Compounds containing polycyclic heteroaromatic groups of triphenylene, organic electroluminescent materials and applications thereof

Abstract

The present invention relates to the field of display technology, and in particular to a compound containing a polycyclic heteroaromatic group of triphenylene, an organic electroluminescent material and applications thereof. The compound containing a polycyclic heteroaromatic group of triphenylene provided by the present invention has a structure shown in formula (I): an organic electroluminescent device containing the material can have a better lifespan, a lower driving voltage and a higher efficiency.

Description

Technical Field

[0001] The invention relates to the field of display technology, and in particular to a compound containing a polycyclic heteroaromatic group of triphenylene, an organic electroluminescent material and applications thereof. Background Art

[0002] Organic electroluminescent devices (OLEDs) convert electrical energy into light by applying power to organic electroluminescent materials, and generally include an anode, a cathode, and an organic layer formed between the two electrodes. The organic layer of an organic EL device may include a hole injection layer, a hole transport layer, a hole auxiliary layer, a luminescent auxiliary layer, an electron blocking layer, a luminescent layer (containing a host material and a dopant material), an electron buffer layer, a hole blocking layer, an electron transport layer, an electron injection layer, etc. The materials used in the organic layer may be divided into hole injection materials, hole transport materials, hole auxiliary materials, luminescent auxiliary materials, electron blocking materials, luminescent materials, electron buffer materials, hole blocking materials, electron transport materials, electron injection materials, etc. depending on their functions. In an organic EL device, holes from the anode and electrons from the cathode are injected into the luminescent layer by applying a voltage, and excitons with high energy are generated by the recombination of holes and electrons. 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 to the ground state from the excited state.

[0003] At present, the application of organic light-emitting diodes is seriously restricted by the short life of organic light-emitting diodes due to the low stability of organic functional materials and unbalanced carrier mobility. Summary of the invention

[0004] The purpose of the present invention is to overcome the defects of short life of organic electroluminescent diodes caused by low stability of existing organic electroluminescent materials, unbalanced carrier mobility and the like, and further provide a compound containing a polycyclic heteroaromatic group of triphenylene, an organic electroluminescent material and applications thereof.

[0005] Definitions of substituent terms in this invention:

[0006] As used in the present invention, the term "halogen" may include fluorine, chlorine, bromine or iodine.

[0007] As used in the present invention, the term "C1-C30 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.

[0008] As used in the present invention, the term "C3-C30 cycloalkyl" refers to a group derived from a monocyclic hydrocarbon or a polycyclic hydrocarbon having 1 to 30 ring main chain carbon atoms, and the cycloalkane may include cyclopropyl, cyclobutyl, adamantyl, and the like.

[0009] In the present invention, aryl and arylene groups include monocyclic, polycyclic or condensed-ring aromatic groups, the rings may be interrupted by short non-aromatic units, and may contain spiro structures. Aryl groups include but are not limited to phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthracenyl, fluorenyl, spirobifluorenyl, etc., and arylene groups include but are not limited to phenylene, biphenylene, terphenylene, naphthyl, phenanthryl, anthracenyl, fluorenyl, spirobifluorenyl, etc.

[0010] In the present invention, heteroaryl and heteroarylide include monocyclic, polycyclic or condensed ring heteroaryl, and the rings may be interrupted by short non-aromatic units, and the heteroatoms include nitrogen, oxygen and sulfur. Heteroaryl includes, but is not limited to, furanyl, phenylthio, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzimidazolyl, benzo thiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenothiazinyl, phenanthridinyl, benzodioxolyl, dihydroacridinyl, and derivatives thereof; heteroarylene includes but is not limited to furanyl, phenylene thio, pyrroleyl yl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazolyl, pyridyl, pyrazinyl, pyrimidyl, pyridazinyl, benzofuranyl, benzothiophenylene, isobenzofuranyl, dibenzofuranyl, dibenzothiophenylene, benzimidazolyl, oxazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenothiazinyl, phenanthridinyl, benzodioxolyl, acridinyl, and derivatives thereof.

[0011] 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.

[0012] As used herein, unless otherwise specified, hydrogen atoms include protium, deuterium and tritium.

[0013] 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-C30 aromatic group, the number of carbon atoms representing the aromatic group can be any integer within the range of 6-60, such as 6, 8, 10, 13, 15, 17, 20, 22, 25 or 30, etc.

[0014] The scheme adopted by the present invention is as follows:

[0015] A compound containing a polycyclic heteroaromatic group of triphenylene, wherein the compound has a structure shown in formula (I):

[0016]

[0017] Among them, R 1 For—L 1 Ar 1 , R 2 For—L 2 Ar 2 , R 3 For—L 3 Ar 3 ;

[0018] L 1 -L 3 Each is independently selected from a connecting bond, a substituted or unsubstituted C6-C30 arylene group, and a substituted or unsubstituted C3-C30 heteroarylene group;

[0019] Ar 1 -Ar 3 are each independently selected from hydrogen, deuterium, protium, tritium, halogen, cyano, substituted or unsubstituted C6-C60 arylamine, substituted or unsubstituted C3-C60 heteroarylamine, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, wherein Ar 1 -Ar 3 At least one of them is a structure represented by formula (II),

[0020]

[0021] R 4 For—L 4 Ar 4 , R 5 For—L 5 Ar 5 ,

[0022] L 4 -L 5Each is independently selected from a connecting bond, a substituted or unsubstituted C6-C30 arylene group, and a substituted or unsubstituted C3-C30 heteroarylene group;

[0023] Ar 4 -Ar 5 Each is independently selected from substituted or unsubstituted C6-C30 aryl;

[0024] X is selected from O, S, Se;

[0025] The substituents in the substituted C6-C30 arylene group, substituted C3-C30 heteroarylene group, substituted C6-C60 arylamine group, substituted C3-C60 heteroarylamine group, substituted C6-C60 aryl group and substituted C3-C60 heteroaryl group are selected from one or a combination of two of deuterium, halogen, cyano, C1-C6 alkyl group, C3-C30 cycloalkyl group, C6-C30 aryl group and C3-C30 heteroaryl group.

