An organic electroluminescent compound and an organic electroluminescent device

Abstract

This invention discloses an organic electroluminescent compound and an organic electroluminescent device. The organic compound has a structure represented by F-L-Ar, where L has the structure represented by Formula 1 and F has the structure represented by Formula 2. When used as a luminescent material in an organic electroluminescent device, this compound exhibits significantly reduced evaporation temperature, better thermal stability, effectively reduced energy consumption, improved device efficiency, and lower device driving voltage.

Description

Technical Field

[0001] This invention belongs to the field of organic electroluminescence technology, specifically relating to an organic electroluminescent compound and an organic electroluminescent device. Background Technology

[0002] Organic electronic devices include, but are not limited to, organic light-emitting diodes (OLEDs), organic field-effect transistors (O-FETs), organic light-emitting transistors (OLETs), organic photovoltaic devices (COPVs), dye-sensitized solar cells (DSSCs), organic optical detectors, organic photosensors, organic field-effect devices (OFQDs), light-emitting electrochemical cells (LEGS), organic laser diodes, and organic plasma light-emitting devices.

[0003] In 1987, Tang and Van Slyke of Eastman Kodak reported a bilayer organic electroluminescent device comprising an arylamine hole transport layer and a tri-8-hydroxyquinoline aluminum layer as both an electron transport layer and a light-emitting layer (Applied Physics Letters, 1987, 51(12): 913-915). Once a bias voltage was applied to the device, green light was emitted. This invention laid the foundation for the development of modern organic light-emitting diodes (OLEDs). State-of-the-art OLEDs can include multiple layers, such as charge injection and transport layers, charge and exciton blocking layers, and one or more light-emitting layers between the cathode and anode. Because OLEDs are self-emissive solid-state devices, they offer enormous potential for display and lighting applications. Furthermore, the inherent properties of organic materials, such as their flexibility, make them well-suited for specialized applications, such as in the fabrication of flexible substrates.

[0004] OLEDs can be categorized into three different types based on their light-emitting mechanism. The OLED invented by Tang and Van Slyke is a fluorescent OLED. It uses only singlet state emission. The triplet state generated in the device is wasted through non-radiative decay channels. Therefore, the internal quantum efficiency (IQE) of fluorescent OLEDs is only 25%. This limitation hindered the commercialization of OLEDs. In 1997, Forrest and Thompson reported phosphorescent OLEDs, which use triplet emission from complexed heavy metals as the emitter. Therefore, both singlet and triplet states can be harvested, achieving 100% IQE. Due to its high efficiency, the discovery and development of phosphorescent OLEDs directly contributed to the commercialization of active-matrix OLEDs (AMOLEDs). Recently, Adachi achieved high efficiency through thermally activated delayed fluorescence (TADF) of organic compounds. These emitters have small singlet-triplet gaps, making it possible for excitons to return from the doublet state to the singlet state. In TADF devices, triplet excitons can generate singlet excitons through reverse intersystem crossing, resulting in high IQE. OLEDs can also be classified into small-molecule and polymer OLEDs based on the form of the materials used. Small molecules refer to any organic or organometallic material that is not a polymer. Small molecules can have large molecular weights, provided they have a precise structure. Dendritic polymers with well-defined structures are considered small molecules. Polymer OLEDs include conjugated polymers and non-conjugated polymers with side-chain luminescent groups. Small-molecule OLEDs can become polymer OLEDs if post-polymerization occurs during manufacturing. Various OLED manufacturing methods exist. Small-molecule OLEDs are typically manufactured via vacuum thermal evaporation. Polymer OLEDs are manufactured using solution methods such as spin coating, inkjet printing, and nozzle printing. Small-molecule OLEDs can also be manufactured using solution methods if the material can be dissolved or dispersed in a solvent. The emission color of an OLED can be achieved through the design of the luminescent material structure. OLEDs can include one or more luminescent layers to achieve a desired spectrum. Green, yellow, and red OLEDs using phosphorescent materials have been successfully commercialized. Blue phosphorescent devices still suffer from problems such as blue unsaturation, short device lifetime, and high operating voltage. Commercial full-color OLED displays typically employ a hybrid strategy, using blue fluorescence and phosphorescent yellow, or red and green. Currently, the rapid decrease in efficiency of phosphorescent OLEDs at high brightness levels remains a problem. Furthermore, a more saturated emission spectrum, higher efficiency, and longer device lifetime are desired.

[0005] Currently reported main materials still have room for improvement. To meet the industry's ever-increasing demands, especially for higher device efficiency, longer device lifespan, and lower drive voltage, new materials still require further research and development. Summary of the Invention

[0006] The purpose of this invention is to provide a compound formed by Y-shaped aryl or heteroaryl bonds, which can be used as a host material in organic electroluminescent devices. This compound has significantly reduced evaporation temperature, higher device efficiency and better thermal stability, can effectively reduce energy consumption, is more conducive to the device fabrication process, and can also reduce the device driving voltage, thus providing better device performance.

[0007] In a first aspect, the present invention provides an organic compound having a structure represented by FL-Ar, wherein L has a structure represented by Formula 1, which is:

[0008]

[0009] In Formula 1, ring 1 and ring 2 are selected from carbon rings having 5-18 carbon atoms or heterocycles having 3-18 carbon atoms each time they appear; and A can be arbitrarily chosen as a carbon atom or a nitrogen atom.

[0010] R X Each occurrence, whether identical or different, indicates monosubstitution, polysubstitution, or no substitution;

[0011] F has a structure represented by Equation 2:

[0012]

[0013] In Formula 2, rings A, B, and C are selected from carbon rings having 5-18 carbon atoms or heterocycles having 3-18 carbon atoms each time they appear;

[0014] R Y Each occurrence, whether identical or different, indicates monosubstitution, polysubstitution, or no substitution;

[0015] Y 1 Y 2 and Y 3 Each occurrence is selected from NR, either identically or differently. N or CR Y ;

[0016] Ar has the structure represented by Equation 3, which is as follows:

[0017]

[0018] In Equation 3, Z 1 To Z 5 Each occurrence is selected from NR, either identically or differently. N or CR a R b ;

