CN113563348A - Compound and application thereof in organic electroluminescent device - Google Patents

Compound and application thereof in organic electroluminescent device Download PDF

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CN113563348A
CN113563348A CN202110842493.3A CN202110842493A CN113563348A CN 113563348 A CN113563348 A CN 113563348A CN 202110842493 A CN202110842493 A CN 202110842493A CN 113563348 A CN113563348 A CN 113563348A
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温洁
梁现丽
陈婷
段陆萌
杭德余
班全志
曹占广
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Beijing Yunji Technology Co Ltd
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Abstract

The invention relates to a compound and application thereof, in particular to application thereof in an organic electroluminescent device, and belongs to the technical field of organic electroluminescent materials and display. The organic compound has a structure shown in a formula (I). The compound has higher triplet state energy level, better carrier mobility, higher thermal stability and film forming stability, and can reduce driving voltage and improve the luminous efficiency of a device when being used as an organic electroluminescent material applied to an OLED device.

Description

Compound and application thereof in organic electroluminescent device
Technical Field
The invention relates to a compound and application thereof, in particular to application thereof in an organic electroluminescent (OLED) device, belonging to the technical field of organic electroluminescent materials and display.
Background
Organic electroluminescent diodes (OLEDs) are also known as organic electroluminescent displays, organic light emitting semiconductors. Originally discovered in 1979 by professor dung Qing cloud in the laboratory, there has been a development history of over 40 years. Since the OLED has a series of advantages of self-luminescence, lightness, thinness, power saving, high contrast, wide viewing angle, high response speed, rich colors and the like, the OLED is often used in the fields of display and illumination, is expected to replace the existing liquid crystal display and fluorescent illumination, has a very wide application prospect, and attracts the attention of numerous researchers. In order to improve light emitting efficiency and extend a life span, development and research of light emitting devices are increasingly active.
Materials used to make OLEDs generally include electrode materials, light emitting materials, and auxiliary materials. Wherein the auxiliary material mainly comprises a carrier transport material, a carrier injection material, and a carrier blocking material. Different assist materials play different roles in the device and therefore often have different performance requirements for the different assist materials.
The hole transport material has the main functions of transporting holes, improving the transport efficiency of the holes in the device, blocking electrons in the light emitting layer and realizing the maximum recombination of carriers. Therefore, the hole transport material for OLED needs to satisfy the following performance requirements: (1) has high hole mobility; (2) the triplet state energy level of the molecule is higher than the excitation energy of the light-emitting layer; (3) the film has good film forming property, and can form a uniform and amorphous thin film without defects; (4) the melting point and the glass transition temperature are higher; (5) the appropriate HOMO energy level can ensure the effective injection and transmission of holes between various interfaces.
At present, more and more display manufacturers are invested in research and development, and the industrialization process of the OLED is greatly promoted. However, the conventional organic electroluminescent materials still have room for improvement in light-emitting properties, and development of new organic electroluminescent materials is urgently needed in the art.
Disclosure of Invention
The invention aims to develop an organic hole transport material which has higher hole mobility, higher glass transition temperature, good film-forming property and proper HOMO and LUMO energy levels, is applied to an OLED device, can reduce the driving voltage and improve the luminous efficiency of the device.
The invention provides an organic compound, which has a structure shown as a general formula (I):
Figure BDA0003179537660000011
in formula (I):
R1、R2、R3are respectively and independently selected from groups shown in formula (A), or are respectively and independently selected from one of hydrogen, halogen, amino, alkylamino, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted C3-C60 heteroaryl amino, substituted or unsubstituted C6-C60 aryl and substituted or unsubstituted C3-C60 heteroaryl, and R is1、R2、R3At least one of them is a group represented by the formula (A);
R4、R5and R6Each independently selected from one or two of hydrogen, halogen, amino, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted C3-C60 heteroaryl amino, substituted or unsubstituted C6-C60 aryl and substituted or unsubstituted C3-C60 heteroaryl;
q is an integer of 1 to 4;
m, n and p are each independently an integer of 1 to 4; preferably, m, n and p are each independently 1 or 2; more preferably, m, n and p are each independently 1;
in the formula (A): r7、R8Each independently selected from substituted or unsubstituted C6-C60 aryl, substituted or unsubstitutedOne of unsubstituted C3-C60 heteroaryl;
specifically, R is as defined above1、R2、R3Which may be the same or different, R7、R8May be the same or different.
R is as defined above1～R8When a substituent group exists, the substituent group is respectively and independently selected from one or a combination of two of chain alkyl of C1-C20, cycloalkyl of C3-C20, alkoxy of C1-C10, thioalkoxy of C1-C10, arylamino of C6-C30, heteroarylamino of C3-C30, aryl of C6-C30 and heteroaryl of C3-C30.
Further, the compound of the present invention is preferably represented by the general formula (II):
Figure BDA0003179537660000021
in the formula (II), R is1、R2、R3M, n and p are as defined in formula (I).
In the formula (II), preferably, m, n and p are each independently 1 or 2; more preferably, m, n and p are each independently 1.
Further, the compound of the present invention is preferably a compound represented by any one of the following formulae (1), (2), (3), (4), (5), (6), (7) and (8):
Figure BDA0003179537660000031
in the formula (1), the formula (2), the formula (3), the formula (4), the formula (5), the formula (6), the formula (7) and the formula (8), R1、R2、R3Are as defined in formula (I).
The R is1、R2、R3May be the same or different. Preferably, said R is1、R2、R3Are not identical.
In the present specification, the above "substituted or unsubstituted" group may be substituted with one substituent, or may be substituted with a plurality of substituents, and when a plurality of substituents are present, they may be selected from different substituents, and when the same expression mode is involved in the present invention, they all have the same meaning, and the selection range of the substituents is as shown above and is not repeated.
In the present specification, the expression of Ca to Cb means that the group has carbon atoms of a to b unless otherwise specified. Each group in the present specification has a substituent, and the carbon number thereof does not include the carbon number of the substituent.
In the present specification, "independently" means that the subject may be the same or different when a plurality of subjects are provided.
In the present specification, the expression of chemical elements includes the concept of chemically identical isotopes, for example, hydrogen (H) includes1H (protium or H),2H (deuterium or D), etc.; carbon (C) then comprises12C、13C and the like.
In the present specification, the hetero atom in the heteroaryl group generally means an atom or an atomic group selected from N, O, S, P, Si and Se, and preferably N, O or S atom.
In the present specification, the halogen atom is F, Cl, Br or I.
