An organic electroluminescent device

Abstract

This invention provides an organic electroluminescent device, characterized in that the organic electroluminescent device includes a first electrode, a second electrode facing the first electrode, a light-emitting layer between the first electrode and the second electrode, and a light-emitting auxiliary layer between the light-emitting layer and the first electrode, wherein the light-emitting layer includes a compound having the structure shown in formula (1). The organic electroluminescent device of this invention has a lower driving voltage, higher current efficiency, and longer lifetime.

Description

Technical Field

[0001] This invention belongs to the field of electroluminescent devices and relates to an organic electroluminescent device. Background Technology

[0002] Organic light-emitting diodes (OLEDs) convert electrical energy into light by injecting charge into organic light-emitting materials, and typically include an anode, a cathode, and an organic layer formed between these two electrodes. The organic layer of an OLED can consist of a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer (containing a host material and dopant materials), an electron transport layer, and an electron injection layer, etc. Based on their function, the materials used in the organic layer are classified as hole injection materials, hole transport materials, electron blocking materials, light-emitting materials, electron buffer materials, hole blocking materials, electron transport materials, and electron injection materials, etc. In an OLED, holes from the anode and electrons from the cathode are injected into the light-emitting layer by voltage, and the recombination of holes and electrons generates high-energy excitons. The organic light-emitting compound moves to an excited state by energy and emits light by the energy when the organic light-emitting compound returns from the excited state to the ground state.

[0003] The most important factor determining the luminescent efficiency of organic electroluminescent devices is the luminescent material. Luminescent materials are required to possess the following characteristics: high external quantum efficiency, high electron and hole mobility, and stability of the formed luminescent material layer. Recently, an urgent task has been to develop organic electroluminescent devices with high efficiency and long lifetime. Specifically, considering the electroluminescent characteristics required for large and medium-sized OLED panels, there is an urgent need to develop highly superior luminescent materials that outperform conventional materials.

[0004] In organic electroluminescent (OLED) devices, electron transport materials actively transport electrons from the cathode to the emissive layer and suppress the transport of holes that have not recombinated in the emissive layer, thereby increasing the recombination opportunities between holes and electrons in the emissive layer. Organometallic complexes such as Alq3 are excellent at electron transport and are therefore conventionally used as electron transport materials. However, Alq3 has the problem of short device lifetime. Therefore, there is a need for new electron transport materials that do not have the above-mentioned problems and can rapidly transport electrons in organic electroluminescent devices to provide organic electroluminescent devices with high luminous efficiency. Summary of the Invention

[0005] In view of the shortcomings of the prior art, the purpose of this invention is to provide an organic electroluminescent device.

[0006] To achieve this objective, the present invention adopts the following technical solution:

[0007] On one hand, the present invention provides an organic electroluminescent device, the organic electroluminescent device comprising a first electrode, a second electrode facing the first electrode, a light-emitting layer between the first electrode and the second electrode, and a light-emitting auxiliary layer between the light-emitting layer and the first electrode, wherein the light-emitting layer comprises a compound having the structure shown in formula (1):

[0008]

[0009] R 1 -R 6 Each is independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, C1-C30 alkyl in which one or more methylene groups are substituted with -O- or -S- in a manner where O or S atoms are not adjacent, substituted or unsubstituted C2-C30 alkenyl, C2-C30 alkenyl in which one or more methylene groups are substituted with -O- or -S- in a manner where O or S atoms are not adjacent, substituted or unsubstituted C2-C30 alkynyl, etc. Substituted or unsubstituted C7-C30 aryl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C3-C30 cycloalkenyl, substituted or unsubstituted C1-C30 alkoxy, or substituted or unsubstituted C6-C30 aryloxy.

[0010] R 1 -R 6 Each exists independently or two adjacent rings are connected to form a ring, wherein the ring is a substituted or unsubstituted benzene ring.

[0011] L is selected from the linking bond, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C5-C30 heteroarylene.

[0012] Ar 1 Selected from substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C5-C60 heteroaryl, substituted or unsubstituted C6-C60 aromatic amino, substituted or unsubstituted C5-C60 heteroaryl, and substituted or unsubstituted C5-C60 aryl heteroaryl.

[0013] n is an integer selected from 0 to 3 (for example, it can be 0, 1, 2 or 3).

[0014] m is selected from integers between 0 and 5 (for example, it can be 0, 1, 2, 3, 4, or 5).

[0015] n1 is an integer selected from 0 to 1.

[0016] m1 is selected from integers between 0 and 1.

[0017] Preferably, n1 + m1 = 1.

[0018] Preferably, -L-Ar 1 Selected from

[0019] Among them, Ar 2 Ar 3 Each is independently selected from substituted or unsubstituted C6-C60 aryl groups and substituted or unsubstituted C5-C60 heteroaryl groups.

[0020] Preferably, Ar 2 Ar 3 Each of the following groups, whether substituted or unsubstituted, is independently selected: phenyl, biphenyl, terphenyl, naphthyl, phenyl-substituted naphthyl, naphthyl-substituted phenyl, pyridyl, dibenzofuranyl, dibenzothiophene, carbazole, phenyl-substituted carbazole, pyridyl-substituted carbazole, naphthyl-substituted carbazole, biphenyl-substituted carbazole, dibenzofuranyl, dibenzothiophene-substituted phenyl, dimethylfluorenyl, diphenyl-substituted fluorenyl, spirodifluorenyl, benzonaphthuryl, benzonaphthiophene, benzocarbazole, or dibenzocarbazole;

[0021] Preferably, -L-Ar1 is selected from The dashed lines represent L and Ar. 3 They are linked together in rings by chemical bonds;

[0022] More preferably, -L-Ar1 is selected from substituted or unsubstituted groups:

[0023]

[0024]

[0025] Preferably, -L-Ar 1 Selected from The dashed line represents Ar. 2 Ar 3 They are linked together to form rings through chemical bonds.

