CN113549081A - Organic compound and organic electroluminescent device using same - Google Patents

Organic compound and organic electroluminescent device using same Download PDF

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CN113549081A
CN113549081A CN202110842621.4A CN202110842621A CN113549081A CN 113549081 A CN113549081 A CN 113549081A CN 202110842621 A CN202110842621 A CN 202110842621A CN 113549081 A CN113549081 A CN 113549081A
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substituted
unsubstituted
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aromatic hydrocarbon
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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 an organic compound and application thereof, and also relates to an organic electroluminescent (OLED) device adopting the organic compound, belonging to the technical field of organic electroluminescent materials and display. The organic compound has a structure shown as a formula (I), and R1、R2、R3At least one group in the (B) is a substituted or unsubstituted monocyclic aromatic hydrocarbon group or polycyclic aromatic hydrocarbon group of C6-C40. The compound has higher triplet state energy level, better carrier mobility, higher thermal stability and film forming stability, and can effectively improve O when being used as an organic electroluminescent material applied to OLED devices, particularly used as a hole transport materialPhotoelectric properties of the LED device.

Description

Organic compound and organic electroluminescent device using same
Technical Field
The invention relates to an organic compound and also relates to an organic electroluminescent (OLED) device adopting the organic compound, 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. Therefore, the development of stable and efficient host materials can reduce the driving voltage and improve the luminous efficiency of the device, and the method has important practical application value.
Disclosure of Invention
The invention aims to provide a hole transport material which has higher triplet state energy level, better carrier transport capability and proper HOMO/LUMO energy level, is particularly suitable for being used as a hole transport material in an OLED device, can reduce driving voltage and improves the luminous efficiency of the device.
The invention provides an organic compound, which has a structure shown as a general formula (I):
Figure BDA0003179586380000011
in formula (I):
R1、R2、R3each independently selected from one of hydrogen, halogen, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl and substituted or unsubstituted C6-C40 monocyclic aromatic hydrocarbon or polycyclic aromatic hydrocarbon, and R is1、R2、R3At least one group in (a) is a substituted or unsubstituted monocyclic aromatic hydrocarbon group or polycyclic aromatic hydrocarbon group of C6-C40;
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;
R4、R5and R6Each independently selected from one 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;
r is as defined above1～R6When 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 BDA0003179586380000021
in the formula (II), R is1、R2、R3、R4M, n, p and q are as defined in formula (I).
In the formula (II), m, n and p are respectively and independently 1 or 2; preferably, m, n and p are each independently 1.
Still further, the compound of the present invention is preferably a compound having a structure represented by the general formula (III):
Figure BDA0003179586380000022
in the formula (III), the R1、R2、R3M, n and p are as defined in formula (I).
In the formula (III), m, n and p are each independently 1 or 2; 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 BDA0003179586380000031
formula (1), formula (2), formula (3), formula (4), formula(5) In the formula (6), the formula (7) and the formula (8), R is1、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 chain alkyl group includes a straight-chain alkyl group and an alkyl group containing a branched chain. Straight chain alkyl refers to the general formula CnH2n+1Straight chain alkyl of (E) -including but not limited to methyl, ethyl, propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and the like. Preferably, n is a linear alkyl group of 1-5. Branched alkyl groups include, but are not limited to, isopropyl, isobutyl, sec-butyl, tert-butyl, and,Isopentyl, neopentyl, and the like. The preferred branched alkyl group has 1 to 5 carbon atoms.
In the present specification, cycloalkyl includes, but is not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and the like. Cycloalkyl groups having 3 to 6 carbon atoms are preferable.
In the specification, the monocyclic aromatic hydrocarbon group in the monocyclic aromatic hydrocarbon group or polycyclic aromatic hydrocarbon group of C6 to C40 is preferably an aromatic hydrocarbon group containing one benzene ring; the polycyclic aromatic hydrocarbon group is polyphenyl aliphatic hydrocarbon group, biphenyl and biphenyl type polycyclic aromatic hydrocarbon group, spirobifluorene group or condensed ring aromatic hydrocarbon group.