In the present specification, the substituted or unsubstituted C6 to C60 aryl group includes monocyclic aryl groups and condensed ring aryl groups, preferably C6 to C30 aryl groups, and more preferably C6 to C20 aryl groups. By monocyclic aryl is meant that the molecule contains at least one phenyl group, and when the molecule contains at least two phenyl groups, the phenyl groups are independent of each other and are linked by a single bond, as exemplified by: phenyl, biphenyl, terphenyl, and the like. Specifically, the biphenyl group includes 2-biphenyl, 3-biphenyl, and 4-biphenyl; the terphenyl group includes p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl and m-terphenyl-2-yl. The fused ring aryl group means a group having at least two aromatic rings in a molecule, and the aromatic rings are not independent of each other but are fused to each other with two adjacent carbon atoms in common. Exemplary are as follows: naphthyl, anthrylPhenanthryl, indenyl, fluorenyl, fluoranthenyl, triphenylenyl, pyrenyl, perylenyl, perylene, and the like,
Figure BDA0003179537660000032
And mesitylene, and derivatives thereof. The naphthyl group includes a 1-naphthyl group or a 2-naphthyl group; the anthracene group is selected from 1-anthracene group, 2-anthracene group and 9-anthracene group; the fluorenyl is selected from 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl; the pyrenyl is selected from 1-pyrenyl, 2-pyrenyl and 4-pyrenyl; the tetracenyl is selected from the group consisting of 1-tetracenyl, 2-tetracenyl, and 9-tetracenyl. The derivative group of the fluorene is selected from 9, 9-dimethylfluorenyl, 9-diethylfluorenyl, 9-dipropylfluorenyl, 9-dibutylfluorenyl, 9-diamylfluorenyl, 9-dihexylfluorenyl, 9-diphenylfluorenyl, 9-dinaphthylfluorenyl, 9' -spirobifluorene and benzofluorenyl.
In the present specification, the heteroaryl group having 3 to 60 includes monocyclic heteroaryl groups and fused heteroaryl groups, preferably heteroaryl groups having 3 to 30, more preferably heteroaryl groups having 4 to 20, and still more preferably heteroaryl groups having 5 to 12. The monocyclic heteroaryl group means that at least one heteroaryl group is contained in the molecule, and when one heteroaryl group and another group (for example, aryl group, heteroaryl group, alkyl group, etc.) are contained in the molecule, the heteroaryl group and the other group are independently connected by a single bond, and examples of the monocyclic heteroaryl group include: furyl, thienyl, pyrrolyl, pyridyl and the like. The fused ring heteroaryl group means a group which has at least one aromatic heterocyclic ring and one aromatic ring (aromatic heterocyclic ring or aromatic ring) in a molecule, and which are not independent of each other but share two adjacent atoms fused with each other. Examples of fused heteroaryl groups include: benzofuranyl, benzothienyl, isobenzofuranyl, indolyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, acridinyl, isobenzofuranyl, isobenzothiophenyl, benzocarbazolyl, azacarbazolyl, phenothiazinyl, phenazinyl, 9-phenylcarbazolyl, 9-naphthylcarbazolyl, dibenzocarbazolyl, indolocarbazolyl, and the like.
Examples of the C6-C30 arylamino group in the present invention include: phenylamino, methylphenylamino, naphthylamino, anthrylamino, phenanthrylamino, biphenylamino and the like.
Examples of the heteroarylamino group having C3 to C30 in the present invention include: pyridylamino, pyrimidylamino, dibenzofuranylamino and the like.
The C1-C20 linear alkyl group in the present invention includes a linear alkyl group and a branched alkyl group unless otherwise specified. Straight chain alkyl refers to straight chain alkyl of the general formula CnH2n + 1-. Specifically, the substituted or unsubstituted C1-C30 chain alkyl group is preferably a substituted or unsubstituted C1-C16 chain alkyl group, and more preferably a substituted or unsubstituted C1-C10 chain alkyl group. Examples of the substituted or unsubstituted C1-C10 chain alkyl group include: methyl, ethyl, n-propyl, isopropyl, n-butyl, n-hexyl, n-octyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.
The cycloalkyl group having 3-20 carbon atoms in the present invention includes, but is not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, etc.
The alkylamino group in the present invention refers to a group in which at least one H of the amino groups is substituted with an alkyl group.
As a preferred embodiment of the present invention, in the formula (A), R7、R8Each independently selected from one or a combination of two of the following substituted or unsubstituted groups: phenyl, naphthyl, anthryl, phenanthryl, indenyl, anthryl, triphenylene, pyrenyl, perylenyl,
Figure BDA0003179537660000042
A phenyl group, a tetracenyl group, a 2-biphenyl group, a 3-biphenyl group, a 4-biphenyl group, a 9, 9-dimethylfluorenyl group, a 9, 9-diethylfluorenyl group, a 9, 9-dipropylfluorenyl group, a 9, 9-dibutylfluorenyl group, a 9, 9-dipentyfluorenyl group, a 9, 9-dihexylfluorenyl group, a 9, 9-diphenylfluorenyl group, a 9, 9-dinaphthylfluorenyl group, a spirofluorenyl group, a benzofluorenyl group, a furyl group, a thienyl group, a pyrrolyl group, a benzofuranyl group, a benzothienyl group, an isobenzofuranyl group, an indolyl group, a dibenzofuranyl group, a dibenzothienyl group, a carbazolyl group, an acridinyl group, an isobenzofuranyl group, an isobenzothienyl group, an acridinyl group, a pyridyl group, a benzocarbazolyl group, an azacarbazolyl group, a phenothiazinyl group or a phenazinyl group;
r is as defined above7、R8When present, the substituents are each independently selected from the following groups: methyl, ethyl, n-propyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, phenyl, biphenyl, naphthyl, pyridyl, quinazolinyl, benzopyrazinyl, triazolyl, oxadiazolyl, benzimidazolyl, fluorenyl.
Further preferably, said R1、R2、R3Is selected from the group shown in formula (a), and formula (a) is selected from any one of the following groups:
Figure BDA0003179537660000041
Figure BDA0003179537660000051
the dotted line in the above formula represents the position of the access bond of the group.
Still further preferably, the formula (a) is selected from any one of the following groups:
Figure BDA0003179537660000052
Figure BDA0003179537660000061
most preferably, the formula (a) is selected from any one of the following groups:
Figure BDA0003179537660000062
Figure BDA0003179537660000071
preferably, said m, n andp is all 1, R1、R2、R3One of the groups is selected from any one of the following groups, R1、R2、R3Is selected from any one of hydrogen, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted spirobifluorenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenyl, and substituted or unsubstituted biphenyl:
Figure BDA0003179537660000072
Figure BDA0003179537660000081
the dotted line in the above formula represents the position of the access bond of the group.
Preferably, said R is1、R2、R3One or two of the groups are selected from any one of the following groups, R1、R2、R3Is selected from hydrogen, said m, n and p are each 1:
Figure BDA0003179537660000082
Figure BDA0003179537660000091
the dotted line in the above formula represents the position of the access bond of the group.
The compounds of this type of the invention are preferably, but not exclusively, the following specific compounds:
Figure BDA0003179537660000092
Figure BDA0003179537660000101
Figure BDA0003179537660000111
Figure BDA0003179537660000121
Figure BDA0003179537660000131
Figure BDA0003179537660000141
Figure BDA0003179537660000151
the invention further provides the application of the organic compound containing the spiro pyrrolocarbazole, shown in the general formula (I), disclosed by the invention. Specifically, the organic electronic device is used as a functional material in an organic electronic device, and the organic electronic device comprises an organic electroluminescent device, an optical sensor, a solar cell, a lighting element, an organic thin film transistor, an organic field effect transistor, an organic thin film solar cell, an information tag, an electronic artificial skin sheet, a sheet type scanner or electronic paper.
