CN113801058A - Thermal activation delayed fluorescent material, organic electroluminescent device and application thereof - Google Patents

Thermal activation delayed fluorescent material, organic electroluminescent device and application thereof Download PDF

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CN113801058A
CN113801058A CN202010541874.3A CN202010541874A CN113801058A CN 113801058 A CN113801058 A CN 113801058A CN 202010541874 A CN202010541874 A CN 202010541874A CN 113801058 A CN113801058 A CN 113801058A
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孙磊
魏金贝
李熠烺
李国孟
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Beijing Eternal Material Technology Co Ltd
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Abstract

The invention relates to the technical field of organic electroluminescence, in particular to an organic compound and application thereof, wherein the compound has a structure shown as the following formula (1), D1Selected from the structures represented by formula (I), D2Selected from the structures represented by the general formula (II). When the compound is used as an OLED device, the efficiency of the device can be effectively improved, the driving voltage is reduced, and the compound is a luminescent material with good performance.

Description

Thermal activation delayed fluorescent material, organic electroluminescent device and application thereof
Technical Field
The invention relates to the technical field of organic electroluminescent materials, in particular to a compound, a thermal activation delayed fluorescence material, an organic electronic luminescent device containing the compound and application of the compound and the material.
Background
Under the condition of electric excitation, the organic electroluminescent device can generate 25% of singlet state and 75% of triplet state excitons. The conventional fluorescent material can only utilize 25 singlet excitons due to spin-forbidden, so that the external quantum efficiency is limited to within 5%. Almost all triplet excitons can only be lost thermally. In order to improve the efficiency of the organic electroluminescent device, it is necessary to fully utilize triplet excitons.
For this reason, researchers have proposed many methods, the most notable of which is the use of phosphorescent materials. The phosphorescent material has a spin-orbit coupling effect due to the introduction of heavy atoms, and can fully utilize 75% of triplet excitons and realize 100% of internal quantum efficiency. However, the phosphorescent material uses rare heavy metals, so that the material is expensive and is not favorable for cost control. This problem can be solved well if the fluorescent device can make good use of triplet excitons. Researchers have proposed methods to increase the efficiency of fluorescent devices by using triplet exciton quenching to generate singlet excitons in fluorescent devices, but this method theoretically can achieve maximum external quantum efficiency of only 62.5%, much lower than that of phosphorescent materials. Therefore, it is necessary to find a new technology to fully utilize the triplet level of the fluorescent material to improve the luminous efficiency.
Disclosure of Invention
The present invention is directed to a compound, a thermally activated delayed fluorescence material, an organic electroluminescent device comprising the same, and an application thereof, so as to solve the above technical problems.
The invention discloses a compound, the structure of which is represented by a general formula (1):
Figure BDA0002539230770000011
in formula (1):
R1selected from substituted or unsubstituted C1-C12 chain alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C1-C12 alkoxy, substituted or unsubstituted C1-C12 thioalkoxy, halogen, cyano, nitro, hydroxyl, substituted or unsubstituted C1-C12 silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 monocyclic arylOne or the combination of at least two of substituted C10-C30 condensed ring aryl, substituted or unsubstituted C3-C30 monocyclic heteroaryl and substituted or unsubstituted C6-C30 condensed ring heteroaryl;
D1selected from the structures represented by formula (I):
Figure BDA0002539230770000021
wherein Ar is1And Ar2Are respectively and independently selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, Ar1And Ar2May or may not be joined to form a ring; denotes the attachment site of the group;
D2selected from the structures represented by the general formula (II):
Figure BDA0002539230770000022
wherein A is a structure represented by formula (a1), and the dotted line represents the condensed position of the group;
R2、R3、R4、R5each independently selected from one of substituted or unsubstituted C1-C12 chain alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C1-C12 alkoxy, substituted or unsubstituted C1-C12 thioalkoxy, halogen, cyano, nitro, hydroxyl, substituted or unsubstituted C1-C12 silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 monocyclic aryl, substituted or unsubstituted C10-C30 fused ring aryl, substituted or unsubstituted C3-C30 monocyclic heteroaryl, and substituted or unsubstituted C6-C30 fused ring heteroaryl;
b is an integer of 0 to 4; c is an integer of 0 to 2; d is an integer of 0 to 4; e is an integer of 0 to 8;
m and n are respectively independently selected from integers of 1-4, a is selected from integers of 0-3, and m + n + a is less than or equal to 5; preferably a is 0;
when the above groups have substituents, the substituents are selected from one or a combination of at least two of halogen, cyano, nitro, hydroxyl, C1-C12 chain alkyl, C3-C12 cycloalkyl, C1-C12 alkoxy, C1-C12 thioalkoxy, C1-C12 silyl, amino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 monocyclic aryl, C10-C30 fused ring aryl, C3-C30 monocyclic heteroaryl and C6-C30 fused ring heteroaryl.
Further preferably, the compound of the general formula (I) of the present invention is represented by the following formula (2-1) or (2-2):
Figure BDA0002539230770000031
in the formula (2-1) or (2-2), D1、D2And R1Are as defined in formula (1);
D1' and D1"identical or different, independently selected from the group consisting of formula (I), D2' and D2"is the same or different and is independently selected from the general formula (II), and the definitions of formula (I) and formula (II) are the same as those in claim 1;
n 'is an integer of 1 to 3, a' is an integer of 0 to 2, and n '+ a' is less than or equal to 3; preferably a' is 0;
m 'is an integer of 1 to 3, a' is an integer of 0 to 2, and m '+ a' is less than or equal to 3; preferably a "is 0;
preferably, in the formula (2-1), n' is 1;
preferably, in the formula (2-2), m' is 1.
More preferably, the compound of the general formula of the present invention is represented by the formula (2-1).
Still more preferably, the compound of the general formula (III) of the present invention is represented by the following formula (3-1) or (3-2):
Figure BDA0002539230770000032
formula (3-1) or(3-2) in (D)1、D2And R1Are as defined in formula (1); d1’、D1”、D2’、D2", a' and a" are the same as defined in the formulae (2-1) and (2-2).
More preferably, the compound of the general formula of the present invention is represented by the formula (3-1).