[0026] In the present invention represents a connecting bond, which may be a single bond.

[0027]

[0028] It can be understood that in the present invention, R 1 The substitution may be performed on the ring B or the ring C, R 2 Substitution can be performed on ring D, R 3 Substitutions may be made on ring E.

[0029] Preferably, L 1 -L 3 is a single bond, Ar 1 -Ar 3 One of them is a structure represented by formula (II), and the remaining two are selected from hydrogen and C6-C30 aryl;

[0030] Optional, L 1 -L 3 is a single bond, Ar 1 -Ar 3 One of them is a structure represented by formula (II), and the remaining two are selected from hydrogen.

[0031] Preferably,

[0032] Ar 4 -Ar 5 Each is independently selected from C6-C30 aryl;

[0033] Preferably, Ar 4 -Ar 5 Each independently selected from phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, triphenylene, fluorenyl, dimethylfluorenyl, spirobifluorenyl, fluoranthenyl, diphenylfluorenyl, benzodimethylfluorenyl, benzodiphenylfluorenyl, benzospirobifluorenyl;

[0034] L 4 -L 5 Each is independently selected from a single bond, a C6-C30 arylene group;

[0035] Optional, L 4 -L 5 Each is independently selected from a single bond, a phenylene group, a naphthylene group, and further optionally, L 4 -L 5 Each is independently selected from a single bond.

[0036] Optional, Ar 1 ,Ar 2 is selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted dibenzofuranyl, and substituted or unsubstituted dibenzothienyl.

[0037] Preferably, Ar 4 The structure is shown in the following formula (III), Ar 5 It is a structure shown in the following formula (IV):

[0038]

[0039] R T1 -R T10 are each independently selected from hydrogen, deuterium, halogen, cyano, C1-C30 alkyl, C7-C30 aralkyl, C6-C30 aryl, C3-C30 heteroaryl, C4-C30 heteroaralkyl, C3-C30 cycloalkyl, C3-C30 heterocycloalkyl, C3-C30 cycloalkenyl, C1-C30 alkoxy, C6-C30 aryloxy; or, R T1 -R T5 The two adjacent groups are connected to form a C6-C30 aromatic group, R T6 -R T10 The two adjacent groups are connected to each other to form a C6-C30 aromatic group.

[0040] Preferably, the C6-C30 aryl group is selected from phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, triphenylene, fluorenyl, dimethylfluorenyl, spirobifluorenyl, fluoranthenyl, diphenylfluorenyl, benzodimethylfluorenyl, benzodiphenylfluorenyl, benzospirobifluorenyl.

[0041] Preferably, R T3 and R T8At least one of them is hydrogen or is fused with a group at an adjacent position to form a ring A, wherein the ring A is selected from a C6-C30 aryl group;

[0042] Preferably, ring A is selected from phenyl, naphthyl and phenanthryl.

[0043] Preferably, the compound has a structure shown in any one of Formula I-1 to Formula I-3:

[0044]

[0045] Where R 1 -R 3 , L 1 -L 3 , X is defined as above, R T1 -R T10 The definition of is as above.

[0046] Preferably, the compound has a structure shown in any one of Formula Ia to Formula Im:

[0047]

[0048]

[0049] Where R 1 -R 3 , L 1 -L 3 , X is defined as above, R T1 -R T10 The definition of is as above.

[0050] Preferably, R 1 -R 3 are each independently selected from hydrogen;

[0051] L 1 -L 3 Each is independently selected from a single bond, a C6-C30 arylene group, preferably, L 1 Selected from single bonds, L 2 Selected from phenylene, naphthylene, triphenylene, biphenylene, L 3 is a single bond;

[0052] R T1 -R T10 Each is independently selected from hydrogen, C6-C30 aryl; or, R T1 -R T5 The adjacent two groups are connected to form a C6-C30 aromatic group, R T6 -R T10 The adjacent two are connected to each other to form a C6-C30 aromatic group;

[0053] The C6-C30 aryl group is selected from phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, triphenylene, fluorenyl, dimethylfluorenyl, spirobifluorenyl, fluoranthenyl, diphenylfluorenyl, benzodimethylfluorenyl, benzodiphenylfluorenyl, benzospirobifluorenyl;

[0054] X is selected from O, S, Se.

[0055] Preferably, the compound has the structure shown in Formula I-1.

[0056] Preferably, the compound has a structure shown in any one of Formulas Ia, Ib, Ic, Id, Ig, Ih, and Ik.

[0057] Preferably, the compound has any of the following structures:

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066] The present invention also provides a use of the above-mentioned compound in preparing an optical device.

[0067] The present invention also provides an organic electroluminescent material, which comprises the compound mentioned above.

