A compound and use thereof

Abstract

The present application relates to a kind of compound and its application, the compound is made of the mother nucleus shown in formula I and at least one R group substituted in any position of the mother nucleus.The present application introduces high-branching substituent with large steric exclusion volume in triarylamine mother nucleus, so that the trap of low energy state due to excessive close contact between molecular conjugated systems can be prevented, the formation of interlayer exciplex can be effectively avoided, and then it is beneficial to improve the efficiency and life of device, reduce driving voltage.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic electroluminescence, in particular to a compound and application thereof. BACKGROUND

[0002] In recent years, optoelectronic devices based on organic materials have been developed rapidly and become a research hotspot in the field. Examples of such organic optoelectronic devices include organic light-emitting diodes (OLEDs), organic field-effect transistors, organic photovoltaic cells, organic sensors, and the like. Among them, OLEDs have developed particularly rapidly and have achieved commercial success in the field of information display. OLEDs can provide red, green and blue colors with high saturation, and full-color display devices made therefrom do not require an additional backlight, and have the advantages of bright colors, thinness, softness, and the like.

[0003] The core of an OLED device is a multi-layer thin film structure containing various functional organic materials. Commonly used functional organic materials include hole injection materials, hole transport materials, hole blocking materials, electron injection materials, electron transport materials, electron blocking materials, and light-emitting host materials and light-emitting guests (dyes), and the like. When powered on, electrons and holes are injected and transported to the light-emitting region and recombine there, thereby generating excitons and emitting light.

[0004] Common fluorescent emitters mainly utilize singlet excitons generated when electrons and holes combine, and are still widely used in various OLED products. Some metal complexes, such as iridium complexes, can utilize both triplet and singlet excitons for light emission, and are referred to as phosphorescent emitters, which can have an energy conversion efficiency that is four times higher than that of traditional fluorescent emitters. Thermal activation delayed fluorescence (TADF) technology promotes the conversion of triplet excitons to singlet excitons, and can effectively utilize triplet excitons to achieve high light-emitting efficiency without using metal complexes. Thermal activation sensitized fluorescence (TASF) technology uses a material with TADF properties to sensitize the emitter through energy transfer, and can also achieve high light-emitting efficiency.

[0005] Electron blocking layer materials have a significant impact on the voltage of the device, and the electron blocking layer material also regulates the transport balance of the charge carriers in the device. Improving the charge carrier mobility of the electron blocking layer material can improve the light-emitting efficiency and delay the decay of the device. Although products using OLED display technology have already been commercialized, there is still a need to continuously improve the performance of the device, such as the service life and efficiency, to meet people's pursuit of higher quality.

[0006] Therefore, there is an urgent need in the art to develop more types of organic materials for use in organic electroluminescent devices, so that the devices have high light-emitting efficiency, low driving voltage, and long service life. SUMMARY

[0007] An object of the present application is to provide a compound, and in particular, to provide a compound for an organic electroluminescent device, which is capable of effectively improving luminous efficiency, reducing driving voltage, and prolonging service life of the device, and is particularly suitable as an electron blocking layer material.

[0008] To achieve the object, the present application adopts the following technical solutions:

[0009] The present application provides a compound, which is composed of a mother nucleus shown in formula I and at least one R group substituted at any position of the mother nucleus, the R group having a structure shown in formula II; the "mother nucleus" refers to a structure shown in formula I;

[0010]

[0011] In formula I, ring A is selected from any one of a substituted or unsubstituted C6-C30 aromatic ring and a substituted or unsubstituted C3-C30 heteroaromatic ring;

[0012] In formula I, the Ar 1 is substituted at the ortho position of ring A;

[0013] In formula I, the Ar 1 , G 1 and G 2 are each independently selected from any one of a substituted or unsubstituted C6-C30 aryl group and a substituted or unsubstituted C3-C30 heteroaryl group;

[0014] In formula I, the L 1 and L 2 are each independently selected from any one of a single bond, a substituted or unsubstituted C6-C60 arylene group, and a substituted or unsubstituted C3-C60 heteroarylene group;

[0015] In formula I, the R 0 is a monosubstituent to a maximum allowable substituent, and the R 0 is selected from any one of hydrogen, halogen, amino, hydroxyl, cyano, nitro, a substituted or unsubstituted C1-C20 chain alkyl group, a substituted or unsubstituted C3-C20 cyclic alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C1-C20 silyl group, a substituted or unsubstituted C1-C20 thioalkoxy group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C3-C60 heteroaryl group, a substituted or unsubstituted C6-C60 arylamino group, and a substituted or unsubstituted C3-C60 heteroarylamino group, and any adjacent R 0 is not connected or connected to each other to form a ring;

[0016] ​"Single substituent to maximum allowed substituent" refers to R 0 The number of substitutions can be 1 or multiple (e.g., 2, 3, 4, etc.), and the upper limit of the number of substitutions is the total number of substitutable sites on ring A. The same meaning is used herein and will not be repeated.