In the present specification, the monocyclic aromatic hydrocarbon group or the polycyclic aromatic hydrocarbon group in the monocyclic aromatic hydrocarbon group or the polycyclic aromatic hydrocarbon group of C6 to C40 is any one of a polyphenylalkyl group, a biphenyl-type polycyclic aromatic hydrocarbon group, a spirobifluorene-type group, and a fused ring aromatic hydrocarbon group, including but not limited to: biphenyl, phenanthryl, fluorenyl, anthracyl, fluoranthenyl, triphenylenyl, naphthyl, and the like. The polycyclic arylo group may be phenanthro, anthraco, fluorantheno, triphenylo, naphtho, or the like.
In the present specification, monocyclic aryl is preferably phenyl; monocyclic aryl-and-heteroaryl are preferably benzo; the heterocyclic aryl is a group with aromatic heterocyclic ring, and can be benzothienyl, benzofuranyl, pyridyl, pyrimidyl, thiazolyl and the like; the heterocycloaryl group may be benzothieno, benzofuro, or the like.
As a preferred embodiment of the present invention, the substituted or unsubstituted C6-C40 monocyclic aromatic hydrocarbon group or polycyclic aromatic hydrocarbon group may be selected from:
any of a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted anthryl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted spirobifluorenyl group, a substituted or unsubstituted fluoranthenyl group, a substituted or unsubstituted benzo (a) anthryl group, a substituted or unsubstituted benzo (b) fluoranthenyl group, a substituted or unsubstituted benzo (k) fluoranthenyl group, a substituted or unsubstituted benzo (a) pyrenyl group, a substituted or unsubstituted indenofluoranthenyl group, a substituted or unsubstituted perylenyl group;
the number of the substituted substituents may be 1 to 3, and each of the substituents is independently one or a combination of two selected from a chain alkyl group of C1 to C20, a cycloalkyl group of C3 to C20, an alkoxy group of C1 to C10, a thioalkoxy group of C1 to C10, an arylamino group of C6 to C30, a heteroarylamino group of C3 to C30, an aryl group of C6 to C30, and a heteroaryl group of C3 to C30.
Further preferably, the substituted or unsubstituted monocyclic or polycyclic aromatic hydrocarbon group of C6-C40 is selected from the following groups: substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyrenyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted spirobifluorenyl, substituted or unsubstituted fluoranthenyl, substituted or unsubstituted indenopfluoranthenyl, substituted or unsubstituted perylenyl; the substituted substituent can be 1-2, and the substituent is selected from C1-C5 chain alkyl, C3-C6 cycloalkyl, phenyl, biphenyl, naphthyl, phenanthryl, benzo, triphenylene, naphtho and fluoranthene.
Still more preferably, said R1、R2、R3At least one group in the (A) is a substituted or unsubstituted C6-C40 monocyclic aromatic hydrocarbon group or polycyclic aromatic hydrocarbon group, and the substituted or unsubstituted C6-C40 monocyclic aromatic hydrocarbon group or polycyclic aromatic hydrocarbon group is selected from the following substituted or unsubstituted groups:
Figure BDA0003179586380000041
Figure BDA0003179586380000051
the dotted line in the above formula represents the position of the access bond of the group.
As a further preferred embodiment, in the general formula (I), formula (II), formula (III):
m, n and p are all 1, and when R is1、R2、R3When the aryl is a substituted or unsubstituted monocyclic or polycyclic aromatic hydrocarbon group of C6-C40, R1、R2、R3Same, or R1、R2、R3Different.
As a further preferred embodiment, in the general formula (I), formula (II), formula (III):
the R is1、R2、R3Any one of the groups is substituted or unsubstituted monocyclic aromatic hydrocarbon or polycyclic aromatic hydrocarbon of C6-C40;
or, R1、R2、R3Any two groups are substituted or unsubstituted monocyclic aromatic hydrocarbon or polycyclic aromatic hydrocarbon of C6-C40, the two groups are respectively connected with different benzene rings in a parent nucleus, or the two groups are respectively connected with the same benzene ring in the parent nucleus, and preferably the two groups are respectively connected with different benzene rings in the parent nucleus; the two groups may be the same or different from each other;
preferably, said R is1、R2、R3Any one group is substituted or unsubstituted monocyclic aromatic hydrocarbon or polycyclic aromatic hydrocarbon of C6-C40, and the rest two groups are both hydrogen;
or, R1、R2、R3Any two groups are monocyclic aromatic hydrocarbon or polycyclic aromatic hydrocarbon of substituted or unsubstituted C6-C40, the other is hydrogen, the two groups are respectively connected to different benzene rings in the parent nucleus or are respectively connected to the same benzene ring in the parent nucleus, and preferably the two groups are respectively connected to different benzene rings in the parent nucleus; the two groups may be the same or different from each other.