[0068] The present invention also provides an organic electroluminescent device, which comprises an anode and a cathode, and an organic layer arranged between the anode and the cathode, wherein the organic layer comprises the above-mentioned compound.

[0069] The present invention also provides an organic electroluminescent device, which includes the organic electroluminescent device described above.

[0070] The compound shown in Formula 1 claimed in the present invention can be used alone as the main material of the light-emitting layer, or together with other materials as the main material of the light-emitting layer. The present invention does not specifically limit the types of other materials, which can be conventional main materials of the light-emitting layer in the art. Furthermore, the present invention also provides an organic material composition, comprising the above-mentioned compound containing a polycyclic heteroaromatic group of triphenylene, and a compound having a structure shown in the following formula M:

[0071]

[0072] wherein R' is selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl;

[0073] R 1 'For -L 1 'Ar 1 ', R 2 'For -L 2 'Ar 2 ', R 3 'For -L 3 'Ar 3 ', R 4 'For -L 4 'Ar 4 ',

[0074] L 1 '-L 4 ' are each independently selected from a connecting bond, a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C3-C30 heteroarylene group,

[0075] Ar 1 '-Ar 4 ' are each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, and Ar 1 '-Ar 4 At least one of them is a group represented by formula (a): Formula (a),

[0076] 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 ,

[0077] R X1 -R X5 are each independently selected from hydrogen, deuterium, cyano, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, or R X1 -R X5 The two adjacent rings are connected to form a ring A, and the ring A is a substituted or unsubstituted C6-C30 aryl group;

[0078] The substituents in the substituted C1-C30 alkyl, substituted C3-C30 cycloalkyl, substituted C6-C30 aryl, substituted C3-C30 heteroaryl, substituted C6-C30 arylene and substituted C3-C30 heteroarylene are selected from one or a combination of two of deuterium, halogen, cyano, C1-C6 alkyl, C3-C30 cycloalkyl, C6-C30 aryl and C3-C30 heteroaryl.

[0079] Preferably, the structural compound shown in formula M has the following structure:

[0080]

[0081] R' is selected from C6-C30 aryl;

[0082] L a is selected from a single bond, a C6-C30 arylene group, and a C3-C30 heteroarylene group;

[0083] R", R'" are each independently selected from C6-C30 aryl and C3-C30 heteroaryl.

[0084] Preferably, R' is selected from phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthracenyl, phenylnaphthyl, naphthylphenyl;

[0085] L a is selected from a single bond, phenylene, naphthylene, biphenylene;

[0086] R", R'" are each independently selected from phenyl, deuterated phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthracenyl, phenylnaphthyl, naphthylphenyl, pyridyl, pyridyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, carbazolylphenyl, phenylcarbazolyl, dimethylfluorenyl, diphenylfluorenyl, spirobifluorenyl, dibenzofuranylphenyl, dibenzothiophenylphenyl, dimethylfluorenylphenyl, benzocarbazolyl, benzonaphthofuranyl, benzonaphthothiophenyl.

[0087] Preferably, X 1 N, X 2 N, X 3 CRX3 , X 4 CR X4 , and X 5 CR X5 ;or,

[0088] X 1 N, X 3 N, X 2 CR X2 , X 4 CR X4 , and X 5 CR X5 ;or,

[0089] X 1 N, X 2 N, X 3 N, X 4 CR X4 , and X 5 CR X5 .

[0090] Preferably,

[0091] R X1 -R X5 each independently selected from hydrogen, deuterium, halogen, phenyl, deuterated phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthracenyl, phenylnaphthyl, naphthylphenyl, pyridyl, pyridyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, carbazolylphenyl, phenylcarbazolyl, dimethylfluorenyl, diphenylfluorenyl, spirobifluorenyl, dibenzofuranylphenyl, dibenzothiophenylphenyl, dimethylfluorenylphenyl, benzocarbazolyl, benzonaphthofuranyl, benzonaphthothiophenyl, or R X1 -R X5 Two adjacent rings are connected to form a ring A, and the ring A is a benzene ring or a naphthalene ring.

[0092] L 1 '-L 4 ' are each independently selected from a single bond, phenylene, naphthylene, and biphenylene.

[0093] Preferably, the structural compound represented by formula M has any of the following structures:

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102] Preferably, the mass ratio of the above-mentioned compound containing a polycyclic heteroaromatic group of triphenylene to the compound having a structure represented by formula M is 9:1-1:9;

[0103] Preferably, the mass ratio of the above-mentioned compound containing a triphenylene polycyclic heteroaromatic group to the compound having a structure represented by formula M is 2:8-8:2;

[0104] More preferably, the mass ratio of the above-mentioned compound containing a triphenylene polycyclic heteroaromatic group to the compound having a structure represented by formula M is 3:7-7:3;

[0105] More preferably, the mass ratio of the above-mentioned compound containing a polycyclic heteroaromatic group of triphenylene to the compound having a structure represented by formula M is 4:6-6:4.

[0106] The present invention also provides an organic electroluminescent material, which comprises the organic material composition described above.

[0107] Application of the above-mentioned organic material composition in the preparation of optical devices.

[0108] The present invention also provides an organic electroluminescent device, which comprises an anode and a cathode, and an organic layer arranged between the anode and the cathode, wherein the organic layer comprises the organic material composition described above.

[0109] 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.