[0019] In equations 1 to 3, R X RY R N R a and R b Each time it appears, it is selected from the group consisting of the following, either identically or differently: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1-20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3-20 carbon atoms, substituted or unsubstituted heteroalkyl groups having 1-20 carbon atoms, substituted or unsubstituted heterocycloalkyl groups having 3-20 carbon atoms, substituted or unsubstituted aralkyl groups having 7-30 carbon atoms, substituted or unsubstituted alkoxy groups having 1-20 carbon atoms, substituted or unsubstituted aroxy groups having 6-30 carbon atoms, substituted or unsubstituted alkenyl groups having 2-20 carbon atoms, substituted or unsubstituted alkynyl groups having 2-20 carbon atoms, substituted or unsubstituted... The aryl group having 6-30 carbon atoms, substituted or unsubstituted heteroaryl group having 3-30 carbon atoms, substituted or unsubstituted alkylsilyl group having 3-20 carbon atoms, substituted or unsubstituted arylsilyl group having 6-20 carbon atoms, substituted or unsubstituted amino, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, hydroxyl, mercapto, sulfinyl, sulfonyl, phosphinyl, and combinations thereof having 0-20 carbon atoms, wherein the substituent is selected from deuterium, halogen, alkyl group having 1-10 carbon atoms, cycloalkyl group having 3-10 carbon atoms, aryl group having 6-20 carbon atoms, or heteroaryl group having 3-20 carbon atoms; adjacent substituent R X R Y R N R a and R b They can be connected into a ring at will;

[0020] The asterisk (*) indicates the location where F and L bonds are formed. This indicates the location where L and Ar are bonded.

[0021] According to some embodiments of the present invention, in Formula 1, ring 1 and ring 2 are each independently selected from an alicyclic ring having 5-18 carbon atoms, an aromatic ring having 6-18 carbon atoms, or a heteroaromatic ring having 3-18 carbon atoms. In some specific embodiments, ring 1 and ring 2 are each independently selected from a 5-membered carbon ring, a benzene ring, a naphthalene ring, a 5-membered heteroaromatic ring, a 6-membered heteroaromatic ring, a benzo5-membered heteroaromatic ring, or a fused ring formed by a 5-membered heteroaromatic ring and a 6-membered heteroaromatic ring, wherein the heteroatom in the heteroaromatic ring is selected from N, O, S, Se, and Si.

[0022] According to some embodiments of the present invention, L is selected each time it appears from the structure represented by formulas 1-1 to 1-5:

[0023]

[0024] Among them, X1 To X 6 Each occurrence is selected from NR, either identically or differently. N or CR X R X Define the same as equation 1;

[0025] Each time X appears, select from O, S, Se, NR. N ,CR a R b and SiR a R b The group formed, R N ,R a and R b The definition is the same as in equation 3.

[0026] Preferably, in formulas 1-1 to 1-5, R N ,R a and R b Each time it appears, it is selected from the group consisting of the following, either identically or differently: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1-10 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3-10 carbon atoms, substituted or unsubstituted heteroalkyl groups having 1-10 carbon atoms, substituted or unsubstituted heterocycloalkyl groups having 3-10 carbon atoms, substituted or unsubstituted aralkyl groups having 7-20 carbon atoms, substituted or unsubstituted alkoxy groups having 1-10 carbon atoms, substituted or unsubstituted aroxy groups having 6-20 carbon atoms, substituted or unsubstituted alkenyl groups having 2-10 carbon atoms, substituted or unsubstituted alkynyl groups having 2-10 carbon atoms, substituted or unsubstituted alkyne groups, etc. The substituted aryl group having 6-20 carbon atoms, the substituted or unsubstituted heteroaryl group having 3-20 carbon atoms, the substituted or unsubstituted alkoxyl group having 3-10 carbon atoms, the substituted or unsubstituted arylsilyl group having 6-20 carbon atoms, the substituted or unsubstituted amino, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, hydroxyl, mercapto, sulfinyl, sulfonyl, phosphinyl, and combinations thereof having 0-10 carbon atoms, wherein the substituent used for the substitution is selected from hydrogen, deuterium, halogen, alkyl group having 1-10 carbon atoms, cycloalkyl group having 3-10 carbon atoms, aryl group having 6-20 carbon atoms, or heteroaryl group having 3-20 carbon atoms.

[0027] In some preferred embodiments, L is selected from the structure shown in Equation 1-1 or Equation 1-5 each time it appears. In some specific embodiments, in Equation 1-1 or Equation 1-5, X 1 To X 6 Each time it appears, it is selected from CR in the same or different ways. X X is selected from CR a R b R X Ra and R b The definition is the same as above.

[0028] According to a preferred embodiment of the present invention, in formulas 1-1 to 1-5, R X R N R a and R b Each is independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl having 1-10 carbon atoms, haloalkyl having 1-10 carbon atoms, or aryl having 6-18 carbon atoms, preferably hydrogen, deuterium, fluorine, chlorine, bromine, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, trifluoromethyl, phenyl, naphthyl, and biphenyl.

[0029] In some embodiments, the structure of L is one of the structures shown in L-1 to L-39, or a structure obtained by partially or completely replacing the hydrogen in any of the structures shown in L-1 to L-39 with deuterium; wherein the structures corresponding to L-1 to L-39 are as follows:

[0030]

[0031] In some embodiments, in Formula 2, rings A, B, and C, each time they appear, are selected from alicyclic rings having 5-18 carbon atoms, aromatic rings having 6-18 carbon atoms, or heteroaromatic rings having 3-18 carbon atoms. In some specific embodiments, rings A, B, and C, each time they appear, are selected from 5-membered carbon rings, benzene rings, naphthalene rings, 5-membered heteroaromatic rings, 6-membered heteroaromatic rings, benzo5-membered heteroaromatic rings, or fused rings formed by 5-membered and 6-membered heteroaromatic rings, wherein the heteroatoms in the heteroaromatic rings are selected from N, O, S, Se, and Si.

[0032] In some embodiments, F is selected from structures represented by equations 2-1 to 2-12 each time it appears:

[0033]

[0034]

[0035] Among them, Y 1 To Y 17 Each occurrence is selected from NR, either identically or differently. N or CR Y R Y The definition is the same as in equation 2;

[0036] Each time Y appears, select from O, S, Se, NR. N ,CR a R b and SiRa R b The group formed, R N ,R a and R b The definition is the same as in equation 3.

[0037] In some preferred embodiments, in formulas 2-1 to 2-12, Y 1 To Y 3 Each time it appears, it is selected from CR in the same or different ways. Y R Y The definition is the same as in equation 2.