The spiropyrrolocarbazoles of the present invention are preferably, but not limited to, the following specific compounds:
Figure BDA0003179586380000052
Figure BDA0003179586380000061
Figure BDA0003179586380000071
Figure BDA0003179586380000081
Figure BDA0003179586380000091
Figure BDA0003179586380000101
Figure BDA0003179586380000111
Figure BDA0003179586380000121
Figure BDA0003179586380000131
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. Neutral groups R1-R3 are introduced into active positions in a parent nucleus structure, so that the hole transport performance of the material can be further improved by changing the intermolecular accumulation mode. The compound can be applied to the field of organic electroluminescence, and after the compound is used as an organic electroluminescence material and applied to an OLED device as a hole transport material, the device has the advantages of low driving voltage and high luminous efficiency. 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 BDA0003179586380000141
The synthetic route is as follows:
Figure BDA0003179586380000142
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 BDA0003179586380000151
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 BDA0003179586380000152
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 BDA0003179586380000161
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 BDA0003179586380000162
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 BDA0003179586380000163
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 BDA0003179586380000171
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 BDA0003179586380000172
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 BDA0003179586380000173
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 BDA0003179586380000181
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 BDA0003179586380000182
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 BDA0003179586380000183
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 BDA0003179586380000191
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 BDA0003179586380000192
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 BDA0003179586380000193
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 BDA0003179586380000201
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 percent.
Synthesis of intermediate M17
Figure BDA0003179586380000202
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 BDA0003179586380000203
The synthetic route is as follows:
Figure BDA0003179586380000211
the synthesis of the compound I-1 comprises the following specific steps:
m1(63.1g, 0.1mol), (triphenylen-2-yl) boronic acid pinacol ester (35.4g, 0.1mol), cesium carbonate (117g, 0.36mol), dioxane 800ml, tri-tert-butylphosphine (2.2g, 11mmol) and tris (dibenzylideneacetone) dipalladium (4.1g, 4.5mmol) were added in this order to a 2L three-necked flask equipped with a condenser, a thermometer and a magneton under nitrogen protection. After the addition, heating and raising the temperature, controlling the temperature to be 80-90 ℃ for reaction for 4 hours, and cooling after the reaction is finished. Adjusting to neutrality, separating an organic phase, extracting, drying, performing column chromatography, and spin-drying the solvent to obtain 66.7g of pale yellow solid with the yield of about 78.6%.
Product MS (m/e): 848.32, respectively; elemental analysis (C)65H40N2): theoretical value C: 91.95%, H: 4.75%, N: 3.30 percent; found value C: 91.98%, H: 4.77%, N: 3.26 percent.
Synthesis example 2 Synthesis of Compound I-7
Figure BDA0003179586380000212
The synthetic route is as follows:
Figure BDA0003179586380000213
the synthesis of the compound I-7 comprises the following specific steps:
using M2 instead of M1 and [10- (1-naphthyl) -9-anthracene ] boronic acid instead of (triphenylen-2-yl) boronic acid pinacol ester, the appropriate material ratios were chosen and the other raw materials and procedures were the same as in example 1, yielding 71.2g of a pale yellow solid with a yield of about 79.2%.
Product MS (m/e): 898.33, respectively; elemental analysis (C)69H42N2): theoretical value C: 92.18%, H: 4.17%, N: 3.12 percent; found value C: 92.21%, H: 4.15%, N: 3.14 percent.
Synthesis example 3 Synthesis of Compound I-16
Figure BDA0003179586380000221
The synthetic route is as follows:
Figure BDA0003179586380000222
the synthesis of the compound I-16 comprises the following specific steps:
the M1 was replaced by M3, the ratio of materials was chosen appropriately, the other materials and the procedure were the same as in example 1, 66.47g of a pale yellow solid were obtained with a yield of about 78.3%.
Product MS (m/e): 848.32, respectively; elemental analysis (C)65H40N2): theoretical value C: 91.95%, H: 4.75%, N: 3.30 percent; found value C: 91.97%, H: 4.78%, N: 3.27 percent.