[0026] More preferably, -L-Ar 1 Selected from the following groups, whether substituted or unsubstituted

[0027]

[0028]

[0029] Preferably, Ar 1 Selected from

[0030] Where X 1 Selected from N or CR X1X 2 Selected from N or CR X2 X 3 Selected from N or CR X3 X 4 Selected from N or CR X4 X 5 Selected from N or CR X5 ,

[0031] R X1 R X2 R X3 R X4 R X5 Each of the following is independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, C1-C30 alkyl in which one or more methylene groups are substituted with -O- or -S- in a manner where the O or S atom is not adjacent, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C3-C30 cycloalkenyl, substituted or unsubstituted C1-C30 alkoxy, or substituted or unsubstituted C6-C30 aryloxy.

[0032] R X1 R X2 R X3 R X4 R X5 Each exists independently, or two adjacent rings are connected to form a ring, wherein the ring is a substituted or unsubstituted benzene ring, pyridine ring, naphthyl ring, anthracene ring, phenanthrene ring, naphthooxazole ring, naphthothiazole ring, benzofuran ring, or benzothiophene ring.

[0033] Preferably, Ar 1 Selected from

[0034] Preferably, Ar 1 Selected from

[0035] Where X 1 X 2 X 5 Any two of them are selected from N.

[0036] Y 1 Selected from N, CR Y1 Y 2 Selected from N, CR Y2 Y 3 Selected from N, CR Y3 Y 4 Selected from N, CR Y4 ,

[0037] R Y1 R Y2 R Y3 R Y4 Each of the following is independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, C1-C30 alkyl in which one or more methylene groups are substituted with -O- or -S- in a manner where the O or S atom is not adjacent, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C3-C30 cycloalkenyl, substituted or unsubstituted C1-C30 alkoxy, or substituted or unsubstituted C6-C30 aryloxy.

[0038] R Y1 R Y2 R Y3 R Y4 Each exists independently, or two adjacent rings are connected to form a ring, wherein the ring is a substituted or unsubstituted benzene ring.

[0039] More preferably, X 2 X 5 Selected from N.

[0040] More preferably, X 1 X 5 Selected from N.

[0041] More preferably, Y 1 Selected from CR Y1 Y 2 Selected from CR Y2 Y 3 Selected from CR Y3 Y 4 Selected from CR Y4 ,

[0042] More preferably, R X1 R X2 R X3 R X4 R X5 R Y1 R Y2 R Y3 R Y4Each of the following groups, independently selected from hydrogen, substituted or unsubstituted, consists of: phenyl, biphenyl, terphenyl, naphthyl, phenyl-substituted naphthyl, naphthyl-substituted phenyl, pyridyl, dibenzofuranyl, dibenzothiophene, carbazoyl, phenyl-substituted carbazoyl, pyridyl-substituted carbazoyl, naphthyl-substituted carbazoyl, biphenyl-substituted carbazoyl, dibenzofuran-substituted phenyl, dibenzothiophene-substituted phenyl, dimethylfluorenyl, diphenyl-substituted fluorenyl, and spirodifluorenyl.

[0043] Preferably, each of the L molecules is independently selected from phenylene, biphenylene, and naphthylene.

[0044] Preferably, R 1 -R 6 Each is independently selected from hydrogen, deuterium, cyano, fluorine, methyl, ethyl, tert-butyl, deuterium-substituted methyl, fluorine-substituted methyl, phenyl, biphenyl, pyridyl, dibenzofuranyl, dibenzothiopheneyl, dimethylfluorenyl, carbazole, phenyl-substituted carbazole, pyridyl-substituted carbazole, naphthyl-substituted carbazole, and biphenyl-substituted carbazole.

[0045] Preferably, Ar 1 Selected from phenyl, biphenyl, terphenyl, naphthyl, benzophenanthryl, phenyl-substituted naphthyl, naphthyl-substituted phenyl, dibenzofuranyl, dibenzothiopheneyl, dibenzofuran-substituted phenyl, dibenzothiophene-substituted phenyl, dimethylfluorenyl, diphenyl-substituted fluorenyl, spirodifluorenyl, 2-phenylphenanthrene[3,4-d]oxazolyl, 2-phenylphenanthrene[3,4-d]thiazolyl;

[0046] In this invention, when the group contains substituents, each substituent is independently selected from deuterium, halogen, cyano, unsubstituted or R'-substituted C1-C6 alkyl, unsubstituted or R'-substituted C6-C12 aryl, and unsubstituted or R'-substituted C3-C20 heteroaryl; R' is selected from deuterium, halogen, cyano, deuterium-substituted methyl, and halogen-substituted methyl.

[0047] More preferably, the alkyl group of C1-C6 is selected from methyl, ethyl, and tert-butyl;

[0048] The aryl group of C6-C12 is selected from phenyl, biphenyl, and naphthyl;

[0049] The heteroaryl group of C3-C20 is selected from triazinyl, pyridyl, phenyl-substituted pyridyl, pyridyl-substituted phenyl, dibenzofuranyl, and dibenzothiopheneyl.

[0050] Preferably, the compound having the structure shown in formula (1) is any one of the following compounds:

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069] As used in this invention, the term "halogen" may include fluorine, chlorine, bromine or iodine, preferably fluorine.

[0070] As used in this invention, the term "alkyl" refers to a monovalent substituent derived from a straight-chain or branched saturated hydrocarbon having 1 to 30 carbon atoms, examples of which include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, and hexyl.