[0017] In formula II, R 1 , R 2 , and R 3 are each independently selected from any one of substituted or unsubstituted C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, etc.) chain alkyl, substituted or unsubstituted C3-C10 (e.g., C4, C5, C6, C7, C8, C9, etc.) cycloalkyl, and the number of carbon atoms of R 2 and R 3 is not more than the number of carbon atoms of R 1 ;

[0018] In the formula, the dotted line represents the connecting bond of the group;

[0019] In ring A, Ar 1 , G 1 , G 2 , L 1 , L 2 , R 0 , R 1 , R 2 , and R 3 , the substituted groups are each independently selected from any one or a combination of at least two of halogen, amino, hydroxyl, cyano, nitro, C1-C20 chain alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 silyl, C1-C20 thioalkoxy, C2-C20 alkenyl, C6-C60 aryl, C3-C60 heteroaryl, C6-C60 arylamino, and C3-C60 heteroarylamino, and any adjacent substituents are not connected or connected to each other to form a ring.

[0020] The present application adopts an ortho-substituted arylamine with steric hindrance effect, so that the three substituents on the nitrogen atom of the arylamine adopt a proper spatial arrangement, which can improve the transmission performance and prevent material crystallization. In addition, the arylamine of the present application introduces a highly branched substituent R with a large steric exclusion volume, thereby preventing the formation of low-energy state traps due to excessive close contact between molecular conjugated systems. In particular, when at the interface between the layers of an OLED device, the compound of the present application can effectively prevent the formation of interlayer exciplexes, thereby avoiding the damage of interlayer exciplexes to the efficiency and service life of the device, effectively improving the efficiency and service life of the device, and reducing the driving voltage.

[0021] In fact, not all substituents with large spatial exclusion volume substituted on the mother nucleus of formula I can achieve the effect of improving device efficiency, service life and reducing driving voltage, and the inventors have unexpectedly found that substituting the R group with the structure shown in formula II on the mother nucleus of formula I can achieve the above-mentioned effect, and has the advantages of low sublimation temperature, easy availability of raw materials, etc., and has a broad application prospect in organic electroluminescent devices.

[0022] In the present application, the aromatic ring refers to a ring structure with aromaticity, and the heteroaromatic ring refers to a ring structure formed after introducing heteroatoms (including but not limited to N, O, S, P, Si and Se) into the aromatic ring. Its essence is the same as that of aryl and heteroaryl, but since aryl and heteroaryl usually represent the case of being connected to other groups through one connecting bond, and the number of connecting bonds on ring A is two or more, it is called aromatic ring and heteroaromatic ring.

[0023] In the present application, the "substituted group" refers to the selection range of substituents when the "substituted or unsubstituted" group is substituted, and the number is not specifically limited, as long as the bond requirement of the compound is met. Exemplarily, it can be 1, 2, 3, 4 or 5, and when the number of substituents is 2 or more, the 2 or more substituents can be the same or different.

[0024] In the present application, halogen represents chlorine atom, fluorine atom, bromine atom, iodine atom, etc.

[0025] In the present application, the expression mode of Ca-Cb represents that the number of carbon atoms of the group is a-b, and unless otherwise specified, generally the number of carbon atoms does not include the number of carbon atoms of the substituents.

[0026] In the present application, the expression mode of the ring structure with a dash through it represents that the connecting site is at any position on the ring structure that can form a bond.

[0027] In the present application, for the expression of chemical elements, if not specially mentioned, it generally includes the concept of its isotope, for example, the expression of "hydrogen (H)" includes the concept of its isotope 1 H (protium or H), 2 H (deuterium or D); carbon (C) includes 12 C, 13 C, and the like, which will not be repeated.

[0028] In the present application, the heteroatom in the heteroaryl group generally refers to an atom or atom group selected from N, O, S, P, Si and Se, preferably selected from N, O and S.

[0029] In the present application, the aryl group includes monocyclic aryl group or fused ring aryl group, and the heteroaryl group includes monocyclic heteroaryl group or fused ring heteroaryl group, wherein the monocyclic aryl group refers to a molecule containing at least one phenyl group, and when the molecule contains at least two phenyl groups, the phenyl groups are independent of each other and connected by a single bond; the fused ring aryl group refers to a molecule containing at least two benzene rings, but the benzene rings are not independent of each other, but are fused together by sharing ring edges; the monocyclic heteroaryl group refers to a molecule containing at least one heteroaryl group, and when the molecule contains one heteroaryl group and other groups (such as aryl group, heteroaryl group, alkyl group, etc.), the heteroaryl group and other groups are independent of each other and connected by a single bond; the fused ring heteroaryl group refers to a group fused by at least one phenyl group and at least one heteroaryl group, or a group fused by at least two heteroaryl rings.