Preferably, D is1、D1' and D1"are each independently selected from the structures represented by the formula (I-1) or the formula (I-2):
Figure BDA0002539230770000041
in the formula (I-1), X1-X10Are each independently selected from CR9Or N, R9Independently selected from one or a combination of at least two of substituted or unsubstituted C1-C12 chain alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C1-C12 alkoxy, substituted or unsubstituted C1-C12 thioalkoxy, halogen, cyano, nitro, hydroxyl, substituted or unsubstituted C1-C12 silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 monocyclic aryl, substituted or unsubstituted C10-C30 fused ring aryl, substituted or unsubstituted C3-C30 monocyclic heteroaryl, substituted or unsubstituted C6-C30 fused ring heteroaryl, and X is1-X5Middle and X6-X10Any two adjacent of the two can be connected into a ring;
in the formula (I-2), X11-X18Are each independently selected from CR12Or N, R12Independently selected from substituted or unsubstituted C1-C12 chain alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C1-C12 alkoxy, substituted or unsubstituted C1-C12 thioalkoxy, halogen, cyano, nitro, hydroxyl, substituted or unsubstituted C1-C12 silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C1-C3524 heteroarylOne or a combination of at least two of C6-C30 monocyclic aryl, substituted or unsubstituted C10-C30 fused ring aryl, substituted or unsubstituted C3-C30 monocyclic heteroaryl, substituted or unsubstituted C6-C30 fused ring heteroaryl, and X11-X14Middle and X15-X18Any two adjacent ones of which may be joined to form a ring.
Further preferably, D1、D1' and D1"are respectively and independently selected from any one of the following groups:
Figure BDA0002539230770000051
further preferably, D2、D2' and D2"are respectively and independently selected from any one of the following groups:
Figure BDA0002539230770000052
wherein R is2、R3、R4、R5B, d, c and e are as defined in formula (II).
Preferably, said R is2、R3、R4、R5Independently selected from one of the following substituted or unsubstituted groups:
Figure BDA0002539230770000061
preferably, in the formula (1), the formula (2-2), the formula (3-1) or (3-2), D2、D2' and D2"are respectively and independently selected from any one of the following groups:
Figure BDA0002539230770000062
still more preferably, R in the above formula1Is selected from the group consisting ofAlkyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl, n-octyl, cyclopentyl, cyclohexyl, or from the group consisting of substituted or unsubstituted: phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, indenyl, fluorenyl, 9,9 '-dimethylfluorene, 9, 9' -spirobifluorene, benzofluorene, fluoranthenyl, triphenylene, pyrenyl, perylenyl, perylene, and the like,
Figure BDA0002539230770000063
One of a phenyl group, a tetracenyl group, a furyl group, a thienyl group, a pyrrolyl group, a benzofuryl group, a benzothienyl group, an isobenzofuryl group, an indolyl group, a dibenzofuryl group, a dibenzothienyl group, and a carbazolyl group.
The above "substituted or unsubstituted" group may be substituted with one substituent, or may be substituted with a plurality of substituents, and when a plurality of substituents are present, different substituents may be selected from different substituents.
In the present specification, the expression of Ca to Cb means that the group has carbon atoms of a to b, and the carbon atoms do not generally include the carbon atoms of the substituents unless otherwise specified.
In the present specification, the expression of the "-" underlined loop structure indicates that the linking site is located at an arbitrary position on the loop structure where the linking site can form a bond.
In the present specification, the substituted or unsubstituted C6-C30 aryl group is preferably a C6-C20 aryl group, and more preferably a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, a fluorenyl group and derivatives thereof, a fluoranthyl group, a triphenylene group, a pyrenyl group, a perylenyl group, a triphenylene group,
Figure BDA0002539230770000071
A group of the group consisting of a phenyl group and a tetracenyl group. Specifically, the biphenyl group is selected from 2-biphenyl, 3-biphenyl, and 4-biphenyl; the terphenyl group includes p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl and m-terphenyl-2-yl; the naphthyl group includes a 1-naphthyl group and a 2-naphthyl group; the anthracene group is selected from 1-anthracene group, 2-anthracene group and 9-anthracene group; the fluorenyl is selected from 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl; the fluorenyl derivative is selected from 9,9 '-dimethylfluorene, 9' -spirobifluorene and benzofluorene; the pyrenyl is selected from 1-pyrenyl, 2-pyrenyl and 4-pyrenyl; the tetracenyl group is selected from the group consisting of 1-tetracenyl, 2-tetracenyl, and 9-tetracenyl.
The hetero atom in the present invention generally refers to an atom or group of atoms selected from N, O, S, P, Si and Se, preferably N, O, S.
The atomic names given in this disclosure, including their respective isotopes, for example, hydrogen (H) includes1H (protium or H),2H (deuterium or D), etc.; carbon (C) then comprises12C、13C and the like.
In the present specification, the substituted or unsubstituted heteroaryl group having C3 to C30 is preferably a heteroaryl group having C4 to C20, more preferably a nitrogen-containing heteroaryl group, an oxygen-containing heteroaryl group, a sulfur-containing heteroaryl group, and the like, and specific examples thereof include: furyl, thienyl, pyrrolyl, benzofuryl, benzothienyl, isobenzofuryl, indolyl, dibenzofuryl, dibenzothienyl, carbazolyl and derivatives thereof, wherein the carbazolyl derivative is preferably 9-phenylcarbazole, 9-naphthylcarbazole benzocarbazole, dibenzocarbazole, or indolocarbazole.
In the present specification, the chain alkyl group having from C1 to C12 is preferably a chain alkyl group having from C1 to C10, more preferably a chain alkyl group having from C1 to C6, and examples thereof include: methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, isopropyl, isobutyl, tert-butyl and the like.
In the present specification, the cycloalkyl group of C3 to C12 includes monocycloalkyl and polycycloalkyl groups, preferably alkyl groups of C1 to C10 and cycloalkyl groups of C3 to C10.
Further, the compound of the general formula according to the present invention is preferably any one of compounds having the structures shown in the following S1-S155:
Figure BDA0002539230770000081
Figure BDA0002539230770000091
Figure BDA0002539230770000101
Figure BDA0002539230770000111
Figure BDA0002539230770000121
another object of the present invention is to provide the use of the above-mentioned compounds of the present invention for application to organic electroluminescent devices.
