Organic electroluminescent device and optoelectronic product thereof

Abstract

The present application provides an organic electroluminescent device and an optoelectronic product thereof, 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 hole transport layer between the light-emitting layer and the first electrode, wherein the material of the light-emitting layer comprises a compound having a structure represented by formula (1-1) or formula (1-2). The organic electroluminescent device of the present application has a lower driving voltage, a higher current efficiency and a longer lifetime.

Description

Technical Field

[0001] This invention belongs to the field of organic electroluminescence technology and relates to an organic electroluminescent device and its optoelectronic products. Background Technology

[0002] Organic electroluminescent devices (EL devices) are self-emissive devices that offer advantages such as a wider viewing angle, a higher contrast ratio, and a faster response time. The earliest organic EL device was developed by Eastman Kodak in 1987 using small aromatic diamine molecules and aluminum complexes as materials for forming the luminescent layer [Appl. Phys. Lett. [Applied Physics Letters] 51, 913, 1987].

[0003] To enhance the efficiency and stability of organic EL devices, they possess a multilayer structure comprising a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer. Selecting specific hole transport layer and light-emitting layer compounds is known as one method for improving device characteristics such as hole transport efficiency to the light-emitting layer, luminous efficiency, and lifetime.

[0004] Currently, the materials used in the hole transport layer have very high hole mobility, which disrupts the charge balance between holes and electrons in the light-emitting layer and reduces the quantum yield. 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 and its optoelectronic products.

[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, 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 hole transport layer between the light-emitting layer and the first electrode, wherein the material of the light-emitting layer comprises a compound with the structure shown in formula (1-1) or formula (1-2).

[0008] (1-1) (1-2)

[0009] L is selected from the linking bond, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C5-C30 heteroarylene.

[0010] Ar is selected from substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C5-C60 heteroaryl, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C6-C60 aromatic amino, substituted or unsubstituted C5-C60 heteroaryl, and substituted or unsubstituted C5-C60 aryl heteroaryl.

[0011] R 1 -R 3 Each is independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, 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.

[0012] R n1 -R n8 R m1 -R m6 Each is independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, 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.

[0013] The material of the light-emitting auxiliary layer includes compounds with the structure shown in formula (H1).

[0014]

[0015] Equation (H1)

[0016] Where Y is selected from O, S, NR N1 or CR Y1 R Y2 ,

[0017] The R N1 Selected from substituted or unsubstituted C6-C30 aryl groups and substituted or unsubstituted C5-C30 heteroaryl groups.

[0018] The R Y1 R Y2 Independently selected from substituted or unsubstituted C1-C30 alkyl or substituted or unsubstituted C6-C30 aryl groups,

[0019] The R Y1 R Y2 Independent or related to R 34 or / and R 34 Connect to form a ring A,

[0020] The R 21 -R 36 Selected independently The following are possible combinations of: hydrogen, deuterium, halogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C7-C30 aralkyl, substituted or 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.

[0021] And R 21 -R 36 At least one of them is selected from In the substituted or unsubstituted C1-C30 alkyl group, one or at least two non-adjacent methylene groups are optionally independently substituted with -O- or -S-, and in the substituted or unsubstituted C2-C30 alkenyl group, one or at least two non-adjacent methylene groups are optionally independently substituted with -O- or -S-.

[0022] The R 21 -R 36 Either it exists independently or two adjacent elements connect to form a ring B.

[0023] The ring A is selected from substituted or unsubstituted indole rings and benzene rings.

[0024] The ring B is selected from substituted or unsubstituted benzene rings.

[0025] The L 2 L 3 L 4 Independently selected from any one of single-bonded, substituted or unsubstituted C6-C30 arylene or substituted or unsubstituted C2-C30 heteroarylene.

[0026] The Ar 3 Ar 4 It is independently selected from substituted or unsubstituted C6-C60 aryl or substituted or unsubstituted C2-C60 heteroaryl.

[0027] In this invention, the material of the light-emitting layer of the organic electroluminescent device includes a compound with the structure shown in formula (1-1) or formula (1-2), and the material of the light-emitting auxiliary layer includes a compound with the structure shown in formula (H1), so that the organic electroluminescent device has a lower driving voltage, higher current efficiency and longer lifetime.