[0038] In some preferred embodiments, in formulas 2-1 to 2-12, R N ,R a and R b Each time it appears, it is selected from the group consisting of the following, either identically or differently: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1-10 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3-10 carbon atoms, substituted or unsubstituted heteroalkyl groups having 1-10 carbon atoms, substituted or unsubstituted heterocycloalkyl groups having 3-10 carbon atoms, substituted or unsubstituted aralkyl groups having 7-20 carbon atoms, substituted or unsubstituted alkoxy groups having 1-10 carbon atoms, substituted or unsubstituted aroxy groups having 6-20 carbon atoms, substituted or unsubstituted alkenyl groups having 2-10 carbon atoms, substituted or unsubstituted alkynyl groups having 2-10 carbon atoms, substituted or unsubstituted... The aryl group having 6-20 carbon atoms, the substituted or unsubstituted heteroaryl group having 3-20 carbon atoms, the substituted or unsubstituted alksilyl group having 3-10 carbon atoms, the substituted or unsubstituted arylsilyl group having 6-20 carbon atoms, the substituted or unsubstituted amino group, acyl group, carbonyl group, carboxylic acid group, ester group, cyano group, isocyano group, hydroxyl group, mercapto group, sulfinyl group, sulfonyl group, phosphinyl group, and combinations thereof, wherein the substituent is selected from hydrogen, deuterium, halogen, alkyl group having 1-10 carbon atoms, cycloalkyl group having 3-10 carbon atoms, aryl group having 6-20 carbon atoms, or heteroaryl group having 3-20 carbon atoms; the adjacent substituent R a and R b Optional connections can be made to form a loop.

[0039] In some preferred embodiments, in formulas 2-1 to 2-12, R Y It is selected from the group consisting of: hydrogen, deuterium, halogen, alkyl having 1-10 carbon atoms, haloalkyl having 1-10 carbon atoms, alkenyl having 1-10 carbon atoms, or aryl having 6-18 carbon atoms, preferably hydrogen, deuterium, fluorine, chlorine, bromine, methyl, ethyl, propyl, isopropyl, tert-butyl, trifluoromethyl, vinyl, propenyl, phenyl, naphthyl, and biphenyl.

[0040] In some preferred embodiments, in formulas 2-1 to 2-12, R N R a and R b Each is independently selected from the group consisting of: hydrogen, deuterium, halogen, alkyl having 1-10 carbon atoms, haloalkyl having 1-10 carbon atoms, or aryl having 6-18 carbon atoms, preferably hydrogen, deuterium, fluorine, chlorine, bromine, methyl, ethyl, propyl, isopropyl, tert-butyl, trifluoromethyl, phenyl, naphthyl, and biphenyl.

[0041] In some preferred embodiments, F is selected from the structure shown in Formula 2-1. In some specific embodiments, Y 1 To Y 11 Same or different, and each independently selected from CR Y R Y The definition is the same as above.

[0042] In some preferred embodiments, in the compound, F has the structure of one of the structures numbered F-1 to F-143, or the structure obtained by partially or completely replacing the hydrogen in any of the structures numbered F-1 to F-143 with deuterium; wherein the structures corresponding to F-1 to F-143 are as follows:

[0043]

[0044]

[0045]

[0046]

[0047]

[0048] According to a preferred embodiment of the present invention, in formulas 1 to 3, 1-1 to 1-5, 2-1 to 2-12 and 3-1 to 3-8 above, R X R Y R N R a and R bEach time it appears, it is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1-10 carbon atoms, substituted or unsubstituted heteroalkyl groups having 1-10 carbon atoms, substituted or unsubstituted heterocyclic alkyl groups having 3-10 carbon atoms, substituted or unsubstituted aralkyl groups having 7-20 carbon atoms, substituted or unsubstituted alkoxy groups having 1-10 carbon atoms, substituted or unsubstituted aroxy groups having 6-20 carbon atoms, and substituted or unsubstituted alkenyl groups having 2-10 carbon atoms. The substituted or unsubstituted aryl group having 6-20 carbon atoms, the substituted or unsubstituted heteroaryl group having 3-20 carbon atoms, the substituted or unsubstituted amino, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, hydroxyl, mercapto, sulfinyl, sulfonyl, phosphinyl, and combinations thereof having 0-10 carbon atoms; wherein the substituent is selected from deuterium, halogen, alkyl group having 1-10 carbon atoms, cycloalkyl group having 3-10 carbon atoms, aryl group having 6-15 carbon atoms, or heteroaryl group having 3-15 carbon atoms. In some embodiments, R X R Y R N R a and R b At least one of them is selected from deuterium, a substituted or unsubstituted aryl group having 6-20 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3-20 carbon atoms. In some embodiments, R X R Y R N R a and R b At least one of them is selected from deuterium, phenyl, biphenyl, naphthyl or pyridyl.

[0049] In some embodiments, Ar in the compound is selected from structures represented by formulas 3-1 to 3-8 each time it appears:

[0050]

[0051] Among them, Z 1 To Z 5 Each time it appears, it is selected from CR. a R b R a and R b The definition is the same as in formula 3; adjacent substituents R a and R b They can be optionally connected into saturated or unsaturated 3-15 member rings.

[0052] In some preferred embodiments, Ar is selected from the structure shown in Formula 3-1 each time it appears.

[0053] Preferably, in formulas 3-1 to 3-8, Ra and R b Each of the following is independently selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl group having 1-10 carbon atoms, substituted or unsubstituted alkenyl group having 1-10 carbon atoms, substituted or unsubstituted aryl group having 6-18 carbon atoms, substituted or unsubstituted heteroaryl group having 3-18 carbon atoms, mercapto or hydroxyl group, wherein the substituent is selected from deuterium, halogen, alkyl group having 1-5 carbon atoms, aryl group having 6-15 carbon atoms or heteroaryl group having 3-15 carbon atoms.

[0054] Preferably, in formulas 3-1 to 3-8, R a and R b Each is independently selected from the group consisting of: hydrogen, deuterium, fluorine, chlorine, bromine, methyl, ethyl, propyl, isopropyl, tert-butyl, trifluoromethyl, substituted or unsubstituted vinyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted triazine, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazoleyl, mercapto, or hydroxyl, wherein the substituent used for the substitution is selected from deuterium, fluorine, methyl, ethyl, isopropyl, tert-butyl, phenyl, biphenyl, naphthyl, benzofuranyl, benzothiophenyl, fluorenyl, dibenzofuranyl, dibenzothiophenyl, or carbazoleyl.