Preferably, the compounds of the invention are suitable for use as luminescent dyes and/or sensitizers in the light-emitting layer of organic electroluminescent devices. The application field is not limited to the organic electroluminescent material, and the organic electroluminescent material can be applied to the technical fields of large-area sensors such as optical sensors, solar cells, lighting elements, organic thin-film transistors, organic field effect transistors, organic thin-film solar cells, information labels, electronic artificial skin sheets, sheet-type scanners, and electronic paper.
The invention also discloses a thermally activated delayed fluorescent material, which comprises the compound.
The invention also discloses an application of the thermal activation delayed fluorescence material in an organic electroluminescent device, preferably an application as a luminescent layer in the organic electroluminescent device, and more preferably an application as a luminescent dye and/or a sensitizer in the luminescent layer of the organic electroluminescent device.
The invention also discloses an organic electroluminescent device comprising a first electrode, a second electrode and one or more organic layers interposed between the first and second electrodes, wherein the organic layers comprise at least one compound of the invention as described above. Specifically, the organic layer may include a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, and an electron transport layer, wherein the light emitting layer contains the compound of the general formula of the present invention represented by the above general formula (1), formula (2-2), formula (3-1), and formula (3-2).
The invention also discloses a display screen or a display panel, wherein the display screen or the display panel adopts the organic electroluminescent device; preferably, the display screen or the display panel is an OLED display.
The invention also discloses electronic equipment, wherein the electronic equipment is provided with a display screen or a display panel, and the display screen or the display panel adopts the organic electroluminescent device.
The specific reason why the above-mentioned compound of the present invention is excellent in the performance as a luminescent dye and/or sensitizer in an organic electroluminescent device is not clear, and the following reason is presumed to be possible:
1. d1 is a donor with a small twist angle, an inert protecting group is arranged on the periphery of the donor, and the HOMO and LUMO between acceptors are overlapped to a certain extent, so that the fluorescent quantum yield is improved;
2. d2 adopts carbazole spirofluorene large rigid donor to increase the molecular distance. The molecule has small singlet state-triplet state energy level difference, and the TADF property is favorably improved.
3. Under the synergistic action of the two donors, the TADF material is ensured to have smaller singlet state-triplet state energy level difference and higher fluorescence quantum yield, and the energy transfer of the Dexter can be inhibited at the same time.
Detailed Description
Specific embodiments of the present invention will be described in detail below, and it should be noted that the embodiments described herein are only for illustration and are not intended to limit the embodiments of the present invention. In the following description, numerous specific details are set forth in order to provide a thorough understanding of embodiments of the invention. It will be apparent, however, to one skilled in the art that these specific details need not be employed to practice embodiments of the present invention. In other instances, well-known structures, materials, or methods have not been described in detail in order to avoid obscuring embodiments of the present invention.
Throughout the specification, reference to "some embodiments," "an embodiment," "one example," or "an example" means: the particular features, structures, or characteristics described in connection with the embodiment or example are included in at least one embodiment of the invention. Thus, the appearances of the phrases "in one embodiment," "in an embodiment," "one example" or "an example" in various places throughout this specification are not necessarily all referring to the same embodiment or example. Furthermore, the particular features, structures, or characteristics may be combined in any suitable combination and/or sub-combination in one or more embodiments or examples. Further, as used herein, the term "and/or" will be understood by those of ordinary skill in the art to include any and all combinations of one or more of the associated listed items.
The basic concept of the invention is to provide a compound, a donor with a smaller twist angle is introduced at the ortho-position of a cyano group, so that HOMO and LUMO between donor and acceptor are overlapped to a certain extent, and the improvement of the fluorescence quantum yield is facilitated; a donor with high rigidity is introduced into a cyano para position, so that the molecular distance can be increased, the molecular has smaller singlet state-triplet state energy level difference, and the TADF property of the molecule is improved; under the synergistic action of the two donors, the energy transfer of the Dexter can be inhibited, and the TADF property and the fluorescence quantum yield of the molecule can be improved.
The present invention will be described in detail by taking a plurality of specific examples as examples, and the compounds of the examples of the present invention can be synthesized by referring to the specific synthetic examples shown below, but it should be noted that the obtaining of the compounds is not limited to the synthetic methods and raw materials used in the present invention, and those skilled in the art can also select other methods or routes to obtain the novel compounds proposed in the present invention. The compounds of the present invention, for which no synthetic method is mentioned, are commercially available starting products or are prepared by the starting products according to known methods.
Solvents and reagents used in the synthesis examples, such as methylene chloride, petroleum ether, ethanol, tetrahydrofuran, N-dimethylacetamide, anhydrous magnesium sulfate, carbazole, benzimidazole and other chemical reagents, can be purchased from domestic chemical product markets, such as reagents from national drug group, TCI, shanghai Bide pharmaceutical, Bailingwei reagents, and the like. In addition, they can be synthesized by a known method by those skilled in the art.
Analytical testing of synthetic examples intermediates and compounds an abciex mass spectrometer (4000QTRAP) was used.
The synthesis general formula is as follows:
Figure BDA0002539230770000141
synthesis example 1: synthesis of S1
Figure BDA0002539230770000142
Synthesis of intermediate S1-1:
carbazole-spirofluorene (14.54g, 35.85mmol), 2, 6-dibromo-4-fluorobenzonitrile (10g, 35.85mmol), cesium carbonate (23.36g, 71.71mmol), N-dimethylformamide (200ml) were added to a 500ml single-neck flask at room temperature, and reacted overnight at 120 ℃ under nitrogen. Stopping heating, cooling to room temperature, adding 500ml of water, stirring for 10min, separating out a large amount of white solid, performing suction filtration, boiling and washing the filter cake with ethanol for 2h, cooling, and performing suction filtration to obtain 18g of a white solid product with the yield of 75.6%. Mass spectrometric analysis determined molecular ion mass: 664.34 (theoretical value: 664.40).