[0030] In the present application, the carbon number of C6-C30 aryl group, C3-C60 aryl group or C6-C30 aromatic ring includes but is not limited to C6, C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, etc., and exemplary groups are selected from fluorenyl group, phenyl group, biphenyl group, terphenyl group, naphthyl group, anthracenyl group, phenanthryl group, indenyl group, fluorenyl group and its derivatives, fluoranthene group, triphenylene group, pyrene group, perylene group, and naphthacene group. Specifically, the biphenyl group is selected from 2-biphenyl group, 3-biphenyl group and 4-biphenyl group; the terphenyl group includes p-terphenyl-4-yl group, p-terphenyl-3-yl group, p-terphenyl-2-yl group, m-terphenyl-4-yl group, m-terphenyl-3-yl group and m-terphenyl-2-yl group; the naphthyl group includes 1-naphthyl group and 2-naphthyl group; the anthracenyl group is selected from 1-anthracenyl group, 2-anthracenyl group and 9-anthracenyl group; the fluorenyl group is selected from 1-fluorenyl group, 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group, 9-fluorenyl group and fluorenyl derivatives; the fluorenyl derivatives are selected from 9,9-dimethylfluorene, 9,9-spirofluorene, 9,9-diphenylfluorenyl group, spirofluorenyl group and benzofluorene; the pyrene group is selected from 1-pyrenyl group, 2-pyrenyl group and 4-pyrenyl group; and the naphthacene group is selected from 1-naphthacene group, 2-naphthacene group and 9-naphthacene group.

[0031] In the present application, the C6-C60 arylene group is a divalent group formed by substituting one hydrogen atom of the C6-C60 aryl group, and exemplary groups can be divalent groups formed by substituting one hydrogen atom of the above-mentioned groups, such as phenylene group, fluorenylene group, etc.

[0032] In the present application, the C6-C60 arylamino group represents a group formed by substituting one or two C6-C60 aryl groups on the hydrogen of the amino group, wherein the connection site of the C6-C60 arylamino group can be connected with the aryl group in arylamino group, or can be connected with N in arylamino group, and the exemplary carbon number and specific groups of the C6-C60 aryl group in the C6-C60 arylamino group are the same as above.

[0033] The number of carbons of the C3-C30 heteroaryl group, C3-C60 heteroaryl group or C3-C30 heterocyclic ring in the present application includes, but is not limited to, C4, C5, C6, C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, and the like, and exemplary groups are selected from the following: furanyl, thienyl, pyrrolyl, benzofuranyl, benzothienyl, isobenzofuranyl, indolyl, dibenzofuranyl, dibenzothienyl, carbazolyl and derivatives thereof, wherein the carbazolyl derivatives are preferably 9-phenylcarbazole, 9-naphthylcarbazole, benzocarbazole, dibenzocarbazole, or indolocarbazole. The number of carbons of the C3-C60 heteroaryl group in the C3-C60 heteroaryl amino group is the same as described above.

[0034] The C1-C20 chain alkyl group in the present application includes branched alkyl and straight chain alkyl, and is preferably a C1-C10 chain alkyl group, and the number of carbons includes, but is not limited to, C1, C2, C3, C4, C5, C6, C7, C8, C9, and the like, and exemplary groups are methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, isopropyl, isobutyl, t-butyl, and the like.

[0035] The C3-C20 cycloalkyl group in the present application is preferably a C3-C10 cycloalkyl group, and the number of carbons includes, but is not limited to, C4, C5, C6, C7, C8, C9, and the like, and exemplary groups are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and the like.

[0036] The C1-C20 alkyl group in the present application is preferably a C1-C10 alkyl group, and the number of carbons includes, but is not limited to, C1, C2, C3, C4, C5, C6, C7, C8, C9, and the like, and exemplary groups are the same as described above; and the number of carbons of the C1-C6 thioalkoxy group includes, but is not limited to, C2, C3, C4, C5, and the like.

[0037] The C1-C20 thioalkoxy group in the present application is preferably a C1-C6 thioalkoxy group, and the number of carbons includes, but is not limited to, C1, C2, C3, C4, C5, and the like.

[0038] Preferably, the R group is substituted on any one or at least two of Ar 1 , G 1 or G 2 .

[0039] The R group is preferably substituted on one or more of the three groups described above, and this structure can effectively block excitons and maintain high charge transport performance, thereby further improving device performance.

[0040] Preferably, the number of substitutions of the R group is one or two.

[0041] Preferably, the compound has any one of the following structures:

[0042]

[0043] Ring A, Ar 1 , G 1 , G 2 , L 1 , L 2 , R 0 and R each have the same selection range as the foregoing.

[0044] Preferably, the ring A is selected from any one of a substituted or unsubstituted C6-C30 aromatic ring, preferably a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted biphenyl ring;

[0045] In the ring A, each of the substituted groups is independently selected from any one or a combination of at least two of halogen, amino, hydroxyl, cyano, nitro, C1-C20 chain alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 silyl, C1-C20 thioalkoxy, C2-C20 alkenyl, C6-C60 aryl, C3-C60 heteroaryl, C6-C60 arylamino, C3-C60 heteroarylamino, and any adjacent substituents are not connected or connected to each other to form a ring.

