Compounds, materials for organic light-emitting devices, organic light-emitting devices and electronic devices

Abstract

The compound shown in formula (1) below provides an organic electroluminescent device with further improved efficiency and lifetime. In formula (1), R1 to R15, Cy1 to Cy2 and X1 are exactly the same as defined in the specification.

Description

Technical Field

[0001] The present invention relates to compounds, materials for organic electroluminescent devices containing the compounds, organic electroluminescent devices containing the compounds, and electronic devices containing the organic electroluminescent devices. Background Technology

[0002] The principle of organic light-emitting diodes (OLEDs) is that after applying a certain voltage to the anode and cathode, the injected holes and electron carriers recombine within the emitting layer to form a high-energy excited state. Subsequently, when the excited state reverts to the ground state, it releases photons. Therefore, developing compounds that efficiently transport holes or electron carriers to the emitting layer, promote the recombination of holes and electrons, and release more photons is crucial for obtaining high-performance OLEDs.

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Chinese Publication No. CN116574118A

[0006] Patent Document 2: International Publication No. WO2021194216A1

[0007] Patent Document 3: Chinese Publication No. CN113416206A

[0008] Patent Document 4: Chinese Publication No. CN117050101A

[0009] Patent Document 5: Chinese Publication No. CN117209517A

[0010] Patent Document 6: Chinese Publication No. CN202411353453.2

[0011] Patent Document 7: International Publication No. W2020080872A1 Summary of the Invention

[0012] The problem to be solved by the present invention

[0013] In the past, a large number of compounds have been reported as materials for manufacturing blue organic light-emitting devices, but there is still a need for compounds that can further improve the performance of blue organic light-emitting devices.

[0014] This invention was made to solve the above-mentioned problems, and aims to provide a blue organic electroluminescent device with further improved efficiency and lifespan, as well as a novel compound for realizing such a blue organic electroluminescent device.

[0015] means for solving problems

[0016] In order to achieve the above objectives, the inventors have conducted repeated and in-depth research and found that the compound shown in the following formula (1) can achieve an organic electroluminescent device with further improved efficiency and lifetime.

[0017] In one embodiment, the present invention provides a compound of formula (1) (hereinafter sometimes also referred to as compound (1)).

[0018] [Chemistry 1]

[0019] In equation (1),

[0020] X1 can be an oxygen atom, a sulfur atom, or a selenium atom;

[0021] The two adjacent substituents in R8 to R11 are single bonds that bond with formula (A);

[0022] R1-R7, R12-R15, and R8-R11 (which are not bonded to formula (A)) are each independently a substituent, a hydrogen atom, or a deuterium atom. The substituents are nitro, halogen, cyano, substituted or unsubstituted alkyl groups with 1-30 carbon atoms, substituted or unsubstituted cycloalkyl groups with 3-30 carbon atoms, substituted or unsubstituted aryl groups with 6-30 carbon atoms, substituted or unsubstituted aralkyl groups with 7-36 carbon atoms, etc. The group consisting of a heteroaryl group having 5 to 30 cyclic atoms (substituted or unsubstituted), a diarylamino group having a cyclic carbon group selected from aryl groups having 6 to 30 cyclic carbons, a diarylamino group having a cyclic carbon group selected from heteroaryl groups having 5 to 30 cyclic carbons, an aryl-heteroarylamino group having a cyclic carbon group selected from aryl groups having 6 to 30 cyclic carbons and a heteroaryl group having 5 to 30 cyclic carbons, and a silyl group having a cyclic carbon group selected from aryl groups having 6 to 30 cyclic carbons and a heteroaryl group having 5 to 30 cyclic carbons.

[0023] Among them, R1~R7, R12~R15 and R8~R11, which are not single bonds bonded to formula (A), each of the two adjacent ones independently represents a deuterium atom, a hydrogen atom or the above-mentioned substituents, or they are bonded to each other to form a ring structure.

[0024] Cy1 to Cy2 may be the same as or different from each other, and each is independently a substituted or unsubstituted hydrocarbon cyclic group or a substituted or unsubstituted heterocyclic group;

[0025] The asterisk (*) indicates the location where a chemical bond occurs.

[0026] In another embodiment, the present invention provides an organic electroluminescent device having a cathode, an anode, and an organic electroluminescent device having one or more light-emitting units disposed between the cathode and the anode, wherein at least one light-emitting unit in the light-emitting layer having one or more light-emitting units contains a compound (1) as a dopant of the light-emitting unit.

[0027] The effects of the invention

[0028] The compound (1) has the function of improving blue light emission efficiency and improving device lifespan. Attached Figure Description

[0029] Figure 1 This is a schematic diagram of a device comprising compound (1) and having one light-emitting unit according to the present invention.

[0030] Figure 2 This is a schematic diagram of a device comprising compound (1) and having two light-emitting units according to the present invention. Detailed Implementation

[0031] In this specification, the phrase "CC group with AA to BB carbon atoms, whether substituted or unsubstituted" refers to the number of carbon atoms in the CC group when it is unsubstituted, that is, the number of carbon atoms in the CC group when it is substituted.

[0032] In this specification, the phrase "atom number AA~BB" in the expression "CC group with substituted or unsubstituted atoms AA~BB" means the number of atoms in the CC group when it is unsubstituted, that is, the number of atoms that do not contain the substituents when it is substituted.

[0033] In this specification, the term "unsubstituted or unsubstituted CC group" means that the hydrogen atoms of the CC group are not replaced by substituents.

[0034] In this specification, "deuterium" refers to hydrogen isotopes containing different numbers of neutrons, such as protium, deuterium, or tritium.

[0035] In this specification, the term "ring carbon number" refers to the number of carbon atoms in the ring of a compound that forms a cyclic structure by atomic bonding. When the cyclic compound is substituted with a substituent, the number of carbon atoms in the substituent is not included in the carbon number of the cyclic compound.