[0028] In this invention, the compound containing the quinazoline structure has a ring structure in its LUMO energy level distribution. When used as the main material of the light-emitting layer, it facilitates the transport of charge carriers within the light-emitting layer and promotes the combination of electrons and holes. When used as an electron transport material, it can effectively improve electron mobility, increase device efficiency, and extend device life.

[0029] Preferably, Ar is selected from the following carbazole groups: ,

[0030] R 4 -R 11 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 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, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C6-C3 0 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 alkoxy, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted C5-C60 heteroarylamino, substituted or unsubstituted C5-C60 arylheteroarylamino,

[0031] R 4 -R 11 Each exists independently or two adjacent elements are connected to form a ring; and / or R 4 With R 11 Linked via benzene rings or naphthalene rings;

[0032] Preferably, the ring is a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthyl ring, a substituted or unsubstituted benzothiophene ring, a substituted or unsubstituted benzofuran ring, a substituted or unsubstituted indene ring, a substituted or unsubstituted indole ring, a substituted or unsubstituted benzoindole ring, or a substituted or unsubstituted naphthoindole ring.

[0033] Preferably, R4 -R 11 Any two adjacent molecules in the group are fused with the benzene ring, and / or R 4 With R 11 Linked via benzene rings or naphthalene rings;

[0034] Preferably, R 4 -R 11 Each of the following groups, whether substituted or unsubstituted, is independently selected: phenyl, carbazolyl, phenyl-substituted carbazolyl, biphenyl-substituted carbazolyl, pyridyl-substituted carbazolyl, dibenzofuran-substituted carbazolyl, triphenyl-substituted carbazolyl;

[0035] Preferably, R 4 -R 11 either of them and connect,

[0036] L 1 Selected from linking bonds, phenylene, naphthylene, and biphenylene.

[0037] Ar 1 Ar 2 Each of the following groups, whether substituted or unsubstituted, is independently selected: phenyl, biphenyl, terphenyl, naphthyl, pyridyl, phenyl-substituted naphthyl, naphthyl-substituted phenyl, dibenzofuranyl, dibenzothiophene, dimethylfluorenyl, diphenylfluorenyl, spirodifluorenyl, carbazolyl, phenyl-substituted carbazolyl, pyridyl-substituted carbazolyl, biphenyl-substituted carbazolyl, benzonaphthofuranyl, benzonaphthothiophene;

[0038] Preferably, Ar is selected from W is selected from O, S, NL 2 Ar 3 CR 16 R 17 ,

[0039] L 2 Selected from linking bonds, phenylene, naphthylene, and biphenylene.

[0040] Ar 3 Selected from phenyl, biphenyl, terphenyl, naphthyl, pyridyl, phenyl-substituted naphthyl, naphthyl-substituted phenyl, dibenzofuranyl, dibenzothiophenyl, dibenzofuran-substituted phenyl, dibenzothiophene-substituted phenyl, dimethylfluorenyl, dimethylfluorenyl-substituted phenyl, diphenylfluorenyl, diphenylfluorenyl-substituted phenyl, spirodifluorenyl;

[0041] R 4 R 5 R 6 R 7 R 8 R 9 R 10 R11 R 12 R 13 R 14 R 15 Each element is independently selected from hydrogen, deuterium, phenyl, and / or two adjacent elements linked together to form a benzene ring.

[0042] R 16 R 17 Each is independently selected from methyl, phenyl, or R 16 R 17 The linkage forms a fluorene group.

[0043] and / or R 4 With R 11 Linked by benzene rings or naphthalene rings.

[0044] More preferably, Ar is selected from substituted or unsubstituted groups:

[0045]

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

[0057] The wavy lines represent the connection sites of the functional groups.