Synthesis of compound S1:
s1-1(5g, 7.53mmol), carbazole (2.52g, 12.05mmol), Pd were added at room temperature2(dba)3(0.69g，0.75mmol)，P(t-Bu)3(0.30g, 1.51mmol), sodium tert-butoxide (2.17g, 22.58mmol), xylene (50ml) were added to a 100ml single neck flask, nitrogen was purged three times and heated toThe reaction was carried out at 130 ℃ overnight. The reaction was cooled to room temperature, filtered, the filtrate was concentrated with silica gel and column chromatographed (PE: EA ═ 100:1) to give 6g of crude product, which was recrystallized from toluene/ethanol to give 4g of white solid in 63.5% yield. Mass spectrometric analysis determined molecular ion mass: 836.89 (theoretical value: 837.00).
Synthesis example 2: synthesis of S2
Figure BDA0002539230770000151
Synthesis of compound S2:
s1-1(5g, 7.53mmol), 3, 6-dimethylcarbazole (2.94g, 15.05mmol), Pd were added at room temperature2(dba)3(0.69g，0.75mmol)，P(t-Bu)3(0.30g, 1.51mmol), sodium t-butoxide (2.17g, 22.58mmol), xylene (50ml) were added to a 100ml single neck flask, nitrogen was purged three times, and the flask was heated to 130 ℃ for reaction overnight. The reaction was cooled to room temperature, filtered, the filtrate was concentrated with silica gel and column chromatographed (PE: EA ═ 100:1) to give 5g of crude product, which was recrystallized from toluene/ethanol to give 4g of white solid in 59.5% yield. Mass spectrometric analysis determined molecular ion mass: 864.44 (theoretical value: 864.33).
Synthesis example 3: synthesis of S4
Figure BDA0002539230770000152
Synthesis of compound S4:
s1-1(5g, 7.53mmol), 3-isopropylcarbazole (3.78g, 15.05mmol), Pd were added at room temperature2(dba)3(0.69g，0.75mmol)，P(t-Bu)3(0.30g, 1.51mmol), sodium t-butoxide (2.17g, 22.58mmol), xylene (50ml) were added to a 100ml single neck flask, nitrogen was purged three times, and the flask was heated to 130 ℃ for reaction overnight. The reaction was cooled to room temperature, filtered, the filtrate was concentrated with silica gel and column chromatographed (PE: EA ═ 100:1) to give 5.2g of crude product, which was recrystallized from toluene/ethanol to give 4.5g of white solid in 46.7% yield. Mass spectrometric analysis determined molecular ion mass: 920.41 (Li)Theoretical value: 920.39).
Synthesis example 4: synthesis of S5
Figure BDA0002539230770000161
Synthesis of compound S5:
s1-1(5g, 7.53mmol), 3-tert-butylcarbazole (3.78g, 15.05mmol), Pd were added at room temperature2(dba)3(0.69g，0.75mmol)，P(t-Bu)3(0.30g, 1.51mmol), sodium t-butoxide (2.17g, 22.58mmol), xylene (50ml) were added to a 100ml single neck flask, nitrogen was purged three times, and the flask was heated to 130 ℃ for reaction overnight. The reaction was cooled to room temperature, filtered, the filtrate was concentrated with silica gel and column chromatographed (PE: EA ═ 100:1) to give 6.7g of crude product, which was recrystallized from toluene/ethanol to give 5.5g of white solid in 77% yield. Mass spectrometric analysis determined molecular ion mass: 949.34 (theoretical value: 949.21).
Synthesis example 5: synthesis of S6
Figure BDA0002539230770000162
Synthesis of compound S6:
s1-1(5g, 7.53mmol), 3-methoxy carbazole (3.42g, 15.05mmol), Pd were added at room temperature2(dba)3(0.69g，0.75mmol)，P(t-Bu)3(0.30g, 1.51mmol), sodium t-butoxide (2.17g, 22.58mmol), xylene (50ml) were added to a 100ml single neck flask, nitrogen was purged three times, and the flask was heated to 130 ℃ for reaction overnight. The reaction was cooled to room temperature, filtered, the filtrate was concentrated with silica gel and column chromatographed (PE: EA ═ 100:1) to give 6g of crude product, which was recrystallized from toluene/ethanol to give 5g of white solid in 74.1% yield. Mass spectrometric analysis determined molecular ion mass: 957.01 (theoretical value: 956.34).
Synthesis example 6: synthesis of S7
Figure BDA0002539230770000163
Synthesis of compound S7:
s1-1(5g, 7.53mmol), 3, 6-dimethylcarbazole (2.94g, 15.05mmol), Pd were added at room temperature2(dba)3(0.69g，0.75mmol)，P(t-Bu)3(0.30g, 1.51mmol), sodium t-butoxide (2.17g, 22.58mmol), xylene (50ml) were added to a 100ml single neck flask, nitrogen was purged three times, and the flask was heated to 130 ℃ for reaction overnight. The reaction was cooled to room temperature, filtered, the filtrate was concentrated with silica gel and column chromatographed (PE: EA ═ 100:1) to give 6g of crude product, which was recrystallized from toluene/ethanol to give 5g of white solid in 74.4% yield. Mass spectrometric analysis determined molecular ion mass: 892.44 (theoretical value: 892.36).
Synthesis example 7: synthesis of S8
Figure BDA0002539230770000171
Synthesis of compound S8:
s1-1(5g, 7.53mmol), 3, 6-diethylcarbazole (3.36g, 15.05mmol), Pd were added at room temperature2(dba)3(0.69g，0.75mmol)，P(t-Bu)3(0.30g, 1.51mmol), sodium t-butoxide (2.17g, 22.58mmol), xylene (50ml) were added to a 100ml single neck flask, nitrogen was purged three times, and the flask was heated to 130 ℃ for reaction overnight. The reaction was cooled to room temperature, filtered, the filtrate was concentrated with silica gel and column chromatographed (PE: EA ═ 100:1) to give 6.7g of crude product, which was recrystallized from toluene/ethanol to give 5.8g of white solid in 81.2% yield. Mass spectrometric analysis determined molecular ion mass: 848.33 (theoretical value: 948.42).