[0036] In this specification, the term "number of cyclic atoms" refers to the number of atoms constituting the cyclic structure itself in a compound formed by atomic bonding. That is, atoms that do not constitute the cyclic structure, or atoms contained in substituents when the cyclic structure is replaced by substituents, are not included in the number of cyclic atoms.

[0037] One embodiment of the present invention relates to compound (1) represented by formula (1).

[0038] [Chemistry 2]

[0039] Among them, the two adjacent substituents in R8 to R11 are single bonds that are bonded to formula (A).

[0040] In one embodiment of the present invention, the two adjacent substituents R9 and R10 in R8 to R11 are single bonds bonded to formula (A), and compound (1) is represented by the following formulas (2) and (3).

[0041] [Chemistry 3]

[0042] [Chemistry 4]

[0043] In one embodiment of the present invention, compound (1) is preferably represented by the above formula (3).

[0044] The symbols in equations (1) to (3) above will be explained below.

[0045] In R8 to R11, the two adjacent substituents are single bonds that are bonded to formula (A). That is, compound (1) is a compound in which adjacent R8 and R9 are single bonds that are bonded to formula (A), adjacent R9 and R10 are single bonds that are bonded to formula (A), or adjacent R10 and R11 are single bonds that are bonded to formula (A).

[0046] In one embodiment of the present invention, the two adjacent substituents R9 and R10 in R8 to R11 are single bonds bonded to formula (A).

[0047] R1-R7, R12-R15, and R8-R11 (which are not bonded to formula (A)) are each independently represented as a substituent, a hydrogen atom, or a deuterium atom. The substituents are nitro; halogen; cyano; alkyl with 1-30, preferably 1-18, more preferably 1-8 carbon atoms, substituted or unsubstituted; cycloalkyl with 3-30, preferably 3-10, more preferably 3-8 cyclic carbon atoms, substituted or unsubstituted; aryl with 6-30, preferably 6-25, more preferably 6-18 cyclic carbon atoms, substituted or unsubstituted; and aralkyl with 7-36, preferably 7-26, more preferably 7-20 cyclic carbon atoms. The group consisting of a heteroaryl group having 5 to 30, preferably 5 to 24, more preferably 5 to 13, substituted or unsubstituted cyclic atoms; a diarylamino group having an aryl group having 6 to 30, preferably 6 to 18, cyclic carbon atoms; a diheteroarylamino group having a heteroaryl group having 5 to 30, preferably 5 to 24, cyclic atoms; an arylheteroarylamino group having an aryl group having 6 to 30, preferably 6 to 18, cyclic carbon atoms and a heteroaryl group having 5 to 30, preferably 5 to 13, cyclic atoms; and a silyl group having an aryl group having 6 to 30, preferably 6 to 18, cyclic carbon atoms and a heteroaryl group having 5 to 30, preferably 5 to 13, cyclic atoms.

[0048] In this context, two adjacent atoms of R1–R7, R12–R15, and R8–R11 (which are not single bonds to formula (A)) independently represent a deuterium atom, a hydrogen atom, or the aforementioned substituents, or are bonded together to form a ring structure. That is, the two adjacent atoms do not form a ring structure but are independently a deuterium atom, the aforementioned substituents, or a hydrogen atom, or are bonded together to form a ring structure.

[0049] In one embodiment of the invention, adjacent pairs of R1-R7, R12-R15, and R8-R11 (which are not single bonds to formula (A)) do not form a ring structure but are each independently a hydrogen atom, a deuterium atom, or one of the aforementioned substituents. In another embodiment of the invention, at least one set of adjacent pairs of R1-R7, R12-R15, and R8-R11 (which are not single bonds to formula (A)) are bonded together to form a ring structure.

[0050] As a specific example of the halogen of the present invention, it may be one or more of fluorine, chlorine, bromine and iodine, preferably fluorine atoms.

[0051] Specific examples of substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms as described in this invention may include, but are not limited to, methyl, sec-butyl, ethyl, pentyl, heptyl, nonyl, isobutyl, undecyl, tert-butyl, hexyl, octyl, n-propyl, decyl, n-butyl, or dodecyl, wherein methyl or tert-butyl is preferred.

[0052] Specific examples of cyclic alkyl groups with 3 to 30 cyclic carbon atoms, whether substituted or unsubstituted, as described in this invention may include, but are not limited to, cyclopentyl, cycloheptyl, cyclohexyl, cyclobutyl, adamantyl, cyclooctyl, decahydronaphthyl, tetradecylhydrophenanthryl, or cyclopropyl, wherein cyclopentyl, adamantyl, or cyclohexyl are preferred.

[0053] Specific examples of aryl groups with 6 to 30 cyclic carbon atoms, whether substituted or unsubstituted, as described in this invention may include, but are not limited to, triphenylene, phenatenyl, fluorenyl, naphthyl, anthraceneyl, terphenyl, fenenyl, benzophenanthryl, biphenyl, benzoanthryl, biphenylenyl, perylene, pyrene, fluoranyl, or phenyl, wherein phenyl, biphenyl, or terphenyl are preferred.

[0054] Specific examples of substituted or unsubstituted aralkyl groups having 7 to 36 carbon atoms as described in this invention may include, but are not limited to, benzyl, phenethyl, or phenylpropyl, wherein benzyl is preferred.

[0055] Specific examples of heteroaryl groups with 5 to 30 cyclic atoms, whether substituted or unsubstituted, as described in this invention include, but are not limited to, indazole, phenoxazinyl, quinoxalinyl, phenazinyl, acridineyl, phenazinyl, naphthobenzofuranyl, naphthobenzothiophenyl, pyridinyl, pyrazinyl, isoindolyl, furanyl, isoquinolinyl, quinazinyl, imidazopyridinyl, benzoxazolyl, carbazole, isothiazolyl, oxadiazolyl, benzofuranyl, oxazolyl, benzoisothiazolyl, pyrazolyl, indazole, triazinyl, etc. The following groups are acceptable: azole, xanthonyl, pyrrole, pyridazinyl, imidazolyl, thiadiazolyl, indolyl, quinolinyl, benzothiophene, isobenzofuranyl, terolinyl, thiophene, tetrazolyl, phenanthrololinyl, isobenzothiophene, benzimidazolyl, triazinyl, benzisoxazolyl, thiazolyl, quinazolinyl, benzothiazolyl, phenanthidyl, phenothiazinyl, dibenzofuranyl, dibenzothiophene, or isoxazolyl. The heteroatom type only needs to be oxygen, nitrogen, or sulfur, and the number of heteroatoms must be 1 to 5.