[0058] Preferably, Ar is selected from substituted or unsubstituted groups of the following: phenyl, biphenyl, terphenyl, naphthyl, phenyl-substituted naphthyl, naphthyl-substituted phenyl, anthracene, phenanthrene, benzo[a]phenanthrene, pyridyl, dibenzofuranyl, dibenzothiophene, carbazolyl, phenyl-substituted carbazolyl, pyridyl-substituted carbazolyl, naphthyl-substituted carbazolyl, biphenyl-substituted carbazolyl, dibenzofuranyl, dibenzothiophene, dimethylfluorenyl, diphenyl-substituted fluorenyl, spirodifluorenyl, benzo[a]naphthofranyl, benzo[a]naphthiophene, benzo[a]carbazolyl, dibenzo[a]carbazolyl, triazine, quinoxolinyl, quinazolinyl, 2-phenylphenanthrene[3,4-d]oxazolyl or 2-phenylphenanthrene[3,4-d]thiazolyl.

[0059] Preferably, R n1 -R n8 R m1 -R m6 Each group is independently selected from the following substituted or unsubstituted groups: hydrogen, deuterium, phenyl, biphenyl, terphenyl, naphthyl, phenyl-substituted naphthyl, naphthyl-substituted phenyl, anthracene, phenanthrene, benzo[a]phenanthrene, pyridyl, dibenzofuranyl, dibenzothiophene, carbazolyl, phenyl-substituted carbazolyl, pyridyl-substituted carbazolyl, naphthyl-substituted carbazolyl, biphenyl-substituted carbazolyl, dibenzofuranyl-substituted phenyl, dibenzothiophene-substituted phenyl, dimethylfluorenyl, diphenyl-substituted fluorenyl, spirodifluorenyl, benzo[a]naphthofuranyl, benzo[a]naphthophene, benzo[a]carbazolyl, dibenzo[a]carbazolyl, triazine, quinoxolinyl, quinazolinyl, 2-phenylphenanthrene[3,4-d]oxazolyl or 2-phenylphenanthrene[3,4-d]thiazolyl.

[0060] Preferably, L is selected from the linking bond, phenylene, biphenylene, naphthylene, or dibenzofuranyl.

[0061] When the groups described above contain substituents in this invention, 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 C2-C20 heteroaryl.

[0062] R' is selected from deuterium, halogen, cyano, deuterium-substituted methyl, halogen-substituted methyl;

[0063] Preferably, the aryl group is selected from phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthrene, benzo[a]phenanthrene, naphthyl-substituted phenyl, dimethylfluorenyl, diphenyl-substituted fluorenyl, and spirodifluorenyl.

[0064] Preferably, the heteroaryl group is selected from pyridyl, dibenzofuranyl, dibenzothiophenyl, carbazole, phenyl-substituted carbazole, pyridyl-substituted carbazole, naphthyl-substituted carbazole, biphenyl-substituted carbazole, dibenzofuran-substituted phenyl, dibenzothiophene-substituted phenyl, benzonaphthofuranyl, benzonaphthothiophenyl, benzocarbazole, and dibenzocarbazole.

[0065] Preferably, the alkyl group is selected from methyl, ethyl, propyl, tert-butyl, cyclohexyl, and adamantyl.

[0066] Preferably, the compound having the structure shown in formula (1-1) containing a quinazoline structure is any one of the following compounds:

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095] .

[0096] Preferably, the compound having the structure shown in formula (1-2) containing a quinazoline structure is any one of the following compounds:

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110]

[0111]

[0112]

[0113]

[0114]

[0115]

[0116]

[0117]

[0118] .

[0119] Preferably, R in formula (H1) 21 R 34 R 35 R 36 Any one of the options is selected from ,

[0120] Preferably, the L 4 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;

[0121] Preferably, the Ar 3 Ar 4 The group is independently selected from the following groups, whether substituted or unsubstituted: phenyl, biphenyl, terphenyl, naphthyl, pyridyl, phenyl-substituted naphthyl, naphthyl-substituted phenyl, dimethylfluorenyl, diphenylfluorenyl, spirodifluorenyl, dibenzofuranyl, dibenzothiopheneyl, benzonaphthiofuranyl, benzonaphthiopheneyl, dinaphthiofuranyl, dinaphthiopheneyl, carbazoyl, phenyl-substituted carbazoyl, naphthyl-substituted carbazoyl, or pyridyl-substituted carbazoyl.