[0055] In some embodiments, the structure of Ar is one of the structures shown in Ar-1 to Ar-108, or a structure obtained by partially or completely replacing the hydrogen in any of the structures shown in Ar-1 to Ar-108 with deuterium; wherein the structures corresponding to Ar-1 to Ar-108 are as follows:

[0056]

[0057]

[0058]

[0059]

[0060] In some embodiments, F is selected from the group consisting of the structures shown in F-1 to F-143 above, L is selected from the group consisting of the structures shown in L-1 to L-39 above, Ar is selected from the group consisting of the structures shown in Ar-1 to Ar-108 above, and optionally the hydrogen in the compound is partially or completely replaced by deuterium.

[0061] In some embodiments, the compound is selected from the compounds corresponding to numbers C1 to C1533, or compounds obtained by partially or completely replacing the hydrogen in any of the structures corresponding to numbers C1 to C1533 with deuterium. The structures shown in numbers C1 to C1533 have an FL-Ar structure, wherein F, L, and Ar correspond to structures selected from Table 1 below.

[0062] Table 1

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081] Secondly, the present invention provides the application of the above-mentioned organic electroluminescent compounds in the preparation of organic electroluminescent devices.

[0082] Preferably, the compound is used as the host material of the light-emitting layer in an organic electroluminescent device.

[0083] Thirdly, the present invention provides an organic electroluminescent device, including a light-emitting layer, wherein the main material of the light-emitting layer contains the organic electroluminescent compound described in the first aspect.

[0084] Preferably, the organic electroluminescent device comprises: an anode, a cathode, and a light-emitting layer disposed between the anode and the cathode. In some embodiments, the light-emitting layer further comprises a dopant. In some embodiments, the dopant included in the organic electroluminescent device of the present invention may be at least one phosphorescent or fluorescent dopant, preferably a phosphorescent dopant. The phosphorescent dopant material is not particularly limited, but may preferably be selected from metallized complexes of iridium (Ir), osmium (Os), copper (Cu), and platinum (Pt), more preferably from ortho-metallized complexes of iridium (Ir), osmium (Os), copper (Cu), and platinum (Pt), and even more preferably from ortho-metallized iridium complexes. In some embodiments, the doping concentration (mass percentage) of the dopant relative to the host material in the light-emitting layer is 1 wt% to 20 wt%, preferably 1 wt% to 10 wt%, more preferably 2 wt% to 8 wt%.

[0085] Preferably, the organic electroluminescent device further includes one or more of the following: a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer.

[0086] Fourthly, the present invention provides a display component / device comprising the organic electroluminescent compound described in the first aspect of the present invention or the organic electroluminescent device described in the third aspect of the present invention.

[0087] The beneficial effects of this invention are as follows: The novel aryl or heteroaryl compounds with a "Y"-shaped linkage disclosed in this invention can be used as the host material in electroluminescent devices. This designed compound connects hole transport units and electron transport units via a "Y"-shaped linkage, giving these compound molecules a unique spatial structure that brings unexpected effects. This novel compound exhibits significantly reduced evaporation temperature, effectively improves device efficiency, has better thermal stability, and effectively reduces energy consumption, which is beneficial for the device fabrication process. Furthermore, it provides better device performance. Attached Figure Description

[0088] Figure 1 This is a schematic diagram of an organic light-emitting device according to a specific embodiment of the present invention.

[0089] Figure 2 This is a schematic diagram of an organic light-emitting device according to another specific embodiment of the present invention.

[0090] The attached figures are labeled as follows:

[0091] 100, First organic light-emitting device; 101, Substrate; 110, Anode; 120, Hole injection layer; 130, Hole transport layer; 140, Electron blocking layer; 150, Light-emitting layer; 160, Hole blocking layer; 170, Electron transport layer; 180, Electron injection layer; 190, Cathode; 102, Encapsulation layer; 200, Second organic light-emitting device. Detailed Implementation

[0092] The technical solution of the present invention will be described in detail below with reference to specific embodiments and accompanying drawings. The following embodiments and accompanying drawings are used to illustrate the present invention, but are not intended to limit the scope of the present invention. All equivalent changes or modifications made without departing from the spirit disclosed in the present invention should be included within the scope of the claims.

[0093] OLEDs can be manufactured on various substrates, such as glass, plastic, and metal. Figure 1 A first organic light-emitting device 100 is illustrated schematically and non-limitingly. The figures are not necessarily drawn to scale, and some layer structures may be omitted as needed. Device 100 may include a substrate 101, an anode 110, a hole injection layer 120, a hole transport layer 130, an electron blocking layer 140, a light-emitting layer 150, a hole blocking layer 160, an electron transport layer 170, an electron injection layer 180, and a cathode 190. Device 100 may be fabricated by sequentially depositing the described layers. The properties and functions of each layer, as well as exemplary materials, are described in more detail in columns 6-10 of U.S. Patent 7,279,704B2, the entire contents of which are incorporated herein by reference.

[0094] Each of these layers has numerous examples. For instance, a flexible and transparent substrate-anode combination is disclosed in U.S. Patent No. 5,844,363, which is incorporated herein by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated herein by reference in its entirety. An example of a host material is disclosed in U.S. Patent No. 6,303,238 to Thompson et al., which is incorporated herein by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated herein by reference in its entirety. Examples of cathodes are disclosed in U.S. Patent Nos. 5,703,436 and 5,707,745, which are incorporated herein by reference in their entirety. These cathodes comprise composite cathodes having a thin metal layer, such as Mg:Ag, overlaid with a transparent, conductive, sputter-deposited ITO layer. The principles and use of barrier layers are described in more detail in U.S. Patent No. 6,097,147 and U.S. Patent Application Publication No. 2003 / 0230980, which are also incorporated herein by reference in their entirety. Examples of implantation layers are provided in U.S. Patent Application Publication No. 2004 / 0174H6, which is incorporated herein by reference in its entirety. A description of protective layers can be found in U.S. Patent Application Publication No. 2004 / 0174H6, which is incorporated herein by reference in its entirety.

[0095] The layered structure described above is provided through non-limiting embodiments. The functionality of an OLED can be achieved by combining the various layers described above, or some layers can be omitted entirely. It may also include other layers not explicitly described. Within each layer, a single material or a mixture of multiple materials can be used to achieve optimal performance. Any functional layer may include several sublayers. For example, a light-emitting layer may have two different light-emitting materials to achieve a desired emission spectrum.

[0096] In one embodiment, an OLED can be described as having an "organic layer" disposed between a cathode and an anode. This organic layer may include one or more layers.

