A condensed heterocyclic compound containing quinoxaline structure and its application

Abstract

The present invention provides a condensed heterocyclic compound containing a quinoxaline structure and its application. The condensed heterocyclic compound containing a quinoxaline structure has a structure shown in formula (1). The compound of the present invention enables an organic electroluminescent device to have a lower driving voltage, a higher current efficiency and a longer life.

Description

Technical Field

[0001] The invention belongs to the field of organic electroluminescent materials and relates to a condensed heterocyclic compound containing a quinoxaline structure and application thereof. Background Art

[0002] Organic electroluminescent (OLED) devices are semiconductor light-emitting devices based on organic materials. Compared with traditional light-emitting technologies, they have a wider viewing angle, a larger contrast ratio, and a faster response time. They can achieve full-color display without an additional backlight source and have attracted much attention in recent years.

[0003] Organic electroluminescent devices can be composed of hole injection layer, hole transport layer, luminescence auxiliary layer, luminescent layer, electron transport layer, electron injection layer and other layers. The materials of each layer correspond to hole injection material, hole transport material, luminescence auxiliary material, luminescent material, electron transport material and electron injection material. With the optimization of device structure, the types of materials are constantly increasing. Among them, the luminescent layer material is the key material of OLED, which is crucial to the entire OLED industry chain and also the field with the highest technical barriers.

[0004] CN105713016A discloses an OLED material, the structure of which is as follows: R1 is selected from any one of methyl, ethyl, isopropyl, tert-butyl, linear or branched C1-C12 oxygen-containing alkyl, benzene-substituted nitrogen-containing heterocyclic structure or C5-C60 polycyclic aromatic conjugated structure group. However, it is mainly used as an electron transport material to reduce the driving voltage and improve the electron efficiency.

[0005] CN107216330A discloses an OLED material, which has the following structure: R1 is any one of the C5-C60 polycyclic aromatic conjugated structural groups; R2 is any one of the straight-chain or branched C1-C12 alkyl groups or C5-C60 polycyclic aromatic conjugated structural groups; it can be used as a light-emitting layer or a transport layer in an organic electroluminescent device to obtain a more stable effect, excellent photoelectric performance and a longer service life.

[0006] CN107602568A discloses a triarylamine derivative based on indole-quinoxaline, which has the following structure: Wherein, Ar1, Ar2, L are independently selected from one of C6-C50 substituted or unsubstituted aryl, C10-C50 substituted or unsubstituted condensed aryl, C6-C50 substituted or unsubstituted heteroaryl, C10-C50 substituted or unsubstituted condensed heteroaryl. It can be used as the main luminescent material, guest luminescent material, electron transport material or hole transport material in an organic light-emitting device. In particular, when used as the main material in an organic light-emitting device, the triarylamine derivatives of indole and quinoxaline with a rigid structure have a higher glass transition temperature, which are beneficial to prolonging the life of the organic light-emitting device and showing the advantages of high efficiency, low driving voltage and not easy to crystallize.

[0007] Although the above materials can be used as light-emitting layer materials in OLED devices, the driving voltage of the devices is still relatively high and the lifespan improvement is not ideal. In this field, it is expected to further develop light-emitting layer materials with better performance to further reduce the driving voltage, improve current efficiency, and extend lifespan. Summary of the invention

[0008] In view of the deficiencies in the prior art, the purpose of the present invention is to provide a

[0009] To achieve this object, the present invention adopts the following technical solutions:

[0010] In one aspect, the present invention provides a condensed heterocyclic compound containing a quinoxaline structure, wherein the compound has a structure shown in formula (1):

[0011]

[0012] R 1 -R 6 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 by -O- or -S- in a non-adjacent O atom or S atom, substituted or unsubstituted C2-C30 alkenyl, C2-C30 alkenyl in which one or more methylene groups are substituted by -O- or -S- in a non-adjacent O atom or S atom, 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 heteroaralkyl, 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] R 1 -R 6Each exists independently or two adjacent groups are connected to form a ring, and the ring is a substituted or unsubstituted benzene ring,