[0110] Preferably, the organic layer comprises a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer stacked in sequence from the anode side to the cathode side;

[0111] Preferably, the material of the light-emitting layer comprises a host material and a guest material, and the host material comprises the organic material composition as described above.

[0112] Preferably, the guest material comprises a phosphorescent dopant, and the phosphorescent dopant comprises a complex containing a transition metal.

[0113] In the present invention, the organic compound represented by formula (I) can be prepared by the following synthetic route:

[0114] Step 1:

[0115]

[0116] Step 2:

[0117]

[0118] Step 3:

[0119]

[0120] X is selected from O, S, Se,

[0121] R 4 For—L 4 Ar 4 , R 5 For—L 5 Ar 5 ,

[0122] L 4 -L 5 are each independently selected from a connecting bond, a substituted or unsubstituted C6-C30 arylene group, and a substituted or unsubstituted C3-C30 heteroarylene group,

[0123] Ar 4 -Ar 5 Each is independently selected from a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted C3-C30 heteroaryl group.

[0124] In the present invention, the organic compound substituted at each position as shown in Formula M can be prepared by the following synthetic route:

[0125]

[0126] R5" is chlorine, R5' is X is halogen, preferably chlorine or bromine;

[0127]

[0128] R6" is chlorine, R6' is X is halogen, preferably chlorine or bromine;

[0129]

[0130] R7" is chlorine, R7' is X is halogen, preferably chlorine or bromine;

[0131]

[0132] R8" is chlorine, R8' is X is halogen, preferably chlorine or bromine.

[0133] The above R1-R4 may be hydrogen.

[0134] Beneficial effects of the present invention:

[0135] 1. The present invention provides a compound containing a polycyclic heteroaromatic group of triphenylene, in which a specific aromatic amine structure is connected to a specific parent structure, which is beneficial for matching the HOMO and LUMO energy levels with adjacent energy levels, so that the organic electroluminescent compound obtains higher stability and a more balanced carrier mobility, thereby making the organic electroluminescent device containing the material have a better lifespan, and also has a lower driving voltage and higher efficiency.

[0136] 2. The present invention provides a compound containing a polycyclic heteroaromatic group of triphenylene, further having a structure shown in any one of Formulas I-1 to I-3, and Formulas Ia to Im. The organic electroluminescent device containing the material has a better lifespan, and also has a lower driving voltage and higher efficiency.

[0137] 3. The present invention provides an organic material composition, comprising the above-mentioned compound containing a polycyclic heteroaromatic group of triphenylene, and a compound having a structure shown in the following formula M containing a polycyclic heteroaromatic group of triphenylene. By cooperating with each other, the organic electroluminescent device can have a better lifespan, and also has a lower driving voltage and higher efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0138] In order to more clearly illustrate the specific implementation methods of the present invention or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0139] Figure 1 FIG. 4 is a structural diagram of an organic electroluminescent device in a device embodiment of the present invention.

[0140] Among them, 1 is the anode, 2 is the hole injection layer, 3 is the hole transport layer, 4 is the light-emitting layer, 5 is the electron transport layer, 6 is the electron injection layer, and 7 is the cathode. DETAILED DESCRIPTION

[0141] The following examples are provided for a better understanding of the present invention, but are not intended to limit the best mode of implementation, nor to limit the content and protection scope of the present invention. Any product identical or similar to the present invention obtained by anyone under the inspiration of the present invention or by combining the features of the present invention with other prior arts shall fall within the protection scope of the present invention.

[0142] If no specific experimental steps or conditions are specified in the examples, the conventional experimental steps or conditions described in the literature in the field can be used. If no manufacturer is specified for the reagents or instruments used, they are all conventional reagent products that can be obtained commercially.

[0143] Example 1

[0144] This embodiment provides a compound N-3, and the preparation method of compound N-3 specifically comprises the following steps:

[0145]

[0146] Synthesis of Intermediate N-3B'

[0147] In a 1000 mL three-necked flask equipped with a mechanical stirrer, a reflux condenser, and a thermometer, 20 g of compound 3a, 29.9 g of compound 3b, and 2.3 g of Pd[P(C 6 H 5 ) 3 ] 4 , 27.9g K 2 CO 3 , 280 mL of toluene, H 2 O 120mL, ethanol 120mL. Nitrogen replacement three times, under nitrogen protection, reaction at 85℃. The reaction lasted 150min from the start of heating. After the reaction, 120mL of water was added to quench the reaction. After separation, the oil (wet weight 44g) was obtained by spin drying. After vacuuming, 25g of N-3B' was obtained.

[0148] Synthesis of intermediate N-3B

[0149] Add 25g of N-3B' crude product (oil) and 750mL of dichloromethane to a 2L three-necked flask equipped with a stirrer and a thermometer, control the temperature at -5°C, add ferric chloride in two batches, add 3 equivalents of ferric chloride in each batch with an interval of 15min, and control the temperature at -5°C. After the reaction is completed, slowly add 750mL of ethanol and control the temperature below 0°C. After adding, continue stirring for 0.5h, and a yellow-white solid will precipitate. Filter and rinse the filter cake with 250mL of ethanol to obtain a yellow solid. Then use 1.75L of chlorobenzene to dissolve and crystallize. When the temperature naturally drops to 55°C, add 250mL of n-hexane solution and filter to obtain 20g of crude product N-3B.