Preferably, the organic compound containing spiro pyrrolocarbazole of the present invention represented by the general formula (I) can be used in organic electroluminescent devices. The organic compound is preferably used as a hole transport material in a hole transport layer in an organic electroluminescent device.
As another preferred embodiment, the present invention provides an organic electroluminescent device comprising an anode, a cathode, and one or more luminescent functional layers interposed between the anode and the cathode, wherein the luminescent functional layer contains the spirocyclic pyrrolocarbazole-containing organic compound of the present invention represented by general formula (I).
Preferably, the light-emitting functional layer comprises an electron blocking layer and at least one of a hole injection layer, a hole transport layer, a light-emitting layer and an electron transport layer, and the hole transport layer contains the spiro pyrrolocarbazole-containing organic compound of the present invention represented by general formula (I).
The organic compound provided by the invention takes a spiro pyrrolocarbazole structure as a parent nucleus structure, and the parent structure has a rigid structural unit, good thermal stability, and appropriate HOMO and LUMO energy levels and Eg. By introducing an electron-donating group with a hole transport property into an active position in a parent nucleus structure, namely by introducing an arylamine structure with strong electron-donating capability into the structure and taking an aromatic compound as an end group, the specific molecular structure design can obtain a compound with high hole mobility, better film stability, proper molecular energy level and good thermal stability. The device can be applied to the field of display or illumination.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention, and it should be understood by those skilled in the art that they are merely examples to assist understanding of the invention and should not be construed as specifically limiting the invention.
According to the method for synthesizing the compound and the method for manufacturing the organic electroluminescent device provided by the present invention, a person skilled in the art can use known common means to realize the method, and the present invention is not particularly limited thereto. If not specifically stated, the starting materials for the preparation of solvents, catalysts, bases, etc. may be obtained by published commercial routes or by methods known in the art.
The synthesis of the compounds of the present invention is briefly described below. The compounds of the general formula (I) of the present invention can be synthesized by a known organic synthesis method. An exemplary synthetic route is given below, which allows the synthesis of the compounds of formula (I) according to the invention to be completed according to the following synthetic methods for intermediates M1-M17 of the compounds of the invention. The method can also be obtained by other known methods, such as further selecting suitable catalyst and solvent, and determining suitable reaction temperature, time, material ratio, etc.
Synthesis of intermediate M1
Figure BDA0003179537660000161
The synthetic route is as follows:
Figure BDA0003179537660000171
the specific operation steps are as follows:
(1) m-01(29.8g, 0.1mol), iodobenzene (30.6g, 0.15mol), copper powder (0.64g, 0.01mol), DMF and potassium hydroxide (11.2g, 0.2mol) were added to a dry 1L three-necked flask under nitrogen protection, stirred, heated to reflux and reacted for 2h with heat preservation. After the reaction was completed, the organic phase was separated, extracted, dried, column-chromatographed, and the solvent was spin-dried to obtain 28.4g of compound M-02 with a yield of 76%.
(2) Adding 2-chloro-6-iodobiphenyl (31.4g, 0.10mol) and anhydrous tetrahydrofuran into a dry 1L three-necked bottle under the protection of nitrogen, cooling to-70 ℃ by using liquid nitrogen, slowly dropwise adding n-butyllithium (0.17mol, 68mL), and stirring for 1 h; an anhydrous tetrahydrofuran solution of M-02(41.1g, 0.11mol) was slowly added dropwise to a three-necked flask under nitrogen protection, then naturally warmed to room temperature, stirred for 10h, and quenched with a saturated sodium bicarbonate solution. Separating organic phase, extracting, drying, column chromatography and spin drying solvent to obtain 45.6g of product M-03 with yield of 81%.
(3) In a 1L three-necked flask equipped with mechanical stirring, 560mL of acetic acid and 9mL of hydrochloric acid, respectively, followed by M-03(56.3g, 0.1mol) were added, the stirring was turned on, and the mixture was heated to 120 ℃ to react for 12 hours. After the reaction was completed, the organic phase was separated, extracted, dried, column chromatographed, and the solvent was spin-dried to obtain 40.9g of product M-04 with a yield of 75%.
(4) Under the protection of nitrogen, respectively adding M-04(54.5g, 0.1mol), 550mL of toluene, dibenzylidene acetone dipalladium (0.092g, 0.001mol), N-phenyl-2-chloroaniline (20.4g, 0.1mol), sodium tert-butoxide (14.4g, 0.15mol) and 1mL of tri-tert-butylphosphine into a 1L three-neck bottle, magnetically stirring, heating to reflux, keeping the temperature for reaction for 8h, separating an organic phase after the reaction is finished, extracting, drying, carrying out column chromatography, and spin-drying a solvent to obtain 48g of a compound M-05 with the yield of 72%.
(5) Under the protection of nitrogen, M-05(66.7g, 0.1mol), 660ml of dimethylformamide, 27.6g of potassium carbonate (0.2 mol) and 0.23g of palladium acetate (0.001 mol) are respectively added into a 1L three-mouth bottle provided with a condenser tube, a magneton and a thermometer, stirring is started, heating is carried out until reflux is achieved, heat preservation reaction is carried out for 4 hours, and the reaction is finished. The organic phase was separated, extracted, dried, column chromatographed and the solvent dried to give 43.5g of intermediate M1 in 69% yield.
Product MS (m/e): 630.19, respectively; elemental analysis (C)45H27ClN2): theoretical value C: 85.63%, H: 4.31%, N: 4.44 percent; found value C: 85.69%, H: 4.29%, N: 4.47 percent.
Synthesis of intermediate M2
Figure BDA0003179537660000181
Referring to the synthesis method of the intermediate M1, 2-bromo-2' -iodobiphenyl is used for replacing 2-chloro-6-iodobiphenyl, a proper material ratio is selected, and other raw materials and steps are the same as those of the synthesis method of the intermediate M1, so that the intermediate M2 is obtained.
Product MS (m/e): 630.19, respectively; elemental analysis (C)45H27ClN2): theoretical value C: 85.63%, H: 4.31%, N: 4.44 percent; found value C: 85.60%, H: 4.35%, N: 4.42 percent.
Synthesis of intermediate M3
Figure BDA0003179537660000182
Referring to the synthesis method of the intermediate M1, 3 '-chloro-2-iodo-1, 1' -biphenyl is used for replacing 2-chloro-6-iodobiphenyl, a proper material ratio is selected, and other raw materials and steps are the same as those of the synthesis method of the intermediate M1, so that the intermediate M3 is obtained.
Product MS (m/e): 630.19, respectively; elemental analysis (C)45H27ClN2): theoretical value C: 85.63%, H: 4.31%, N: 4.44 percent; found value C: 85.66%, H: 4.36%, N: 4.39 percent.
Synthesis of intermediate M4
Figure BDA0003179537660000183
Referring to the synthesis method of the intermediate M1, 7-bromo-2-chloroindene [1,2-b ] indole 10(5H) -one is used for replacing the compound M-01, 4 '-chloro-2-iodo-1, 1' -biphenyl for replacing 2-chloro-6-iodobiphenyl, a proper material ratio is selected, and other raw materials and steps are the same as those of the synthesis method of the intermediate M1, so that the intermediate M4 is obtained.