Synthesis example 8: synthesis of S9
Figure BDA0002539230770000172
Synthesis of compound S9:
s1-1(5g, 7.53mmol), 3, 6-diisopropylcarbazole (3.78g, 15.05mmol) was added at room temperaturel)，Pd2(dba)3(0.69g，0.75mmol)，P(t-Bu)3(0.30g, 1.51mmol), sodium t-butoxide (2.17g, 22.58mmol), xylene (50ml) were added to a 100ml single neck flask, nitrogen was purged three times, and the flask was heated to 130 ℃ for reaction overnight. The reaction was cooled to room temperature, filtered, the filtrate was concentrated with silica gel and column chromatographed (PE: EA ═ 100:1) to give 7g of crude product, which was recrystallized from toluene/ethanol to give 6g of white solid in 79.3% yield. Mass spectrometric analysis determined molecular ion mass: 1004.52 (theoretical value: 1004.48).
Synthesis example 9: synthesis of S10
Figure BDA0002539230770000181
Synthesis of compound S10:
s1-1(5g, 7.53mmol), 3, 6-di-tert-butylcarbazole (4.21g, 15.05mmol), Pd were added at room temperature2(dba)3(0.69g，0.75mmol)，P(t-Bu)3(0.30g, 1.51mmol), sodium t-butoxide (2.17g, 22.58mmol), xylene (50ml) were added to a 100ml single neck flask, nitrogen was purged three times, and the flask was heated to 130 ℃ for reaction overnight. The reaction was cooled to room temperature, filtered, the filtrate was concentrated with silica gel and column chromatographed (PE: EA ═ 100:1) to give 7.5g of crude product, which was recrystallized from toluene/ethanol to give 6.6g of white solid in 82.6% yield. Mass spectrometric analysis determined molecular ion mass: 1060.66 (theoretical value: 1060.54).
Synthesis example 10: synthesis of S26
Figure BDA0002539230770000182
Synthesis of compound S26:
s1-1(5g, 7.53mmol), diphenylamine (2.55g, 15.05mmol), Pd were added at room temperature2(dba)3(0.69g，0.75mmol)，P(t-Bu)3(0.30g, 1.51mmol), sodium t-butoxide (2.17g, 22.58mmol), xylene (50ml) were added to a 100ml single neck flask, nitrogen was purged three times, and the flask was heated to 130 ℃ for reaction overnight. Reaction ofThe solution was cooled to room temperature, filtered, the filtrate was concentrated with silica gel and column chromatographed (PE: EA ═ 100:1) to give 5g of crude product, which was recrystallized from toluene/ethanol to give 4g of white solid in 63.2% yield. Mass spectrometric analysis determined molecular ion mass: 841.34 (theoretical value: 841.03).
Synthesis example 11: synthesis of S141
Figure BDA0002539230770000191
Synthesis of intermediate S141-1:
carbazole-spirofluorene (14.54g, 35.85mmol), 2, 6-dibromo-4-fluorobenzonitrile (10g, 35.85mmol), cesium carbonate (23.36g, 71.71mmol), N-dimethylformamide (200ml) were added to a 500ml single-neck flask at room temperature, and reacted overnight at 120 ℃ under nitrogen. Stopping heating, cooling to room temperature, adding 500ml of water, stirring for 10min, separating out a large amount of white solid, performing suction filtration, boiling and washing the filter cake with ethanol for 2h, cooling, and performing suction filtration to obtain 15g of a white solid product with the yield of 63%. Mass spectrometric analysis determined molecular ion mass: 664.36 (theoretical value: 664.40).
Synthesis of compound S141:
s141-1(5g, 7.53mmol), carbazole (2.52g, 12.05mmol), Pd were added at room temperature2(dba)3(0.69g，0.75mmol)，P(t-Bu)3(0.30g, 1.51mmol), sodium t-butoxide (2.17g, 22.58mmol), xylene (50ml) were added to a 100ml single neck flask, nitrogen was purged three times, and the flask was heated to 130 ℃ for reaction overnight. The reaction was cooled to room temperature, filtered, the filtrate was concentrated with silica gel and column chromatographed (PE: EA ═ 100:1) to give 6g of crude product, which was recrystallized from toluene/ethanol to give 3g of white solid in 48% yield. Mass spectrometric analysis determined molecular ion mass: 836.85 (theoretical value: 837.00).
Synthesis example 12: synthesis of S142
Figure BDA0002539230770000192
Compound S142The synthesis of (2):
s1-1(5g, 7.53mmol), 3, 6-dimethylcarbazole (2.94g, 15.05mmol), Pd were added at room temperature2(dba)3(0.69g，0.75mmol)，P(t-Bu)3(0.30g, 1.51mmol), sodium t-butoxide (2.17g, 22.58mmol), xylene (50ml) were added to a 100ml single neck flask, nitrogen was purged three times, and the flask was heated to 130 ℃ for reaction overnight. The reaction was cooled to room temperature, filtered, the filtrate was concentrated with silica gel and column chromatographed (PE: EA ═ 100:1) to give 5g of crude product, which was recrystallized from toluene/ethanol to give 4.5g of white solid in 67% yield. Mass spectrometric analysis determined molecular ion mass: 864.35 (theoretical value: 864.33).
Synthesis example 13: synthesis of S149
Figure BDA0002539230770000201
Synthesis of intermediate S149-1:
carbazole-spirofluorene (14.54g, 35.85mmol), 2, 6-dibromo-4-fluorobenzonitrile (10g, 35.85mmol), cesium carbonate (23.36g, 71.71mmol), N-dimethylformamide (200ml) were added to a 500ml single-neck flask at room temperature, and reacted overnight at 120 ℃ under nitrogen. Stopping heating, cooling to room temperature, adding 500ml of water, stirring for 10min, separating out a large amount of white solid, performing suction filtration, boiling and washing the filter cake with ethanol for 2h, cooling, and performing suction filtration to obtain 16g of a white solid product with the yield of 67%. Mass spectrometric analysis determined molecular ion mass: 664.38 (theoretical value: 664.40).