[0046] Preferably, the compound is composed of a parent nucleus shown in formula I-1, formula I-2 or formula I-3, and at least one R group substituted at any position of the parent nucleus, the R group having a structure shown in formula II;

[0047]

[0048] The Ar 2 is selected from any one of a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C3-C60 heteroaryl group;

[0049]

[0050] The R 1 , R 2 and R 3 are each independently selected from any one of a substituted or unsubstituted C1-C10 chain alkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, and the carbon atom number of the R 2 and R 3 is not more than the carbon atom number of the R 1 ;

[0051] In which the dotted line represents the connecting bond of the group;

[0052] Ar2 , R 1 , R 2 , and R 3 , the substituted groups are each independently selected from any one or at least two combinations of halogen, amino, hydroxyl, cyano, nitro, C1-C20 chain alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 silyl, C1-C20 thioalkoxy, C2-C20 alkenyl, C6-C60 aryl, C3-C60 heteroaryl, C6-C60 arylamino, C3-C60 heteroarylamino, and any adjacent substituents are not connected or connected to each other to form a ring;

[0053] the Ar 1 , G 1 , G 2 , L 1 , L 2 all have the same selection range as in formula I.

[0054] Preferably, in formula II, the carbon atom numbers of the R 1 , R 2 , and R 3 are all the same.

[0055] Preferably, the R group has any one or at least two combinations of the following structures:

[0056]

[0057] wherein the dotted line represents the connecting bond of the group.

[0058] R is "any one or at least two combinations" means that when there are at least two R groups on the mother nucleus, they can be the same group or different groups, and when there are different groups, it is "at least two combinations".

[0059] In the preferred technical solution of the present application, R is isopentyl, which can better balance the charge transport performance and exciton blocking effect after substitution compared to other groups, so that the compound is used in an organic electroluminescent device, which is more conducive to improving the performance of the device.

[0060] Preferably, the Ar 1 , G 1 , and G 2 are each independently selected from any one of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted triphenylene, substituted or unsubstituted phenanthryl, substituted or unsubstituted biphenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted spirofluorenyl, and substituted or unsubstituted benzofluorenyl;

[0061] Ar 1 , G 1 and G 2 , the substituted groups are each independently selected from any one or a combination of at least two of halogen, amino, hydroxyl, cyano, nitro, C1-C20 chain alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 silyl, C1-C20 thioalkoxy, C2-C20 alkenyl, C6-C60 aryl, C3-C60 heteroaryl, C6-C60 arylamino, C3-C60 heteroarylamino, any adjacent substituents being either unconnected or connected to each other to form a ring.

[0062] Preferably, the Ar 2 is selected from any one of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted biphenylyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted spirofluorenyl, substituted or unsubstituted benzofluorenyl;

[0063] Ar 2 , the substituted groups are each independently selected from any one or a combination of at least two of halogen, amino, hydroxyl, cyano, nitro, C1-C20 chain alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 silyl, C1-C20 thioalkoxy, C2-C20 alkenyl, C6-C60 aryl, C3-C60 heteroaryl, C6-C60 arylamino, C3-C60 heteroarylamino, any adjacent substituents being either unconnected or connected to each other to form a ring.

[0064] Preferably, the L 1 and L 2 are each independently selected from any one of a single bond, substituted or unsubstituted C6-C60 arylene, preferably a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene;

[0065] L 1 and L 2 , the substituted groups are each independently selected from any one or a combination of at least two of halogen, amino, hydroxyl, cyano, nitro, C1-C20 chain alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 silyl, C1-C20 thioalkoxy, C2-C20 alkenyl, C6-C60 aryl, C3-C60 heteroaryl, C6-C60 arylamino, C3-C60 heteroarylamino, any adjacent substituents being either unconnected or connected to each other to form a ring.

[0066] Preferably, the compound has any one of the structures shown in P1 to P100 below:

[0067]

[0068]

[0069]

[0070]

[0071]

[0072] A second object of the present application is to provide the use of a compound according to one of the preceding objects in an electronic device.

[0073] Preferably, the electronic device is an organic electroluminescent device, an organic field effect transistor, an organic thin film solar cell, an information tag, an electronic artificial skin sheet, a sheet-type scanner or an electronic paper, preferably an organic electroluminescent device.

[0074] Preferably, the compound is used as an electron blocking layer material in an organic electroluminescent device.

[0075] A third object of the present application is to provide an organic electroluminescent device comprising a first electrode, a second electrode and at least one organic layer interposed between the first and second electrodes, the organic layer comprising at least one compound according to one of the preceding objects.

[0076] Preferably, the organic layer comprises an electron blocking layer comprising at least one compound according to one of the preceding objects.

[0077] In particular, one of the first and second electrodes is an anode and the other is a cathode.

[0078] In particular embodiments, the organic layer comprises at least one of a hole injection layer, a hole transport layer, an emission layer, an electron blocking layer, an electron transport layer, wherein the electron blocking layer comprises at least one compound according to the present application.

[0079] An OLED comprises a first electrode and a second electrode, and an organic layer interposed between the electrodes. The organic layer can be further divided into multiple regions. For example, the organic layer can comprise a hole transport region, an emission layer, an electron transport region.