Product MS (m/e): 630.19, respectively; elemental analysis (C)45H27ClN2): theoretical value C: 85.63%, H: 4.31%, N: 4.44 percent; found value C: 85.62%, H: 4.33%, N: 4.40 percent.
Synthesis of intermediate M5
Figure BDA0003179537660000191
Referring to the synthesis method of the intermediate M1, 3' -chloro-2-iodo-biphenyl is used to replace 2-chloro-6-iodo-biphenyl, a proper material ratio is selected, and other raw materials and steps are the same as those of the synthesis method of the intermediate M1, so that the intermediate M5 is obtained.
Product MS (m/e): 630.19, respectively; elemental analysis (C)45H27ClN2): theoretical value C: 85.63%, H:4.31%, N: 4.44 percent; found value C: 85.66%, H: 4.36%, N: 4.39 percent.
Synthesis of intermediate M6
Figure BDA0003179537660000192
Referring to the synthesis method of the intermediate M1, 5 '-chloro-2-iodo-1, 1' -biphenyl is used for replacing 2-chloro-6-iodobiphenyl, a proper material ratio is selected, and other raw materials and steps are the same as those of the synthesis method of the intermediate M1, so that the intermediate M6 is obtained.
Product MS (m/e): 630.19, respectively; elemental analysis (C)45H27ClN2): theoretical value C: 85.63%, H: 4.31%, N: 4.44 percent; found value C: 85.59%, H: 4.33%, N: 4.48 percent.
Synthesis of intermediate M7
Figure BDA0003179537660000193
Referring to the synthesis method of the intermediate M1, 4 '-chloro-2-iodo-1, 1' -biphenyl is used for replacing 2-chloro-6-iodobiphenyl, a proper material ratio is selected, and other raw materials and steps are the same as those of the synthesis method of the intermediate M1, so that the intermediate M7 is obtained.
Product MS (m/e): 630.19, respectively; elemental analysis (C)45H27ClN2): theoretical value C: 85.63%, H: 4.31%, N: 4.44 percent; found value C: 85.68%, H: 4.35%, N: 4.41 percent.
Synthesis of intermediate M8
Figure BDA0003179537660000201
Referring to the synthesis method of the intermediate M1, 3', 5-dichloro-2-iodo-1, 1' -biphenyl is used for replacing 2-chloro-6-iodobiphenyl, a proper material ratio is selected, and other raw materials and steps are the same as those of the synthesis method of the intermediate M1, so that the intermediate M8 is obtained.
Product MS (m/e): 664.25, respectively; elemental analysis (C)45H26Cl2N2): theoretical value C: 81.20%, H: 3.94%, N: 4.21 percent; found value C: 81.25%, H: 3.92%, N: 4.14 percent.
Synthesis of intermediate M9
Figure BDA0003179537660000202
Referring to the synthesis method of the intermediate M1, 7-bromo-3-chloroindene [1,2-b ] indol-10 (5H) -one is used for replacing the compound M-01, 3 '-chloro-2-iodo-1, 1' -biphenyl for replacing 2-chloro-6-iodobiphenyl, a proper material ratio is selected, and other raw materials and steps are the same as those of the synthesis method of the intermediate M1, so that the intermediate M9 is obtained.
Product MS (m/e): 664.25, respectively; elemental analysis (C)45H26Cl2N2): theoretical value C: 81.20%, H: 3.94%, N: 4.21 percent; found value C: 81.23%, H: 3.96%, N: 4.19 percent.
Synthesis of intermediate M10
Figure BDA0003179537660000203
Referring to the synthesis method of the intermediate M1, 2,4 '-dichloro-6-iodo-1, 1' -biphenyl is used for replacing 2-chloro-6-iodobiphenyl, a proper material ratio is selected, and other raw materials and steps are the same as those of the synthesis method of the intermediate M1, so that the intermediate M10 is obtained.
Product MS (m/e): 664.25, respectively; elemental analysis (C)45H26Cl2N2): theoretical value C: 81.20%, H: 3.94%, N: 4.21 percent; found value C: 81.26%, H: 3.91%, N: 4.22 percent.
Synthesis of intermediate M11
Figure BDA0003179537660000211
Referring to the synthesis method of intermediate M1, compound M-01 is replaced by 7-bromo-3-chloro-5-phenylindeno [1,2-b ] indol-10 (5H) -one, and an appropriate material ratio is selected, and other raw materials and steps are the same as those of the synthesis method of intermediate M1, so that intermediate M11 is obtained.
Product MS (m/e): 664.25, respectively; elemental analysis (C)45H26Cl2N2): theoretical value C: 81.20%, H: 3.94%, N: 4.21 percent; found value C: 81.24%, H: 3.97%, N: 4.18 percent.
Synthesis of intermediate M12
Figure BDA0003179537660000212
Referring to the synthesis method of the intermediate M1, 7-iodoindene [1,2-b ] indol-10 (5H) -one is used for replacing the compound M-01, a proper material ratio is selected, and other raw materials and steps are the same as those of the synthesis method of the intermediate M1, so that the intermediate M12 is obtained.
Product MS (m/e): 708.10, respectively; elemental analysis (C)45H26BrClN2): theoretical value C: 76.12%, H: 3.69%, N: 3.95 percent; found value C: 76.16%, H: 3.72%, N: 3.97 percent.
Synthesis of intermediate M13
Figure BDA0003179537660000213
Referring to the synthesis method of the intermediate M1, 3-bromo-7-iodoindene [1,2-b ] indol-10 (5H) -one is used for replacing the compound M-01, a proper material ratio is selected, and other raw materials and steps are the same as those of the synthesis method of the intermediate M1, so that the intermediate M13 is obtained.
Product MS (m/e): 708.10, respectively; elemental analysis (C)45H26BrClN2): theoretical value C: 76.12%, H: 3.69%, N: 3.95 percent; found value C: 76.10%, H: 3.73%, N: 3.93 percent.
Synthesis of intermediate M14
Figure BDA0003179537660000221
Referring to the synthesis method of the intermediate M1, 2-bromo-7-iodoindene [1,2-b ] indol-10 (5H) -one is used for replacing the compound M-01, 3' -chloro-2-iodo-1, 1' -biphenyl for replacing 2-chloro-6-iodo-1, 1' -biphenyl, a proper material ratio is selected, and other raw materials and steps are the same as those of the synthesis method of the intermediate M1, so that the intermediate M14 is obtained.
Product MS (m/e): 708.10, respectively; elemental analysis (C)45H26BrClN2): theoretical value C: 76.12%, H: 3.69%, N: 3.95 percent; found value C: 76.13%, H: 3.71%, N: 3.92 percent.
Synthesis of intermediate M15
Figure BDA0003179537660000222
Referring to the synthesis method of the intermediate M1, 7-iodoindene [1,2-b ] indol-10 (5H) -one is used for replacing the compound M-01, 4' -bromo-2-chloro-6-iodo-1, 1' -biphenyl for replacing 2-chloro-6-iodo-1, 1' -biphenyl, a proper material ratio is selected, and other raw materials and steps are the same as those of the synthesis method of the intermediate M1, so that the intermediate M15 is obtained.