[0071] As used herein, unless otherwise stated, the term "cycloalkyl" refers to a monovalent substituent derived from a monocyclic or polycyclic nonaromatic hydrocarbon having 3 to 30 carbon atoms. Examples of such cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, adamantane, etc.

[0072] In this invention, heteroaryl and hypoaryl groups include monocyclic, polycyclic, or fused-ring aryl groups, and the rings can be interrupted by short non-aromatic units, including but not limited to furanyl, phenylthio, pyrroleyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetraazinyl, triazolyl, tetraazolyl, furazolidyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzo[] Thiopheneyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxoxazolyl, isoindolyl, indolyl, indazoleyl, benzothiadiazolyl, quinolinyl, isoquinolinyl, cenolinyl, quinazolinyl, quinoxolinyl, carbazoleyl, phenoxazinyl, phenthiazinyl, phenanthidyl, benzo-m-dioxacyclopentenyl, dihydroacridyl, and their derivatives, etc.

[0073] Preferably, the aryl group is selected from phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthryl, 9,9'-dimethylfluorenyl, 9,9'-diphenylfluorenyl or spirodifluorenyl.

[0074] Preferably, the heteroaryl group is selected from dibenzofuranyl, dibenzothiopheneyl, carbazoleyl, triazinyl, pyridyl, pyrimidinyl, imidazoleyl, oxazolyl, thiazolyl, benzimidazoleyl, benzoxazolyl, benzothiazolyl, naphthimazoleyl, naphthiazolyl, naphthiazolyl, phenanthimazoleyl, phenanthiazolyl, phenanthiazolyl, quinoxalinyl, quinazolinyl, indole-carbazoleyl Azolyl, indolofluorenyl, benzothiophene-pyrazinyl, benzothiophene-pyrimidinyl, benzofuranopyrazinyl, benzofuranopyrimidinyl, indolopyrazinyl, indolopyrimidinyl, indenepyrazinyl, indenepyrimidinyl, spiro(fluorene-9,1'-indene)pyrazinyl, spiro(fluorene-9,1'-indene)pyrimidinyl, benzofuranocarbazoyl or benzothiophene-carbazoyl.

[0075] As used in this invention, the term "aryloxy group" refers to a monovalent substituent represented by RO-, where R represents an aryl group having 6 to 30 carbon atoms. Examples of such aryloxy groups include, but are not limited to, phenoxy, naphthoxy, diphenoxy, etc.

[0076] As used in this invention, the term "substituted" means that a hydrogen atom in a compound is replaced by another substituent. This position is not limited to a specific position, as long as the hydrogen at that position can be replaced by a substituent. When two or more substituents are present, the two or more substituents can be the same or different.

[0077] As used in this invention, unless otherwise stated, a hydrogen atom includes protium, deuterium, and tritium.

[0078] In this invention, "two adjacent groups linked together to form a ring" means that two substituents located in adjacent positions within the same ring or adjacent rings can be linked together to form a ring through chemical bonds. This invention does not limit the specific method of ring formation (examples include single-bond linkage, linkage through a benzene ring, linkage through a naphthalene ring, etc.). Thick and through Thick and through Thick and through Thick and through Thick and; of which (Indicates density and location), and has the same meaning when the same description is used in the following text.

[0079] In this invention, the definition of a group specifies a range of carbon atoms, and the number of carbon atoms is any integer within the defined range, such as C6-C60 aryl. The number of carbon atoms representing an aryl group can be any integer within the range of 6-60, such as 6, 8, 10, 15, 20, 30, 35, 40, 45, 50, 55 or 60, etc.

[0080] In this invention, the preparation route of the compound having the structure shown in formula (1) is as follows:

[0081]

[0082] Where OTf represents Preferably, the difference between the HOMO energy level of the compound having the structure shown in formula (1) and the HOMO energy level of the material of the light-emitting auxiliary layer is less than 0.5 eV. In this invention, controlling the energy level difference to be less than 0.5 eV enables the OLED device to obtain a smaller driving voltage.

[0083] Preferably, the material of the light-emitting auxiliary layer is selected from compounds having the structure shown in formula (2):

[0084]

[0085] Where Y is selected from O, S, NR N1 or CR Y1 R Y2 ,

[0086] The R N1 Selected from substituted or unsubstituted C6-C30 aryl groups and substituted or unsubstituted C5-C30 heteroaryl groups.

[0087] The R Y1 R Y2 Independently selected from substituted or unsubstituted C1-C30 alkyl or substituted or unsubstituted C6-C30 aryl groups,

[0088] The R Y1R Y2 Independent or related to R 34 or / and R 34 Connect to form a ring A,

[0089] The R 21 -R 36 Selected independently Hydrogen, deuterium, halogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, a group obtained by independently substituting one or more non-adjacent methylene groups of a substituted or unsubstituted C1-C30 alkyl with -O- or -S-, a group obtained by independently substituting one or more non-adjacent methylene groups of a substituted or unsubstituted C2-C30 alkenyl with -O- or -S-, a group obtained by independently substituting one or more non-adjacent methylene groups of a substituted or unsubstituted C2-C30 alkenyl with -O- or -S-, a group obtained by independently substituting one or more non-adjacent methylene groups of a substituted or unsubstituted C2-C30 alkynyl, a group obtained by independently substituting one or more non-adjacent methylene groups of a substituted or unsubstituted C7-C30 aralkyl, a group obtained by independently substituting one or more methylene groups of a substituted or unsubstituted C2-C30 alkenyl with -O- or -S-, a group obtained by independently substituting one or more methylene groups of a substituted or unsubstituted C2-C30 alkenyl with -O- or -S-, a group obtained by independently substituting one or more methylene groups of a substituted or unsubstituted C2-C30 alkenyl with -O- or -S-, a group obtained by independently substituting one or more methylene groups of a substituted or unsubstituted C7-C30 alkenyl with -O- or -S-, a group obtained by independently substituting one or more methylene groups of a substituted or unsubstituted C1-C30 alkyl ... Any one of the following: unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C3-C30 heteroarylalkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C3-C30 cycloalkenyl, substituted or unsubstituted C1-C30 alkylamino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C1-C30 alkoxy, or substituted or unsubstituted C6-C30 aryloxy.