[0080] In specific embodiments, a substrate can be used under the first electrode or over the second electrode. The substrates are glass or polymer materials having excellent mechanical strength, thermal stability, water resistance, and transparency. In addition, a thin film transistor (TFT) can be provided on the substrate for display.

[0081] The first electrode can be formed by sputtering or depositing a material used as the first electrode on the substrate. When the first electrode is used as an anode, indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (Sn02), zinc oxide (ZnO), and the like, or any combination thereof, can be used as an oxide transparent conductive material. When the first electrode is used as a cathode, magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), ytterbium (Yb), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), and the like, or any combination thereof, can be used as a metal or an alloy.

[0082] The organic layer can be formed on the electrode by vacuum thermal evaporation, spin coating, printing, or the like. The compound used as the organic layer can be an organic small molecule, an organic macromolecule, and a polymer, or a combination thereof.

[0083] The hole transport zone is located between the anode and the light-emitting layer. The hole transport zone can be a single-layer structure of a hole transport layer (HTL), including a single-layer hole transport layer containing only one compound and a single-layer hole transport layer containing multiple compounds. The hole transport zone can also be a multi-layer structure including at least one of a hole injection layer (HIL), a hole transport layer (HTL), and an electron blocking layer (EBL) containing a compound provided by the present application.

[0084] The material of the hole transport zone can be selected from, but not limited to, a phthalocyanine derivative such as CuPc, a conductive polymer or a polymer containing a conductive dopant such as polyphenylene vinylene, polyaniline / dodecylbenzenesulfonic acid (Pani / DBSA), poly(3,4-ethylenedioxythiophene) / poly(4-styrenesulfonate) (PEDOT / PSS), polyaniline / camphor sulfonic acid (Pani / CSA), polyaniline / poly(4-styrenesulfonate) (Pani / PSS), an aromatic amine derivative, wherein the aromatic amine derivative includes the compounds shown in HT-1 to HT-51 below, or any combination thereof.

[0085]

[0086]

[0087]

[0088] The hole injection layer is located between the anode and the hole transport layer. The hole injection layer can be a single compound material or a combination of multiple compounds. For example, the hole injection layer can employ one or more of the compounds described above as HT-1 to HT-51, or one or more of the compounds described below as HI-1 to HI-3; or one or more of the compounds described above as HT-1 to HT-51 doped with one or more of the compounds described below as HI-1 to HI-3.

[0089]

[0090] The light emitting layer includes light emitting dyes (i.e., dopants) that can emit different wavelengths of light, and can also include host materials. The light emitting layer can be a single color light emitting layer that emits a single color such as red, green, blue, etc. Multiple different color single color light emitting layers can be arranged in a planar pattern according to a pixel pattern, or can be stacked together to form a color light emitting layer. When different color light emitting layers are stacked together, they can be separated from each other or connected to each other. The light emitting layer can also be a single color light emitting layer that can emit multiple different colors such as red, green, blue, etc.

[0091] Depending on the technology, the light emitting layer material can employ different materials such as fluorescent electroluminescent materials, phosphorescent electroluminescent materials, thermally activated delayed fluorescent light emitting materials, etc. In an OLED device, a single light emitting technology can be employed, or a combination of multiple different light emitting technologies can be employed. These different light emitting materials classified by technology can emit the same color of light, or can emit different colors of light.

[0092] In an aspect of the present application, the light emitting layer employs fluorescent electroluminescent technology. The fluorescent host material of the light emitting layer can be selected from, but not limited to, a combination of one or more of the following BFH-1 to BFH-17.

[0093]

[0094] In an aspect of the present application, the light emitting layer employs fluorescent electroluminescent technology. The fluorescent dopant of the light emitting layer can be selected from, but not limited to, a combination of one or more of the following BFD-1 to BFD-24.

[0095]

[0096]

[0097]

[0098] In an aspect of the present application, the light emitting layer employs phosphorescent electroluminescent technology. The host material of the light emitting layer is selected from, but not limited to, a combination of one or more of PH-1 to PH-85.

[0099]

[0100]

[0101]

[0102]

[0103] In an aspect of the application, the light-emitting layer employs phosphorescent electroluminescence technology. The phosphorescent dopant of the light-emitting layer can be selected from, but not limited to, a combination of one or more of GPD-1 to GPD-47 listed below.

[0104]

[0105]

[0106]

[0107] wherein D is deuterium.

[0108] In an aspect of the application, the light-emitting layer employs phosphorescent electroluminescence technology. The phosphorescent dopant of the light-emitting layer can be selected from, but not limited to, a combination of one or more of RPD-1 to RPD-28 listed below.

[0109]

[0110]

[0111] In an aspect of the application, the light-emitting layer employs phosphorescent electroluminescence technology. The phosphorescent dopant of the light-emitting layer can be selected from, but not limited to, a combination of one or more of YPD-1 to YPD-11 listed below.

[0112]

[0113] The OLED organic layer can also include an electron transport zone between the light-emitting layer and the cathode. The electron transport zone can be an electron transport layer (ETL) of a single layer structure, including a single-layer electron transport layer containing only one compound and a single-layer electron transport layer containing multiple compounds. The electron transport zone can also be a multi-layer structure including at least one of an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL).