[0014] L is selected from a connecting bond, a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C5-C30 heteroarylene group,

[0015] Ar 1 is selected from substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C5-C60 heteroaryl, substituted or unsubstituted C6-C60 arylamine, substituted or unsubstituted C5-C60 heteroarylamine, substituted or unsubstituted C5-C60 arylheteroarylamine,

[0016] n is an integer selected from 0-3 (for example, 0, 1, 2 or 3),

[0017] m is an integer selected from 0-5 (for example, 0, 1, 2, 3, 4 or 5),

[0018] n1 is an integer selected from 0-1,

[0019] m1 is an integer selected from 0-1.

[0020] In the present invention, the quinoxaline structure in the fused heterocyclic compound containing a quinoxaline structure is fused with a structure containing a seven-membered aromatic ring. Such a mother core structure makes the electron and hole combination more effective, avoiding the decrease in current efficiency and shortened device life due to unbalanced hole-hole transmission.

[0021] Preferably, n1+m1=1.

[0022] Preferably, L-Ar 1 Selected from

[0023] Among them, Ar 2 ,Ar 3 Each is independently selected from a substituted or unsubstituted C6-C60 aryl group and a substituted or unsubstituted C5-C60 heteroaryl group.

[0024] Preferably, Ar 2 ,Ar 3 Each independently selected from the following substituted or unsubstituted groups: phenyl, biphenyl, terphenyl, naphthyl, phenyl substituted naphthyl, naphthyl substituted phenyl, pyridyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, phenyl substituted carbazolyl, pyridyl substituted carbazolyl, naphthyl substituted carbazolyl, biphenyl substituted carbazolyl, dibenzofuran substituted phenyl, dibenzothiophene substituted phenyl, dimethylfluorenyl, diphenyl substituted fluorenyl, spirobifluorenyl, benzonaphthofuranyl, benzonaphthothiophenyl, benzocarbazolyl, dibenzocarbazolyl;

[0025] Preferably, L-Ar1 is selected from The dotted lines represent L and Ar 3 Connected into rings by chemical bonds;

[0026] More preferably, L-Ar1 is selected from the following substituted or unsubstituted groups:

[0027]

[0028]

[0029] Preferably, L-Ar 1 Selected from The dotted line represents Ar 2 ,Ar 3 Connected into rings by chemical bonds,

[0030] More preferably, L-Ar 1 Selected from the following substituted or unsubstituted groups

[0031]

[0032]

[0033] Preferably, Ar 1 Selected from

[0034] Where X 1 Select from N or CR X1 , X 2 Select from N or CR X2 , X 3 Select from N or CR X3 , X 4 Select from N or CR X4 , X 5 Select from N or CR X5 ,

[0035] R X1 , R X2 , R X3 , R X4 , R X5each 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 non-adjacent O atom or S atom, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C3-C30 heteroaralkyl, 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,

[0036] 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, naphthalene ring, anthracene ring, phenanthrene ring, naphthoxazole ring, naphthothiazole ring, benzofuran ring or benzothiophene ring,

[0037] Preferably, Ar 1 Selected from

[0038] Preferably, Ar 1 Selected from

[0039] Where X 1 , X 2 , X 5 Any two of them are selected from N,

[0040] 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 ,

[0041] R Y1 , R Y2 , R Y3 , R Y4each 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 non-adjacent O atom or S atom, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C3-C30 heteroaralkyl, 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,

[0042] R Y1 , R Y2 , R Y3 , R Y4 They exist independently or are connected to form a ring, which is a substituted or unsubstituted benzene ring.

[0043] More preferably, X 2 , X 5 Selected from N.

[0044] More preferably, X 1 , X 5 Selected from N.