[0090] And R 21 -R 36 At least one of them is selected from

[0091] The R 21 -R 36 Either it exists independently or two adjacent elements connect to form a ring B.

[0092] The ring A is selected from substituted or unsubstituted indole rings or benzene rings.

[0093] The ring B is selected from substituted or unsubstituted benzene rings.

[0094] The L 1 L 2 L 3 Independently selected from any one of single-bonded, substituted or unsubstituted C6-C30 arylene or substituted or unsubstituted C2-C30 heteroarylene.

[0095] The Ar 1 '、Ar 2 'Independently selected from substituted or unsubstituted C6-C60 aryl or substituted or unsubstituted C2-C60 heteroaryl.'

[0096] Preferably, R in formula (2) 27 R28 R 29 R 30 Any one of the options is selected from

[0097] Preferably, R in formula (2) 27 R 29 Any one of the options is selected from

[0098] Preferably, the L 1 L 2 L 3 It is independently selected from any one of the following: single bond, substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted fluorene, substituted or unsubstituted dibenzofuranyl or substituted or unsubstituted dibenzothiopheneyl;

[0099] Preferably, the Ar 1 '、Ar 2 The following groups are selected independently, either substituted or unsubstituted: phenyl, biphenyl, terphenyl, naphthyl, pyridyl, phenyl-substituted naphthyl, naphthyl-substituted phenyl, dimethylfluorenyl, diphenylfluorenyl, spirodifluorenyl, dibenzofuranyl, dibenzothiopheneyl, benzonaphthiopheneyl, benzonaphthiopheneyl, dinaphthiopheneyl, dinaphthiopheneyl, carbazoyl, phenyl-substituted carbazoyl, naphthyl-substituted carbazoyl, pyridyl-substituted carbazoyl.

[0100] Preferably, the material of the light-emitting auxiliary layer is selected from compounds having the structures shown in formulas (2-1) and (2-2):

[0101]

[0102] Preferably, the compound having the structure shown in formula (2) is any one of the following compounds:

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110]

[0111]

[0112]

[0113]

[0114] Where D represents deuterium.

[0115] In this invention, compounds having the structure shown in formula (2) are prepared by the following preparation method:

[0116] Compound H1' and The reaction yields compound (2), and the reaction equation is as follows:

[0117] Where R 21 -R 36 Ar 1’ Ar 2’ L 1 L 2 L 3 Y has the same limiting range as described above, and in compound H1', ​​R 21’ -R 36’ At least one of the components is a halogen, and the definitions of the remaining groups are the same as those for R. 21 -R 36 (e.g. R) 21’ If it is not a halogen, then its definition is the same as R. 21 ).

[0118] On the other hand, the present invention provides an optoelectronic product comprising the organic electroluminescent device as described above.

[0119] Compared with the prior art, the present invention has the following beneficial effects:

[0120] The organic electroluminescent device of the present invention has a lower driving voltage (below 4.02V), higher current efficiency (above 24Cd / A) and longer lifetime (above 225h). Detailed Implementation

[0121] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0122] Example 1: Synthesis of the compound

[0123]

[0124] Nitrogen gas was introduced into a 100 mL three-necked flask, and compound HT-1-A (1 mmol), compound HT-1-B (1 mmol), sodium tert-butoxide (2 mmol), tris(dibenzylacetone)dipalladium (0) (0.05 mmol), 50% tri-tert-butylphosphine solution (0.08 mmol), and 50 mL of toluene were added. The mixture was then refluxed and stirred. After cooling to 25 °C, the organic layer was extracted with ethyl acetate and H₂O. The extracted organic layer was dried over MgSO₄ and filtered. The filtrate was concentrated under reduced pressure and purified by silica gel column chromatography (DCM / hexane), followed by recrystallization purification using a DCM / acetone mixed solvent to obtain compound H-1 (0.54 g, 83% yield).

[0125] Elemental analysis: C 49 H 31 NOS theoretical values: C, 86.31; H, 4.58; N, 2.05; S, 4.70; measured values: C, 86.28; H, 4.60; N, 2.05; S, 4.72; HRMS(ESI) m / z(M+): theoretical value: 681.2126; measured value: 681.2133.

[0126]

[0127] Synthesis of H-2: Same as the synthesis of H-1, except that HT-2-A is used instead of HT-1-A and HT-2-B is used instead of HT-1-B to obtain H-2 (0.52 g, yield 80%).

[0128] Elemental analysis: C 49 H 33 NO theoretical values: C, 90.29; H, 5.10; N, 2.15; measured values: C, 90.28; H, 5.12; N, 2.15; HRMS(ESI) m / z(M+): theoretical value: 651.2562; measured value: 651.2572.

[0129]

[0130] Synthesis of H-3: Same as the synthesis of H-1, except that HT-3-A is used instead of HT-1-A and HT-3-B is used instead of HT-1-B to obtain H-3 (0.56 g, yield 81%).

[0131] Elemental analysis: C 52 H 36 Theoretical N2 values: C, 90.67; H, 5.27; N, 4.07; Measured values: C, 90.63; H, 5.29; N, 4.08; HRMS(ESI) m / z(M+): Theoretical value: 688.2878; Measured value: 688.2886.