[0150]

[0151] Synthesis of Compound N-3

[0152] In a 1000 mL three-necked flask equipped with a mechanical stirrer, a reflux condenser, and a thermometer, 25 g of N-3A, 40.48 g of N-3B, and 1.86 g of Pd 2 (dba) 3 , 1.67g sphos (2-dicyclohexylphosphino-26-dimethoxy-11-biphenyl-3-sulfonic acid sodium salt), 24.4g t-BuONa, 500mL toluene. Nitrogen replacement three times, under nitrogen protection, react at 110℃. The reaction lasted 120min from the start of heating. After the reaction, 120mL water was added to quench the reaction, the liquid was separated, and the reaction was dried by spin drying. After column drying, 35g crude product N-3 was obtained.

[0153] Elemental analysis: C 42 H 27 NO; theoretical value: C, 89.81; H, 4.85; N, 2.49; O, 2.85; found value: C, 89.78; H, 4.86; N, 2.51; HRMS (ESI) m / z (M+): theoretical value: 561.21; found value: 562.29.

[0154] Example 2

[0155] This embodiment provides a compound N-5, and the preparation method of compound N-5 specifically comprises the following steps:

[0156]

[0157] Synthesis of Compound N-5

[0158] In a 500 mL three-necked flask equipped with a mechanical stirrer, a reflux condenser, and a thermometer, 14 g of N-5A, 18.8 g of N-3B, and 0.86 g of Pd 2 (dba) 3 , 1.9g sphos, 9.1g t-BuONa, 150mL toluene. Replace with nitrogen three times, react at 110℃ under nitrogen protection. React for 120min from heating. After the reaction, add 150mL water to quench the reaction, separate the liquid, spin dry, slurry with ethanol, and desolventize and crystallize with toluene to obtain 16g N-5 compound.

[0159] Elemental analysis: C 46 H 29NO theoretical value: C, 90.32; H, 4.78; N, 2.29; O, 2.62; found value: C, 90.30; H, 4.77; N, 2.32; HRMS (ESI) m / z (M+): theoretical value: 611.22; found value: 612.45.

[0160] Example 3-17

[0161] The preparation of Example 3-17 is similar to that of Example 1. Specifically, the raw materials used in Example 3-17 and the products obtained are shown in the following table:

[0162]

[0163]

[0164]

[0165] The product characterization data are as follows:

[0166]

[0167]

[0168] Embodiment 18

[0169] This embodiment provides a compound M6, and the preparation method of compound M6 specifically comprises the following steps:

[0170]

[0171] Synthesis of M6-B: M6-A (10 mmol), nitrobenzene (10 mmol), potassium hydroxide (22 mmol), cuprous thiocyanate (1 mmol) and anhydrous tetrahydrofuran (10 ml) were placed in a 25 ml three-necked flask, replaced with nitrogen three times, heated to 90 degrees Celsius under nitrogen protection, the reaction was completed after 48 hours, quenched with water, the reaction system was extracted with ethyl acetate, and the organic solvent was removed by rotary evaporation to obtain a crude product. The crude product was separated by column chromatography (ethyl acetate: n-hexane (volume ratio 1:50)) to obtain M6-B (1.34 g, yield 49%).

[0172] Synthesis of M6-B': 2-bromo-4-chlorobenzaldehyde (10 mmol), biboronic acid pinacol ester (12 mmol), potassium acetate (100 mmol), [1,1'-bis(diphenylphosphino)ferrocene] dichloropalladium (0.2 mmol), 1,4-dioxane (25 ml) were added to a 50 ml three-necked flask, and nitrogen was replaced. The mixture was heated to 100 degrees Celsius under nitrogen protection. After the reaction was completed, the reaction mixture was quenched with water and extracted with dichloromethane to obtain a crude product. The crude product was separated by column chromatography (dichloromethane: n-hexane (volume ratio 1:50)) to obtain M6-B' (1.7 g, yield 64%).

[0173] Synthesis of M6-C: M6-B (10 mmol), M6-B' (10 mmol), sodium bicarbonate (20 mmol), tetrakistriphenylphosphine palladium (0.2 mmol), tetrahydrofuran (20 ml), water (10 ml) were added to a 50 ml three-necked flask, replaced with nitrogen, and heated to 60 degrees Celsius under nitrogen protection for overnight reaction. After the reaction, the reaction mixture was quenched with water, extracted with dichloromethane, and the organic solvent was removed by rotary evaporation to obtain a crude product. The crude product was separated by column chromatography (ethyl acetate: n-hexane (volume ratio 1:50)) to obtain M6-C (3.06 g, yield 92%).

[0174] Synthesis of M6-D: In a 50 ml three-necked flask, put M6-C (10 mmol), (methoxymethyl)triphenylphosphonium chloride ((methoxymethyl)triphenylphosphonium chloride) (20 mmol), tetrahydrofuran (10 ml), the temperature is reduced to 0 degrees Celsius, and potassium tert-butoxide (2 mmol) is dissolved in 5 ml tetrahydrofuran. The three-necked flask is replaced with nitrogen, and the potassium tert-butoxide solution is added dropwise at 0 degrees Celsius under nitrogen protection. After the addition is completed, a mixture is obtained, and the mixture is stirred for half an hour. After the reaction is completed, the reaction mixture is quenched with water, extracted with dichloromethane, and the organic solvent is removed by rotary evaporation to obtain a crude product. The crude product is separated by column chromatography (ethyl acetate: n-hexane (volume ratio 1:50)) to obtain M6-D (1.8 grams, yield 50%).