Product MS (m/e): 708.10, respectively; elemental analysis (C)45H26BrClN2): theoretical value C: 76.12%, H: 3.69%, N: 3.95 percent; found value C: 76.14%, H: 3.73%, N: 3.91 percent.
Synthesis of intermediate M16
Figure BDA0003179537660000223
Referring to the synthesis method of the intermediate M1, 2-bromo-7-iodoindene [1,2-b ] indol-10 (5H) -one is used for replacing the compound M-01, 2-chloro-2 ' -iodo-1, 1' -biphenyl for replacing 2-chloro-6-iodo-1, 1' -biphenyl, a proper material ratio is selected, and other raw materials and steps are the same as those of the synthesis method of the intermediate M1, so that the intermediate M16 is obtained.
Product MS (m/e): 708.10, respectively; elemental analysis (C)45H26BrClN2): theoretical value C: 76.12%, H: 3.69%, N: 3.95 percent; found value C: 76.08%, H: 3.73%, N:3.98％。
synthesis of intermediate M17
Figure BDA0003179537660000231
Referring to the synthesis method of intermediate M1, 3-bromo-7-iodoindene [1,2-b ] indol-10 (5H) -one is used for replacing compound M-01, 4,4' -chloro-2-iodo-1, 1' -biphenyl for replacing 2-chloro-6-iodo-1, 1' -biphenyl, a proper material ratio is selected, and other raw materials and steps are the same as those of the synthesis method of intermediate M1, so that intermediate M17 is obtained.
Product MS (m/e): 708.10, respectively; elemental analysis (C)45H26BrClN2): theoretical value C: 76.12%, H: 3.69%, N: 3.95 percent; found value C: 76.17%, H: 3.72%, N: 3.92 percent.
The following are specific synthetic examples of representative compounds of the present invention:
synthesis example 1 Synthesis of Compound I-1
Figure BDA0003179537660000232
The synthetic route is as follows:
Figure BDA0003179537660000233
the synthesis of the compound I-1 comprises the following specific steps:
to a 1 liter three-necked flask equipped with a magneton, a condenser tube and a thermometer under nitrogen protection were added potassium tert-butoxide (36.2g, 0.376mol), 3, 4' -dimethyldiphenylamine (21.7g, 0.11mol) and 100ml of toluene in this order. Then, under nitrogen protection, tri-tert-butylphosphine (1.2g, 0.006mol) and palladium acetate (0.7g, 0.003mol) were added to the reaction flask in this order. After the addition, the temperature was raised to 85 ℃. And (3) beginning to dropwise add a solution consisting of M1(63.1g, 0.1mol) and 100ml of toluene, controlling the temperature within the range of 80-120 ℃ to react for 4 hours, and finishing the reaction. Adjusting to neutrality, separating an organic phase, extracting, drying, performing column chromatography, and spin-drying the solvent to obtain 65.89g of a product with the yield of about 83.2%.
Product MS (m/e): 791.33, respectively; elemental analysis (C)59H41N3): theoretical value C: 89.48%, H: 5.22%, N: 5.31 percent; found value C: 8.52%, H: 5.25%, N: 4.29 percent.
Synthesis example 2:
Figure BDA0003179537660000241
the synthetic route is as follows:
Figure BDA0003179537660000242
the synthesis of the compound I-5 comprises the following specific steps:
the 3,4 '-dimethyldiphenylamine and M1 described in example 1 were replaced with N- (1,1' -biphenyl) -3-yl) naphthalen-1-amine and M2, respectively, in equivalent amounts, and the other reaction conditions and operations were the same as in example 1 to obtain 74.23g of a product with a yield of about 86%.
Product MS (m/e): 889.35, respectively; elemental analysis (C)66H42N2): theoretical value C: 90.41%, H: 4.87%, N: 4.72 percent; found value C: 90.44%, H: 4.91%, N: 4.68 percent.
Synthetic example 3:
Figure BDA0003179537660000243
the synthetic route is as follows:
Figure BDA0003179537660000251
the synthesis of the compound I-14 comprises the following specific steps:
the 3, 4' -dimethyldiphenylamine and M1 described in example 1 were replaced with N- [1,1' -biphenyl ] -3-yl- [1,1' -biphenyl ] -4-amine and M3, respectively, in equivalent amounts, and the other reaction conditions and operations were the same as in example 1 to obtain 73.0g of a product with a yield of about 79.7%.
Product MS (m/e): 915.36, respectively; elemental analysis (C)69H45N3): theoretical value C: 90.46%, H: 4.95%, N: 4.59 percent; found value C: 90.48%, H: 4.92%, N: 4.61 percent.
Synthetic example 4:
Figure BDA0003179537660000252
the synthetic route is as follows:
Figure BDA0003179537660000253
the synthesis of the compound I-19 comprises the following specific steps:
respectively replacing 3, 4' -dimethyldiphenylamine and M1 described in example 1 with N- (naphthyl-2-yl) phenanthroline-9-amine and M4 in equivalent, and performing other reactions under the same conditions and in the same operation as in example 1 to obtain 75.3g of a product, namely a light yellow solid, wherein the yield is about 82.4%.
Product MS (m/e): 913.35, respectively; elemental analysis (C)69H43N3): theoretical value C: 90.66%, H: 4.74%, N: 4.60 percent; found value C: 90.69%, H: 4.70%, N: 4.63 percent.
Synthesis example 5:
Figure BDA0003179537660000254
the synthetic route is as follows:
Figure BDA0003179537660000261
the synthesis of the compound I-23 comprises the following specific steps:
the 3,4 '-dimethyldiphenylamine and M1 described in example 1 were replaced with N- ([1,1' -biphenyl ] -4-yl) anthracen-9-amine and M5, respectively, in equivalent amounts, and the other reaction conditions and operation were the same as in example 1 to give the product 80.1g of a pale yellow solid with a yield of about 85.2%.
Product MS (m/e): 939.36, respectively; elemental analysis (C)71H45N3): theoretical value C: 90.71%, H: 4.82%, N: 4.47%; found value C: 90.74%, H: 4.87%, N: 4.44 percent.
Synthetic example 6:
Figure BDA0003179537660000262
the synthetic route is as follows:
Figure BDA0003179537660000263
the synthesis of the compound I-24 comprises the following specific steps:
the 3, 4' -dimethyldiphenylamine and M1 described in example 1 were replaced with N- (naphthalen-2-yl) naphthalen-1-amine and M6, respectively, in equivalent amounts, and the other reaction conditions and operations were the same as in example 1 to give 67.7g of a product with a yield of about 78.4%.
Product MS (m/e): 863.33, respectively; elemental analysis (C)65H41N3): theoretical value C: 90.35%, H: 4.78%, N: 4.86 percent; found value C: 90.40%, H: 4.80%, N: 4.83 percent.