Synthesis of compound S149:
s141-1(5g, 7.53mmol), carbazole (2.52g, 12.05mmol), Pd were added at room temperature2(dba)3(0.69g，0.75mmol)，P(t-Bu)3(0.30g, 1.51mmol), sodium t-butoxide (2.17g, 22.58mmol), xylene (50ml) were added to a 100ml single neck flask, nitrogen was purged three times, and the flask was heated to 130 ℃ for reaction overnight. The reaction was cooled to room temperature, filtered, the filtrate was concentrated with silica gel and column chromatographed (PE: EA ═ 100:1) to give 6g of crude product, which was recrystallized from toluene/ethanol to give 3.5g of white solid in 56% yield. Mass spectrometric analysisDetermined molecular ion mass: 836.88 (theoretical value: 837.00).
Synthesis example 14: synthesis of S150
Figure BDA0002539230770000202
Synthesis of compound S150:
s149-1(5g, 7.53mmol), 3, 6-dimethylcarbazole (2.94g, 15.05mmol), Pd were added at room temperature2(dba)3(0.69g，0.75mmol)，P(t-Bu)3(0.30g, 1.51mmol), sodium t-butoxide (2.17g, 22.58mmol), xylene (50ml) were added to a 100ml single neck flask, nitrogen was purged three times, and the flask was heated to 130 ℃ for reaction overnight. The reaction was cooled to room temperature, filtered, the filtrate was concentrated with silica gel and column chromatographed (PE: EA ═ 100:1) to give 5g of crude product, which was recrystallized from toluene/ethanol to give 5g of white solid in 74% yield. Mass spectrometric analysis determined molecular ion mass: 864.29 (theoretical value: 864.33).
Device embodiments
Detailed description of the preferred embodiments
The OLED includes first and second electrodes, and an organic material layer between the electrodes. The organic material may in turn be divided into a plurality of regions. For example, the organic material layer may include a hole transport region, a light emitting layer, and an electron transport region.
In a specific embodiment, a substrate may be used below the first electrode or above the second electrode. The substrate is a glass or polymer material having excellent mechanical strength, thermal stability, water resistance, and transparency. In addition, a Thin Film Transistor (TFT) may be provided on a substrate for a display.
The first electrode may be formed by sputtering or depositing a material used as the first electrode on the substrate. When the first electrode is used as an anode, an oxide transparent conductive material such as Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), tin dioxide (SnO2), zinc oxide (ZnO), or any combination thereof may be used. When the first electrode is used as a cathode, a metal or an alloy such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), or any combination thereof can be used.
The organic material layer may be formed on the electrode by vacuum thermal evaporation, spin coating, printing, or the like. The compound used as the organic material layer may be an organic small molecule, an organic large molecule, and a polymer, and a combination thereof.
The hole transport region is located between the anode and the light emitting layer. The hole transport region may be a Hole Transport Layer (HTL) of a single layer structure including a single layer containing only one compound and a single layer containing a plurality of compounds. The hole transport region may also be a multi-layer structure including at least one of a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), and an Electron Blocking Layer (EBL); wherein the HIL is located between the anode and the HTL and the EBL is located between the HTL and the light emitting layer.
The material of the hole transport region may be selected from, but is not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or polymers containing conductive dopants such as polyphenylenevinylene, polyaniline/dodecylbenzenesulfonic acid (Pani/DBSA), poly (3, 4-ethylenedioxythiophene)/poly (4-styrenesulfonate) (PEDOT/PSS), polyaniline/camphorsulfonic acid (Pani/CSA), polyaniline/poly (4-styrenesulfonate) (Pani/PSS), aromatic amine derivatives such as compounds shown below in HT-1 to HT-51; or any combination thereof.
Figure BDA0002539230770000221
Figure BDA0002539230770000231
Figure BDA0002539230770000241
The hole injection layer is located between the anode and the hole transport layer. The hole injection layer may be a single compound material or a combination of a plurality of compounds. For example, the hole injection layer may employ one or more compounds of HT-1 to HT-51 described above, or one or more compounds of HI-1-HI-3 described below; one or more of the compounds HT-1 to HT-51 may also be used to dope one or more of the compounds HI-1-HI-3 described below.
Figure BDA0002539230770000242
The light-emitting layer includes a light-emitting dye (i.e., dopant) that can emit different wavelength spectra, and may also include a Host material (Host). The light emitting layer may be a single color light emitting layer emitting a single color of red, green, blue, or the like. The single color light emitting layers of a plurality of different colors may be arranged in a planar manner in accordance with a pixel pattern, or may be stacked to form a color light emitting layer. When the light emitting layers of different colors are stacked together, they may be spaced apart from each other or may be connected to each other. The light-emitting layer may be a single color light-emitting layer capable of emitting red, green, blue, or the like at the same time.
According to different technologies, the luminescent layer material can be different materials such as fluorescent electroluminescent material, phosphorescent electroluminescent material, thermal activation delayed fluorescent luminescent material, and the like. In an OLED device, a single light emitting technology may be used, or a combination of a plurality of different light emitting technologies may be used. These technically classified different luminescent materials may emit light of the same color or of different colors.
In one aspect of the invention, the light-emitting layer employs a thermally activated delayed fluorescence emission technique. The host material of the light-emitting layer is selected from, but not limited to, one or more of the combinations of PH-1 to PH-85.
Figure BDA0002539230770000251
Figure BDA0002539230770000261
Figure BDA0002539230770000271
Figure BDA0002539230770000281
In one aspect of the invention, an Electron Blocking Layer (EBL) is located between the hole transport layer and the light emitting layer. The electron blocking layer may be, but is not limited to, one or more compounds of HT-1 to HT-51 described above, or one or more compounds of PH-47 to PH-77 described above; mixtures of one or more compounds from HT-1 to HT-51 and one or more compounds from PH-47 to PH-77 may also be used, but are not limited thereto.
The OLED organic material layer may further include an electron transport region between the light emitting layer and the cathode. The electron transport region may be an Electron Transport Layer (ETL) of a single-layer structure including a single-layer electron transport layer containing only one compound and a single-layer electron transport layer containing a plurality of compounds. The electron transport region may also be a multilayer structure including at least one of an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), and a Hole Blocking Layer (HBL).
In one aspect of the invention, the electron transport layer material may be selected from, but is not limited to, the combination of one or more of ET-1 through ET-65 listed below.