[0132]

[0133] H-4: Take a 50 mL double-necked round-bottom flask, add a stir bar and a reflux tube, dry it, and then purge it with nitrogen. Add compounds H-4-A (1 mmol), H-4-B (1 mmol), potassium carbonate (K2CO3, 1.5 mmol), ethanol (3 mL), water (3 mL), toluene (15 mL), and tetrakis(triphenylphosphine)palladium (Pd(PPh3)4, 0.05 mmol), respectively. Heat to 60 °C and react for 12 hours. After the reaction is complete, cool to room temperature, quench with 20 mL of water, and extract with dichloromethane (3 × 20 mL). Add magnesium sulfate to the obtained extract, dry, filter, and evaporate to dryness. Purify the crude product by column chromatography (ethyl acetate / n-hexane: 1 / 10 v / v) to obtain H-4 (0.52 g, yield 72%).

[0134] Elemental analysis: C 55 H 36 Theoretical N2 values: C, 91.13; H, 5.01; N, 3.86; Measured values: C, 91.16; H, 4.99; N, 3.85; HRMS(ESI) m / z(M+): Theoretical value: 724.2878; Measured value: 724.2869.

[0135]

[0136] Synthesis of H-5: Same as the synthesis of H-1, except that HT-5-A is used instead of HT-1-A and HT-5-B is used instead of HT-1-B, to obtain H-5 (0.54 g, yield 79%).

[0137] Elemental analysis: C 49 H 32 Theoretical N2S values: C, 86.44; H, 4.74; N, 4.11; S, 4.71; Measured values: C, 86.39; H, 4.76; N, 4.13; S, 4.72; HRMS(ESI) m / z(M+): Theoretical value: 680.2286; Measured value: 680.2277.

[0138]

[0139] Synthesis of H-6: Same as the synthesis of H-1, except that HT-6-A is used instead of HT-1-A and HT-6-B is used instead of HT-1-B, to obtain H-6 (0.61 g, yield 85%).

[0140] Elemental analysis: C 55 H 43Theoretical N: C, 92.01; H, 6.04; N, 1.95; Measured: C, 91.99; H, 6.06; N, 1.95; HRMS(ESI) m / z(M+): Theoretical: 717.3396; Measured: 717.3403.

[0141]

[0142] Synthesis of H-7: Same as the synthesis of H-1, except that HT-7-A is used instead of HT-1-A and HT-7-B is used instead of HT-1-B to obtain H-7 (0.57 g, yield 83%).

[0143] Elemental analysis: C 53 H 35 Theoretical N: C, 92.81; H, 5.14; N, 2.04; Measured: C, 92.85; H, 5.12; N, 2.03; HRMS(ESI) m / z(M+): Theoretical: 685.2770; Measured: 685.2778.

[0144]

[0145] Synthesis of H-8: Same as the synthesis of H-1, except that HT-8-A is used instead of HT-1-A and HT-8-B is used instead of HT-1-B, to obtain H-8 (0.62 g, yield 87%).

[0146] Elemental analysis: C 54 H 35 NO theoretical values: C, 90.85; H, 4.94; N, 1.96; measured values: C, 90.84; H, 4.96; N, 1.96; HRMS(ESI) m / z(M+): theoretical value: 713.2719; measured value: 713.2728.

[0147]

[0148] (1) Synthesis of 1-C: Take a 50 mL double-necked round-bottom flask and place a stir bar and a reflux tube on top. After drying, purge with nitrogen. Add compounds 1-A (1 mmol), 1-B (1 mmol), potassium carbonate (K2CO3, 1.5 mmol), ethanol (3 mL), water (3 mL), toluene (15 mL), and tetrakis(triphenylphosphine)palladium (Pd(PPh3)4, 0.05 mmol), respectively. Heat to 60 °C and react for 12 hours. After the reaction is complete, cool to room temperature, add 20 mL of water to quench, and extract with dichloromethane (3 × 20 mL). Add magnesium sulfate to the obtained extract, dry, filter, and evaporate to dryness. Purify the crude product by column chromatography (ethyl acetate / n-hexane: 1 / 10 v / v) to obtain 1-C (0.17 g, yield 54%).

[0149] (2) Synthesis of 1-D: Take a 50 mL double-necked round-bottom flask, add a stir bar and a reflux tube, dry it and then purge it with nitrogen. Add 1-C (1 mmol), bis(pinacolyl)diboron (1.2 mmol), potassium acetate (2 mmol), and 1,4-dioxane (20 mL). Under nitrogen protection, add [1,1-bis(diphenylphosphine)ferrocene]palladium(II) dichloride (0.05 mmol) and reflux for 12 hours. After the reaction is complete, the crude product is purified by column chromatography (ethyl acetate / n-hexane: volume ratio 1 / 10) to obtain 1-D (0.27 g, yield 97%).

[0150] (3) Synthesis of 1-F: Same as the synthesis of 1-C, except that 1-D is used to replace 1-B and 1-E is used to replace 1-A, to obtain 1-F (0.24 g, yield 61%).

[0151] (4) Synthesis of 1-G: Take a 50 mL double-necked round-bottom flask, add a stir bar and a reflux tube, dry it and purge it with nitrogen. Add 1-F (1 mmol), dichlorobis(tricyclohexylphosphine)palladium (PdCl2(PCy3)2, 0.05 mmol), tervaponic acid (t-BuCO2H, 2 mmol), cesium carbonate (Cs2CO3, 2 mmol) and dimethylacetamide (20 mL). Stir at 120 °C for 10 hours. After the reaction is complete, cool to room temperature. The reaction system is concentrated and the crude product is purified by column chromatography (ethyl acetate / n-hexane: volume ratio 1 / 10) to obtain 1-G (0.17 g, yield 47%).