[0175] Synthesis of M6-E: In a 25 ml three-necked flask, put M6-D (1 mmol) and hexafluoroisopropanol (5 ml), cool to 0 degrees Celsius, replace with nitrogen, and drop trifluoromethanesulfonic acid (1 ml) under nitrogen protection to obtain a mixture, and continue to stir the mixture for half an hour to obtain a crude product. The crude product is separated by column chromatography (ethyl acetate: n-hexane (volume ratio 1:50)) to obtain M6-E (0.24 g, yield 73%).

[0176] Synthesis of M6-F: In a 50 ml three-necked round-bottom flask, put M6-E (10 mmol), diboric acid pinacol ester (12 mmol), sodium acetate (20 mmol), tris (dibenzylideneacetone) dipalladium (0) (0.5 mmol) and 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl (1.5 mmol), then add 1,4-dioxane (20 ml), and replace with nitrogen three times. Under nitrogen protection, heat to 100 ° C for reaction. After the reaction is completed, the reaction mixture is quenched with water, extracted with dichloromethane, and the organic solvent is removed by rotary evaporation to obtain a crude product. The crude product is separated by column chromatography (ethyl acetate: n-hexane (volume ratio 1:50)) to obtain M6-F (3.24 g, yield 77%).

[0177] Synthesis of compound M6: Take a 100 ml three-necked round-bottom flask and put in a stirrer and a reflux tube. After drying, fill with nitrogen, add M6-F (10 mmol), M6-G (10 mmol, CAS1689576-03-1), sodium bicarbonate (23 mmol), tetrakistriphenylphosphine palladium (0.5 mmol), dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine palladium (0.5 mmol), toluene (25 ml), ethanol (7 ml) and water (7 ml), and replace with nitrogen three times. Under nitrogen protection, the temperature is raised to 80 ° C for 8 hours. After the reaction is completed, the reaction mixture is extracted with ethyl acetate, and the obtained extract is sequentially added with magnesium sulfate for drying, filtration and spin drying to obtain a crude product. The crude product is purified by column chromatography (ethyl acetate: n-hexane (volume ratio 1:10)) to obtain compound M6 (4.13 g, yield 69%).

[0178] Elemental analysis: C41H26N6 theoretical value: C, 81.71; H, 4.35; N, 13.94; measured value: C, 81.78;

[0179] H, 4.33; N, 13.89; HRMS (ESI) m / z [M+H]+: theoretical value: 602.22; found value: 603.40.

[0180] Embodiment 19

[0181] This embodiment provides a compound M160, and the preparation method of the compound M160 specifically comprises the following steps:

[0182]

[0183] Synthesis of M160-B" is the same as the synthesis of M6-B', except that 2-bromo-5-chlorobenzaldehyde is used instead of 2-bromo-4-chlorobenzaldehyde to obtain M160-B" (1.60 g, yield 60%).

[0184] Synthesis of M160-C: The synthesis was the same as that of M6-C, except that 4-chloro-2-formylphenylboronic acid pinacol ester was used instead of 5-chloro-2-formylphenylboronic acid pinacol ester to obtain M160-C (2.13 g, yield 64%).

[0185] Synthesis of M160-D: The synthesis was the same as that of M6-D, except that M160-C was used instead of M6-C to obtain M160-D (3.21 g, yield 89%).

[0186] Synthesis of M160-E: The synthesis was the same as that of M6-E, except that M160-D was used instead of M6-D to obtain M160-E (0.16 g, yield 48%).

[0187] Synthesis of M160-F: The same as the synthesis of M6-F, except that M160-E was used instead of M6-E to obtain M160-F (4.00 g, yield 95%).

[0188] Synthesis of M160: The synthesis was the same as that of compound M6, except that M160-F was used instead of M6-F, and M160-G was used instead of M6-G, to obtain compound M160 (4.70 g, yield 78%).

[0189] Elemental analysis: C41H26N6 theoretical value: C, 81.71; H, 4.35; N, 13.94; found value: C, 81.73; H, 4.37; N, 13.90; HRMS (ESI) m / z (M+): theoretical value: 602.22; found value: 603.29.

[0190] Examples 20-26

[0191] The preparation of Examples 20-26 is similar to that of Example 18 or Example 19, and the corresponding products can be prepared by referring to the above method. Specifically, the raw materials used in Examples 20-26 and the obtained products are shown in the following table:

[0192]

[0193]

[0194] The product characterization data are as follows:

[0195]

[0196] Device Embodiment

[0197] This embodiment provides an organic electroluminescent device, such as Figure 1As shown, it includes an anode 1, a hole injection layer 2, a hole transport layer 3, a light-emitting layer 4, an electron transport layer 5, an electron injection layer 6 and a cathode 7 which are sequentially stacked on a substrate, and its device structure is: anode (indium tin oxide (ITO) coated glass substrate) / hole injection layer (HIL) / hole transport layer (HTL) / light-emitting layer (EML) / electron transport layer (ETL) / electron injection layer (EIL) / cathode (Al).

[0198] The materials for manufacturing the organic electroluminescent device are as follows:

[0199]

[0200] The preparation of the organic electroluminescent device comprises the following steps:

[0201] 1) Substrate cleaning:

[0202] The glass substrate coated with transparent ITO is ultrasonically treated in an aqueous cleaning agent (the composition and concentration of the aqueous cleaning agent: ethylene glycol solvent ≤ 10wt%, triethanolamine ≤ 1wt%), then rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone and ethanol (the volume ratio of acetone to ethanol is 1:1), baked in a clean environment until the moisture is completely removed, and then cleaned with ultraviolet light and ozone.