Synthesis example 4 Synthesis of Compound I-22
Figure BDA0003179586380000223
The synthetic route is as follows:
Figure BDA0003179586380000224
the synthesis of the compound I-22 comprises the following specific steps:
using M4 instead of M1, 9, 10-bis (2-naphthyl) anthracene-2-boronic acid instead of (triphenylen-2-yl) boronic acid pinacol ester, an appropriate material ratio was selected and other raw materials and procedures were the same as in example 1 to obtain 76.3g of a pale yellow solid with a yield of about 74.4%.
Product MS (m/e): 1025.27, respectively; elemental analysis (C)79H48N2): theoretical value C: 92.55%, H: 4.72%, N: 2.73 percent; found value C: 92.51%, H: 4.75%, N: 2.70 percent.
Synthesis example 5 Synthesis of Compound I-25
Figure BDA0003179586380000231
The synthetic route is as follows:
Figure BDA0003179586380000232
the synthesis of the compound I-25 comprises the following specific steps:
using M5 instead of M1, 10- (2-biphenyl) -9-anthracene boronic acid pinacol ester instead of (triphenylen-2-yl) boronic acid pinacol ester by selecting an appropriate material ratio, the other raw materials and procedures were the same as in example 1, to obtain 69.9g of a pale yellow solid with a yield of about 75.6%.
Product MS (m/e): 924.35, respectively; elemental analysis (C)71H44N2): theoretical value C: 92.18%, H: 4.79%, N: 3.03 percent; found value C: 92.22%, H: 4.76%, N: 3.05 percent.
Synthesis example 6 Synthesis of Compound I-31
Figure BDA0003179586380000233
The synthetic route is as follows:
Figure BDA0003179586380000241
the synthesis of the compound I-31 comprises the following specific steps:
using M6 instead of M1 and phenylboronic acid instead of (triphenylen-2-yl) boronic acid pinacol ester with the appropriate material ratios and the other materials and procedures identical to those of example 1, 56.4g of a pale yellow solid was obtained with a yield of about 84%.
Product MS (m/e): 672.26, respectively; elemental analysis (C)51H32N2): theoretical value C: 91.04%, H: 4.79%, N: 4.16 percent; found value C: 91.08%, H: 4.82%, N: 4.14 percent.
Synthesis example 7 Synthesis of Compound I-36
Figure BDA0003179586380000242
The synthetic route is as follows:
Figure BDA0003179586380000243
the synthesis of the compound I-36 comprises the following specific steps:
using M7 instead of M1 and naphthaleneboronic acid instead of (triphenylen-2-yl) boronic acid pinacol ester, the appropriate material ratios were chosen and the other starting materials and procedures were the same as in example 1, giving 59.4g of a pale yellow solid with a yield of about 82.2%.
Product MS (m/e): 722.27, respectively; elemental analysis (C)55H34N2): theoretical value C: 92.18%, H: 4.79%, N: 3.03 percent; found value C: 92.22%, H: 4.76%, N: 3.05 percent.
Synthesis example 8 Synthesis of Compound I-52
Figure BDA0003179586380000251
The synthetic route is as follows:
Figure BDA0003179586380000252
the synthesis of the compound I-52 comprises the following specific steps:
using M8 instead of M1, 2-biphenylboronic acid instead of (triphenylen-2-yl) boronic acid pinacol ester with the appropriate material ratios chosen and the other starting materials and procedures identical to those of example 1, 75.4g of a pale yellow solid was obtained with a yield of about 83.7%.
Product MS (m/e): 900.35, respectively; elemental analysis (C)69H44N2): theoretical value C: 91.97%, H: 4.92%, N: 3.11 percent; found value C: 92.01%, H: 4.96%, N: 3.08 percent.
Synthesis example 9 Synthesis of Compound I-57
Figure BDA0003179586380000253
The synthetic route is as follows:
Figure BDA0003179586380000254
the synthesis of the compound I-57 comprises the following specific steps:
the appropriate material ratios were selected using M9 instead of M1, 2- (9-9-dimethyl-9-fluoren-2-yl) -4,4,5, 5-tetramethyl-1, 3-dioxaborane instead of (triphenylen-2-yl) boronic acid pinacol ester, and the other raw materials and procedures were the same as in example 1 to give g of a pale yellow solid with a yield of about 78.2%.
Product MS (m/e): 722.27, respectively; elemental analysis (C)55H34N2): theoretical value C: 92.18%, H: 4.79%, N: 3.03 percent; found value C: 92.22%, H: 4.76%, N: 3.05 percent.