[0056] As a specific example of a diarylamino group selected from substituted or unsubstituted aryl groups having a cyclic carbon number of 6 to 30, the aryl group having a cyclic carbon number of 6 to 30 includes, but is not limited to, triphenylene, phenatenyl, fluorenyl, naphthyl, anthraceneyl, terphenyl, fenenyl, benzo[a]phenenyl, biphenyl, benzo[a]anthrayl, biphenylenyl, perylene, pyrene, fluoranyl, or phenyl, wherein phenyl, biphenyl, or terphenyl are preferred.

[0057] As a specific example of the heteroaryl group selected from substituted or unsubstituted groups having a diheteroaryl amino group, the heteroaryl group having 5 to 30 cyclic atoms may include, but is not limited to, dibenzothiopheneyl, imidazolyl, triazolyl, thiopheneyl, pyrazinyl, isoxazolyl, cenolinyl, isobenzothiopheneyl, xanthonyl, indolyl, phenanthridine, benzothiazolyl, inazinyl, benzoisooxazolyl, oxadiazolyl, benzoimidazolyl, imidazopyridyl, benzofuranyl, benzo[…]. Thiopheneyl, pyridazinyl, triazinyl, oxazolyl, tetrazolyl, quinazinyl, isoquinolinyl, phenazinyl, pyrroleyl, isoindolyl, pyrazolyl, phenazinyl, quinazolinyl, thiazolyl, furanyl, phenanthrolinel, isobenzofuranyl, phenothiazinyl, quinolinyl, dibenzofuranyl, pyridinyl, acridineyl, indazoleyl, thiadiazolyl, naphthobenzothiopheneyl, carbazolyl, isothiazolyl, phenothiazinyl, benzoisothiazolyl, benzooxazolyl, naphthobenzofuranyl, or quinoxolinyl.

[0058] As a specific example of the aryl heteroaryl amino groups selected from substituted or unsubstituted aryl groups described in this invention, the aryl site having 6 to 30 carbon atoms in the ring formation includes, but is not limited to, triphenylene, finadenoyl, fluorenyl, naphthyl, anthraceneyl, terphenyl, styrene, benzophenanthryl, biphenyl, benzoanthryl, biphenylenyl, perylene, pyrene, fluoranyl, or phenyl, wherein phenyl, biphenyl, or terphenyl are preferred. The heteroaryl site having 5 to 30 carbon atoms in the ring formation may include, but is not limited to, dibenzothiophene, imidazolyl, triazolyl, thiophene, pyrazinyl, isoxazolyl, borazinyl, isobenzothiophene, and thallium. The following are listed: yl, indolyl, phenanthridine, benzothiazolyl, inazinyl, benzoisoxazolyl, oxadiazolyl, benzoimidazolyl, imidazopyridyl, benzofuranyl, benzothiophene, pyridazinyl, triazinyl, oxazolyl, tetrazolyl, quinazinyl, isoquinolinyl, phenazinyl, pyrroleyl, isoindolyl, pyrazolyl, phenazinyl, quinazolinyl, thiazolyl, furanyl, phenanthrolinyl, isobenzofuranyl, phenothiazinyl, quinolinyl, dibenzofuranyl, pyridinyl, acridineyl, inazolyl, thiadiazolyl, naphthobenzothiophene, carbazolyl, isothiazolyl, phenothiazinyl, benzoisothiazolyl, benzoxazolyl, naphthobenzofuranyl, or quinoxolinyl.

[0059] As a specific example of the silyl group substituted with an aryl group having 6 to 30 cyclic carbon atoms and a heteroaryl group having 5 to 30 cyclic atoms as described in this invention, the aryl group having 6 to 30 cyclic carbon atoms includes, but is not limited to, triphenylene, finadenoyl, fluorenyl, naphthyl, anthraceneyl, terphenyl, styrene, phenanthreneyl, biphenyl, benzanthraceneyl, biphenylenyl, perylene, pyrene, fluoranthraceneyl, or phenyl, wherein phenyl, biphenyl, or terphenyl are preferred. The heteroaryl group having 5 to 30 cyclic atoms may include, but is not limited to, dibenzothiopheneyl, imidazolyl, triazolyl, thiopheneyl, pyrazinyl, isoxazolyl, or zoline. The following are listed: yl, isobenzothiophene, xanthonyl, indolyl, phenanthridine, benzothiazolyl, inazinyl, benzoisoxazolyl, oxadiazolyl, benzoimidazolyl, imidazopyridyl, benzofuranyl, benzothiophene, pyridazinyl, triazinyl, oxazolyl, tetrazolyl, quinazinyl, isoquinolinyl, phenazinyl, pyrroleyl, isoindolyl, pyrazolyl, phenazinyl, quinazolinyl, thiazolyl, furanyl, phenanthridine, isobenzofuranyl, phenothiazinyl, quinolinyl, dibenzofuranyl, pyridinyl, acridineyl, inazolyl, thiadiazolyl, naphthobenzothiophene, carbazolyl, isothiazolyl, phenothiazinyl, benzoisothiazolyl, benzooxazolyl, naphthobenzofuranyl, or quinoxolinyl.

[0060] X1 can be an oxygen atom, a sulfur atom, or a selenium atom. In one embodiment of the invention, X1 is an oxygen atom; in another embodiment, X1 is a sulfur atom.