[0114] In an aspect of the application, the electron transport layer material can be selected from, but not limited to, a combination of one or more of ET-1 to ET-73 listed below.

[0115]

[0116]

[0117]

[0118]

[0119] An electron injection layer can also be included in the device between the electron transport layer and the cathode, and the electron injection layer material includes, but is not limited to, one or a combination of the following: LiQ, LiF, NaCl, CsF, Li2O, Cs2CO3, BaO, Na, Yb, Li, or Ca.

[0120] Compared with the prior art, the present application has the following beneficial effects:

[0121] The present application introduces a highly branched substituent R with a large steric exclusion volume into the triarylamine compound, thereby preventing the formation of a low-energy state trap due to excessively close contact between molecular conjugated systems, effectively avoiding the formation of interlayer exciplexes, and thus improving the efficiency and service life of the device and reducing the driving voltage. DETAILED DESCRIPTION

[0122] The technical solutions of the present application are further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only to help understand the present application and should not be regarded as specific limitations of the present application.

[0123] The compound provided by the present application can be prepared by a commonly known reaction without any difficulty. For example, the compound of the present application can be obtained by a common coupling reaction between different halogenated aromatic hydrocarbons and aromatic amines.

[0124] More specifically, the following synthesis examples exemplarily provide detailed preparation methods of some intermediates and target compounds:

[0125] Synthesis Example 1

[0126] Synthesis of Intermediate M1

[0127]

[0128] 4-tert-Pentyl-1-naphthol (20 g) and triethylamine (18 g) were dissolved in tetrahydrofuran (THF, 200 mL), and trifluoromethanesulfonic anhydride (Tf2O, 42 g) was added dropwise at -10 °C. The temperature was raised to room temperature, and stirring was performed for 2 h. After volatilizing the solvent, the residue was purified by silica gel column to obtain Int-1' (25 g) as a white oil.

[0129] Int-1' (17 g), 2-amino-1-naphthaleneboronic acid (12 g), Pd(PPh3)4(2 g), K2CO3(15 g) in a mixture of dioxane (200 mL) / water (50 mL) was stirred and refluxed overnight under nitrogen atmosphere. The reaction was cooled to room temperature, extracted with ethyl acetate, concentrated and purified by silica gel column chromatography to give Int-2 (12 g) as a yellowish white solid.

[0130] Int-2 (17 g), 3-bromo-9,9-dimethylfluorene (13.5 g), Pd2(dba)3(2 g), 1,1'- bis(2,6-diisopropylphenyl)imidazolium chloride (IPr.HCl, 4 g), sodium tert-butoxide (tert-BuONa) (12 g) in toluene was heated to 90 °C and stirred for 5 h. The reaction was stopped and filtered hot. To the filtrate, methanol was added and a yellowish white solid was precipitated as M1 (20 g).

[0131] M / Z Calcd: 531; Found: 532 (M+1).

[0132] Synthesis Example 2

[0133] Synthesis of intermediate Int-3

[0134]

[0135] 4-tert-Pentylbromobenzene (22 g), p-chlorophenylboronic acid (18 g), Pd(PPh3)4(2 g), K2CO3(26 g) in toluene (300 mL) / water (150 mL) was heated to 100 °C under nitrogen atmosphere and stirred for 2 h. It was cooled to room temperature, the organic phase was separated and concentrated. It was purified by silica gel column chromatography to give Int-3 (21 g) as a white solid.

[0136] M / Z Calcd: 285; Found: 289 (M+1).

[0137] Synthesis Example 3

[0138] Synthesis of compound P33:

[0139]

[0140] M2 (9 g), 4-bromo-1-tert-pentylbenzene (12 g), tris(dibenzylideneacetone)dipalladium (Pd2(dba)3, 1 g); vacuum-nitrogen replacement for 3 times, then add tri-tert-butylphosphine ((tert-Bu)3P, 1 mol / L, 2 mL), sodium tert-butoxide (tert-BuONa) (4 g), heat to boiling, react for 5 h, stop heating after the reaction is completed, filter with diatomite while hot, and evaporate the solvent in the filtrate. Purify the residue by silica gel column chromatography, and wash the obtained crude product with ethyl acetate to obtain white solid P33 (8 g). M / Z theoretical value: 607; found: 608 (M+1).

[0141] The synthesis method of the following compounds P6-P97 is only different from that of compound P33 in that raw material 1 and raw material 2 are the compounds shown in Table 1, and the rest are the same.

[0142] Table 1

[0143]

[0144]

[0145] Synthesis Example 4

[0146] Synthesis of compound P31

[0147]

[0148] M-21 (8.7 g), 4-bromo-1-tert-pentylbenzene (12 g), tris(dibenzylideneacetone)dipalladium (Pd2(dba)3, 1 g); vacuum-nitrogen replacement for 3 times, then add tri-tert-butylphosphine ((tert-Bu)3P, 1 mol / L, 1.5 mL), sodium tert-butoxide (tert-BuONa) (4.5 g), heat to boiling, react for 24 h, stop heating after the reaction is completed, filter with diatomite while hot, and evaporate the solvent in the filtrate. Purify the residue by silica gel column chromatography, and wash the obtained crude product with ethyl acetate to obtain white solid P31 (11 g). M / Z theoretical value: 729; found: 730 (M+1).