[0045] 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 ,

[0046] More preferably, R X1 , R X2 , R X3 , R X4 , R X5 , R Y1 , R Y2 , R Y3 , R Y4 Each is independently selected from hydrogen, substituted or unsubstituted: phenyl, biphenyl, terphenyl, naphthyl, phenyl substituted naphthyl, naphthyl substituted phenyl, pyridyl, dibenzofuranyl, dibenzothienyl, carbazolyl, phenyl substituted carbazolyl, pyridyl substituted carbazolyl, naphthyl substituted carbazolyl, biphenyl substituted carbazolyl, dibenzofuran substituted phenyl, dibenzothiophene substituted phenyl, dimethylfluorenyl, diphenyl substituted fluorenyl, spirobifluorenyl.

[0047] Preferably, each of the L's is independently selected from phenylene, biphenylene, naphthylene,

[0048] Preferably, R 1 -R 6 each independently selected from hydrogen, deuterium, cyano, fluorine, methyl, ethyl, tert-butyl, deuterium-substituted methyl, fluorine-substituted methyl, phenyl, biphenyl, pyridyl, dibenzofuranyl, dibenzothienyl, dimethylfluorenyl, carbazolyl, phenyl-substituted carbazolyl, pyridyl-substituted carbazolyl, naphthyl-substituted carbazolyl, biphenyl-substituted carbazolyl,

[0049] Preferably, Ar 1 Selected from phenyl, biphenyl, terphenyl, naphthyl, triphenylenyl, phenyl-substituted naphthyl, naphthyl-substituted phenyl, dibenzofuranyl, dibenzothiophenyl, dibenzofuran-substituted phenyl, dibenzothiophene-substituted phenyl, dimethylfluorenyl, diphenyl-substituted fluorenyl, spirobifluorenyl, 2-phenylphenanthren[3,4-d]oxazolyl, 2-phenylphenanthren[3,4-d]thiazolyl.

[0050] In the present invention, when the group contains substituents, the substituents are each independently selected from deuterium, halogen, cyano, unsubstituted or R'-substituted C1-C6 alkyl, unsubstituted or R'-substituted C6-C12 aryl, unsubstituted or R'-substituted C2-C20 heteroaryl; R' is selected from deuterium, halogen, cyano, deuterium-substituted methyl, and halogen-substituted methyl.

[0051] More preferably, the C1-C6 alkyl group is selected from methyl, ethyl, and tert-butyl;

[0052] The C6-C12 aryl group is selected from phenyl, biphenyl and naphthyl;

[0053] The C3-C20 heteroaryl group is selected from triazine group, pyridyl group, phenyl-substituted pyridyl group, pyridyl-substituted phenyl group, dibenzofuranyl group, and dibenzothiophenyl group.

[0054] Preferably, the condensed heterocyclic compound containing a quinoxaline structure is any one of the following compounds:

[0055]

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074] As used in the present invention, the term "halogen" may include fluorine, chlorine, bromine or iodine, preferably fluorine.

[0075] As used herein, the term "alkyl" refers to a monovalent substituent derived from a straight or branched chain 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.

[0076] As used herein, unless otherwise specified, the term "cycloalkyl" refers to a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 30 carbon atoms. Examples of such cycloalkyls include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, adamantane, and the like.

[0077] The heteroaryl and heteroarylene groups in the present invention include monocyclic, polycyclic or condensed ring aromatic groups, and the rings may be interrupted by short non-aromatic units, including but not limited to furanyl, phenylthio, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzo Thienyl, isobenzofuranyl, dibenzofuranyl, dibenzothienyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenothiazinyl, phenanthridinyl, benzodioxolyl, dihydroacridinyl, and derivatives thereof.

[0078] Preferably, the aryl group is selected from phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, 9,9'-dimethylfluorenyl, 9,9'-diphenylfluorenyl or spirobifluorenyl.