[0061] Cy1 to Cy2 may be the same as or different from each other, and each is independently a substituted or unsubstituted hydrocarbon cyclic group or a substituted or unsubstituted heterocyclic group.

[0062] The hydrocarbon ring of the aforementioned hydrocarbon cyclic group can be an aromatic ring or an alicyclic ring.

[0063] The aromatic hydrocarbon ring can be selected from the examples of the aryl groups described above, except that the aromatic hydrocarbon ring is divalent. That is, the description of the aryl group described above can be applied to the aromatic hydrocarbon ring, except that the aromatic hydrocarbon ring is divalent.

[0064] The alicyclic hydrocarbon rings referred to are hydrocarbon rings other than aromatic hydrocarbon rings, and alicyclic hydrocarbon rings include rings containing double bonds, such as substituted or unsubstituted tetrahydronaphthalene. Substituted or unsubstituted cyclopentene Substituted or unsubstituted cyclohexene Substituted or unsubstituted indene Substituted or unsubstituted anthracene And so on, but not limited to these.

[0065] The above description of heteroaryl rings can be applied to the description of heterocycles in the aforementioned heterocyclic group, except that the heterocycles in the aforementioned heterocyclic group are divalent.

[0066] The following are specific examples of the compound (1) of the present invention, but are not limited thereto.

[0067] [Chemistry 5]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083] There are no particular limitations on the method of manufacturing compound (1). Those skilled in the art can easily manufacture it by means of the methods described in the following examples or by reference to known synthetic methods.

[0084] Materials for OLED devices

[0085] The organic electroluminescent device material of the present invention comprises compound (1). The content of compound (1) in the organic electroluminescent device material of the present invention is selected in the range of WW ≤ 50% by mass, preferably WW ≤ 10% by mass, more preferably WW ≤ 5% by mass.

[0086] Explanation of OLED device structure

[0087] The organic electroluminescent device of the present invention comprises an anode, a cathode, and a light-emitting layer having one or more light-emitting units disposed between the cathode and the anode. At least one light-emitting unit in the light-emitting layer comprising compound (1) as a dopant for the light-emitting unit. A hole transport unit is further disposed between the anode and the light-emitting layer, and an electron transport unit is disposed between the light-emitting layer and the cathode.

[0088] The light-emitting layer can be a single light-emitting unit or a layer of multiple light-emitting units. That is, the compound (1) can be a fluorescent light-emitting dopant in the fluorescent light-emitting layer of a monochromatic device, a fluorescent-phosphorescent hybrid white light device, a stacked device with multiple light-emitting units, or a series device with multiple light-emitting units, and the light-emitting layer also contains anthracene compounds, pyrene compounds, or fluorene compounds as the main material.

[0089] In devices with stacked units, it is particularly important to note that each light-emitting unit can be a layer that emits different or the same light color from each other. For example, anode / (hole injection layer / )hole transport layer / red phosphorescent light-emitting unit / green phosphorescent light-emitting unit / spacer layer / blue fluorescent light-emitting unit containing compound (1) / electron transport layer / electron injection layer / cathode.

[0090] Figure 1 This provides a schematic diagram of an OLED device structure 500. The device structure 500 is characterized by including a substrate 51, an anode 52 formed on the substrate 51, a light-emitting unit 55 formed on the anode 52, and a cathode 58 on the light-emitting unit 55. Between the anode 52 and the light-emitting unit 55, a hole transport unit 53 composed of a first hole transport layer 53a and a second hole transport layer 53b, and an electron blocking layer 54 formed on the hole transport unit 53, are sequentially formed. Between the light-emitting unit 55 and the cathode 58, an electron transport unit 56 composed of a first electron transport layer 56a and a second electron transport layer 56b, and an electron injection layer 57 formed on the electron transport unit 56, are sequentially formed. The compound (1) acts on the fluorescent dopant within the light-emitting layer 55.

[0091] Figure 2This document provides a schematic diagram of an OLED device structure 600 containing two light-emitting units. The device structure 600 is characterized by comprising a substrate 61, an anode 62 formed on the substrate 61, a first light-emitting unit 65 formed sequentially on the anode 62, a second light-emitting unit 66 formed on the first light-emitting unit 65, and a cathode 69 on the second light-emitting unit 66. Between the anode 62 and the first light-emitting unit 65, a hole transport unit 63 composed of a first hole transport layer 63a and a second hole transport layer 63b, and an electron blocking layer 64 formed on the hole transport unit 63, are formed sequentially. Between the second light-emitting unit 66 and the cathode 69, an electron transport unit 66 composed of a first electron transport layer 66a and a second electron transport layer 66b, and an electron injection layer 67 formed on the electron transport unit 66, are formed sequentially. The compound (1) acts simultaneously on the fluorescent dopant within both the first light-emitting unit 65 and the second light-emitting unit 66.

[0092] The layers of the aforementioned organic electroluminescent devices can be formed using conventionally known processes such as vacuum thermal evaporation and inkjet printing. There are no particular limitations on the film thickness of each layer; generally, a thickness of 1 nm to 1000 nm is typically chosen.

[0093] Example

[0094] The present invention is further described in detail below using examples, but is not limited to the following examples.

[0095] Example 1: Synthesis of intermediate m-1

[0096]

[0097] Intermediate m-1 was synthesized using the same procedure as described in the legal method of CN115611937A. Under complete nitrogen purging, 1 mmol of starting materials 1-a, 1 mmol of 1-b, 1.6 g of tris(dibenzylacetone)dipalladium(O), 1.2 g of bis(diphenylphosphine)-1,1'-binaphthyl, sodium tert-butyloxide, and a toluene solution were added to a reaction flask, and the mixture was refluxed for 8 hours. After the reaction was complete, the mixture was cooled to room temperature and purified by silica gel column chromatography.