Figure BDA0002539230770000282
Figure BDA0002539230770000291
Figure BDA0002539230770000301
Figure BDA0002539230770000311
In one aspect of the invention, a Hole Blocking Layer (HBL) is located between the electron transport layer and the light emitting layer. The hole blocking layer can adopt, but is not limited to, one or more compounds from ET-1 to ET-65 or one or more compounds from PH-1 to PH-46; mixtures of one or more compounds from ET-1 to ET-65 with one or more compounds from PH-1 to PH-46 may also be used, but are not limited thereto.
An electron injection layer may also be included in the device between the electron transport layer and the cathode, the electron injection layer materials including, but not limited to, combinations of one or more of the following.
LiQ,LiF,NaCl,CsF,Li2O,Cs2CO3,BaO,Na,Li,Ca，Mg。
Device example 1 the organic electroluminescent device was prepared as follows:
the glass plate coated with the ITO transparent conductive layer was sonicated in a commercial detergent, rinsed in deionized water, washed in acetone: ultrasonically removing oil in an ethanol mixed solvent, baking in a clean environment until the water is completely removed, cleaning by using ultraviolet light and ozone, and bombarding the surface by using low-energy cationic beams;
placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to<1×10-5Pa, performing vacuum thermal evaporation on the anode layer film in sequence to obtain a 10nm HT-4: HI-3(97/3, w/w) mixture as a hole injection layer, a 60nm compound HT-4 as a hole transport layer and a 5nm compound HT-51 as an electron blocking layer; a binary mixture of compounds PH-54: S6(100:40, w/w) with the wavelength of 40nm as a light-emitting layer, PH-28 with the wavelength of 5nm as a hole blocking layer, a mixture of compounds ET-61: ET-57(50/50, w/w) with the wavelength of 25nm as an electron transport layer, LiF with the wavelength of 1nm as an electron injection layer, and metallic aluminum with the wavelength of 150nm as a cathode. The total evaporation rate of all the organic layers and LiF is controlled at 0.1 nm/s, and the evaporation rate of the metal electrode is controlled at 1 nm/s.
Device examples 2 to 13 and comparative examples 1 to 3 were fabricated in the same manner as in device example 1 except that the compound S6 of the present invention as a luminescent dye was replaced with the compounds S2, S4, S5, S7, S8, S9, S10, S26, S141, S142, S149, S150 of the present invention, the compound R-1 of the prior art, the compound R-2 of the prior art, and the compound R-3 of the prior art, respectively.
Compounds of the prior art employed in the comparative examples R-1, R-2 and R-3:
Figure BDA0002539230770000321
the organic electroluminescent device prepared by the above process was subjected to the following performance measurement:
measuring the driving voltage of the organic electroluminescent device prepared from the compound and the comparative material by using a digital source meter and a luminance meter under the same luminance; external quantum efficiency of the organic electroluminescent device was measured using an integrating sphere: using a luminance meter at 1000cd/m2The luminance drop of the organic electroluminescent device was measured to 950cd/m by maintaining a constant current at luminance2Time in hours.
Specific performance data of the organic electroluminescent devices prepared in the above examples 1 to 13 and comparative examples 1 to 3 of the present invention are detailed in the following table 1, wherein the life value of comparative example 1 is standard 1.0, and the life value in other examples is a ratio thereof.
TABLE 1
Figure BDA0002539230770000322
Figure BDA0002539230770000331
The above results show that the compounds in the examples have significant TADF properties compared to the compound of comparative example 1, and thus there is a significant improvement in device efficiency and lifetime. Compared with the compound in the comparative example 2, the cyano para-position is carbazole spirofluorene, the donor group has stronger plane rigidity, the overall charge transport property of the material molecule can be improved, and the molecule stability is enhanced, so that the device efficiency is improved and the service life is prolonged. Compared with the compound in the comparative example 3, the ortho-position of the cyano group is two carbazole groups, the ortho-position groups have a certain twist angle, but have a certain degree of overlap without excessive twist, which is beneficial to improving the transition rate of the molecule and keeping the stability of the molecule, so that the service life of the device is obviously prolonged under the condition of slightly improving the efficiency.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims (11)

1. A compound of the formula (1):
Figure FDA0002539230760000011
in formula (1):
R1selected from substituted or unsubstituted C1-C12 chain alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C1-C12 alkoxy, substituted or unsubstituted C1-C12 thioalkoxy, halogen, cyano, nitro, hydroxyl, substituted or unsubstituted C1-C12 silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, and substituted or unsubstituted C6-C30 monocyclic ringOne or the combination of at least two of aryl, substituted or unsubstituted C10-C30 condensed ring aryl, substituted or unsubstituted C3-C30 monocyclic heteroaryl and substituted or unsubstituted C6-C30 condensed ring heteroaryl;
D1selected from the structures represented by formula (I):
Figure FDA0002539230760000012
in the formula (I), Ar1And Ar2Are respectively and independently selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, Ar1And Ar2May or may not be joined to form a ring;
denotes the attachment site of the group;
D2selected from the structures represented by the general formula (II):
Figure FDA0002539230760000021
in the formula (II), A is a structure represented by the formula (a1), and the dotted line represents the condensed position of the group;
in the formula (II), R2、R3、R4、R5Each independently selected from one of substituted or unsubstituted C1-C12 chain alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C1-C12 alkoxy, substituted or unsubstituted C1-C12 thioalkoxy, halogen, cyano, nitro, hydroxyl, substituted or unsubstituted C1-C12 silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 monocyclic aryl, substituted or unsubstituted C10-C30 fused ring aryl, substituted or unsubstituted C3-C30 monocyclic heteroaryl, and substituted or unsubstituted C6-C30 fused ring heteroaryl;
b is an integer of 0 to 4; c is an integer of 0 to 2; d is an integer of 0 to 4; e is an integer of 0 to 8;
m and n are respectively independently selected from integers of 1-4, a is selected from integers of 0-3, and m + n + a is less than or equal to 5; preferably a is 0;
when the above groups have substituents, the substituents are selected from one or a combination of at least two of halogen, cyano, nitro, hydroxyl, C1-C12 chain alkyl, C3-C12 cycloalkyl, C1-C12 alkoxy, C1-C12 thioalkoxy, C1-C12 silyl, amino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 monocyclic aryl, C10-C30 fused ring aryl, C3-C30 monocyclic heteroaryl and C6-C30 fused ring heteroaryl.