[0079] Preferably, the heteroaryl group is selected from dibenzofuranyl, dibenzothiophenyl, carbazolyl, triazine, pyridyl, pyrimidinyl, imidazolyl, oxazolyl, thiazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, naphthoimidazolyl, naphthoxazolyl, naphthothiazolyl, phenanthroimidazolyl, phenanthroxazolyl, phenanthrothiazolyl, quinoxalinyl, quinazolinyl, indolecarbazolyl, oxazolyl, indolefluorenyl, benzothienopyrazinyl, benzothienopyrimidinyl, benzofuranopyrazinyl, benzofuranopyrimidinyl, indolepyrazinyl, indolepyrimidinyl, indenopyrazinyl, indenopyrimidinyl, spiro(fluorene-9,1'-indenyl)pyrazinyl, spiro(fluorene-9,1'-indenyl)pyrimidinyl, benzofuranocarbazolyl or benzothienocarbazolyl.

[0080] As used in the present invention, the term "aryloxy" refers to a monovalent substituent represented by RO-, wherein R represents an aryl group having 6 to 30 carbon atoms. Examples of such aryloxy include, but are not limited to, phenoxy, naphthoxy, diphenoxy, and the like.

[0081] As used in the present invention, the term "substituted" refers to a hydrogen atom in a compound being replaced by another substituent. The position is not limited to a specific position, as long as the hydrogen at the position can be replaced by a substituent. When two or more substituents are present, the two or more substituents may be the same or different.

[0082] As used herein, unless otherwise specified, hydrogen atoms include protium, deuterium and tritium.

[0083] In the present invention, "two adjacent groups are connected to form a ring" means that two substituents in adjacent positions in the same ring or adjacent rings can be connected to each other through chemical bonds to form a ring. The present invention does not limit the specific way of connecting to form a ring (for example, connecting through a single bond, connecting through a benzene ring, connecting through a naphthalene ring, connecting through a Thick, through Thick, through Thick, through Thick, through Thick and; Indicates the position of the thick and thin), and when referring to the same description below, it has the same meaning.

[0084] In the present invention, the range of the number of carbon atoms is defined in the definition of the group, and the number of carbon atoms is any integer within the defined range. For example, C6-C60 aromatic group, the number of carbon atoms representing the aromatic group can be any integer within the range of 6-60, for example 6, 8, 10, 15, 20, 30, 35, 40, 45, 50, 55 or 60, etc.

[0085] In the present invention, the preparation route of the condensed heterocyclic compound containing a quinoxaline structure is as follows:

[0086]

[0087] Where OTf stands for

[0088] In another aspect, the present invention provides an organic electroluminescent material, which comprises any one or a combination of at least two of the above-mentioned condensed heterocyclic compounds containing a quinoxaline structure.

[0089] In another aspect, the present invention provides an organic electroluminescent composition, which comprises any one or a combination of at least two of the above-mentioned condensed heterocyclic compounds containing a quinoxaline structure.

[0090] In another aspect, the present invention provides use of the condensed heterocyclic compound containing a quinoxaline structure as described above in the preparation of an optical device.

[0091] Preferably, the optical device comprises any one of an organic electroluminescent device, an organic field effect transistor, an organic thin film transistor, an organic light emitting transistor, an organic integrated circuit, an organic solar cell, an organic field quenching device, a light emitting electrochemical cell, an organic laser diode or an organic photoreceptor.

[0092] On the other hand, the present invention provides an organic electroluminescent device, comprising an anode and a cathode, and an organic layer arranged between the anode and the cathode, wherein the organic layer comprises any one or a combination of at least two of the above-mentioned condensed heterocyclic compounds containing a quinoxaline structure.

[0093] Preferably, the organic layer at least includes a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.

[0094] Preferably, the material of the light-emitting layer comprises a host material and a guest material, and the host material comprises any one or a combination of at least two of the condensed heterocyclic compounds containing a quinoxaline structure as described above;

[0095] Preferably, the guest material is a phosphorescent dopant, and the phosphorescent dopant is a complex containing a transition metal, preferably a complex containing Ir or Pt.

[0096] Preferably, the material of the electron transport layer comprises at least any one or a combination of at least two of the above-mentioned condensed heterocyclic compounds containing a quinoxaline structure.