[0122] Preferably, the compound with the structure shown in formula (H1) is any one of the following compounds:

[0123]

[0124]

[0125]

[0126]

[0127]

[0128]

[0129]

[0130]

[0131]

[0132]

[0133]

[0134]

[0135]

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153]

[0154]

[0155]

[0156]

[0157]

[0158]

[0159] Where D represents deuterium.

[0160] As used in this invention, the term "halogen" may include fluorine, chlorine, bromine or iodine, preferably fluorine.

[0161] 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.

[0162] 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.

[0163] 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.

[0164] Preferably, the aryl group is selected from phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthryl, 9,9'-dimethylfluorenyl, 9,9'-diphenylfluorenyl or spirodifluorenyl.

[0165] 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.

[0166] 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.

[0167] 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.

[0168] As used in this invention, unless otherwise stated, a hydrogen atom includes protium, deuterium, and tritium.

[0169] 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, 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.

[0170] 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.

[0171] In this invention, the preparation route of the compound containing the quinazoline structure is as follows:

[0172] General formula for the synthesis of compounds with the structure shown in formula (1-1)

[0173]

[0174] When L is selected as the connector key, the third step uses the path of (2);

[0175] General formula for the synthesis of compounds with the structure shown in formula (1-2)

[0176]

[0177]

[0178] When L is selected as the connector key, the second step uses the path of (2).

[0179] In this invention, the compound having the structure of formula (H1) is prepared by the following method: reacting compound H1' with... The reaction yields a compound with the structure (H1), as shown in the following reaction formula:

[0180]

[0181] Where B(OH)2 / Bpin represents or R 21 -R 36 Ar 3’ Ar 4’ L 4 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 (For example, if R) 21’ If it is not a halogen, then its definition is the same as R. 21 ).

[0182] On the other hand, the present invention provides an optoelectronic product comprising the organic electroluminescent device as described above.

[0183] Compared with the prior art, the present invention has the following beneficial effects:

[0184] The organic electroluminescent device of the present invention has a lower driving voltage (below 3.65V), higher current efficiency (above 26Cd / A) and longer lifetime (above 405h). Detailed Implementation

[0185] 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.

[0186] Preparation Examples

[0187] Compound Synthesis

[0188]

[0189] Nitrogen gas was introduced into a 100 mL three-necked flask, and compound 1-HT-1 (1 mmol), compound 2-HT-1 (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 HT-1 (0.53 g, 83% yield).

[0190] Elemental analysis: C 47 H 29 NO2 theoretical values: C, 88.24; H, 4.57; N, 2.19; measured values: C, 88.27; H, 4.55; N, 2.20; HRMS (ESI) m / z (M+): theoretical value: 639.2198; measured value: 639.2205.

[0191]

[0192] Synthesis of HT-2: Same as the synthesis of HT-1, except that 1-HT-2 is used to replace 1-HT-1 and 2-HT-2 is used to replace 2-HT-1, yielding HT-2 (0.51 g, yield 78%).

[0193] Elemental analysis: C 49 H 32 Theoretical N2 values: C, 90.71; H, 4.97; N, 4.32; Measured values: C, 90.68; H, 4.99; N, 4.33; HRMS (ESI) m / z (M+): Theoretical value: 648.2565; Measured value: 648.2573.

[0194]

[0195] Synthesis of HT-3: Same as the synthesis of HT-1, except that 1-HT-3 is used to replace 1-HT-1 and 2-HT-3 is used to replace 2-HT-1, yielding HT-3 (0.52 g, 75% yield).

[0196] Elemental analysis: C 52 H 38 Theoretical N2 values: C, 90.40; H, 5.54; N, 4.05; Measured values: C, 90.42; H, 5.52; N, 4.06; HRMS (ESI) m / z (M+): Theoretical value: 690.3035; Measured value: 690.3044.

[0197]

[0198] In Example 1, compound 1-HT-1 was replaced with an equal amount of 1-HT-4, and compound 2-HT-1 was replaced with an equal amount of 2-HT-4, with the rest remaining the same as in Example 1. The final product was compound HT-4 (0.52 g, yield: 75%).