[0152] (5) Synthesis of 1-H: 1-G (1 mmol) and dichloromethane (20 mL) were added to a 50 mL three-necked flask. A dichloromethane solution of boron tribromide (2 mmol) was added dropwise at 0 °C. After the reaction was completed, the solvent was removed and the crude product was purified by column chromatography (ethyl acetate / n-hexane, 1 / 10) to give 1-H (0.29 g, yield 84%).

[0153] (6) Synthesis of 1-J: A 50 mL double-necked round-bottom flask was placed with a stir bar and a reflux tube attached. 1-H (1 mmol), dichloromethane (20 mL), and pyridine (6 mmol) were added. The reaction system was cooled to 0 °C, and Tf₂O (1.5 mmol) was added. The system was stirred at room temperature for 30 minutes, then cooled to 0 °C. 30 mL of dichloromethane and 40 mL of water were added. The organic phase was dried over anhydrous magnesium sulfate. The solvent was removed by vacuum distillation. The crude product was separated by column chromatography (ethyl acetate / n-hexane, 1 / 10) to obtain 1-J (0.42 g, 88% yield).

[0154] (7) Synthesis of 1: Take a 50 mL double-necked round-bottom flask and place a stir bar and a reflux tube on top. After drying, purge with nitrogen. Add 1-J (1 mmol), 1-K (1 mmol), cesium carbonate (0.012 mol), tris(dibenzylacetone)palladium (Pd2(dba)3, 0.05 mmol) and 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl (xphos, 0.055 mmol), respectively. Then add toluene. Reflux the mixture for 24 hours. After the reaction, cool to room temperature. Filter the reaction system and concentrate. Purify the crude product by column chromatography (dichloromethane / n-hexane, 1 / 10 (volume ratio)) to obtain compound 1 (0.46 g, yield 70%).

[0155] Elemental analysis: C 48 H 31 Theoretical N3 values: C, 88.72; H, 4.81; N, 6.47; Measured values: C, 88.67; H, 4.83; N, 6.50; HRMS(ESI) m / z(M+): Theoretical value: 649.2518; Measured value: 649.2525.

[0156]

[0157] (1) Synthesis of 7-C: Same as the synthesis of 1-C, except that 7-A is used to replace 1-A and 7-B is used to replace 1-B, to obtain 7-C (0.16 g, yield 51%).

[0158] (2) The synthesis of 7-D is the same as that of 1-D, except that 7-C is used instead of 1-C to obtain 7-D (0.26 g, yield 94%).

[0159] (3) Synthesis of 7-F: Same as the synthesis of 1-C, except that 7-D is used to replace 1-B and 7-E is used to replace 1-A, to obtain 7-F (0.23 g, yield 58%).

[0160] (4) Synthesis of 7-G: Same as the synthesis of 1-G, except that 7-F is used instead of 1-F to obtain 7-G (0.2 g, yield 55%).

[0161] (5) Synthesis of 7-H: Same as the synthesis of 1-H, except that 7-G is used instead of 1-G to obtain 7-H (0.3 g, yield 88%).

[0162] (6) Synthesis of 7-J: Same as the synthesis of 1-J, except that 7-H is used instead of 1-H to obtain 7-J (0.41 g, yield 86%).

[0163] (7) Synthesis of compound 7: Same as the synthesis of compound 1, except that 7-J is used to replace 1-J and 7-K is used to replace 1-K, to obtain compound 7 (0.41 g, yield 75%).

[0164] Elemental analysis: C 40 H 23 Theoretical N3 values: C, 88.05; H, 4.25; N, 7.70; Measured values: C, 88.10; H, 4.23; N, 7.67; HRMS(ESI) m / z(M+): Theoretical value: 545.1892; Measured value: 545.1897.

[0165]

[0166] (1) Synthesis of 8-C: Same as the synthesis of 1-C, except that 8-B is used instead of 1-B to obtain 8-C (0.16 g, yield 51%).

[0167] (2) The synthesis of 8-D is the same as that of 1-D, except that 8-C is used instead of 1-C to obtain 8-D (0.25 g, 90% yield).

[0168] (3) Synthesis of 8-F: Same as the synthesis of 1-C, except that 1-B is replaced by 8-D and 1-A is replaced by 8-E, to obtain 8-F (0.21 g, yield 53%).

[0169] (4) Synthesis of 8-G: Same as the synthesis of 1-G, except that 8-F is used instead of 1-F to obtain 8-G (0.18 g, yield 50%).

[0170] (5) Synthesis of 8-H: Same as the synthesis of 1-H, except that 8-G is used instead of 1-G to obtain 8-H (0.31 g, yield 89%).

[0171] (6) Synthesis of 8-J: Same as the synthesis of 1-J, except that 8-H is used instead of 1-H to obtain 8-J (0.41 g, yield 86%).

[0172] (7) Synthesis of compound 8: Same as the synthesis of compound 1, except that 8-J is used to replace 1-J and 8-K is used to replace 1-K, to obtain compound 8 (0.53 g, yield 81%).

[0173] Elemental analysis: C46 H 25 Theoretical N3S values: C, 84.77; H, 3.87; N, 6.45; S, 4.92; Measured values: C, 84.76; H, 3.86; N, 6.47; S, 4.91; HRMS(ESI) m / z(M+): Theoretical value: 651.1769; Measured value: 651.1775.

[0174] The same preparation method as above was used, except that the raw materials listed in Table 1 were used to prepare the corresponding products. The elemental analysis and HRMS test results of the products are shown in Table 2.