[0097] In another aspect, the present invention provides an organic electroluminescent device, comprising the organic electroluminescent device as described above.

[0098] Compared with the prior art, the present invention has the following beneficial effects:

[0099] The condensed heterocyclic compound containing a quinoxaline structure of the present invention effectively improves the combination rate of electrons and holes, improves the luminous efficiency of the device and prolongs the service life of the device. The compound of the present invention enables the organic electroluminescent device to have a lower driving voltage (below 3.98V), a higher current efficiency (above 26Cd / A) and a longer service life (above 206h). DETAILED DESCRIPTION

[0100] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0101] Synthesis Example

[0102]

[0103] (1) Synthesis of 1-C: A 50 ml two-necked round-bottom flask was placed with a stirring bar and a reflux tube. After drying, the flask was filled with nitrogen. 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) were added respectively. The mixture was heated to 60 degrees Celsius and reacted for 12 hours. After the reaction was completed, the mixture was cooled to room temperature and quenched by adding 20 ml of water. The mixture was extracted with dichloromethane (3×20 ml). The extract was dried over magnesium sulfate, filtered and dried by spin drying. The crude product was purified by column chromatography (ethyl acetate / n-hexane: volume ratio 1 / 10) to obtain 1-C (0.17 g, yield 54%).

[0104] (2) Synthesis of 1-D: A 50 ml double-necked round-bottom flask was placed with a stirring bar and a reflux tube. After drying, nitrogen was introduced and 1-C (1 mmol), bis(pinacol)diboron (1.2 mmol), potassium acetate (2 mmol), and 1,4-dioxane (20 ml) were added respectively. Under nitrogen protection, [1,1-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (0.05 mmol) was added and refluxed for 12 hours. After the reaction was completed, the crude product was purified by column chromatography (ethyl acetate / n-hexane: volume ratio 1 / 10) to obtain 1-D (0.27 g, yield 97%).

[0105] (3) Synthesis of 1-F: The synthesis was the same as that of 1-C, except that 1-D was used to replace 1-B, and 1-E was used to replace 1-A, to obtain 1-F (0.24 g, yield 61%).

[0106] (4) Synthesis of 1-G: A 50 ml double-necked round-bottom flask was placed with a stirring bar and a reflux tube. After drying, nitrogen was introduced into the flask. 1-F (1 mmol), dichlorobis(tricyclohexylphosphine)palladium (PdCl2(PCy3)2, 0.05 mmol), pivalic acid (t-BuCO2H, 2 mmol), cesium carbonate (Cs2CO3, 2 mmol) and dimethylacetamide (20 ml) were added respectively. The mixture was stirred at 120 degrees Celsius 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 column chromatography (ethyl acetate / n-hexane: volume ratio 1 / 10) to obtain 1-G (0.17 g, yield 47%).

[0107] (5) Synthesis of 1-H: In a 50 ml three-necked flask, 1-G (1 mmol) and dichloromethane (20 ml) were added dropwise at 0°C, and a dichloromethane solution of boron tribromide (2 mmol) was added. 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 obtain 1-H (0.29 g, yield 84%).

[0108] (6) Synthesis of 1-J: A 50 ml two-necked round-bottom flask was placed with a stirring bar and a reflux tube, 1-H (1 mmol), dichloromethane (20 ml), and pyridine (6 mmol) were added, the reaction system was cooled to 0°C, Tf2O (1.5 mmol) was added, the system was stirred at room temperature for 30 minutes, then cooled to 0°C, 30 ml dichloromethane and 40 ml water were added, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed by distillation under reduced pressure, and the crude product was separated by column chromatography (ethyl acetate / n-hexane, 1 / 10) to obtain 1-J (0.42 g, yield 88%).