[0098] The obtained solid product 1-c was added to a glass vial containing 1 mmol of 1-d, followed by the addition of bis(tri-tert-butylphosphine)palladium(0), sodium tert-butyloxide, and toluene solution. After purging with nitrogen, the mixture was refluxed for 8 hours. After the reaction was completed and cooled to room temperature, the product was purified by silica gel column chromatography to obtain intermediate m-1.

[0099] Example 2: Synthesis of intermediate m-2

[0100]

[0101] After complete purging with nitrogen, 1 mmol of 1-e, 1 mmol of 1-b, 1.20 g of tris(dibenzylacetone)dipalladium(O), 0.96 g of bis(diphenylphosphine)-1,1'-binaphthyl, sodium tert-butyloxide, and toluene solution were added to the reaction flask. The mixture was then refluxed for 6 hours, cooled to room temperature, and purified by silica gel column chromatography.

[0102] Under a full nitrogen atmosphere, the obtained solid product 1-f was added to a glass vial containing 1 mmol of 1-d, along with bis(tri-tert-butylphosphine)palladium(0), sodium tert-butyloxide, and toluene solution. The mixture was then refluxed for 10 hours. After the reaction was completed and cooled to room temperature, the product was purified by silica gel column chromatography to obtain intermediate m-2.

[0103] Example 3: Synthesis of intermediate m-3

[0104]

[0105] Intermediate m-3 is synthesized by using the same operation as intermediate m-1, except that intermediates 1-b and 1-a are replaced with 1-g and 1-h.

[0106] Example 4: Synthesis of intermediate m-4

[0107]

[0108] Use the same operation as intermediate m-1, except replace intermediate 1-a with 1-j to synthesize intermediate m-4.

[0109] Example 5: Synthesis of intermediate m-5

[0110]

[0111] Use the same operation as intermediate m-1, except replace intermediate 1-a with 1-l to synthesize intermediate m-5.

[0112] Example 6: Synthesis of intermediate m-6

[0113]

[0114] Use the same operation as intermediate m-1, except replace intermediates 1-a and 1-b with 1-n and 1-o to synthesize intermediate m-6.

[0115] Example 7: Synthesis of intermediate m-7

[0116]

[0117] Use the same operation as intermediate m-1, except replace intermediate 1-a with 1-q to synthesize intermediate m-7.

[0118] Example 8: Synthesis of intermediate m-8

[0119]

[0120] Intermediate m-8 is synthesized by using the same operation as intermediate m-1, except that intermediates 1-a and 1-d are replaced with 1-l and 1-s.

[0121] Example 9: Synthesis of intermediate m-9

[0122]

[0123] Use the same operation as intermediate m-1, except replace intermediate 1-a with 1-t to synthesize intermediate m-9.

[0124] Example 10: Synthesis of intermediate m-10

[0125]

[0126] Under nitrogen purging, 2.2 g of tris(dibenzylacetone)dipalladium(0), 22 g of sodium tert-butyloxide, 1.5 g of bis(diphenylphosphine)-1,1'-binaphthylene and 450 mL of toluene were added to a reaction flask containing 1 mmol 2-a and 1 mmol 1-q, and the mixture was refluxed for 8 hours. After cooling to room temperature, the mixture was purified by silica gel column chromatography to obtain intermediate m-10.

[0127] Example 11: Synthesis of intermediate m-11

[0128]

[0129] Use the same operation as intermediate m-10, except replace intermediate 2-a with 2-b to synthesize intermediate m-11.

[0130] Example 12: Synthesis of intermediate m-12

[0131]

[0132] Use the same operation as intermediate m-10, except replace intermediate 1-q with 2-c to synthesize intermediate m-12.

[0133] Synthesis of intermediate m-13, Example 13

[0134]

[0135] Use the same operation as intermediate m-10, except replace intermediate 1-q with 2-d to synthesize intermediate m-13.

[0136] Example 14: Synthesis of intermediate m-14

[0137]

[0138] The same operation as intermediate m-10 is used, except that intermediate 1-q is replaced with 2-e to synthesize intermediate m-14.

[0139] Synthesis of Intermediate 15: Synthesis of Intermediate m-15

[0140]

[0141] Use the same operation as intermediate m-10, except replace intermediate 1-q with 1-t to synthesize intermediate m-15.

[0142] Example 16: Synthesis of intermediate m-16

[0143] Use the same operation as intermediate m-10, except replace intermediate 1-q with 2-f to synthesize intermediate m-16.

[0144] Example 17: Synthesis of intermediate m-17

[0145]

[0146] Intermediate m-17 is synthesized by using the same operation as intermediate m-10, except that intermediate 1-q is replaced with 2-g.

[0147] Example 18: Synthesis of intermediate m-18

[0148]

[0149] Intermediate m-18 is synthesized by using the same operation as intermediate m-10, except that intermediate 1-q is replaced with 2-h.

[0150] Synthesis of intermediate m-19, Example 19

[0151]

[0152] Use the same operation as intermediate m-1, except replace intermediate 1-d with 1-x to synthesize intermediate m-19.

[0153] Synthesis of Compound 1 in Example 1

[0154]

[0155] After purging with nitrogen, 1 mmol m-1 and 1 mmol m-10 of intermediates were added to a solution containing 1.0 g of bis(tri-tert-butylphosphine)palladium(0), 4.5 g of sodium tert-butoxide, and 450 mL of toluene. The mixture was heated under reflux for 8 hours. After the reaction was completed, the mixture was cooled to room temperature and purified by silica gel column chromatography to obtain intermediate n-1.

[0156] The obtained intermediate n-1 was added to a reaction flask containing 500 ml of tert-butylbenzene solution, and 60 ml of 1.7 M tert-butyllithium pentane solution was added dropwise at -78 °C. The mixture was then heated to 60 °C and stirred for 5 hours, during which nitrogen gas was blown in at 60 °C to completely remove the pentane. After cooling to -78 °C, 30 ml of boron tribromide was added dropwise, and the mixture was heated to room temperature and stirred for 5 hours. After cooling to 0 °C, 15 ml of N,N-diisopropylethylamine was added dropwise. The mixture was heated to 120 °C and stirred for 10 hours. After cooling to room temperature, the organic layer was separated and purified by silica gel column chromatography to obtain the product.