[0097] OLEDs also require an encapsulation layer, such as Figure 2 The second organic light-emitting device 200 is shown schematically and non-limitingly, which is related to... Figure 1The difference lies in the fact that an encapsulation layer 102 may also be included above the cathode 190 to protect against harmful substances from the environment, such as moisture and oxygen. Any material capable of providing encapsulation can be used as the encapsulation layer, such as glass or an organic-inorganic hybrid layer. The encapsulation layer should be placed directly or indirectly on the outside of the OLED device. Multilayer thin-film encapsulation is described in U.S. Patent 7,968,146B2, the entire contents of which are incorporated herein by reference.

[0098] Devices manufactured according to embodiments of the present invention can be incorporated into a variety of consumer products having one or more electronic component modules (or units). Some examples of such consumer products include flat panel displays, monitors, medical monitors, televisions, billboards, lights for indoor or outdoor lighting and / or signaling, head-up displays, fully or partially transparent displays, flexible displays, smartphones, tablet computers, phablets, wearable devices, smartwatches, laptop computers, digital cameras, portable camcorders, viewfinders, microdisplays, 3D displays, vehicle displays, and taillights.

[0099] The materials and structures described in this article can also be used in other organic electronic devices listed above.

[0100] Definition of the term "substituent group"

[0101] Halogens or halides—as used herein—include fluorine, chlorine, bromine, and iodine.

[0102] Alkyl groups—as used herein—include straight-chain and branched alkyl groups. An alkyl group can be an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 12 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. Examples of alkyl groups include methyl, ethyl, propyl, isolaryl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecanyl, n-hexadecyl, n-heptadecyl, n-octadecyl, neopentyl, 1-methylpentyl, 2-methylpentyl, 1-pentylhexyl, 1-butylpentyl, 1-heptyloctyl, and 3-methylpentyl. Additionally, alkyl groups may optionally be substituted. Among the above, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, and n-hexyl are preferred. Additionally, alkyl groups may optionally be substituted.

[0103] Cycloalkyl – as used herein, comprises cyclic alkyl groups. The cycloalkyl group can be a cycloalkyl group having 3 to 20 carbon atoms, preferably a cycloalkyl group having 4 to 10 carbon atoms. Examples of cycloalkyl groups include cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4,4-dimethylcyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl, etc. Among the above, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, and 4,4-dimethylcyclohexyl are preferred. Furthermore, the cycloalkyl group may optionally be substituted.

[0104] Heteroalkyl – As used herein, a heteroalkyl group comprises one or more carbon atoms in an alkyl chain that are replaced by heteroatoms selected from the group consisting of nitrogen, oxygen, sulfur, selenium, phosphorus, silicon, germanium, and boron atoms. The heteroalkyl group can be a heteroalkyl group having 1 to 20 carbon atoms, preferably a heteroalkyl group having 1 to 10 carbon atoms, and more preferably a heteroalkyl group having 1 to 6 carbon atoms. Examples of heteroalkyl groups include methoxymethyl, ethoxymethyl, ethoxyethyl, methylthiomethyl, ethylthiomethyl, ethylthioethyl, methoxymethoxymethyl, ethoxymethoxymethyl, ethoxyethoxyethyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, mercaptomethyl, mercaptoethyl, mercaptopropyl, aminomethyl, aminoethyl, aminolactone, dimethylaminomethyl, trimethylsilyl, dimethylethylsilyl, dimethylisolactone, tert-butyldimethylsilyl, triethylsilyl, triisolactone, trimethylsilylmethyl, trimethylsilylethyl, and trimethylsilylisolactone. In addition, heteroalkyl groups may be optionally substituted.

[0105] Alkenyl – as used herein – encompasses straight-chain, branched, and cyclic olefinic groups. An alkenyl group can be an alkenyl group containing 2 to 20 carbon atoms, preferably an alkenyl group having 2 to 10 carbon atoms. Examples of alkenyl groups include vinyl, propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, 1-methylvinyl, styryl, 2,2-diphenylvinyl, 1,2-diphenylvinyl, 1-methylallyl, 1,1-dimethylallyl, 2-methylallyl, 1-phenylallyl, 2-phenylallyl, 3-phenylallyl, 3,3-diphenylallyl, 1,2-dimethylallyl, 1-phenyl-1-butenyl, 3-phenyl-1-butenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cycloheptenyl, cycloheptanetrienyl, cyclooctenyl, cyclooctatetraenyl, and norbornyl. In addition, the alkenyl group can be optionally substituted.

[0106] Alkynyl – as used herein, encompasses straight-chain alkynyl groups. An alkynyl group can be one containing 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms. Examples of alkynyl groups include ethynyl, propynyl, propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3,3-dimethyl-1-butynyl, 3-ethyl-3-methyl-1-pentynyl, 3,3-diisopropyl-1-pentynyl, phenylethynyl, phenylpropynyl, etc. Among the above, ethynyl, propynyl, propynyl, butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, and phenylethynyl are preferred. Furthermore, the alkynyl group may be optionally substituted.

[0107] Aryl or aromatic group – as used herein, both non-fused and fused systems are considered. The aryl group can be an aryl group having 6 to 30 carbon atoms, preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms. Examples of aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthyl, anthracene, ferroyl, phenanthryl, fluorenyl, pyrene, etc. The aryl group can be substituted with phenyl, peryl, and azulel, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorenyl, and naphthyl. Additionally, the aryl group may be optionally substituted. Examples of non-fused aryl groups include phenyl, biphenyl-2-yl, biphenyl-3-yl, biphenyl-4-yl, p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl, m-terphenyl-2-yl, o-tolyl, m-tolyl, p-tolyl, p-(2-phenylpropyl)phenyl, 4'-methylbiphenyl, 4”-tert-butyl-p-terphenyl-4-yl, o-cumyl, m-cumyl, p-cumyl, 2,3-xylyl, 3,4-xylyl, 2,5-xylyl, mesitylene, and m-tetraphenyl. Additionally, the aryl group may be optionally substituted.

[0108] Heterocyclic groups or heterocycles – as used herein, consider non-aromatic cyclic groups. Non-aromatic heterocyclic groups include saturated heterocyclic groups having 3-20 ring atoms and unsaturated non-aromatic heterocyclic groups having 3-20 ring atoms, wherein at least one ring atom is selected from the group consisting of nitrogen, oxygen, sulfur, selenium, silicon, phosphorus, germanium, and boron atoms. Preferred non-aromatic heterocyclic groups are those having 3 to 7 ring atoms, including at least one heteroatom such as nitrogen, oxygen, silicon, or sulfur. Examples of non-aromatic heterocyclic groups include ethylene oxide, oxetane, tetrahydrofuranyl, tetrahydropyranyl, dioxopentacyclic, dioxacyclocyclic, acrylidine, dihydropyrroleyl, tetrahydropyrroleyl, piperidinyl, oxazolidinyl, morpholinyl, piperazine, oxetane-heptanetrienyl, thioheptanyl, azirane-heptanetrienyl, and tetrahydrothiorroleyl. In addition, the heterocyclic group can be optionally substituted.