Synthesis example 10 Synthesis of Compound I-62
Figure BDA0003179586380000261
The synthetic route is as follows:
Figure BDA0003179586380000262
the synthesis of the compound I-62 comprises the following specific steps:
using M10 instead of M1 and naphthaleneboronic acid instead of (triphenylen-2-yl) boronic acid pinacol ester, the appropriate material ratios were chosen and the other starting materials and procedures were the same as in example 1, yielding 68.3g of a pale yellow solid with a yield of about 80.4%.
Product MS (m/e): 848.32, respectively; elemental analysis (C)65H40N2): theoretical value C: 91.95%, H: 4.75%, N: 3.30 percent; found value C: 91.99%, H: 4.71%, N: 3.25 percent.
Synthesis example 11 Synthesis of Compound I-65
Figure BDA0003179586380000263
The synthetic route is as follows:
Figure BDA0003179586380000271
the synthesis of the compound I-65 comprises the following specific steps:
using M11 instead of M1 and phenanthrene-2-boronic acid instead of (triphenylen-2-yl) boronic acid pinacol ester with the appropriate material ratios chosen and the other starting materials and procedures identical to those of example 1, 75.4g of a pale yellow solid was obtained with a yield of about 79.4%.
Product MS (m/e): 948.35, respectively; elemental analysis (C)73H44N2): theoretical value C: 92.38%, H: 4.67%, N: 2.95 percent; found value C: 92.33%, H: 4.70%, N: 2.91 percent.
Synthesis example 12 Synthesis of Compound I-73
Figure BDA0003179586380000272
The synthetic route is as follows:
Figure BDA0003179586380000273
the synthesis of the compound I-73 comprises the following specific steps:
m12(71.0g, 0.1mol), naphthalene boronic acid (17.2g, 0.1mol), sodium carbonate (15.9g,0.15mol), toluene 250mL, ethanol 150mL, and water 100mL were added to a 1L three-necked flask equipped with a condenser, a thermometer, and a magneton, and Pd (PPh) was added after the reaction system was replaced with nitrogen gas for protection3)4(11.5g, 10mmol), stirring, heating to reflux reaction (the temperature in the system is 70-80 ℃) for 3 hours, and stopping the reaction. The solvent is evaporated, dichloromethane is extracted, anhydrous magnesium sulfate is dried, filtration is carried out, petroleum ether/ethyl acetate (2:1) column chromatography is carried out, the solvent is dried in a rotating mode, the ethyl acetate is pulped, and the filtration is carried out, so that 59.7 compound I-73-1 is obtained, and the yield is 78.8%.
To a 1L three-necked flask equipped with a condenser tube, a thermometer and a magneton, I-73-1(75.7g, 0.1mol), 3-methylphenylboronic acid (13.6g, 0.1mol), cesium carbonate (39g, 0.12mol) and 400ml of dioxane were sequentially added under nitrogen protection, and stirring was started. Tri-tert-butylphosphine (0.8g, 4mmol) and tris (dibenzylideneacetone) dipalladium (1.4g, 1.5mmol) were added to the reaction flask under nitrogen. Then heating to 85 ℃, keeping the temperature for reaction for 4 hours, and cooling after the reaction is finished. Adjusting to neutrality, separating an organic phase, extracting, drying, performing column chromatography, and spin-drying the solvent to obtain 59.0g of product I-73 with a yield of 72.6%.
Product MS (m/e): 812.32, respectively; elemental analysis (C)55H34N2): theoretical value C: 91.59%, H: 4.87%, N: 3.45 percent; found value C: 91.63%, H: 4.90%, N: 3.41 percent.
Synthesis example 13 Synthesis of Compound I-75
The synthetic route is as follows:
Figure BDA0003179586380000281
the synthesis of the compound I-75 comprises the following specific steps:
using 4-biphenylboronic acid and M13, I-75-1 and 4- (naphthalene-2-) phenylboronic acid in place of the naphthaleneboronic acid and M12, I-73-1 and 3-methylphenylboronic acid, respectively, in equivalent amounts as described in example 12, the other reaction conditions and operations were the same as in example 12 to obtain 71.0g of a product with a yield of about 74.7%.
Product MS (m/e): 950.37, respectively; elemental analysis (C)86H52N6): theoretical value C: 92.18%, H: 4.87%, N: 2.95 percent; found value C: 92.22%, H: 4.83%, N: 2.90 percent.