Synthetic example 7:
Figure BDA0003179537660000264
the synthetic route is as follows:
Figure BDA0003179537660000271
the synthesis of the compound I-29 comprises the following specific steps:
the 3, 4' -dimethyldiphenylamine and M1 described in example 1 were replaced with N- ([1,1' -biphenyl ] -4-yl) -9,9' -spirobifluorene ] -2-amine and M7, respectively, in equivalent amounts, and the other reaction conditions and operations were the same as in example 1 to obtain 83.3g of a product with a yield of about 77.3%.
Product MS (m/e): 1077.41, respectively; elemental analysis (C)70H42N2O2): theoretical value C: 91.34%, H: 4.77%, N: 3.90 percent; found value C: 91.37%, H: 4.74%, N: 3.95 percent.
Synthesis example 8:
Figure BDA0003179537660000272
the synthetic route is as follows:
Figure BDA0003179537660000273
the synthesis of the compound I-49 comprises the following specific steps:
the reaction conditions and operation were the same as in example 1 except that diphenylamine and M8 were used in a molar ratio of 2.1:1 in place of the 3, 4' -dimethyldiphenylamine and M1 described in example 1 to give 76.9g of a product in a yield of about 82.7%.
Product MS (m/e): 929.38, respectively; elemental analysis (C)70H47N3): theoretical value C: 90.39%, H: 5.09%, N: 4.52 percent; found value C: 90.36%, H: 5.06%, N: 4.49 percent.
Synthetic example 9:
Figure BDA0003179537660000274
the synthetic route is as follows:
Figure BDA0003179537660000281
the synthesis of the compound I-52 comprises the following specific steps:
the molar ratio of M1, 3, 4' -dimethyldiphenylamine to M1 was 2.1:1 instead of M9, and the other reaction conditions and operation were the same as in example 1 to obtain 78.4g of a product with a yield of about 79.4%.
Product MS (m/e): 986.43, respectively; elemental analysis (C)73H54N4): theoretical value C: 88.81%, H: 5.51%, N: 5.68 percent; found value C: 88.85%, H: 5.54%, N: 5.66 percent.
Synthetic example 10:
Figure BDA0003179537660000282
the synthetic route is as follows:
Figure BDA0003179537660000283
the synthesis of the compound I-55 comprises the following specific steps:
the reaction conditions and operation were the same as in example 1 except that bis- (4-isopropyl-phenyl) -amine and M10 were used in a molar ratio of 2.1:1 in place of the 3, 4' -dimethyldiphenylamine and M1 described in example 1 to give 85.83g of a product in a yield of about 78.1%.
Product MS (m/e): 1098.56, respectively; elemental analysis (C)81H70N4): theoretical value C: 88.49%, H: 6.42%, N: 5.10 percent; found value C: 88.52%, H: 6.46%, N: 5.08 percent.
Synthetic example 11:
Figure BDA0003179537660000291
the synthetic route is as follows:
Figure BDA0003179537660000292
the synthesis of the compound I-57 comprises the following specific steps:
the reaction conditions and operation were the same as in example 1 except that N- (p-tolyl) -1-naphthylamine and M11 were used in a molar ratio of 2.1:1 in place of the 3, 4' -dimethyldiphenylamine and M1 described in example 1 to give 79.6g of a product in a yield of about 75.2%.
Product MS (m/e): 1058.43, respectively; elemental analysis (C)79H54N4): theoretical value C: 89.57%, H: 5.14%, N: 5.29 percent; found value C: 89.60%, H: 5.17%, N: 5.26 percent.
Synthetic example 12:
Figure BDA0003179537660000293
the synthesis steps are as follows:
Figure BDA0003179537660000294
Figure BDA0003179537660000301
the synthesis of the compound I-68 comprises the following specific steps:
N2m12(71g, 0.1mol), N- ([1,1' -biphenyl) was added to a 2L three-necked flask equipped with a mechanical stirrer and thermometer under protection]-3-yl) dibenzo [ b, d]Thiophene-4-amine (14.1g, 0.04mol), cuprous chloride (2.97g, 0.03mol), 1, 10-phenanthroline hydrate (3.96g, 0.02mol), potassium hydroxide (16.8g, 0.3mol), and 400mL of xylene. Stirring is started, the system is changed from black to khaki when the temperature is increased to about 80 ℃, the system is changed from khaki to tan when the temperature is increased to 130 ℃, and at the moment, N- ([1,1' -biphenyl) (28.1g and 0.08mol) is dropwise added into the system]-3-yl) dibenzo [ b, d]Thiophene-4-amine and 200mL of xylene. After the addition was complete, the reaction was maintained at reflux (about 138 ℃ C.) for 16 h. Cooling the reaction liquid to 60 ℃, dropwise adding concentrated hydrochloric acid into the reaction liquid for acidification, and stirring for 1h after the dropwise adding is finished. Filtration and spin-drying of the filtrate gave a brownish black oil. Pulping with ethanol, and heating to reflux for 1 hr. Down to the roomStirring for about 8-10h after warming, filtering, leaching a filter cake with ethanol, and drying to obtain a brown yellow solid. Performing column chromatography by using petroleum ether, and performing spin drying to obtain 72.3g of light yellow solid I-68-1 with the yield of about 76.4%.
A1L three-necked flask is taken, stirred by magnetic force, and added with potassium tert-butoxide (14.4g, 0.15mol), diphenylamine (16.9g, 0.1mol) and 100ml of toluene in turn after nitrogen replacement. After nitrogen replacement again, (1.2g, 0.006mol) tri-tert-butylphosphine and (0.7g, 0.003mol) palladium acetate were added in this order. After the addition, the temperature was raised to 85 ℃. And (3) beginning to dropwise add a solution consisting of (94.6g, 0.1mol and 99% purity) I-68-1 and 100ml of toluene, controlling the temperature to be 80-120 ℃ and reacting for 4 hours, and finishing the reaction. Adjusting to neutrality, separating organic phase, extracting, drying, column chromatography, and spin-drying solvent to obtain 83.1g pale yellow solid with yield of about 74.7%.
Product MS (m/e): 1112.39, respectively; elemental analysis (C)81H62N4S): theoretical value C: 87.38%, H: 4.71%, N: 5.03 percent; found value C: 87.41%, H: 4.76%, N: 5.07 percent.
Synthetic example 13:
Figure BDA0003179537660000302
the synthesis steps are as follows:
Figure BDA0003179537660000303
Figure BDA0003179537660000311
the synthesis of the compound I-70 comprises the following specific steps:
n- ([1,1' -biphenyl ] -3-yl) dibenzo [ b, d ] furan-4-amine and M13, 3, 4' -dimethyldiphenylamine and I-70-1 were used in the equivalent amount instead of N- ([1,1' -biphenyl ] -3-yl) dibenzo [ b, d ] thiophen-4-amine and M12, diphenylamine and I-68-1, respectively, described in example 9, and the other reaction conditions and operations were the same as in example 12 to obtain 82.0g of a product in about 72.9% yield.
Product MS (m/e): 1124.45, respectively; elemental analysis (C)83H56N4O): theoretical value C: 88.58%, H: 5.02%, N: 4.98%, O: 1.42 percent; found value C: 88.62%, H: 5.05%, N: 4.94 percent.