[0109] Heteroaryl – as used herein – can be a non-fused or fused heteroaryl group comprising 1 to 5 heteroatoms, wherein at least one heteroatom is selected from the group consisting of nitrogen, oxygen, sulfur, selenium, silicon, phosphorus, germanium, and boron. Isoaryl also refers to heteroaryl. Heteroaryl can be a heteroaryl having 3 to 30 carbon atoms, preferably a heteroaryl having 3 to 20 carbon atoms, and more preferably a heteroaryl having 3 to 12 carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridoindole, pyrrolopyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxtriazole, dioxazole, thiadiazol, pyridine, pyrazine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzoisoxazole, benzothiazole, quinoline, iso Quinoline, cyclophosphine, quinazolin, quinoxaline, naphthidine, phthalazine, pteridine, guarbenzine, acridine, phenazine, phenothiazine, benzofuranopyridine, furanodipyridine, benzothiophenopyridine, thiophenodipyridine, benzoselenophenopyridine, selenobenzodipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborane, 1,3-azaborane, 1,4-azaborane, boronazole and its aza analogues. Additionally, the heteroaryl group may optionally be substituted.

[0110] Alkoxy groups—as used herein—are represented by -O-alkyl, -O-cycloalkyl, -O-heteroalkyl, or -O-heterocyclic groups. Examples and preferred examples of alkyl, cycloalkyl, heteroalkyl, and heterocyclic groups are the same as described above. An alkoxy group can be an alkoxy group having 1 to 20 carbon atoms, preferably an alkoxy group having 1 to 6 carbon atoms. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, cyclopropyloxy, cyclobutyloxy, cyclopentoxy, cyclohexyloxy, tetrahydrofuranyloxy, tetrahydropyranyloxy, methoxypropyloxy, ethoxyethyloxy, methoxymethyloxy, and ethoxymethyloxy. Additionally, alkoxy groups may optionally be substituted.

[0111] Aryloxy group – As used herein, aryl and heteroaryl groups are represented by -O-aryl or -O-heteroaryl. Examples and preferred examples are the same as described above. The aryloxy group can be an aryloxy group having 6 to 30 carbon atoms, preferably an aryloxy group having 6 to 20 carbon atoms. Examples of aryloxy groups include phenoxy and biphenyloxy groups. Additionally, the aryloxy group may optionally be substituted.

[0112] Arylalkyl – as used herein, encompasses aryl-substituted alkyl groups. An arylalkyl group can be an arylalkyl group having 7 to 30 carbon atoms, preferably an arylalkyl group having 7 to 20 carbon atoms, and more preferably an arylalkyl group having 7 to 13 carbon atoms. Examples of arylalkyl groups include benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl, 2-phenylisopropyl, phenyl tert-butyl, α-naphthylmethyl, 1-α-naphthylethyl, 2-α-naphthylethyl, 1-α-naphthylisopropyl, 2-α-naphthylisopropyl, β-naphthylmethyl, 1-β-naphthyl-ethyl, 2-β-naphthyl-ethyl, 1-β-naphthylisopropyl, 2-β-naphthylisopropyl, p-methylbenzyl, m-methylbenzyl The compounds include alkyl groups, such as o-methylbenzyl, p-chlorobenzyl, m-chlorobenzyl, o-chlorobenzyl, p-bromobenzyl, m-bromobenzyl, o-bromobenzyl, p-iodobenzyl, m-iodobenzyl, o-iodobenzyl, p-hydroxybenzyl, m-hydroxybenzyl, o-hydroxybenzyl, p-aminobenzyl, m-aminobenzyl, o-aminobenzyl, p-nitrobenzyl, m-nitrobenzyl, o-nitrobenzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-hydroxy-2-phenylisopropyl, and 1-chloro-2-phenylisopropyl. Among the above, benzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl, and 2-phenylisopropyl are preferred. Additionally, the alkyl group may optionally be substituted.

[0113] Alkylsilyl – as used herein, encompasses alkyl-substituted silyl groups. The alkylsilyl group can be an alkylsilyl group having 3 to 20 carbon atoms, preferably an alkylsilyl group having 3 to 10 carbon atoms. Examples of alkylsilyl groups include trimethylsilyl, triethylsilyl, methyldiethylsilyl, ethyldimethylsilyl, tripropylsilyl, tributylsilyl, triisopropylsilyl, methyldiisopropylsilyl, dimethylisopropylsilyl, tritert-butylsilyl, triisobutylsilyl, dimethyltert-butylsilyl, and methylditert-butylsilyl. Furthermore, the alkylsilyl group may optionally be substituted.

[0114] Arylsilane – as used herein, encompasses at least one aryl-substituted silane group. The arylsilane can be an arylsilane having 6 to 30 carbon atoms, preferably an arylsilane having 8 to 20 carbon atoms. Examples of arylsilanes include triphenylsilyl, phenyldiphenylsilyl, diphenylbiphenylsilyl, phenyldiethylsilyl, diphenylethylsilyl, phenyldimethylsilyl, diphenylmethylsilyl, phenyldiisopropylsilyl, diphenylisopropylsilyl, diphenylbutylsilyl, diphenylisobutylsilyl, diphenyltert-butylsilyl, tri-tert-butylsilyl, dimethyltert-butylsilyl, and methyldi-tert-butylsilyl. Additionally, the arylsilane may optionally be substituted.

[0115] The term "aza" in azadibenzofuran, azadibenzothiophene, etc., refers to the substitution of one or more CH groups in the corresponding aromatic fragment by a nitrogen atom. For example, azatriphenylene includes dibenzo[f,h]quinoline, dibenzo[f,h]quinoline, and other analogs having two or more nitrogen atoms in the ring system. Other nitrogen analogs of the aforementioned aza derivatives will readily conceive of those skilled in the art, and all such analogs are identified as being included in the terminology used herein.