Synthesis example 14 Synthesis of Compound I-77
Figure BDA0003179586380000282
The synthetic route is as follows:
Figure BDA0003179586380000291
the synthesis of the compound I-77 comprises the following specific steps:
using 4-isopropylphenylboronic acid and M14, I-77-1 and 2-boratabenzenes, respectively, in equivalent amounts instead of the naphthaleneboronic acid and M12, I-73-1 and 3-methylphenylboronic acid described in example 12, the other reaction conditions and operation were the same as in example 12 to obtain 62.5g of a product with a yield of about 70.2%.
Product MS (m/e): 890.37, respectively; elemental analysis (C)68H46N2): theoretical value C: 91.65%, H: 5.20%, N: 3.14 percent; found value C: 91.68%, H: 5.25%, N: 3.11 percent.
Synthesis example 15 Synthesis of Compound I-79
Figure BDA0003179586380000292
The synthetic route is as follows:
Figure BDA0003179586380000293
Figure BDA0003179586380000301
the synthesis of the compound I-79 comprises the following specific steps:
using 2- (9-9-dimethyl-9-fluoren-2-yl) -4,4,5, 5-tetramethyl-1, 3-dioxaborane and M15, I-79-1 and 4-isopropylphenylboronic acid, respectively, in place of the naphthaleneboronic acid and M12, I-73-1 and 3-methylphenylboronic acid described in example 12 in equivalent amounts, the other reaction conditions and operation were the same as in example 12 to obtain 63.1g of a product in a yield of about 69.6%.
Product MS (m/e): 906.40, respectively; elemental analysis (C)69H50N2): theoretical value C: 91.36%, H: 5.56%, N: 3.09%; found value C: 91.39%, H: 5.60%, N: 3.04 percent.
Synthesis example 16 Synthesis of Compound I-85
Figure BDA0003179586380000302
The synthetic route is as follows:
Figure BDA0003179586380000303
the synthesis of the compound I-85 comprises the following specific steps:
using 2-biphenylboronic acid and M16, I-85-1 and 3, 4-dimethylbenzeneboronic acid in place of the naphthaleneboronic acid and M12, I-73-1 and 3-methylbenzeneboronic acid, respectively, in equivalent amounts as described in example 12, the other reaction conditions and operations were the same as in example 12 to obtain 57.9g of a product with a yield of about 67.9%.
Product MS (m/e): 952.35, respectively; elemental analysis (C)65H44N2): theoretical value C: 91.52%, H: 5.20%, N: 3.28 percent; found value C: 91.55%, H: 5.24%, N: 3.23 percent.
Synthesis example 17 Synthesis of Compound I-90
Figure BDA0003179586380000311
The synthetic route is as follows:
Figure BDA0003179586380000312
the synthesis of the compound I-90 comprises the following specific steps:
using 2-boronic acid anthracene and M17, I-90-1 and naphthalene boronic acid in place of the naphthalene boronic acid and M12, I-73-1 and 3-methylbenzeneboronic acid, respectively, in equivalent amounts as described in example 12, the other reaction conditions and operation were the same as in example 12 to obtain 59.0g of a product with a yield of about 65.6%.
Product MS (m/e): 898.33, respectively; elemental analysis (C)69H42N2): theoretical value C: 92.18%, H: 4.71%, N: 3.12 percent; found value C: 92.21%, H: 4.74%, N: 3.08 percent.
According to the synthetic methods of the above synthetic examples 1 to 17, other compounds among the compounds I-1 to I-94 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 include a light-emitting layer, and the light-emitting functional layers include 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 hole transport layer uses the organic compound of the present invention of the type described above in the present 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 may be formed by sputtering or depositing a material serving as an anode on the 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 may 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), or 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-1 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 BDA0003179586380000321
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 by using the I-1 compound prepared in the example 1, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 20 nm;
(3) EML 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 compounds I-7, I-16, I-22, I-25, I-31, I-36, I-52, I-57, I-62, I-65, I-73, I-75, I-77, I-79, I-85, I-90, respectively, as detailed in Table 1 below.
Device comparative example 1:
a comparative example device, OLED-18, was prepared following the same procedure as described above for device example 1, replacing only the hole transport material in step (2) with the prior art compound PSA, which has the following structural formula:
Figure BDA0003179586380000331
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 BDA0003179586380000332
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 brightness.