[0157] The mass spectrometry analysis of the obtained product showed a relative molecular weight of 1169.49 and m / e = 1168, indicating that it is compound 1.

[0158] Synthesis of Compound 2 in Example 2

[0159]

[0160] The same procedure as for compound 1 was used, except that intermediates m-1 and m-10 were used to replace m-2 and m-11 to synthesize the product. Mass spectrometry analysis of the obtained product showed a relative molecular weight of 1115.40 and m / e = 1114, identifying it as compound 2.

[0161] Synthesis of Compound 3 in Example 3

[0162]

[0163] The same procedure as for compound 1 was used, except that intermediate m-1 was used to replace m-3 to synthesize the product.

[0164] The mass spectrometry analysis of the obtained product showed a relative molecular weight of 1147.48 and m / e = 1146, indicating that it is compound 3.

[0165] Synthesis of Compound 4 in Example 4

[0166]

[0167] The same procedure as for compound 1 was used, except that intermediates m-1 and m-10 replaced m-4 and m-12 to synthesize the product. Mass spectrometry analysis of the obtained product showed a relative molecular weight of 1185.49 and m / e = 1184, identifying it as compound 4.

[0168] Synthesis of Compound 5 in Example 5

[0169]

[0170] The same procedure as for compound 1 was used, except that intermediates m-1 and m-10 were used to replace m-4 and m-13 to synthesize the product. Mass spectrometry analysis of the obtained product showed a relative molecular weight of 1131.40 and m / e = 1130, identifying it as compound 5.

[0171] Synthesis of Compound 6 in Example 6 The same procedure as for compound 1 was used, except that intermediates m-1 and m-10 replaced m-14 and m-5 to synthesize the product. Mass spectrometry analysis of the obtained product showed a relative molecular weight of 1145.45 and m / e = 1144, identifying it as compound 6.

[0172] Synthesis of Compound 7 in Example 7

[0173]

[0174] The same procedure as for compound 1 was used, except that intermediates m-1 and m-10 were used to replace m-6 and m-15 to synthesize the product. Mass spectrometry analysis of the obtained product showed a relative molecular weight of 1151.39 and m / e = 1150, identifying it as compound 7.

[0175] Synthesis of Compound 8 in Example 8

[0176]

[0177] The same procedure as for compound 1 was used, except that intermediates m-1 and m-10 were used to replace m-7 and m-16 to synthesize the product.

[0178] The mass spectrometry analysis of the obtained product showed a relative molecular weight of 1149.37 and m / e = 1148, indicating that it is compound 8.

[0179] Synthesis of Compound 9 in Example 9

[0180]

[0181] The same procedure as for compound 1 was used, except that intermediates m-1 and m-10 were used to replace m-7 and m-17 to synthesize the product.

[0182] The mass spectrometry analysis of the obtained product showed a relative molecular weight of 1073.28 and m / e = 1072, indicating that it is compound 9.

[0183] Synthesis of Compound 10 in Example 10

[0184]

[0185] The same procedure as for compound 1 was used, except that intermediates m-1 and m-10 were used to replace m-8 and m-15 to synthesize the product.

[0186] The mass spectrometry analysis of the obtained product showed a relative molecular weight of 1183.47 and m / e = 1182, indicating that it is compound 10.

[0187] Synthesis of Compound 11 in Example 11

[0188]

[0189] The same procedure as for compound 1 was used, except that intermediates m-1 and m-10 were used to replace m-7 and m-18 to synthesize the product.

[0190] The mass spectrometry analysis of the obtained product showed a relative molecular weight of 1123.34 and m / e = 1122, indicating that it is compound 11.

[0191] Synthesis of Compound 12 in Example 12

[0192]

[0193] The same procedure as for compound 1 was used, except that intermediates m-1 and m-10 were used to replace m-19 and m-16 to synthesize the product.

[0194] The mass spectrometry analysis of the obtained product showed a relative molecular weight of 1133.31 and m / e = 1132, indicating that it is compound 12.

[0195] Synthesis of Compound 13 in Example 13

[0196]

[0197] The same procedure as for compound 1 was used, except that intermediates m-1 and m-10 were used to replace m-9 and m-10 to synthesize the product.

[0198] The mass spectrometry analysis of the obtained product showed a relative molecular weight of 1073.28 and m / e = 1072, indicating that it is compound 13.

[0199] Example 1: Fabrication of a device with one light-emitting unit

[0200] The first hole transport layer 53a is composed of HATCN (3wt%):HT1; the second hole transport layer 53b is composed of HT1; the electron blocking layer 54 is composed of HT2; the light-emitting layer 55 is composed of BH1:compound 1 (2wt%); the first electron transport layer 56a is composed of ET1; the second electron transport layer 56b is composed of ET1:LiQ; the electron injection layer 57 is composed of Yb; the cathode layer 58 is composed of Mg:Ag (1:9) alloy; the photoextraction layer is HT2.

[0201] Material structure used in devices

[0202]

[0203] Characterization of device performance

[0204] At 10mA / cm 2 Efficiency tests were conducted under the given conditions, and the results are recorded in Table 1.

[0205] At 20mA / cm 2 The 95th value is defined as the brightness decaying to 95% of the initial brightness, and the results are shown in Table 1 below.

[0206] Examples 2-7

[0207] The fluorescent dopants in the light-emitting layer 55 were replaced with compounds 2 to 7 respectively, and the devices 2 to 7 were manufactured in the same manner as in Example 1. The device performance was then tested, and the results are shown in Table 1.

[0208] Comparative Examples 1-5

[0209] Compound 1 was replaced with "Comparative Compounds 1-3" (compounds described in Patent Document 1) or "Comparative Compounds 4-5" (compounds described in Patent Document 2) and used as a material in the light-emitting layer 55. Using the same device fabrication process and measurement conditions, the results are shown in Table 1.