[0199] Elemental analysis: C 53 H 41 Theoretical N: C, 92.00; H, 5.97; N, 2.02; Measured: C, 92.03; H, 5.95; N, 2.02; HRMS (ESI) m / z (M+): Theoretical: 691.3239; Measured: 691.3247.

[0200]

[0201] The compound 1-HT-1 in Example 1 was replaced with an equal amount of 1-HT-5, and the compound 2-HT-1 was replaced with an equal amount of 2-HT-5, with the rest being the same as in Example 1. The final product was compound HT-5 (0.56 g, yield: 73%).

[0202] Elemental analysis: C 60 H 39 Theoretical N: C, 93.11; H, 5.08; N, 1.81; Measured: C, 93.15; H, 5.05; N, 1.80; HRMS (ESI) m / z (M+): Theoretical: 773.3083; Measured: 773.3077.

[0203]

[0204] Synthesis of 1-B: A 50 mL double-necked round-bottom flask was placed with a stir bar and a reflux tube attached. After drying, nitrogen gas was introduced. 1-A (1 mmol), bis(pinacolyl)diboron (1.2 mmol), potassium acetate (2 mmol), and 1,4-dioxane (20 mL) were added separately. Under nitrogen protection, [1,1-bis(diphenylphosphine)ferrocene]palladium(II) dichloride (0.05 mmol) was added. The mixture was refluxed for 12 hours. After the reaction was completed, the crude product was purified by column chromatography (ethyl acetate / n-hexane: 1 / 10 v / v) to give 1-B (0.11 g, 47% yield).

[0205] Synthesis of 1-D: A 50 mL double-necked round-bottom flask was placed with a stir bar and a reflux tube attached. After drying, nitrogen gas was introduced. Compounds 1-C (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) were added. The mixture was heated to 60 °C and reacted for 12 hours. After the reaction was completed, the mixture was cooled to room temperature and quenched with 20 mL of water. The mixture was extracted with dichloromethane (3 × 20 mL). The resulting extract was dried with magnesium sulfate, filtered, and evaporated to dryness. The crude product was purified by chromatography (ethyl acetate / n-hexane: 1 / 10 v / v) to give 1-D (0.15 g, 43% yield).

[0206] Synthesis of 1-F: A 100 mL double-necked round-bottom flask was placed with a stir bar and a reflux tube attached. After drying, nitrogen gas was introduced. 1-D (1 mmol), carbazole (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) were added. Toluene was then added. The mixture was refluxed for 24 hours. After the reaction, the mixture was cooled to room temperature. The reaction system was filtered and concentrated. The crude product was purified by chromatography (dichloromethane / n-hexane, 1 / 10 (v / v)) to give 1-F (0.38 g, 79% yield).

[0207] Synthesis of Compound 1: A 50 mL double-necked round-bottom flask was placed with a stir bar and a reflux tube attached. After drying, nitrogen gas was introduced. 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) were added. The mixture was stirred at 120 °C for 10 hours. After the reaction was completed, the mixture was cooled to room temperature. The reaction system was concentrated, and the crude product was purified by chromatography (ethyl acetate / n-hexane: v / v 1 / 10) to give 1 (0.27 g, yield 61%).

[0208] Elemental analysis: C 32 H 19 Theoretical N3 values: C, 86.27; H, 4.30; N, 9.43; Measured values: C, 86.32; H, 4.28; N, 9.40; HRMS (ESI) m / z (M+): Theoretical value: 445.1579; Measured value: 445.1584.

[0209]

[0210] Synthesis of 2-F: Same as the synthesis of 1-F, except that 2-C is used instead of carbazole to obtain 2-F (0.47 g, yield 77%).

[0211] Synthesis of compound 2: Same as the synthesis of compound 1, except that 2-F is used instead of 1-F to obtain compound 2 (0.38 g, yield 67%).

[0212] Elemental analysis: C 42 H 23 Theoretical N3 values: C, 88.55; H, 4.07; N, 7.38; Measured values: C, 88.59; H, 4.05; N, 7.36; HRMS (ESI) m / z (M+): Theoretical value: 569.1892; Measured value: 569.1898.