[0109] (7) Synthesis of 1: A 50 ml double-necked round-bottom flask was placed with a stirring bar and a reflux tube. After drying, nitrogen was filled into the flask. 1-J (1 mmol), 1-K (1 mmol), cesium carbonate (0.012 mol), tris(dibenzylideneacetone)dipalladium (Pd2(dba)3, 0.05 mmol) and 2-dicyclohexylphosphine-2′,4′,6′-triisopropylbiphenyl (xphos, 0.055 mmol) were added respectively. 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 column chromatography (dichloromethane / n-hexane, 1 / 10 (volume ratio)) to obtain compound 1 (0.46 g, yield 70%).

[0110] Elemental analysis: C 48 H 31 Theoretical value for N3: C, 88.72; H, 4.81; N, 6.47; Found: C, 88.67; H, 4.83; N, 6.50; HRMS (ESI) m / z (M+): Theoretical value: 649.2518; Found: 649.2525.

[0111]

[0112] (1) Synthesis of 7-C: The synthesis was the same as that of 1-C, except that 7-A was used instead of 1-A, and 7-B was used instead of 1-B, to obtain 7-C (0.16 g, yield 51%).

[0113] (2) Synthesis of 7-D: The same as that of 1-D, except that 7-C was used instead of 1-C to obtain 7-D (0.26 g, yield 94%)

[0114] (3) Synthesis of 7-F: The same as the synthesis of 1-C, except that 7-D was used to replace 1-B, and 7-E was used to replace 1-A, to obtain 7-F (0.23 g, yield 58%)

[0115] (4) Synthesis of 7-G: The same as the synthesis of 1-G, except that 7-F was used instead of 1-F to obtain 7-G (0.2 g, yield 55%)

[0116] (5) Synthesis of 7-H: The same as the synthesis of 1-H, except that 7-G was used instead of 1-G to obtain 7-H (0.3 g, yield 88%)

[0117] (6) Synthesis of 7-J: The same as the synthesis of 1-J, except that 7-H was used instead of 1-H to obtain 7-J (0.41 g, yield 86%)

[0118] (7) Synthesis of compound 7: The synthesis was the same as that of compound 1, except that 7-J was used instead of 1-J, and 7-K was used instead of 1-K, to obtain compound 7 (0.41 g, yield 75%).

[0119] Elemental analysis: C 40 H 23 N3 theoretical value: C, 88.05; H, 4.25; N, 7.70; found value: C, 88.10; H, 4.23; N, 7.67; HRMS (ESI) m / z (M+): theoretical value: 545.1892; found value: 545.1897.

[0120]

[0121] (1) Synthesis of 8-C: The synthesis was the same as that of 1-C, except that 8-B was used instead of 1-B to obtain 8-C (0.16 g, yield 51%).

[0122] (2) Synthesis of 8-D: The same as that of 1-D, except that 8-C was used instead of 1-C to obtain 8-D (0.25 g, yield 90%)

[0123] (3) Synthesis of 8-F: The same as the synthesis of 1-C, except that 8-D was used to replace 1-B, and 8-E was used to replace 1-A, to obtain 8-F (0.21 g, yield 53%)

[0124] (4) Synthesis of 8-G: The same as the synthesis of 1-G, except that 8-F was used instead of 1-F to obtain 8-G (0.18 g, yield 50%)

[0125] (5) Synthesis of 8-H: The same as the synthesis of 1-H, except that 8-G was used instead of 1-G to obtain 8-H (0.31 g, yield 89%)

[0126] (6) Synthesis of 8-J: The same as the synthesis of 1-J, except that 8-H was used instead of 1-H to obtain 8-J (0.41 g, yield 86%)

[0127] (7) Synthesis of compound 8: The synthesis was the same as that of compound 1, except that 8-J was used instead of 1-J, and 8-K was used instead of 1-K, to obtain compound 8 (0.53 g, yield 81%).

[0128] Elemental analysis: C46 H 25 N3S theoretical value: C, 84.77; H, 3.87; N, 6.45; S, 4.92; found value: C, 84.76; H, 3.86; N, 6.47; S, 4.91; HRMS (ESI) m / z (M+): theoretical value: 651.1769; found value: 651.1775.