[0210] Example 8: Fabrication of an OLED top-emitting device with two light-emitting units

[0211] The first hole transport layer 63a is composed of HATCN (3wt%):HT1; the second hole transport layer 63b is composed of HT1; an electron blocking layer 64 is formed on the second hole transport layer 63b, composed of HT2; a first luminescent layer 65 is formed on the electron blocking layer 64, composed of BH2:compound 8 (2wt%); a second luminescent layer 66 is formed of BH1:compound 8 (2wt%); a first electron transport layer 67a is formed on the second luminescent layer 66, composed of ET1; a second electron transport layer 67b is formed of ET1:LiQ; an electron injection layer 68 is formed on the second electron transport layer 67b, composed of Yb; a cathode layer 69 is composed of Mg:Ag (1:9) alloy; and a photoextraction layer: HT2.

[0212] Characterization of device performance

[0213] At 10mA / cm 2 Efficiency tests were conducted under the given conditions, and the results are recorded in Table 1.

[0214] At 20mA / cm 2 The 95th value is defined as the brightness decaying to 95% of the initial brightness, and the results are shown in Table 1 below.

[0215] Examples 9-13

[0216] The fluorescent dopants in the first luminescent layer 65 and the second luminescent layer 66 were replaced with compounds 9-13, respectively, and the devices 9-13 were manufactured in the same manner as in Example 8. The device performance was then tested, and the results are shown in Table 1.

[0217] Comparative Examples 6-10

[0218] Compound 8 was replaced with "Comparative Compound 6" (the compound recorded in Patent Document 3), or "Comparative Compound 7" (the compound recorded in Patent Document 4), or "Comparative Compound 8" (the compound recorded in Patent Document 5), or "Comparative Compound 9" (the compound recorded in Patent Document 6), or "Comparative Compound 10" (the compound recorded in Patent Document 7) and used as a fluorescent dopant in the first emitting layer 65 and the second emitting layer 66. Using the same device fabrication process and measurement conditions, the results are shown in Table 1.

[0219] Materials used in Comparative Examples 1-10

[0220]

[0221] It should be particularly noted that compounds 1 to 13 of the present invention simultaneously satisfy two important conditions: molecular structural element Q-1: benzothiophene (or benzofuran) resonates with both electron-rich nitrogen atoms and electron-deficient boron atoms to form the first luminescent core, controlling the quantum efficiency, fluorescence radiation transition rate, heavy atom effect, and luminescence efficiency of the luminescent material; molecular element Q-2: adamantane spirofluorene resonates with both electron-rich nitrogen atoms and electron-deficient boron atoms to form the second luminescent core, further controlling the luminescence quantum efficiency, enhancing photon emission orientation, luminescence spectral morphology (or color purity), fluorescence radiation transition rate constant, and suppressing the exciton annihilation rate between molecules.

[0222] "Comparative compounds 1-9" do not satisfy structural element Q-2, while "comparative compound 10" does not satisfy structural element Q-1.

[0223] [Table 1]

[0224]

[0225]

[0226] [a]: HOMO represents the on-set value of the oxidation curve measured by cyclic voltammetry (CV).

[0227] [b]:LUMO according to equation E LUMO =E HOMO +Eg calculation results;

[0228] [c]: Calculated based on the peak value λpeak of the fluorescence spectrum using S1 = 1238 / ;

[0229] [d]: A 10 nm sample was prepared by vapor deposition, and the fluorescence radiative rate was measured using a transient fluorescence spectrometer under a nitrogen atmosphere (10 nm). 7 / s);

[0230] [e]: Samples with a wavelength of 10 nm were prepared by vapor deposition, and exciton lifetimes (10 nm) were measured using a transient fluorescence spectrometer under a nitrogen atmosphere. - 7 s);

[0231] [f]: The time (hrs) for the initial brightness of a 10nm analyte to decay to 50% under ultraviolet light irradiation at a wavelength of 365nm;

[0232] Referring to Table 1, Examples 1-13 demonstrate the functions of long lifespan and high efficiency.

[0233] Without being bound by theory, it is believed that compounds 1-13 according to the examples significantly improve the quantum efficiency (not shown, acting on molecular elements Q-1 & Q-2), stronger rigid structure (molecular element Q-2), fluorescence radiation transition rate (acting on molecular elements Q-1 & Q-2), heavy atom effect (molecular element Q-1), luminescence efficiency (molecular elements Q-1 & Q-2), enhanced photon emission orientation (molecular elements Q-1 & Q-2), emission spectrum morphology (not shown, molecular element Q-2), and suppressed intermolecular exciton annihilation rate (molecular element Q-2) during the fluorescence emission process by introducing molecular element Q-1: benzothiophene (or benzofuran) resonating with both electron-rich nitrogen atoms and electron-deficient boron atoms to form the first luminescent core, and molecular element Q-2: adamantane spirofluorene resonating with both electron-rich nitrogen atoms and electron-deficient boron atoms to form the second luminescent core.

[0234] To clarify the technical advantages of the present invention and further demonstrate the synergistic effect of molecular elements Q-1 and Q-2, the inventors conducted further in-depth research and obtained the following surprising findings.

[0235] [HOMO level, LUMO level]

[0236] The HOMO and LUMO energy levels obtained by cyclic voltammetry and optical band measurements are recorded in Table 1. As shown in Table 1, compounds 1–13, comparative compounds 1–7 and 9–10 are shown as suitable blue light emitting materials, while comparative compound 8 is a green light emitting material.

[0237] [Fluorescence rate constant, exciton lifetime]

[0238] The fluorescence radiative rate constant reflects the rate of light emission from the excited state to the ground state of a fluorescent small molecule. A large fluorescence radiative rate constant weakens the non-radiative rate constant, thus increasing fluorescence luminescence and further shortening the exciton lifetime, which is beneficial for obtaining ideal fluorescence luminescence lifetime or efficiency. The fluorescence radiative rate constant and exciton lifetime were measured using a FluoroMax-4 transient fluorescence spectrometer, and the results are recorded in Table 1.