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 (10)

1. An organic compound having a structure represented by general formula (I):
Figure FDA0003179586370000011
in formula (I):
R1、R2、R3each independently selected from one of hydrogen, halogen, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl and substituted or unsubstituted C6-C40 monocyclic aromatic hydrocarbon or polycyclic aromatic hydrocarbon, and R is1、R2、R3At least one group in (a) is a substituted or unsubstituted monocyclic aromatic hydrocarbon group or polycyclic aromatic hydrocarbon group of C6-C40;
m, n and p are each independently an integer of 1 to 4;
R4、R5and R6Each independently selected from one 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;
r is as defined above1～R6When 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 organic compound of claim 1, having a structure represented by formula (ii):
Figure FDA0003179586370000012
in the formula (II), R is1、R2、R3、R4M, n, p and q are as defined in formula (I);
m, n and p are each independently 1 or 2;
preferably, m, n and p are each independently 1.
3. The organic compound of claim 1, having a structure represented by general formula (iii):
Figure FDA0003179586370000021
in the formula (III), the R1、R2、R3M, n and p are as defined in formula (I);
m, n and p are each independently 1 or 2;
preferably, m, n and p are each independently 1.
4. The organic 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 FDA0003179586370000022
in formula (1), formula (2), formula (3), formula (4), formula (5), formula (6), formula (7) and formula (8), R1、R2、R3Are as defined in formula (I);
preferably, said R is1、R2、R3Are not identical.
5. According to claim1 to 4, R1、R2、R3When at least one of the above groups is a substituted or unsubstituted monocyclic or polycyclic aromatic hydrocarbon group of C6 to C40, it is selected from any one of the following groups:
substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyrenyl, substituted or unsubstituted anthryl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted spirobifluorenyl, substituted or unsubstituted fluoranthenyl, substituted or unsubstituted benzo (a) anthryl, substituted or unsubstituted benzo (b) fluoranthenyl, substituted or unsubstituted benzo (k) fluoranthenyl, substituted or unsubstituted benzo (a) pyrenyl, substituted or unsubstituted indenofluoranthenyl, substituted or unsubstituted perylenyl;
when the above groups have substituents, the substituents are 1 to 3, and the substituents are 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.
6. The organic compound according to any one of claims 1 to 4, R1、R2、R3When at least one of the above groups is a substituted or unsubstituted monocyclic or polycyclic aromatic hydrocarbon group of C6 to C40, the group is selected from any one of the following substituted or unsubstituted groups:
Figure FDA0003179586370000031
the dotted line in the above formula represents the position of the access bond of the group.
7. The organic compound according to any one of claims 1 to 4, wherein in the general formula (I), the formula (II), and the formula (III), m, n, and p are each 1, and:
the above-mentionedR1、R2、R3Any one of the groups is substituted or unsubstituted monocyclic aromatic hydrocarbon or polycyclic aromatic hydrocarbon of C6-C40;
or, R1、R2、R3Any two groups are substituted or unsubstituted monocyclic aromatic hydrocarbon or polycyclic aromatic hydrocarbon of C6-C40, the two groups are respectively connected with different benzene rings in a parent nucleus, or the two groups are respectively connected with the same benzene ring in the parent nucleus, and preferably the two groups are respectively connected with different benzene rings in the parent nucleus; the two groups may be the same or different from each other;
preferably, said R is1、R2、R3Any one group is substituted or unsubstituted monocyclic aromatic hydrocarbon or polycyclic aromatic hydrocarbon of C6-C40, and the rest two groups are both hydrogen;
or, R1、R2、R3Any two groups are monocyclic aromatic hydrocarbon or polycyclic aromatic hydrocarbon of substituted or unsubstituted C6-C40, the other is hydrogen, the two groups are respectively connected to different benzene rings in the parent nucleus or are respectively connected to the same benzene ring in the parent nucleus, and preferably the two groups are respectively connected to different benzene rings in the parent nucleus; the two groups may be the same or different from each other.
8. The compound of claim 1, having the structure shown below:
Figure FDA0003179586370000041
Figure FDA0003179586370000051
Figure FDA0003179586370000061
Figure FDA0003179586370000071
Figure FDA0003179586370000081
Figure FDA0003179586370000091
Figure FDA0003179586370000101
Figure FDA0003179586370000111
9. use of the organic compound according to any one of claims 1 to 8 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.
10. 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 8 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 8.
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