[0149] Synthesis Example 5

[0150] Synthesis of compound P56

[0151]

[0152] Similar to the method for synthesizing P31, except that M-21 is replaced by an equivalent amount of beta-amino-1,1'-binaphthyl (M-22), and 4-bromo-1- tert-pentylbenzene is replaced by Int-3. M / Z theoretical value: 713; found: 714 (M+1).

[0153] Example 1

[0154] This example provides an OLED device, which is prepared as follows:

[0155] The ITO transparent conductive layer coated glass substrate was thoroughly cleaned, dried, and the surface was treated with ultraviolet light and ozone, and was ready for use. The device was fabricated under high vacuum (<1 x 10 -5 Pa), and 10 nm of a mixture of HTL-4:HI-3 (97 / 3, w / w) was vacuum thermal evaporated as a hole injection layer, 60 nm of compound HT-4 was vacuum thermal evaporated as a hole transport layer, 5 nm of compound P23 was vacuum thermal evaporated as an electron blocking layer, 40 nm of a binary mixture of compound PH-34:RPD-10 (100:3, w / w) was vacuum thermal evaporated as a light emitting layer, 5 nm of ET-23 was vacuum thermal evaporated as a hole blocking layer, 25 nm of a mixture of compound ET-69:ET-57 (50 / 50, w / w) was vacuum thermal evaporated as an electron transport layer, 1 nm of LiF was vacuum thermal evaporated as an electron injection layer, and 150 nm of aluminum metal was vacuum thermal evaporated as a cathode, in the order mentioned above. The total evaporation rate of all organic layers and LiF was controlled at 0.1 nm / s, and the evaporation rate of the metal electrode was controlled at 1 nm / s.

[0156] Examples 2-6 and Comparative Examples 1-5 each provide an OLED device, which is different from the device of Example 1 only in that the electron blocking layer is replaced by the material shown in Table 2.

[0157] The structures of the electron blocking layer materials used in the comparative examples are as follows:

[0158]

[0159] Performance test

[0160] The driving voltage and current efficiency of the organic electroluminescent devices of the examples and comparative examples, and the lifetime of the devices were measured at the same brightness using a digital source meter and a luminance meter. Specifically, the voltage was increased at a rate of 0.1 V per second, and the voltage when the brightness of the organic electroluminescent device reached 3000 cd / m 2 was measured, and the ratio of the brightness to the current density was the current efficiency;

[0161] The lifetime test of LT97 was as follows: a constant current (60 mA / cm 2), the time for measuring the luminance decay of the organic electroluminescent device to 97% of the initial luminance is measured in hours.

[0162] The obtained data are summarized in Table 2, in which the performance indicators of Comparative Example 1 are set to 100, and the performances of other devices are relative values relative to Comparative Example 1.

[0163] Table 2

[0164] Electron blocking layer materials Voltage (%) Efficiency (%) Lifetime (%) Comparative Example 1 CP1 100 100 100 Comparative Example 2 CP2 84 140 325 Comparative Example 3 CP3 97 122 133 Comparative Example 4 CP4 93 99 337 Comparative Example 5 CP5 104 86 210 Example 1 P23 84 125 360 Example 2 P33 78 141 535 Example 3 P45 100 101 127 Example 4 P56 79 138 340 Example 5 P61 79 133 350 Example 6 P81 82 125 296

[0165] As can be seen from the data in Table 2, in the case of the same or similar parent nucleus, the introduction of the R group represented by formula II in the present application can make the device have more excellent performance compared with the case of not introducing a substituent group or introducing a tert-butyl group, an adamantyl group or other groups.

[0166] Specifically, the difference between P45 and CP1 is only that P45 uses isopentyl instead of tert-butyl as a substituent on the benzene ring, and the service life of Example 3 using P45 as the electron blocking layer material is better than that of Comparative Example 1 using CP1 as the electron blocking layer; similarly, P33 is only replaced by isopentyl instead of adamantyl compared with CP2, and the voltage and service life of Example 2 using P33 as the electron blocking layer material are more excellent than those of Comparative Example 2; P23 is only substituted with one more isopentyl on the benzene ring compared with CP4, and the efficiency of Example 1 using P23 as the electron blocking layer material is more excellent than that of Comparative Example 4; P56 is only replaced by isopentyl instead of tert-butyl compared with CP3, and Example 4 using P56 as the electron blocking layer material is more excellent in voltage and efficiency than Comparative Example 3; P61 is only replaced by isopentyl instead of tert-butyl compared with CP5, and Example 5 using P61 as the electron blocking layer material is more excellent in voltage, efficiency and service life than Comparative Example 5.