Synthesis example 14:
Figure BDA0003179537660000312
the synthesis steps are as follows:
Figure BDA0003179537660000313
the synthesis of the compound I-72 comprises the following specific steps:
bis- (4-isopropyl-phenyl) -amine and M14, I-72-1 were used in place of the N- ([1,1' -biphenyl ] -3-yl) dibenzo [ b, d ] thiophen-4-amine and M12, I-68-1, respectively, in equivalent amounts as described in example 12, and the reaction conditions and operation were otherwise the same as in example 12, to give 71.5g of product in about 70.4% yield.
Product MS (m/e): 1014.47, respectively; elemental analysis (C)76H58N4): theoretical value C: 88.72%, H: 5.76%, N: 5.52 percent; found value C: 88.75%, H: 5.80%, N: 4.49 percent.
Synthetic example 15:
Figure BDA0003179537660000321
the synthesis steps are as follows:
Figure BDA0003179537660000322
the synthesis of the compound I-74 comprises the following specific steps:
the N- ([1,1' -biphenyl ] -3-yl) dibenzo [ b, d ] thiophen-4-amine and M12, I-68-1 and diphenylamine described in example 12 were replaced by bis- (4-isopropyl-phenyl) -amine and M15, I-74-1 and N- (p-tolyl) -1-naphthylamine, respectively, in equivalent amounts under the same reaction conditions and procedures as in example 12 to give 74.1g of a product in about 68.7% yield.
Product MS (m/e): 1078.5, respectively; elemental analysis (C)80H62N4): theoretical value C: 89.02%, H: 5.79%, N: 5.19 percent; found value C: 89.04%, H: 5.77%, N: 5.21 percent.
Synthetic example 16:
Figure BDA0003179537660000331
the synthesis steps are as follows:
Figure BDA0003179537660000332
the synthesis of the compound I-74 comprises the following specific steps:
the N- ([1,1' -biphenyl ] -3-yl) dibenzo [ b, d ] thiophen-4-amine and M12, I-68-1 and diphenylamine described in example 12 were replaced by 2, 2-dinaphthylamine and M15, I-76-1 and N- (p-tolyl) -1-naphthylamine, respectively, in equivalent amounts under the same reaction conditions and operation as in example 12 to give 76.1g of a product in a yield of about 69.5%.
Product MS (m/e): 1094.43, respectively; elemental analysis (C)82H54N4): theoretical value C: 89.92%, H: 4.97%, N: 5.12 percent; found value C: 89.96%, H: 4.95%, N: 5.17 percent.
Synthetic example 17:
Figure BDA0003179537660000333
the synthesis steps are as follows:
Figure BDA0003179537660000341
the synthesis of the compound I-78 comprises the following specific steps:
n- [1,1' -biphenyl ] -3-yl- [1,1' -biphenyl ] -4-amine and M17, I-78-1 were used in an equivalent amount instead of N- ([1,1' -biphenyl ] -3-yl) dibenzo [ b, d ] thiophen-4-amine and M12, I-68-1 described in example 12, respectively, and the reaction conditions and procedures were the same as in example 12 to obtain 72.3g of a product with a yield of about 66.8%.
Product MS (m/e): 1082.43, respectively; elemental analysis (C)81H54N4): theoretical value C: 89.80%, H: 5.02%, N: 5.17 percent; found value C: 89.83%, H: 5.04%, N: 5.13 percent.
According to the synthetic methods of the above synthetic examples 1 to 17, other compounds among the compounds I-1 to I-80 which are typically preferred in the present invention can be synthesized by simply replacing the corresponding raw materials without changing any substantial operation.
The organic electroluminescent device has a structure consistent with that of the organic electroluminescent device in the prior art, and comprises an anode layer, a plurality of light-emitting functional layers and a cathode layer; the plurality of light-emitting functional layers at least comprise a light-emitting layer, and the light-emitting functional layer comprises at least one of a hole injection layer, a hole transport layer, a light-emitting layer, an electron blocking layer and an electron transport layer, wherein the light-emitting layer contains the organic compound of the invention.
In embodiments in which organic electroluminescent devices are specifically prepared, a substrate may be used either below the anode or above the cathode. The substrate is a glass or polymer material having excellent mechanical strength, thermal stability, water resistance, and transparency. In addition, a Thin Film Transistor (TFT) may be provided on a substrate for a display.
The anode electrode may be formed by sputtering or depositing a material serving as an anode on a substrate. Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), tin dioxide (SnO)2) And transparent conductive oxide materials such as zinc oxide (ZnO), and any combination thereof. The cathode can be made of magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), ytterbium (Yb), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag)) Etc. and any combination thereof.
The plurality of light-emitting functional layers may be formed on the electrodes by vacuum thermal evaporation, spin coating, printing, or the like. The compound used as the organic material layer may be an organic small molecule, an organic large molecule, and a polymer, and a combination thereof.
The following are examples of organic electroluminescent devices prepared according to the invention using representative compounds of the invention:
device example 1：
The embodiment provides an OLED green light device, the structure of which is as follows:
ITO/HATCN (1nm)/HT01(40nm)/I-4 compound (20nm)/EML (30nm)/Bphen (40nm)/LiF (1nm)/Al
Wherein 1nm, 40nm, 20nm, etc. all represent the thickness of the functional layer.
The molecular structure of each functional layer material is as follows:
Figure BDA0003179537660000351
the specific preparation process of the OLED green device in this embodiment is as follows:
(1) carrying out ultrasonic treatment on the glass plate coated with the ITO transparent conductive layer in a commercial cleaning agent, washing the glass plate in deionized water, ultrasonically removing oil in an acetone-ethanol mixed solvent (the volume ratio is 1: 1), baking the glass plate in a clean environment until the water is completely removed, cleaning the glass plate by using ultraviolet light and ozone, and bombarding the surface by using low-energy cationic beams;
(2) placing the glass substrate with anode in a vacuum chamber, and vacuumizing to 1 × 10-5～9×10-3Pa, performing vacuum evaporation on the anode layer film to form HATCN as a first hole injection layer, wherein the evaporation rate is 0.1nm/s, and the total evaporation film thickness is 1 nm; then evaporating a second hole injection layer HT01 at the evaporation rate of 0.1nm/s and the thickness of 40 nm; then evaporating a hole transport layer, wherein the I-1 compound prepared in the synthesis example 1 is adopted, the evaporation rate is 0.1nm/s, and the evaporation film thickness is 20 nm;
(3) in the skyEML is evaporated on the hole transport layer in vacuum and used as a light emitting layer of the device, the EML comprises a main material and a dye material, the evaporation rate of the main material CBP is adjusted to be 0.1nm/s by using a multi-source co-evaporation method, and the dye material Ir (ppy)3The concentration of (2) is 5%, and the total film thickness of evaporation plating is 30 nm;
(4) bphen is used as an electron transport material of an electron transport layer of the device, the evaporation rate is 0.1nm/s, and the total film thickness of evaporation is 40 nm;
(5) sequentially performing vacuum evaporation on the electron transport layer to form LiF with the thickness of 1nm as an electron injection layer, and forming an Al layer with the thickness of 150nm as a cathode of the device; the OLED-1 green light device is prepared.