[0116] In this disclosure, unless otherwise defined, when any of the terms consisting of the group consisting of alkyl, cycloalkyl, heteroalkyl, substituted heterocyclic, substituted aralkyl, substituted alkoxy, substituted aryloxy, substituted alkenyl, substituted alkynyl, substituted aryl, substituted heteroaryl, substituted alksilyl, substituted arylsilyl, substituted amino, substituted acyl, substituted carbonyl, substituted carboxylic acid, substituted ester, substituted sulfinyl, substituted sulfonyl, substituted phosphinyl, refers to any one of the following groups: alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, alkenyl, aryl, heteroaryl, alksilyl, arylsilyl, amino, acyl, carbonyl, carboxylic acid, ester, sulfinyl, sulfonyl, and phosphinyl, which may be one or more groups selected from deuterium, halogen, unsubstituted alkyl having 1.20 carbon atoms, unsubstituted The substituted group comprises cycloalkyl groups having 3-20 carbon atoms, unsubstituted heteroalkyl groups having 1-20 carbon atoms, unsubstituted heterocyclic groups having 3-20 carbon atoms, unsubstituted aralkyl groups having 7-30 carbon atoms, unsubstituted alkoxy groups having 1-20 carbon atoms, unsubstituted aroxy groups having 6-30 carbon atoms, unsubstituted alkenyl groups having 2-20 carbon atoms, unsubstituted alkynyl groups having 2-20 carbon atoms, unsubstituted aryl groups having 6-30 carbon atoms, unsubstituted heteroaryl groups having 3-30 carbon atoms, unsubstituted alkylsilyl groups having 3-20 carbon atoms, unsubstituted arylsilyl groups having 6-20 carbon atoms, and unsubstituted amino, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, hydroxyl, mercapto, sulfinyl, sulfonyl, phosphin, and combinations thereof having 0-20 carbon atoms.

[0117] It should be understood that when a molecular segment is described as a substituent or otherwise attached to another part, its name may be written according to whether it is a segment (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or according to whether it is a whole molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of specifying substituents or attaching segments are considered equivalent.

[0118] In the compounds mentioned in this disclosure, hydrogen atoms can be partially or completely replaced by deuterium. Other atoms such as carbon and nitrogen can also be replaced by their other stable isotopes. Substitution with other stable isotopes in the compounds is likely preferred due to their ability to enhance device efficiency and stability.

[0119] In the compounds mentioned in this disclosure, multiple substitution refers to the range including disubstitution, up to the maximum number of available substitutions. When a substituent in a compound mentioned in this disclosure represents multiple substitution (including disubstitution, trisubstitution, tetrasubstitution, etc.), it means that the substituent can be present at multiple available substitution positions on its linkage structure. The substituent present at multiple available substitution positions can be the same structure or different structures.

[0120] In the compounds mentioned in this disclosure, unless explicitly specified, for example, that adjacent substituents can optionally connect to form a ring, adjacent substituents in the compounds cannot connect to form a ring. In the compounds mentioned in this disclosure, the optional connection of adjacent substituents to form a ring includes both cases where adjacent substituents can connect to form a ring and cases where adjacent substituents do not connect to form a ring. When adjacent substituents can optionally connect to form a ring, the resulting ring can be a monocyclic or polycyclic ring, and can be an alicyclic, heterocyclic, aromatic, or heteroaromatic ring. In this context, adjacent substituents can refer to substituents bonded to the same atom, substituents bonded to carbon atoms directly bonded to each other, or substituents bonded to carbon atoms further away. Preferably, adjacent substituents refer to substituents bonded to the same carbon atom and substituents bonded to carbon atoms directly bonded to each other.

[0121] The statement that adjacent substituents can optionally connect to form a ring also refers to the formation of a ring by two substituents bonded to the same carbon atom, which can be exemplified by the following formula:

[0122]

[0123] The statement that adjacent substituents can optionally connect to form a ring also refers to the formation of a ring by two substituents that are considered to be bonded to carbon atoms directly bonded to each other, which can be exemplified by the following formula:

[0124]

[0125] Furthermore, the statement that adjacent substituents can optionally connect to form a ring is also intended to mean that, in the case where one of the two substituents bonded to the carbon atom directly bonded to each other represents hydrogen, the second substituent bonds at the position where the hydrogen atom is bonded, thereby forming a ring. This is illustrated by the following example:

[0126]

[0127] The materials described in this invention for specific layers in organic light-emitting devices can be used in combination with a variety of other materials present in the device. These combinations of materials are described in detail in paragraphs 0132-0161 of U.S. Patent Application US2016 / 0359122M, the entire contents of which are incorporated herein by reference. The materials described or mentioned herein are non-limiting examples of materials that can be used in combination with the compounds disclosed herein, and those skilled in the art can readily consult the literature to identify other materials that can be used in combination.

[0128] Materials described herein for use in specific layers in organic light-emitting devices can be used in combination with a variety of other materials present in said devices. For example, the compounds disclosed herein can be used in combination with a variety of host layers, delivery layers, barrier layers, injection layers, electrodes, and other possible layers. These combinations of materials are described in detail in paragraphs 0080-0101 of U.S. Patent Application US2015 / 0349273M, the entire contents of which are incorporated herein by reference. The materials described or mentioned herein are non-limiting examples of materials that can be used in combination with the compounds disclosed herein, and those skilled in the art can readily consult the literature to identify other materials that can be used in combination.

[0129] In the examples of material synthesis, unless otherwise stated, all reactions were carried out under nitrogen protection. All reaction solvents were anhydrous and used as is from commercial sources. The synthesized products were structurally confirmed and characterized using one or more instruments conventional in the art (including but not limited to Agilent liquid chromatographs, liquid chromatography-mass spectrometers, gas chromatography-mass spectrometers, differential scanning calorimeters, fluorescence spectrophotometers, electrochemical workstations, sublimation apparatuses, etc.) in methods well known to those skilled in the art. In the examples of devices, the characteristics of the devices were also tested using conventional instruments in the art (including but not limited to vapor deposition machines manufactured by Nanjing Institute of Microelectronics, optical testing systems and lifetime testing systems manufactured by Suzhou Fushida, ellipsometers manufactured by Wuhan Yiguang Technology, etc.) in methods well known to those skilled in the art. Since those skilled in the art are familiar with the use of the above-mentioned equipment, testing methods, and other related content, and can obtain the inherent data of the samples definitively and unaffected, the above-mentioned related content will not be elaborated further in this patent.