[0167] The present application is described by the above examples to illustrate the detailed method of the present application, but the present application is not limited to the above detailed method, i.e. it does not mean that the present application must rely on the above detailed method to be implemented. It should be understood by those skilled in the art that any improvement of the present application, equivalent replacement of each raw material of the product of the present application, addition of auxiliary ingredients, selection of specific methods, etc. fall within the protection scope and disclosure scope of the present application.​

Claims

1. A compound, characterized in that, The compounds consist of a parent nucleus of Formula I and at least one R group substituted at any position of the parent nucleus, the R group having the structure: ; ； In formula I, ring A is selected from any one of a benzene ring, a naphthalene ring, and a biphenyl ring; In formula I, the Ar 1 with substituted at the ortho position of ring A; In formula I, the Ar 1 , G 1 and G 2 are each independently selected from any one of phenyl, naphthyl, triphenylenyl, phenanthryl, biphenylyl, fluorenyl, dibenzofuranyl, dibenzothiophenyl spirofluorenyl, benzofluorenyl; In formula I, the L 1 and L 2 each independently is selected from any one of a single bond, phenylene, biphenylene; In formula I, the R 0 is a single substituent to the maximum allowed number of substituents, and the R 0 is selected from any one of hydrogen, a substituted or unsubstituted C1-C20 chain alkyl group, a substituted or unsubstituted C3-C20 cyclic alkyl group, a substituted or unsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C1-C20 silyl group, a substituted or unsubstituted C1-C20 thioalkoxy group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C3-C60 heteroaryl group, a substituted or unsubstituted C6-C60 arylamino group, and a substituted or unsubstituted C3-C60 heteroarylamino group, and any adjacent R 0 is not connected or connected to each other to form a ring. wherein the dotted line represents a bond connecting the groups; R 0 In particular, each of the substituents is independently selected from any one or a combination of at least two of C1-C20 linear alkyl, C3-C20 cyclic alkyl, C1-C20 alkoxy, C1-C20 silyl, C1-C20 thioalkoxy, C2-C20 alkenyl, C6-C60 aryl, C3-C60 heteroaryl, C6-C60 arylamino, C3-C60 heteroarylamino, any adjacent substituents being either unconnected or connected to form a ring.

2. The compound of claim 1, wherein The R groups are substituted on any one or at least two of Ar 1 , G 1 , or G 2 .

3. The compound of claim 1, wherein The number of the R groups is 1 or 2.

4. The compound of claim 1, wherein The compound has any one of the following structures: ； Ring A, Ar 1 , G 1 , G 2 , L 1 , L 2 , R 0 and R each have the same defined range as in claim 1.

5. The compound of claim 1, wherein The compounds consist of a parent nucleus of Formula I-1, Formula I-2, or Formula I-3, and at least one R group substituted at any position of the parent nucleus, the R group having the following structure: ; ； said Ar 2 is selected from any one of substituted or unsubstituted C6-C60aryl, substituted or unsubstituted C3-C60heteroaryl; Ar 2 In particular, each of the substituents is independently selected from any one or a combination of at least two of C1-C20 linear alkyl, C3-C20 cyclic alkyl, C1-C20 alkoxy, C1-C20 silyl, C1-C20 thioalkoxy, C2-C20 alkenyl, C6-C60 aryl, C3-C60 heteroaryl, C6-C60 arylamino, C3-C60 heteroarylamino, any adjacent substituents being joined, disconnected or connected into a ring; Ar 1 , G 1 , G 2 , L 1 , L 2 have the same defined ranges as in formula I.

6. The compound of claim 5, wherein Ar2 is selected from any one of a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted spirofluorenyl group, and a substituted or unsubstituted benzofluorenyl group; In Ar2, the substituted groups are each independently selected from any one or a combination of at least two of a C1-C20 chain alkyl group, a C3-C20 cyclic alkyl group, a C1-C20 alkoxy group, a C1-C20 silyl group, a C1-C20 thioalkoxy group, a C2-C20 alkenyl group, a C6-C60 aryl group, a C3-C60 heteroaryl group, a C6-C60 arylamino group, and a C3-C60 heteroarylamino group, and any adjacent substituents are not connected or are connected to each other to form a ring.

7. The compound of claim 1, wherein The compound has any one of the structures shown in P1 to P100 below: .

8. Use of a compound according to any one of claims 1 to 7, characterized in that, The compound is used in an electronic device.

9. Use according to claim 8, characterized in that, The electronic device includes an organic electroluminescent device, 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.

10. Use according to claim 9, characterized in that, The electronic device is an organic electroluminescent device.

11. Use according to claim 9, characterized in that, The compound is used as an electron blocking layer material in an organic electroluminescent device.

12. An organic electroluminescent device, characterized by The organic electroluminescent device includes a first electrode, a second electrode, and at least one organic layer interposed between the first electrode and the second electrode, and the organic layer contains at least one compound according to any one of claims 1 to 7.

13. The organic electroluminescent device according to claim 12, characterized in that The organic layer includes an electron blocking layer, and the electron blocking layer contains at least one compound according to any one of claims 1 to 7.

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