An organic electroluminescent device numbered as OLED-1 was prepared according to the above procedure.
Device example 2 to device example 17:
organic electroluminescent devices, numbered OLED-1-OLED-17, using compounds of this type according to the invention were prepared by following the same procedure as above, except that the hole transport layer material in step (2) was replaced with the compound I-1 prepared in example 1 by I-5, I-14, I-19, I-23, I-24, I-29, I-49, I-52, I-55, I-57, I-68, I-70, I-72, I-74, I-76, I-78, respectively, as detailed in Table 1 below.
Device comparative example 1:
following the same preparation procedure as described above for device example 1, a comparative example device, OLED-18, was obtained by replacing only the hole transport material in step (2) with the prior art compound PSA, which has the following structural formula:
Figure BDA0003179537660000361
the data of the performance test of the organic electroluminescent devices prepared in the above examples 1 to 17 and comparative example 1 of the present invention are detailed in the following table 1.
Table 1:
Figure BDA0003179537660000362
as can be seen from the data in Table 1, when the organic compound containing the spiro pyrrolocarbazole structure provided by the invention is used as a hole transport material, the prepared device has high current efficiency, and the working voltage is obviously lower than that of a comparative device under the condition of the same current density. .
The present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods. It is obvious to those skilled in the art that any modification of the present invention, equivalent substitution of each raw material and addition of auxiliary components, selection of specific modes, etc., of the product of the present invention fall within the protection scope of the present invention.

Claims (9)

1. An organic compound having a structure represented by general formula (I):
Figure FDA0003179537650000011
in formula (I):
R1、R2、R3are respectively and independently selected from groups shown in formula (A), or are respectively and independently selected from one of hydrogen, halogen, amino, alkylamino, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted C3-C60 heteroaryl amino, substituted or unsubstituted C6-C60 aryl and substituted or unsubstituted C3-C60 heteroaryl, and R is1、R2、R3At least one of them is a group represented by the formula (A);
R4、R5and R6Are respectively and independently selected from hydrogen, halogen, amino, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C60 aryl amino, substituted or unsubstituted C3-C60 heteroaryl amino and substituted or unsubstitutedOne or two of C6-C60 aryl and substituted or unsubstituted C3-C60 heteroaryl;
q is an integer of 1 to 4;
m, n and p are each independently an integer of 1 to 4;
in the formula (A): r7、R8Each independently selected from substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl;
r is as defined above1～R8When a substituent group exists, the substituent group is respectively and independently selected from one or a combination of two of chain alkyl of C1-C20, cycloalkyl of C3-C20, alkoxy of C1-C10, thioalkoxy of C1-C10, arylamino of C6-C30, heteroarylamino of C3-C30, aryl of C6-C30 and heteroaryl of C3-C30.
2. The compound of claim 1, having the structure of formula (ii):
Figure FDA0003179537650000012
in the formula (II), R is1、R2、R3M, n and p are as defined in formula (I);
preferably, m, n and p are each independently 1 or 2;
more preferably, m, n and p are each independently 1.
3. The compound according to claim 1, having a structure represented by any one of the following formulae (1), (2), (3), (4), (5), (6), (7), and (8):
Figure FDA0003179537650000021
in the formula (1), the formula (2), the formula (3), the formula (4), the formula (5), the formula (6), the formula (7) and the formula (8), R1、R2、R3Are as defined in formula (I);
preferably, said R is1、R2、R3Are not identical.
4. A compound according to any one of claims 1 to 3, R7、R8Each independently selected from one or a combination of two of the following substituted or unsubstituted groups: phenyl, naphthyl, anthryl, phenanthryl, indenyl, anthryl, triphenylene, pyrenyl, perylenyl,
Figure FDA0003179537650000023
A phenyl group, a tetracenyl group, a 2-biphenyl group, a 3-biphenyl group, a 4-biphenyl group, a 9, 9-dimethylfluorenyl group, a 9, 9-diethylfluorenyl group, a 9, 9-dipropylfluorenyl group, a 9, 9-dibutylfluorenyl group, a 9, 9-dipentyfluorenyl group, a 9, 9-dihexylfluorenyl group, a 9, 9-diphenylfluorenyl group, a 9, 9-dinaphthylfluorenyl group, a spirofluorenyl group, a benzofluorenyl group, a furyl group, a thienyl group, a pyrrolyl group, a benzofuranyl group, a benzothienyl group, an isobenzofuranyl group, an indolyl group, a dibenzofuranyl group, a dibenzothienyl group, a carbazolyl group, an acridinyl group, an isobenzofuranyl group, an isobenzothienyl group, an acridinyl group, a pyridyl group, a benzocarbazolyl group, an azacarbazolyl group, a phenothiazinyl group or a phenazinyl group;
r is as defined above7、R8When a substituent group is present, the substituent group is independently selected from one of the following groups: methyl, ethyl, n-propyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, phenyl, biphenyl, naphthyl, pyridyl, quinazolinyl, benzopyrazinyl, triazolyl, oxadiazolyl, benzimidazolyl, fluorenyl.
5. A compound according to any one of claims 1-3, wherein R1、R2、R3Is selected from the group shown in formula (a), and formula (a) is selected from any one of the following groups:
Figure FDA0003179537650000022
Figure FDA0003179537650000031
the dotted line in the above structural formula represents the position of the access bond of the group;
preferably, m, n and p are all 1, and R is1、R2、R3One of the groups is selected from any one of the following groups, R1、R2、R3Is selected from any one of hydrogen, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted spirobifluorenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenyl, and substituted or unsubstituted biphenyl:
Figure FDA0003179537650000041
the dotted line in the above formula represents the position of the access bond of the group.
6. A compound according to any one of claims 1-3, wherein R1、R2、R3One or two of the groups are selected from any one of the following groups, R1、R2、R3Is selected from hydrogen, said m, n and p are each 1:
Figure FDA0003179537650000051
the dotted line in the above formula represents the position of the access bond of the group.
7. The compound of claim 1, having the structure shown below:
Figure FDA0003179537650000061
Figure FDA0003179537650000071
Figure FDA0003179537650000081
Figure FDA0003179537650000091
Figure FDA0003179537650000101
Figure FDA0003179537650000111
Figure FDA0003179537650000121
8. use of the organic compound according to any one of claims 1 to 7 as a functional material in an organic electronic device comprising an organic electroluminescent device, an optical sensor, a solar cell, a lighting element, an organic thin film transistor, an organic field effect transistor, an organic thin film solar cell, an information label, an electronic artificial skin sheet, a sheet-type scanner or electronic paper;
preferably, the organic compound is applied as a hole transport layer material in an organic electroluminescent device.
9. An organic electroluminescent device comprising an anode, a cathode and one or more light-emitting functional layers interposed between the anode and the cathode, wherein the light-emitting functional layers contain the organic compound according to any one of claims 1 to 7 therein;
preferably, the light emitting function layer includes an electron blocking layer and at least one of a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer, and the hole transport layer contains the organic compound according to any one of claims 1 to 7.
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