[0203] 2) Preparation of organic layer:

[0204] Transfer the ITO transparent substrate to the evaporation equipment and evacuate to 1×10 -6 Up to 2×10 -4 Pa, 10nm hole injection layer (HIL) / 80nm hole transport layer (HTL) / 38nm light-emitting layer (EML) / 30nm electron transport layer (ETL) / 1nm electron injection layer (EIL) / 80nm thick cathode (Al) are deposited on the anode film in sequence.

[0205] in:

[0206] The material of the hole injection layer (HIL) is a mixture of NDP-9 and HT, wherein the mass ratio of NDP-9 to HT is 3:97;

[0207] The material of the hole transport layer (HTL) is HT;

[0208] The material of the light-emitting layer (EML) comprises a host material and a guest material, wherein the host material is a compound containing a polycyclic heteroaromatic group of triphenylene as shown in formula (I) prepared by the present invention, or a compound containing a polycyclic heteroaromatic group of triphenylene as shown in formula (I) prepared by the present invention and a compound having a structure as shown in formula M, and the guest material is (piq)2Ir(acac); the specific materials and proportions are shown in Table 1;

[0209] The materials of the electron transport layer (ETL) are shown in Table 1;

[0210] The material of the electron injection layer (EIL) is LiQ;

[0211] The cathode is aluminum;

[0212] The materials and thicknesses of some layers of the organic electroluminescent device are shown in Table 1.

[0213] Table 1

[0214]

[0215]

[0216]

[0217] Test Examples The organic electroluminescent devices obtained from device examples 1 to 27 and comparative examples 1 to 3 in the device examples were tested.

[0218] 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;

[0219] Test conditions: Photoelectric characteristics test conditions: Current density is 10mA / cm2.

[0220] Life test: The current density is 50 mA / cm2, and the time (in hours) when the device brightness drops to 95% of the original brightness is recorded.

[0221] The device performance test results are shown in Table 2:

[0222] Table 2

[0223] project Driving voltage(V) Current efficiency (Cd / A) Lifespan T95(hrs) Example 1 3.97 16.78 101.8 Example 2 3.87 17.45 115.0 Example 3 3.91 17.12 109.0 Example 4 3.98 17.09 112.1 Example 5 3.90 15.37 106.8 Example 6 4.02 15.63 111.2 Example 7 3.50 18.76 200.5 Example 8 3.39 21.87 202.7 Example 9 3.41 21.01 244.8 Example 10 3.45 21.09 234.7 Embodiment 11 3.47 20.99 221.3 Example 12 3.54 20.98 200.1 Embodiment 13 3.51 19.58 196.7 Embodiment 14 3.55 19.39 193.2 Embodiment 15 3.61 20.16 194.5 Example 16 3.57 19.44 201.5 Embodiment 17 3.49 20.48 195.8 Embodiment 18 3.37 21.74 206.4 Embodiment 19 3.41 21.33 251.4 Embodiment 20 3.50 19.98 241.6 Embodiment 21 3.48 19.65 221.3 Embodiment 22 3.49 19.36 214.2 Embodiment 23 3.46 20.32 230.0 Embodiment 24 3.48 19.95 200.7 Embodiment 25 3.44 20.69 198.2 Embodiment 26 3.51 20.87 199.5 Embodiment 27 4.65 17.54 159.6 Comparative Example 1 4.80 5.00 5.0 Comparative Example 2 4.27 19.76 48.0 Comparative Example 3 4.10 16 35

[0224] As can be seen from Table 2, the compound provided by the present invention can significantly improve the carrier injection efficiency, reduce the interlayer energy level difference, balance the electron and hole transfer rate, effectively prolong the life of the organic electroluminescent diode, and obtain a relatively excellent current efficiency. When the organic electroluminescent material is used as an organic functional layer material, when the compound N and the compound M act synergistically and the mass ratio is 1:1, the device can have a longer life, a lower driving voltage, and a higher current efficiency.

[0225] Obviously, the above embodiments are merely examples for the purpose of clear explanation, and are not intended to limit the implementation methods. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived therefrom are still within the scope of protection of the invention.

Claims

1. A compound containing a polycyclic heteroaromatic group of triphenylene, characterized in that: The compound has a structure shown in Formula I-1 or I-2: Among them, R 1 For—L 1 Ar 1 , R 2 For—L 2 Ar 2 ; R 3 For—L 3 Ar 3 ; L 1 -L 3 is a single bond, Ar 1 -Ar 3 Each independently selected from hydrogen, deuterium, protium, tritium; R T1 -R T5 are each independently selected from hydrogen; or, R T1 -R T5 The two adjacent groups are connected to each other to form a C6-C30 aromatic group; R T6 -R T10 Each is independently selected from hydrogen, C6-C30 aryl; or, R T6 -R T10 The adjacent two are connected to each other to form a C6-C30 aromatic group; X is selected from O, S, Se.

2. The compound according to claim 1, characterized in that The compound has a structure shown in any one of Formula Ia to Formula If: Where R 1 -R 3 , L 2 -L 3 ,X,R T1 -R T10 The definition is the same as that of claim 1.