2. The compound according to claim 1, represented by the following formula (2-1) or (2-2):
Figure FDA0002539230760000022
in the formula (2-1), D2And R1Is the same as defined in the general formula (1);
in the formula (2-1), D1' and D1"is the same or different and is independently selected from formula (i) as defined in claim 1;
in the formula (2-1), n 'is an integer of 1-3, a' is an integer of 0-2, and n '+ a' is less than or equal to 3; preferably a' is 0;
preferably, in the formula (2-1), n' is 1;
in the formula (2-2), D1And R1Is the same as defined in the general formula (1);
in the formula (2-2), D2' and D2"identical or different, each independently selected from the general formula (II) as defined in claim 1;
in the formula (2-2), m 'is an integer of 1-3, a' is an integer of 0-2, and m '+ a' is less than or equal to 3; preferably a "is 0;
preferably, in the formula (2-2), m' is 1;
still more preferably, the compound of claim 1 is represented by formula (2-1).
3. The compound according to claim 2, represented by the following formula (3-1) or (3-2):
Figure FDA0002539230760000031
in the formula (3-1), D2And R1Is as defined in formula (1), D1’、D1", a' are as defined in formula (2-1);
in the formula (3-2), D1And R1Is the same as defined in the general formula (1); d2’、D2", a" are as defined in formula (2-2);
still more preferably, the compound of claim 2 is represented by the formula (3-1).
4. A compound according to any one of claims 1 to 3, wherein D is in the formula (1), the formula (2-2), the formula (3-1) or (3-2)1、D1' and D1"are each independently selected from the structures represented by the formula (I-1) or the formula (I-2):
Figure FDA0002539230760000041
in the formula (I-1), X1-X10Are each independently selected from CR9Or N, R9Independently selected from substituted or unsubstituted C1-C12 chain alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C1-C12 alkoxy, substituted or unsubstituted C1-C12 thioalkoxy, halogen, cyano, nitro, hydroxyl, substituted or unsubstituted C1-C12 silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 monocyclic aryl, substituted or unsubstituted C10-C30 fused ring aryl, substituted or unsubstituted C3-C30 monocyclic heteroaryl, substituted or unsubstituted C6-C6 fused ring arylOne or a combination of at least two of unsubstituted C6-C30 fused ring heteroaryl, and X1-X5Middle and X6-X10Any two adjacent of the two can be connected into a ring;
in the formula (I-2), X11-X18Are each independently selected from CR12Or N, R12Independently selected from one or a combination of at least two of substituted or unsubstituted C1-C12 chain alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C1-C12 alkoxy, substituted or unsubstituted C1-C12 thioalkoxy, halogen, cyano, nitro, hydroxyl, substituted or unsubstituted C1-C12 silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 monocyclic aryl, substituted or unsubstituted C10-C30 fused ring aryl, substituted or unsubstituted C3-C30 monocyclic heteroaryl, substituted or unsubstituted C6-C30 fused ring heteroaryl, and X is11-X14Middle and X15-X18Any two adjacent ones of which may be joined to form a ring.
5. A compound according to any one of claims 1 to 3, wherein D is in the formula (1), the formula (2-2), the formula (3-1) or (3-2)1、D1' and D1"are respectively and independently selected from any one of the following groups:
Figure FDA0002539230760000042
6. a compound according to any one of claims 1 to 3, wherein D is in the formula (1), the formula (2-2), the formula (3-1) or (3-2)2、D2' and D2"are respectively and independently selected from any one of the following groups:
Figure FDA0002539230760000051
wherein R is2、R3、R4、R5B, d, c and e are as defined in formula (II);
preferably, said R is2、R3、R4、R5Independently selected from one of the following substituted or unsubstituted groups:
Figure FDA0002539230760000052
7. a compound according to any one of claims 1 to 3, wherein D is in the formula (1), the formula (2-2), the formula (3-1) or (3-2)2、D2' and D2"are respectively and independently selected from any one of the following groups:
Figure FDA0002539230760000061
8. the compound of any one of claims 1-6, wherein R1Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl, n-octyl, cyclopentyl, cyclohexyl or from substituted or unsubstituted: phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, indenyl, fluorenyl, 9,9 '-dimethylfluorene, 9, 9' -spirobifluorene, benzofluorene, fluoranthenyl, triphenylene, pyrenyl, perylenyl, perylene, and the like,
Figure FDA0002539230760000062
One of a phenyl group, a tetracenyl group, a furyl group, a thienyl group, a pyrrolyl group, a benzofuryl group, a benzothienyl group, an isobenzofuryl group, an indolyl group, a dibenzofuryl group, a dibenzothienyl group, and a carbazolyl group.
9. The compound of claim 1, selected from the compounds of the following structures:
Figure FDA0002539230760000071
Figure FDA0002539230760000081
Figure FDA0002539230760000091
Figure FDA0002539230760000101
Figure FDA0002539230760000111
10. use of the compound according to any one of claims 1 to 9 as a light-emitting material in an optical sensor, a solar cell, a lighting element, an organic thin film transistor, an organic field effect transistor, an organic thin film solar cell, an information label, an electronic artificial skin sheet, a large-area sensor such as a sheet-type scanner, electronic paper, or an organic electroluminescent device, each independently;
preferably, the application is as a luminescent layer dye and/or sensitizer in an organic electroluminescent device.
11. An organic electroluminescent device comprising an anode layer, a plurality of light emitting functional layers and a cathode layer; the plurality of light-emitting functional layers comprise at least one of a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer and an electron transport layer which are sequentially formed, wherein the hole injection layer is formed on the anode layer, and the cathode layer is formed on the electron transport layer; wherein the light-emitting layer contains the organic compound according to any one of claims 1 to 9.
CN202010541874.3A 2020-06-15 2020-06-15 Thermal activation delayed fluorescent material, organic electroluminescent device and application thereof Pending CN113801058A (en)

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