[0213]

[0214] Synthesis of 3-F: Same as the synthesis of 1-F, except that 3-C is used instead of carbazole to obtain 3-F (0.48 g, yield 75%).

[0215] Synthesis of compound 3: Same as the synthesis of compound 1, except that 3-F was used instead of 1-F to obtain compound 3 (0.41 g, yield 69%).

[0216] Elemental analysis: C 42 H 23Theoretical N3S values: C, 83.84; H, 3.85; N, 6.98; S, 5.33; Measured values: C, 83.79; H, 3.86; N, 7.00; S, 5.35; HRMS (ESI) m / z (M+): Theoretical value: 601.1613; Measured value: 601.1621.

[0217]

[0218] Synthesis of 4-F: Same as the synthesis of 1-D, except that 1-D is used to replace 1-C and 4-C is used to replace 1-B, yielding 4-F (0.42 g, yield 64%).

[0219] Synthesis of compound 4: Same as the synthesis of compound 1, except that 1-F was replaced by 4-F, yielding compound 4 (0.44 g, yield 71%).

[0220] Elemental analysis: C 46 H 27 Theoretical N3 values: C, 88.86; H, 4.38; N, 6.76; Measured values: C, 88.90; H, 4.36; N, 6.74; HRMS (ESI) m / z (M+): Theoretical value: 621.2205; Measured value: 621.2212.

[0221]

[0222] Synthesis of 5-F: Same as the synthesis of 1-F, except that 5-C is used instead of carbazole to obtain 5-F (0.49 g, yield 71%).

[0223] Synthesis of compound 5: Same as the synthesis of compound 1, except that 5-F is used instead of 1-F to obtain compound 5 (0.46 g, 70% yield).

[0224] Elemental analysis: C 48 H 28 Theoretical N4 values: C, 87.25; H, 4.27; N, 8.48; Measured values: C, 87.30; H, 4.25; N, 8.45; HRMS (ESI) m / z (M+): Theoretical value: 660.2314; Measured value: 660.2319.

[0225]

[0226] Synthesis of 1'-C: Same as the synthesis of 1-D, except that 1'-A is used to replace 1-C and 1'-B is used to replace 1-B, yielding 1'-C (0.13 g, 40% yield).

[0227] Synthesis of 1'-E: Same as the synthesis of 1-F, except that 1'-C is used instead of 1-D and 1'-D is used instead of carbazole to obtain 1'-E (0.55 g, yield 78%).

[0228] Synthesis of compound 1': Same as the synthesis of compound 1, except that 1'-E is used instead of 1-F to obtain compound 1' (0.53 g, yield 81%).

[0229] Elemental analysis: C 48 H 28 Theoretical N4 values: C, 87.25; H, 4.27; N, 8.48; Measured values: C, 87.30; H, 4.25; N, 8.45; HRMS (ESI) m / z (M+): Theoretical value: 660.2314; Measured value: 660.2309.

[0230]

[0231] Synthesis of 2'-E: Same as the synthesis of 1-F, except that 1'-C is used instead of 1-D and 2'-D is used instead of carbazole to obtain 2'-E (0.53 g, yield 76%).

[0232] Synthesis of compound 2': Same as the synthesis of compound 1, except that 1-F is replaced by 2'-E to obtain compound 2' (0.53 g, 80% yield).

[0233] Elemental analysis: C 48 H 28 Theoretical N4 values: C, 87.25; H, 4.27; N, 8.48; Measured values: C, 87.29; H, 4.26; N, 8.45; HRMS (ESI) m / z (M+): Theoretical value: 660.2314; Measured value: 660.2305.

[0234]

[0235] Synthesis of 3'-E: Same as the synthesis of 1-F, except that 1'-C is used instead of 1-D and 3'-D is used instead of carbazole to obtain 3'-E (0.47 g, yield 77%).

[0236] Synthesis of compound 3': Same as the synthesis of compound 1, except that 1-F was replaced by 3'-E, yielding compound 3' (0.47 g, 82% yield).

[0237] Elemental analysis: C 40 H 21Theoretical N3S values: C, 83.45; H, 3.68; N, 7.30; S, 5.57; Measured values: C, 83.40; H, 3.69; N, 7.32; S, 5.59; HRMS (ESI) m / z (M+): Theoretical value: 575.1456; Measured value: 575.1464.

