bottle equipped with mechanical stirrer, thermometer, and condenser tube with nitrogen, intermediate N537-B (10 mmol), intermediate N537-A (11 mmol), and toluene (100 ml) were added sequentially, then heated and refluxed to separate water for 0.5 hours, the temperature was reduced to 70° C. to 80° C., sodium tert butanol (15 mmol), Pd2(dba)3 (0.05 mmol), and s-phos (0.1 mmol) were added slowly, and waited for the system to stabilize before heating to 100° C. to 110° C. and reacted for 3 hours. The temperature was reduced to 25° C. to 30° C., 100 ml of water and 100 ml of toluene were added, stirred to separate the liquid, the aqueous phase was extracted once with 100 ml of toluene, the liquid was separated, and the organic phase was merged, 7 g of anhydrous sodium sulfate was added into the organic phase, stirred, dried and filtered. The organic phase was concentrated (−0.08 MPa to 0.09 MPa, 55° C. to 60° C.) until no liquid flows out. 40 ml of n-hexane was added under stirring, the material was filtered at room temperature to obtain compound N-537 with a yield of 46%. m/z=755.30 [M+H]+.
Elemental analysis: C56H38N2O; theoretical value: C, 89.10; H, 5.07; N, 3.71; 0, 2.12; measured value: C, 89.12; H, 5.08; N, 3.70; HRMS (ESI) m/z (M+): theoretical value: 754.30; measured value: 755.41.
The synthesis conditions of the compounds in the following examples were the same as those of N-531 or N-532, and the differences were that the raw material N-nA, the raw material N-nB and the structures and yields of products were different, which are specifically shown in Table 3 below; and the elemental analysis results of the prepared compounds were shown in Table 4.
N4-B
N4-A
N-4
N11-B
N4-A
N-11
N17-B
N17-A
N-17
N21-B
N17-A
N-21
N25-B
N25-A
N-25
N28-B
N25-A
N-28
N33-B
N25-A
N-33
N36-B
N36-A
N-36
N45-B
N45-A
N-45
N48-B
N45-A
N-48
N55-B
N55-A
N-55
N63-B
N55-A
N-63
N65-B
N65-A
N-65
N67-B
N65-A
N-67
N71-B
N71-A
N-71
N77-B
N71-A
N-77
N85-B
N85-A
N-85
N87-B
N85-A
N-87
N91-B
N91-A
N-91
N92-B
N92-A
N-92
N99-B
N99-A
N-99
N109-B
N109-A
N-109
N112-B
N109-A
N-112
N119-B
N119-A
N-119
N123-B
N123-A
N-123
N128-B
N123-A
N-128
N134-B
N134-A
N-134
N139-B
N139-A
N-139
N145-B
N145-A
N-145
N151-B
N151-A
N-151
N175-B
N175-A
N-175
N229-B
N229-A
N-229
N233-B
N229-A
N-233
N253-B
N253-A
N-253
N257-B
N253-A
N-257
N269-B
N269-A
N-269
N290-B
N290-A
N-290
N313-A
N313-B
N-313
N432-B
N432-A
N-432
N464-B
N432-A
N-464
N537-B
N537-A
N-537
N545-B
N545-A
N-545
N-i-37-B
N432-A
N-i-37
N-i-38-B
N432-A
N-i-38
N-i-9-B
N432-A
N-i-9
N-i-17-B
N432-A
N-i-17
N-i-1-B
N55-A
N-i-19
N-i-2-B
N55-A
N-i-20
N-i-28-B
N55-A
N-i-28
N-i-36-B
N55-A
N-i-36
The present example provides an organic electroluminescent device, as shown in
The materials for manufacturing the organic electroluminescent device are as follows:
The preparation of the above-mentioned organic electroluminescent device comprises the following steps.
The glass substrate coated with transparent ITO is sonicated in a water-based cleaning agent (the composition and concentration of the water-based cleaning agent are: ethylene glycol based solvent ≤10 wt %, triethanolamine ≤1 wt %), then rinsed in deionized water, sonicated in a mixed solvent of acetone and ethanol (volume ratio of acetone and ethanol is 1:1) to remove the oil, baked in a clean environment to completely remove moisture, and then cleaned with ultraviolet light and ozone.
The ITO transparent substrate was transferred into the evaporation coating equipment and vacuumized to 1×10−6 to 2×10−4 Pa, a 10 nm hole injection layer (HIL)/80 nm hole transport layer (HTL)/38 nm light emitting layer (EML)/30 nm electron transport layer (ETL)/1 nm electron injection layer (EIL)/80 nm thick cathode (Al) was sequentially evaporated and coated on the anode film.
2Ir(acac)
2Ir(acac)
2Ir(acac)
2Ir(acac)
2Ir(acac)
The Examples in Table 5 refer to device Examples, and the Comparative Example refers to device Comparative Example.
The organic electroluminescent devices obtained by Device Examples 1-41 and Comparative Example 1 in the device examples were tested.
Instrument: the current, voltage, brightness, emission spectrum and other characteristics of the devices were synchronously tested using a PR 650 spectral scanning brightness meter and a Keithley K 2400 digital source meter system;
Results of the above device performance testing were shown in Table 6.
Obviously, the above examples are only for the purpose of clearly illustrating the instances provided, rather than limiting the embodiments. For those of ordinary skill in the art, other different forms of changes or variations can also be made based on the above explanation. It is not necessary and impossible to exhaustively list all embodiments here. The obvious changes or variations arising from this are still within the scope of protection of the present application.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202310803157.7 | Jun 2023 | CN | national |
| 202311873192.2 | Dec 2023 | CN | national |