[0129] The same preparation method as above was used, except that the raw materials shown 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.

[0130] Table 1

[0131]

[0132]

[0133]

[0134]

[0135] Table 2

[0136]

[0137]

[0138] Device Embodiment

[0139] An organic electroluminescent device is provided, which has the following layer structure: substrate (indium tin oxide (ITO) coated glass substrate) / hole injection layer (HIL) / hole transport layer (HTL) / luminescent layer (EML) / electron transport layer (ETL) / electron injection layer (EIL), and finally a cathode.

[0140] The materials needed to make OLEDs are as follows:

[0141]

[0142] The preparation of the organic electroluminescent device comprises the following steps:

[0143] (1) Substrate cleaning: The ITO-coated glass substrate is ultrasonically treated in an aqueous cleaning agent (the composition and concentration of the aqueous cleaning agent: ethylene glycol solvent ≤ 10wt%, triethanolamine ≤ 1wt%), rinsed in deionized water, ultrasonically degreased in an acetone:ethanol mixed solvent (volume ratio 1:1), baked in a clean environment until the water is completely removed, and then cleaned with ultraviolet light and ozone.

[0144] (2) Evaporation of organic light-emitting functional layer:

[0145] The glass substrate with the anode layer is placed in a vacuum chamber and evacuated to 1×10 -6 Up to 2×10 -4 Pa, vacuum evaporation HAT(CN)6 as a hole injection layer on the above anode layer film, the evaporation thickness is 5nm;

[0146] A hole transport layer is evaporated on the hole injection layer, and the evaporated film thickness is 80nm;

[0147] The light-emitting layer is deposited on the hole transport layer. The specific preparation method is: vacuum depositing the light-emitting host material and the guest material in a co-evaporation manner, and the total film thickness of the deposition is 30 nm;

[0148] 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 in a co-evaporation manner, and the total film thickness of the evaporation is 30 nm;

[0149] An electron injection layer is vacuum-deposited on the electron transport layer, and the total thickness of the evaporated layer is 1 nm;

[0150] Al was evaporated on the electron injection layer, and the total film thickness of the evaporated layer was 80 nm.

[0151] The parameters of each layer in the device, its material, thickness and so on are shown in Table 3.

[0152] Table 3

[0153]

[0154]

[0155] Device performance test:

[0156] Instruments: The device's current, voltage, brightness, luminous spectrum and other characteristics are tested synchronously using a PR 650 spectrum scanning luminance meter and a Keithley K 2400 digital source meter system;

[0157] Test conditions: current density is 20mA / cm 2 , room temperature.

[0158] Life test: Record the time (in hours) when the device brightness drops to 98% of the original brightness.

[0159] The device performance test results are shown in Table 4:

[0160] Table 4

[0161] Device Example No. Driving voltage(V) Current efficiency (Cd / A) Lifespan (h) 1 3.98 27 206 2 3.92 26 209 3 3.84 28 252 4 3.83 27 233 5 3.86 29 248 6 3.92 28 221 7 3.97 29 228 8 3.82 28 243 9 3.97 30 236 10 3.87 32 210 11 3.86 33 226 12 3.89 32 262 13 3.80 33 271 14 3.83 29 257 15 4.42 21 112

[0162] It can be seen from Table 4 that the compounds of the present invention enable the organic electroluminescent device to have a lower driving voltage (below 3.98 V), a higher current efficiency (above 26 Cd / A) and a longer life (above 206 h).