[0238]

[0239] Synthesis of 4'-E: ​​Same as the synthesis of 1-F, except that 1'-C is used instead of 1-D and 4'-D is used instead of carbazole to obtain 4'-E (0.45 g, yield 78%).

[0240] Synthesis of compound 4': Same as the synthesis of compound 1, except that 1-F is replaced by 4'-E to obtain compound 4' (0.44 g, yield 81%).

[0241] Elemental analysis: C 40 H 21 Theoretical N3 values: C, 88.38; H, 3.89; N, 7.73; Measured values: C, 88.42; H, 3.88; N, 7.70; HRMS (ESI) m / z (M+): Theoretical value: 543.1736; Measured value: 543.1730.

[0242]

[0243] Synthesis of 5'-E: Same as the synthesis of 1-F, except that 1'-C is used instead of 1-D and 5'-D is used instead of carbazole to obtain 5'-E (0.47 g, yield 76%).

[0244] Synthesis of compound 5': Same as the synthesis of compound 1, except that 1-F is replaced by 5'-E, yielding compound 5' (0.47 g, 80% yield).

[0245] Elemental analysis: C 42 H 26 Theoretical N4 values: C, 85.98; H, 4.47; N, 9.55; Measured values: C, 86.03; H, 4.45; N, 9.52; HRMS (ESI) m / z (M+): Theoretical value: 586.2157; Measured value: 586.2165.

[0246] Device Examples

[0247] OLEDs have the following layer structure: substrate ((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.

[0248] The specific materials used are shown in Table 1. The materials required to manufacture OLEDs are as follows.

[0249] , , , , ,

[0250] The fabrication of the above-mentioned organic electroluminescent device includes the following steps:

[0251] (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.

[0252] (2) Evaporation of organic light-emitting functional layer:

[0253] 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, PD is vacuum-deposited on the above-mentioned anode layer as a hole injection layer, with a deposition thickness of 5 nm;

[0254] A hole transport layer is deposited on the hole injection layer, with a film thickness of 80 nm.

[0255] A light-emitting auxiliary layer was deposited on the hole transport layer with a deposition thickness of 20 nm.

[0256] 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 30 nm.

[0257] 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.

[0258] An electron injection layer was vacuum-deposited on the electron transport layer, with a total film thickness of 1 nm.

[0259] Al was deposited on the electron injection layer, with a total film thickness of 80 nm.

[0260] The parameters of each layer in the device, including its material and thickness, are shown in Table 1.

[0261] Table 1

[0262]

[0263] Device performance testing:

[0264] 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;

[0265] Test conditions: Current density 10 mA / cm² 2 , room temperature.

[0266] Lifetime test: Record the time (in hours) when the device brightness drops to 95% of its original brightness.

[0267] The device performance test results are shown in Table 2:

[0268] Table 2

[0269]

[0270] As can be seen from Table 4, the organic electroluminescent device of the present invention has a lower driving voltage (below 3.65V), higher current efficiency (above 26Cd / A) and longer lifetime (above 405h).