3. The compound according to claim 1, characterized in that The C6-C30 aryl group is selected from phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, triphenylene, fluorenyl, dimethylfluorenyl, spirobifluorenyl, fluoranthenyl, diphenylfluorenyl, benzodimethylfluorenyl, benzodiphenylfluorenyl, benzospirobifluorenyl.

4. The compound according to any one of claims 1 to 3, characterized in that The compound has any of the following structures:

5. Use of the compound according to any one of claims 1 to 4 in the preparation of optical devices.

6. An organic electroluminescent material, characterized in that: The organic electroluminescent material comprises the compound according to any one of claims 1 to 4.

7. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises an anode and a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises the compound according to any one of claims 1 to 4.

8. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises the organic electroluminescent device according to claim 7.

9. An organic material composition, characterized in that: A compound comprising a polycyclic heteroaromatic group containing triphenylene as described in any one of claims 1 to 4, and a compound having a structure shown in the following formula M: Wherein, R' is selected from C6-C30 aryl; R 1 'For -L 1 'Ar 1 ', R 2 'For -L 2 'Ar 2 ', R 3 'For -L 3 'Ar 3 ', R 4 'For -L 4 'Ar 4 '; L 1 '-L 4 'Each independently selected from a connecting bond, a substituted or unsubstituted C6-C30 arylene group; Ar 1 '-Ar 4 'One of them is a group represented by formula (a): The rest is hydrogen; 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 , R X1 -R X5 are each independently selected from hydrogen, deuterium, cyano, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, or R X1 -R X5 The two adjacent rings are connected to form a ring A, and the ring A is a substituted or unsubstituted C6-C30 aryl group; The substituents in the substituted C1-C30 alkyl, substituted C3-C30 cycloalkyl, substituted C6-C30 aryl, substituted C3-C30 heteroaryl and substituted C6-C30 arylene are selected from one or a combination of two of deuterium, halogen, cyano, C1-C6 alkyl, C3-C30 cycloalkyl, C6-C30 aryl and C3-C30 heteroaryl.

10. The organic material composition according to claim 9, characterized in that: The structural compound shown in formula M has the following structure: R' is selected from C6-C30 aryl; L a A single bond, a C6-C30 arylene group; R", R'" are each independently selected from C6-C30 aryl and C3-C30 heteroaryl.

11. The organic material composition according to claim 10, characterized in that: R' is selected from phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthracenyl, phenylnaphthyl, naphthylphenyl; L a is selected from a single bond, phenylene, naphthylene, biphenylene; R", R'' are each independently selected from phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthracenyl, phenylnaphthyl, naphthylphenyl, pyridyl, pyridyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, carbazolylphenyl, phenylcarbazolyl, dimethylfluorenyl, diphenylfluorenyl, spirobifluorenyl, dibenzofuranylphenyl, dibenzothiophenylphenyl, dimethylfluorenylphenyl, benzocarbazolyl, benzonaphthofuranyl, benzonaphthothiophenyl.

12. The organic material composition according to claim 9, characterized in that: X 1 N, X 2 N, X 3 CR X3 , X 4 CR X4 , and X 5 CR X5 ;or, X 1 N, X 3 N, X 2 CR X2 , X 4 CR X4 , and X 5 CR X5 ;or, X 1 N, X 2 N, X 3 N, X 4 CR X4 , and X 5 CR X5 .

13. The organic material composition according to claim 9, characterized in that: R X1 -R X5 each independently selected from hydrogen, deuterium, phenyl, deuterated phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthracenyl, phenylnaphthyl, naphthylphenyl, pyridyl, pyridyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, carbazolylphenyl, phenylcarbazolyl, dimethylfluorenyl, diphenylfluorenyl, spirobifluorenyl, dibenzofuranylphenyl, dibenzothiophenylphenyl, dimethylfluorenylphenyl, benzocarbazolyl, benzonaphthofuranyl, benzonaphthothiophenyl, or R X1 -R X5 Two adjacent rings are connected to form a ring A, and the ring A is a benzene ring or a naphthalene ring; L 1 '-L 4 ' are each independently selected from a single bond, phenylene, naphthylene, and biphenylene.

14. The organic material composition according to claim 9, characterized in that: The structural compound shown in formula M has any of the following structures:

15. The organic material composition according to claim 9, characterized in that: The mass ratio of the compound containing a triphenylene polycyclic heteroaromatic group according to any one of claims 1 to 4 to the compound having a structure represented by formula M is 9:1 to 1:

9.

16. The organic material composition according to claim 9, characterized in that: The mass ratio of the compound containing a triphenylene polycyclic heteroaromatic group according to any one of claims 1 to 4 to the compound having a structure represented by formula M is 2:8-8:

2.

17. The organic material composition according to claim 9, characterized in that: The mass ratio of the compound containing a triphenylene polycyclic heteroaromatic group according to any one of claims 1 to 4 to the compound having a structure represented by formula M is 3:7 to 7:

3.

18. The organic material composition according to claim 9, characterized in that: The mass ratio of the compound containing a triphenylene polycyclic heteroaromatic group according to any one of claims 1 to 4 to the compound having a structure represented by formula M is 4:6-6:

4.

19. An organic electroluminescent material, characterized in that: The organic electroluminescent material comprises the organic material composition according to any one of claims 9 to 18.

20. Use of the organic material composition according to any one of claims 9 to 18 in preparing optical devices.

21. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises an anode and a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises the organic material composition according to any one of claims 9 to 18.

22. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises the organic electroluminescent device according to claim 21.

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