[0163] The applicant declares that the present invention illustrates the condensed heterocyclic compound containing quinoxaline structure and its application through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various 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. A condensed heterocyclic compound containing a quinoxaline structure, characterized in that: The compound has a structure shown in formula (1): R 1 -R 6 are each independently selected from hydrogen, deuterium, R 1 -R 6 Each exists independently, L is selected from the group consisting of a connecting bond, Ar 1 is selected from triphenylene radical, phenyl substituted naphthyl, naphthyl substituted phenyl, dibenzofuran substituted phenyl, dibenzothiophene substituted phenyl, diphenyl substituted fluorenyl, spirobifluorenyl, 2-phenylphenanthren[3,4-d]oxazolyl, 2-phenylphenanthren[3,4-d]thiazolyl, Or, -L-Ar 1 Selected from Among them, Ar 2 ,Ar 3 each independently selected from the following substituted or unsubstituted groups: phenyl, biphenyl, terphenyl, naphthyl, phenyl substituted naphthyl, naphthyl substituted phenyl, pyridyl, dibenzofuranyl, dibenzothiophenyl, dibenzofuran substituted phenyl, dibenzothiophene substituted phenyl, dimethylfluorenyl, diphenyl substituted fluorenyl, spirobifluorenyl, benzonaphthofuranyl, benzonaphthothiophenyl, Or, -L-Ar 1 Selected from the following substituted or unsubstituted groups: Or, -L-Ar 1 Selected from X 1 Select from N or CR X1 , X 2 Select from N or CR X2 , X 5 Select from N or CR X5 , and X 1 , X 2 , X 5 Any two of them are selected from N, Y 1 Selected from CH, Y 2 Selected from CH, Y 3 Selected from CH, Y 4 Selected from CH, R X1 , R X2 , R X4 , R X5 Each is independently selected from hydrogen, phenyl, biphenyl, terphenyl, naphthyl, phenyl-substituted naphthyl, naphthyl-substituted phenyl, dibenzofuranyl, dibenzothiophenyl, dibenzofuran-substituted phenyl, dibenzothiophene-substituted phenyl, dimethylfluorenyl, R X2 , R X4 Each exists independently; Or, -L-Ar 1 Selected from the following substituted or unsubstituted groups: When the group contains substituents, the substituents are independently selected from deuterium, halogen, cyano, unsubstituted or R′-substituted C1-C6 alkyl, unsubstituted or R′-substituted C6-C12 aryl; R′ is selected from deuterium, halogen, cyano, deuterium-substituted methyl, halogen-substituted methyl, the C1-C6 alkyl is selected from methyl, ethyl, tert-butyl; the C6-C12 aryl is selected from phenyl, biphenyl, naphthyl; n is an integer selected from 0 to 3, m is an integer selected from 0 to 5, n1 is 0, m1 is 1, Alternatively, n1 is 1 and m1 is 0.

2. A condensed heterocyclic compound containing a quinoxaline structure, characterized in that: The condensed heterocyclic compound containing a quinoxaline structure is any one of the following compounds:

3. An organic electroluminescent material, characterized in that: The organic electroluminescent material comprises any one or a combination of at least two of the condensed heterocyclic compounds containing a quinoxaline structure as described in any one of claims 1 to 2.

4. An organic electroluminescent composition, characterized in that: The organic electroluminescent composition comprises any one or a combination of at least two of the condensed heterocyclic compounds containing a quinoxaline structure as described in any one of claims 1 to 2.

5. Use of the condensed heterocyclic compound containing a quinoxaline structure according to any one of claims 1 to 2 in preparing a light-emitting layer and an electron transport layer of an organic electroluminescent device.

6. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises an anode and a cathode, and an organic layer arranged between the anode and the cathode, wherein the organic layer comprises at least a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer, and the material of the light-emitting layer comprises a host material and a guest material, wherein the host material comprises any one or a combination of at least two of the condensed heterocyclic compounds containing a quinoxaline structure as described in any one of claims 1 to 2, and the guest material is a phosphorescent dopant, and the phosphorescent dopant is a complex containing a transition metal.

7. The organic electroluminescent device according to claim 6, characterized in that: The phosphorescent dopant is a complex containing Ir or Pt.

8. The organic electroluminescent device according to claim 6, characterized in that: The material of the electron transport layer comprises at least one or a combination of at least two of the condensed heterocyclic compounds containing a quinoxaline structure as described in any one of claims 1 to 2.

9. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises the organic electroluminescent device according to any one of claims 6 to 8.

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