[0271] The applicant declares that the organic electroluminescent device and its optoelectronic products of the present invention are illustrated through 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 products 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 device includes a first electrode, a second electrode facing the first electrode, a light-emitting layer between the first electrode and the second electrode, a hole transport layer between the light-emitting layer and the first electrode, and a light-emitting auxiliary layer between the light-emitting layer and the hole transport layer, wherein the material of the light-emitting layer includes a compound with the structure shown in formula (1-1) or formula (1-2). ， L is selected from the linking bond, phenylene, biphenylene, naphthylene, or dibenzofuranyl. R 1 -R 3 Each is independently selected from hydrogen and deuterium. R n1 -R n8 Each is independently selected from hydrogen, unsubstituted benzophenanthrene, unsubstituted spirodifluorenyl, substituted or unsubstituted triazine, substituted or unsubstituted quinazolinyl; R m1 -R m6 Each is independently selected from hydrogen; Ar is selected from the following carbazole groups: , R 4 -R 11 Each of the following groups, independently selected from hydrogen, deuterium, or unsubstituted, can be: phenyl, carbazolyl, phenyl-substituted carbazolyl, naphthyl-substituted carbazolyl, biphenyl-substituted carbazolyl, pyridyl-substituted carbazolyl, or dibenzofuran-substituted carbazolyl. R 4 -R 11 Each exists independently or two adjacent elements are connected to form a ring; or R 4 With R 11 Linked via benzene rings or naphthalene rings; The ring is an unsubstituted benzene ring, an unsubstituted naphthalene ring, an unsubstituted benzothiophene ring, or a substituted or unsubstituted indole ring; or R 4 -R 11 either of them and connect, L 1 Selected from the link key, Ar 1 Ar 2 Each of the following groups is independently selected from unsubstituted groups: phenyl, naphthyl, dibenzofuranyl, dibenzothiophenyl, dimethylfluorenyl; Ar is selected from the following groups: unsubstituted phenyl, unsubstituted phenanthryl, unsubstituted benzophenanthryl, unsubstituted dibenzofuranyl, unsubstituted spirodifluorenyl, substituted or unsubstituted triazineyl, substituted or unsubstituted quinazolinyl, 2-phenylphenanthrene[3,4-d]oxazolyl or 2-phenylphenanthrene[3,4-d]thiazolyl; The material of the light-emitting auxiliary layer includes compounds with the structure shown in formula (H1). ， Where Y is selected from O, S, or CR. Y1 R Y2 , The R Y1 R Y2 Independently selected from methyl or phenyl, The R Y1 R Y2 Independent or related to R 33 or / and R 34 Connect to form a ring A, The R 21 -R 36 Selected independently Any one of hydrogen, deuterium, methyl, tert-butyl, phenyl, or benzoxy. And R 21 -R 36 At least one of them is selected from , The R 21 -R 36 Either it exists independently or two adjacent elements connect to form a ring B. The ring A is selected from substituted or unsubstituted benzene rings. The ring B is selected from an unsubstituted benzene ring. The L 4 L 2 L 3 Independently selected from single bonds or phenylene, The Ar 3 Ar 4 It is independently selected from any one of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, unsubstituted dibenzofuranyl, unsubstituted benzonaphthofuranyl, unsubstituted dibenzothiophenyl, dimethylfluorenyl, phenyl-substituted carbazolyl, diphenyl-substituted fluorenyl or unsubstituted spirodifluorenyl.

2. The organic electroluminescent device according to claim 1, characterized in that, R 4 -R 11 Any two adjacent rings in the middle are fused with the benzene ring, or R 4 With R 11 Linked by benzene rings or naphthalene rings.

3. The organic electroluminescent device according to claim 1, characterized in that, Ar selected W is selected from O, S, NL 2 Ar 3 CR 16 R 17 , L 2 Selected from the link key, Ar 3 Selected from phenyl, biphenyl, naphthyl, and pyridyl. R 4 R 5 R 6 R 7 R 8 R 9 R 10 R 11 R 12 R 13 R 14 R 15 Each is independently selected from hydrogen or two adjacent atoms linked together to form a benzene ring. R 16 R 17 Each is independently selected from methyl, phenyl, or R 16 R 17 The linkage forms a fluorene group. or R 4 With R 11 Linked by benzene rings or naphthalene rings.

4. The organic electroluminescent device according to claim 1, characterized in that, Ar is selected from the following groups, whether substituted or unsubstituted: ， ， ， ， ， ， ， ， ， ， ， ， The wavy lines represent the connection sites of the functional groups.

5. The organic electroluminescent device according to claim 1, characterized in that, The compound having the structure shown in formula (1-1) containing a quinazoline structure is any one of the following compounds: ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， 。 6. The organic electroluminescent device according to claim 1, characterized in that, The compound having the structure shown in formula (1-2) containing a quinazoline structure is any one of the following compounds: ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， 。 7. The organic electroluminescent device according to claim 1, characterized in that, The compound with the structure shown in formula (H1) is any one of the following compounds: ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， Where D represents deuterium.

8. An optoelectronic product, characterized in that, It includes the organic electroluminescent device according to any one of claims 1-7.

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