[0239] As shown in Table 1, compounds 1–13, through the synergistic effect of introducing molecular elements Q-1 and Q-2, significantly improve the fluorescence radiative rate process and shorten the residence time of excited states in chemical bonds, thereby achieving the highest device performance or resistance to photodegradation. The adamantane spirofluorene of molecular element Q-2 is more effective than the spirodifluorene, spirofluorene, or cyclohexane spirofluorene introduced into molecular element Q-1 in inhibiting exciton annihilation rate, increasing radiative transition rate constant, and shortening exciton residence time in the comparative compounds 4–7 compared to those introduced into molecular element Q-1.

[0240] Compared to compounds 1-10, which do not simultaneously possess molecular elements Q-1 and Q-2, exhibiting a poor fluorescence radiative rate process, severe inter-excited state quenching results in reduced device efficiency, shortened device lifetime, or weakened resistance to photodegradation.

[0241] [Photoluminescence Intensity Test]

[0242] A 100 nm thick analyte was prepared on a substrate and then irradiated with 365 nm ultraviolet light to induce photoluminescence and generate light intensity. The time from the initial photoluminescence intensity decaying to 50% was defined as LT50, and the results are recorded in Table 1.

[0243] As shown in Table 1, compounds 1–13 exhibited significantly enhanced resistance to photodegradation through the synergistic effect of the introduction of molecular elements Q-1 and Q-2. In particular, the introduction of molecular element Q-2 not only enabled compounds 1–13 to exhibit a wider carrier delocalization space, but also the electron shielding effect of adamantane spirofluorene was more conducive to suppressing the mutual annihilation rate of excitons between excited states, thereby achieving the best resistance to photodegradation.

[0244] Comparative compounds 1-9, possessing only molecular element Q-1 but lacking molecular element Q-2, exhibit slower fluorescence emission rates and faster multi-channel non-radiative rates, resulting in poorer resistance to photodegradation. Comparative compound 10, possessing only molecular element Q-2 but lacking molecular element Q-1, shows a slight improvement in molecular electron shielding; however, the absence of molecular element Q-1 leads to a slower fluorescence emission rate, thus prolonging the photon dwell time at chemical bonds and further promoting the photon-induced degradation of comparative compound 10.

[0245] Although this application discloses preferred embodiments as described above, it is not intended to limit the claims. Any person skilled in the art can make several possible changes and modifications without departing from the concept of this application. Therefore, the scope of protection of this application should be determined by the scope defined in the claims of this application.

Claims

1. A compound, said compound being represented by the following formula (1), In equation (1), X1 can be an oxygen atom, a sulfur atom, or a selenium atom; The two adjacent substituents in R8 to R11 are single bonds that bond with formula (A); R1-R7, R12-R15, and R8-R11 (which are not bonded to formula (A)) are each independently a substituent, a hydrogen atom, or a deuterium atom. The substituents are nitro, halogen, cyano, substituted or unsubstituted alkyl groups with 1-30 carbon atoms, substituted or unsubstituted cycloalkyl groups with 3-30 carbon atoms, substituted or unsubstituted aryl groups with 6-30 carbon atoms, substituted or unsubstituted aralkyl groups with 7-36 carbon atoms, etc. The group consisting of a heteroaryl group having 5 to 30 cyclic atoms (substituted or unsubstituted), a diarylamino group having a cyclic carbon group selected from aryl groups having 6 to 30 cyclic carbons, a diarylamino group having a cyclic carbon group selected from heteroaryl groups having 5 to 30 cyclic carbons, an aryl-heteroarylamino group having a cyclic carbon group selected from aryl groups having 6 to 30 cyclic carbons and a heteroaryl group having 5 to 30 cyclic carbons, and a silyl group having a cyclic carbon group selected from aryl groups having 6 to 30 cyclic carbons and a heteroaryl group having 5 to 30 cyclic carbons. in, R1~R7, R12~R15 and R8~R11 which are not bonded to formula (A) each independently represent a deuterium atom, a hydrogen atom or the above substituents, or are bonded to each other to form a ring structure. Cy1 to Cy2 may be the same as or different from each other, and each is independently a substituted or unsubstituted hydrocarbon cyclic group or a substituted or unsubstituted heterocyclic group; The asterisk (*) indicates the location where a chemical bond occurs.

2. The compound of claim 1, wherein, When two adjacent substituents R9 and R10 in R8 to R11 are single bonds bonded to formula (A), they are represented by the following formula (2) or (3). In equations (2) and (3), R1~R8, R11~R15, X1 and Cy1~Cy2 are defined in the same way as in equation (1).

3. The compound according to any one of claims 1 to 2, wherein it is represented by the formula (3).

4. The compound according to claims 1 to 3, wherein X1 is an oxygen atom or a sulfur atom.

5. The compound according to claims 1 to 4, wherein it is represented by any one of the following formulas, 6. A material for an organic electroluminescent device, comprising any one of claims 1 to 5.

7. An organic electroluminescent device having a cathode, an anode, and an organic electroluminescent layer having one or more light-emitting units disposed between the cathode and the anode, wherein at least one light-emitting unit in the light-emitting layer having one or more light-emitting units comprises a compound as a dopant of the light-emitting unit according to any one of claims 1 to 6.

8. The organic electroluminescent device according to claim 7, wherein the light-emitting unit comprising the compound according to any one of claims 1 to 6 further comprises anthracene compound, pyrene compound, or fluorene compound as the host material.

9. The organic electroluminescent device according to claims 7-8, wherein a hole transport unit is included between the anode and the light-emitting layer, and an electron transport unit is included between the light-emitting layer and the cathode.

10. An electronic device comprising the organic electroluminescent device according to any one of claims 7 to 9.

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