[0175] Table 1

[0176]

[0177]

[0178]

[0179]

[0180]

[0181] Table 2

[0182]

[0183] Device Examples

[0184] OLEDs have the following layer structure: substrate (indium tin oxide (ITO) coated glass substrate) / hole injection layer (HIL) / hole transport layer (HTL) / light emission layer (EML) / electron transport layer (ETL) / electron injection layer (EIL), and finally a cathode.

[0185] The specific materials used are shown in Table 2. The materials required to manufacture OLEDs are as follows.

[0186]

[0187] The fabrication of the above-mentioned organic electroluminescent device includes the following steps:

[0188] (1) Substrate cleaning: The glass substrate coated with ITO is ultrasonically treated in an aqueous cleaning agent (the composition and concentration of the aqueous cleaning agent are: ethylene glycol solvent ≤10wt%, triethanolamine ≤1wt%), rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone and ethanol (volume ratio 1:1), baked in a clean environment until all moisture is removed, and then cleaned with ultraviolet light and ozone.

[0189] (2) Evaporation of organic light-emitting functional layer:

[0190] The glass substrate with the anode layer was placed in a vacuum chamber and evacuated to a vacuum level of 1×10⁻⁶. -6 Up to 2×10 -4 Pa, HAT(CN)6 is vacuum-deposited on the above-mentioned anode layer as a hole injection layer, with a deposition thickness of 5 nm;

[0191] A hole transport layer is deposited on the hole injection layer, and the deposited film thickness is 80 nm.

[0192] A light-emitting auxiliary layer is deposited on the hole transport layer with a deposition thickness of 20 nm.

[0193] A light-emitting layer is deposited on the hole transport layer. The specific preparation method is as follows: the light-emitting host material and the guest material are vacuum-deposited by co-evaporation, and the total film thickness is 30nm.

[0194] An electron transport layer is vacuum-deposited on the light-emitting layer. The specific preparation method is as follows: Bphen and LiQ are vacuum-deposited by co-evaporation, and the total film thickness is 30 nm.

[0195] An electron injection layer is vacuum-deposited on the electron transport layer, with a total film thickness of 1 nm.

[0196] Al was deposited on the electron injection layer, with a total film thickness of 80 nm. The parameters of each layer, its material, and its thickness in the device are shown in Table 3.

[0197] Table 3

[0198]

[0199]

[0200] Device performance testing:

[0201] Instruments: The current, voltage, brightness, emission spectrum and other characteristics of the device were tested simultaneously using a PR 650 spectral scanning luminance meter and a Keithley K 2400 digital source meter system;

[0202] Test conditions: Current density 20 mA / cm² 2 , room temperature.

[0203] Lifetime test: Record the time (in hours) when the device brightness drops to 98% of its original brightness.

[0204] The device performance test results are shown in Table 4:

[0205] Table 4

[0206] Drive voltage (V) Current efficiency (Cd / A) Lifespan (h) 1 3.81 26 231 2 3.92 27 225 3 3.89 28 264 4 3.98 26 241 5 3.99 27 250 6 3.96 26 233 7 3.92 27 235 8 3.97 29 267 9 3.83 29 266 10 3.82 30 271 11 3.83 28 277 12 3.98 24 238 13 3.90 26 252 14 3.89 24 244 15 3.92 24 266 16 3.94 26 258 17 4.44 21 131 18 4.35 24 148

[0207] As can be seen from Table 4, the compounds of the present invention enable organic electroluminescent devices to have lower driving voltage (below 4.02V), higher current efficiency (above 24Cd / A) and longer lifetime (above 225h).

[0208] The applicant declares that the organic electroluminescent device of the present invention is illustrated by the above embodiments, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. An organic electroluminescent device, characterized in that, The organic electroluminescent device includes a first electrode, a second electrode facing the first electrode, a light-emitting layer between the first electrode and the second electrode, and a light-emitting auxiliary layer between the light-emitting layer and the first electrode, wherein the light-emitting layer comprises a compound having the structure shown in formula (1): Equation (1) Each is independently selected from hydrogen; Selected from ,or, Selected from The dashed line represents L and They are linked together to form rings through chemical bonds, or... Selected from The dotted line represents , They are linked together in rings by chemical bonds; in , Each is independently selected from substituted or unsubstituted C6-C60 aryl groups and substituted or unsubstituted C5-C60 heteroaryl groups; L is selected from connector; n is an integer selected from 0 to 3. m is selected from integers between 0 and 5. n1 is an integer selected from 0 to 1. m1 is selected from integers between 0 and 1. n1 + m1 = 1; The material of the light-emitting auxiliary layer is selected from compounds having the structure shown in formula (2): Equation (2) Where Y is selected from O, S, or , The Selected from substituted or unsubstituted C6-C30 aryl groups, The , Independently selected from substituted or unsubstituted C1-C30 alkyl groups, The , Existing independently or with Connect to form a ring A, The Selected independently Any one of the following: substituted or unsubstituted C3-C30 cycloalkyl groups. and At least one of them is selected from , The Existing independently The ring A is selected from substituted or unsubstituted indole rings or benzene rings. The , , Independently selected from single-bonded, substituted or unsubstituted C6-C30 arylene groups, the , It is independently selected from substituted or unsubstituted C6-C60 aryl or substituted or unsubstituted C2-C60 heteroaryl.

2. The organic electroluminescent device according to claim 1, characterized in that, , Each of the following groups, individually selected from substituted or unsubstituted groups: phenyl, biphenyl, terphenyl, naphthyl, phenyl-substituted naphthyl, naphthyl-substituted phenyl, pyridyl, dibenzofuranyl, dibenzothiophene, carbazole, phenyl-substituted carbazole, pyridyl-substituted carbazole, naphthyl-substituted carbazole, biphenyl-substituted carbazole, dibenzofuranyl, dibenzothiophene-substituted phenyl, dimethylfluorenyl, diphenyl-substituted fluorenyl, spirodifluorenyl, benzonaphthuryl, benzonaphthiophene, benzocarbazole, or dibenzocarbazole.

3. The organic electroluminescent device according to claim 1, characterized in that, Selected from the following groups, whether substituted or unsubstituted: 。 4. The organic electroluminescent device according to claim 1, characterized in that, Selected from the following groups, whether substituted or unsubstituted: 。 5. The organic electroluminescent device according to claim 1, characterized in that, Selected from in Selected from N or , Selected from N or , Selected from N or , Selected from N or , Selected from N or , , , , , Each of the following is independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, C1-C30 alkyl in which one or more methylene groups are substituted with -O- or -S- in a manner where the O or S atom is not adjacent, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C3-C30 cycloalkenyl, substituted or unsubstituted C1-C30 alkoxy, or substituted or unsubstituted C6-C30 aryloxy. , , , , Each exists independently, or two adjacent rings are connected to form a ring, wherein the ring is a substituted or unsubstituted benzene ring, pyridine ring, naphthyl ring, anthracene ring, phenanthrene ring, naphthooxazole ring, naphthothiazole ring, benzofuran ring, or benzothiophene ring.

6. The organic electroluminescent device according to claim 5, characterized in that, Selected from or .

7. The organic electroluminescent device according to claim 1, characterized in that, Selected from , in , , Any two of them are selected from N. Selected from N, , Selected from N, , Selected from N, , Selected from N, , , , , Each of the following is independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, C1-C30 alkyl in which one or more methylene groups are substituted with -O- or -S- in a manner where the O or S atom is not adjacent, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C3-C30 cycloalkenyl, substituted or unsubstituted C1-C30 alkoxy, or substituted or unsubstituted C6-C30 aryloxy. , , , Each exists independently, or two adjacent rings are connected to form a ring, wherein the ring is a substituted or unsubstituted benzene ring.

8. The organic electroluminescent device according to claim 7, characterized in that, Selected from , Selected from , Selected from , Selected from .

9. The organic electroluminescent device according to claim 7, characterized in that, , , , , , , , , Each of the following groups, independently selected from hydrogen, substituted or unsubstituted, consists of: phenyl, biphenyl, terphenyl, naphthyl, phenyl-substituted naphthyl, naphthyl-substituted phenyl, pyridyl, dibenzofuranyl, dibenzothiophene, carbazoyl, phenyl-substituted carbazoyl, pyridyl-substituted carbazoyl, naphthyl-substituted carbazoyl, biphenyl-substituted carbazoyl, dibenzofuran-substituted phenyl, dibenzothiophene-substituted phenyl, dimethylfluorenyl, diphenyl-substituted fluorenyl, and spirodifluorenyl.

10. The organic electroluminescent device according to claim 1, characterized in that, When the group contains substituents, each substituent is independently selected from deuterium, halogen, cyano, unsubstituted, or... Substituted C1-C6 alkyl groups, unsubstituted or Substituted C6-C12 aryl, unsubstituted or Substituted C2-C20 heteroaryl groups; Selected from deuterium, halogen, cyano, deuterium-substituted methyl, halogen-substituted methyl.

11. The organic electroluminescent device according to claim 10, characterized in that, The C1-C6 alkyl groups are selected from methyl, ethyl, and tert-butyl. The aryl group of C6-C12 is selected from phenyl, biphenyl, and naphthyl; The heteroaryl group of C3-C20 is selected from triazine, pyridinyl, phenyl-substituted pyridinyl, pyridinyl-substituted phenyl, dibenzofuranyl, or dibenzothiophene.

12. The organic electroluminescent device according to claim 1, characterized in that, The compound having the structure shown in formula (1) is any one of the following compounds: 。 13. The organic electroluminescent device according to claim 1, characterized in that, The difference between the HOMO energy level of the compound having the structure shown in formula (1) and the HOMO energy level of the material of the light-emitting auxiliary layer is less than 0.5 eV.

14. The organic electroluminescent device according to claim 1, characterized in that, The formula (2) described , , , Any one of the options is selected from .

15. The organic electroluminescent device according to claim 14, characterized in that, In the above formula (2) , Any one of the options is selected from .

16. The organic electroluminescent device according to claim 1, characterized in that, The , , It is independently selected from any one of the following: single bond, substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted fluorene, substituted or unsubstituted dibenzofuranyl or substituted or unsubstituted dibenzothiopheneyl.

17. The organic electroluminescent device according to claim 1, characterized in that, The , The following groups are independently selected from substituted or unsubstituted groups: phenyl, biphenyl, terphenyl, naphthyl, pyridyl, phenyl-substituted naphthyl, naphthyl-substituted phenyl, dimethylfluorenyl, diphenylfluorenyl, spirodifluorenyl, dibenzofuranyl, dibenzothiopheneyl, benzonaphthiopheneyl, benzonaphthiopheneyl, dinaphthiopheneyl, dinaphthiopheneyl, carbazoyl, phenyl-substituted carbazoyl, naphthyl-substituted carbazoyl, pyridyl-substituted carbazoyl.

18. The organic electroluminescent device according to claim 1, characterized in that, The compound having the structure shown in formula (2) is any one of the following compounds: Where D represents deuterium.

19. An optoelectronic product, characterized in that, It includes organic electroluminescent devices as described in any one of claims 1-18.

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