[0130] Material synthesis examples:

[0131] The preparation methods of the compounds of this invention are not limited. Typical but not limited examples are the following compounds, whose synthetic routes and preparation methods are as follows:

[0132] Synthesis Example 1: Synthesis of Compound C97

[0133] Synthesis of intermediate 1:

[0134]

[0135] Under nitrogen protection, 2-bromo-3-chloronitrobenzene (50 g, 213 mmol), pinacol ester of 2-aminophenylboronic acid (51 g, 2.34 mmol), tetrakis(triphenylphosphine)palladium (2.5 g, 213 mmol), potassium carbonate (57 g, 426 mmol), toluene (500 mL), water (100 mL), and ethanol (100 mL) were added to a three-necked flask. The reaction was carried out at 100 °C for 48 h. After the reaction was completed, the mixture was cooled to room temperature, dissolved, and distilled water was added. The mixture was extracted with ethyl acetate, the organic phase was washed with water, dried over anhydrous magnesium sulfate, and dissolved. The organic phase was purified by column chromatography to give yellow oily intermediate 1 (46 g, yield 86%).

[0136] Synthesis of intermediate 2:

[0137]

[0138] Intermediate 1 (90 g, 363 mmol) and acetonitrile (100 mL) were placed in a three-necked flask. Toluenesulfonic acid (195 g, 1.1 mol) was added in portions at 0 °C and stirred for 30 min. At this temperature, a mixed aqueous solution of sodium nitrite (69 g, 726 mmol) and potassium iodide (150.6 g, 907 mmol) was slowly added dropwise. After the addition was complete, the temperature was slowly raised to room temperature, and the reaction was allowed to proceed for 18 h. After the reaction was complete, a saturated aqueous solution of sodium thiosulfate was added dropwise to quench the reaction. The reaction solution was concentrated, diluted with water, and the mixture was extracted three times with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and dissolved. The mixture was subjected to column chromatography to obtain a yellow solid intermediate 2 (89 g, yield: 67%).

[0139] Synthesis of intermediate 3:

[0140]

[0141] Under nitrogen protection, intermediate 2 (20 g, 557 mmol), 1-boronic acid pinacol ester-carbazole (24.5 g, 836 mmol), tetrakis(triphenylphosphine)palladium (19 g, 167 mmol), potassium carbonate (15.4 g, 111.4 mmol), toluene (200 mL), water (100 mL), and ethanol (100 mL) were added to a three-necked flask and reacted at 70 °C for 18 h. After the reaction was completed, the mixture was cooled, dissolved, and extracted with ethyl acetate and water. The organic phase was dried over anhydrous magnesium sulfate and concentrated to remove the solvent. Column chromatography yielded a yellow solid intermediate 3 (12 g, yield: 55%).

[0142] Synthesis of intermediate 4:

[0143]

[0144] Under nitrogen protection, intermediate 3 (12 g, 3 mol), palladium acetate (338 mg, 15 mmol), tri-tert-butylphosphine (606 mg, 3.0 mmol), cesium carbonate (20 g, 603 mmol), and xylene (230 mL) were added to a three-necked flask and reacted at 140 °C for 16 h. After the reaction was complete, the mixture was cooled to room temperature, concentrated to remove the solvent, extracted with ethyl acetate and water, and the organic phase was washed three times with water until neutral. The organic phase was dried over anhydrous magnesium sulfate and the solvent was removed. Column chromatography yielded a yellow solid intermediate 4 (9 g, yield: 80%).

[0145] Synthesis of intermediate 5:

[0146]

[0147] Under nitrogen protection, intermediate 4 (9 g, 24.9 mmol), triphenylphosphine (196 g, 747 mmol), and o-dichlorobenzene (100 mL) were added to a three-necked flask, and the reaction was carried out at 200 °C for 12 h. After the reaction was completed, the solvent was removed under reduced pressure, and the crude product was subjected to column chromatography to give a yellow solid intermediate 5 (7 g, yield: 85%).

[0148] Synthesis of intermediate 6:

[0149]

[0150] In a 250 mL dry three-necked flask, 1-bromo-8-chloronaphthalene (5 g, 20.66 mmol), pinacol diboronate (6.3 g, 24.79 mmol), potassium acetate (4.05 g, 41.32 mmol), and Pd(dppf)Cl2 (0.190 g, 0.26 mmol) were added. Nitrogen gas was purged three times. 50 mL of 1,4-dioxane was added to the reaction flask, and the reaction was allowed to proceed for 12 h. Ethyl acetate and water were added to extract the reaction solution, followed by solvent removal. The mixture was then slurried in heptane for 2 h and filtered to obtain intermediate 6 (4.4 g, yield 73.8%).

[0151] Synthesis of intermediate 7:

[0152]

[0153] Under nitrogen atmosphere, intermediate 6 (5.2 g, 18.02 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (4.38 g, 16.38 mmol), potassium carbonate (6.78 g, 49.14 mmol), and tetraphenylphosphine palladium (0.9 g, 0.8 mmol) were added sequentially to a three-necked flask. Dioxane (50 mL) and water (25 mL) were then added. The reaction was carried out at approximately 110 °C for 12 hours. After cooling to room temperature, ethyl acetate and water were added to extract the reaction solution. The organic phase was washed with water until neutral, dried, and then dissolved. After stirring in heptane for 2 hours, the mixture was filtered to obtain white intermediate 7 (3.7 g, 52% yield).

[0154] C97 synthesis:

[0155]

[0156] Under a nitrogen atmosphere, intermediate 7 (3.42 g, 8.68 mmol), intermediate 5 (3.01 g, 9.12 mmol), dipalladium (0.46 g, 0.8 mmol), sodium tert-butoxide (1.25 g, 13.02 mmol), and tritert-butylphosphine tetrafluoroborate (5.036 g, 17.36 mmol), and toluene (70 mL) were added sequentially to a three-necked flask. The mixture was reacted at approximately 200 °C for 18 hours. After cooling to room temperature, ethyl acetate and water were added to extract the reaction mixture. The organic phase was desolvated, and column chromatography yielded a bright yellow solid C97 (2.1 g, yield 35.17%).

[0157] 1 H NMR (400MHz, CDCl3) δ=8.45–8.36(m,4H),8.22–8.17(m,2H),8.08(d,J=9.5Hz,1H),8.04(dd,J=8.5,1.7Hz,1H),7.83(dt,J=7.2,1.4Hz,1H), 7.73(dd,J=7.0,0.7Hz,1H),7.73–7.56(m,6H),7.58–7.51(m,2H),7.5 4–7.47(m,6H),7.51–7.45(m,2H),7.40–7.33(m,2H),7.34–7.28(m,1H)

[0158] MS = 687.3.

[0159] Synthesis Example 2: Compound C98

[0160]

[0161] 2-chloro-4,6-diphenyl-1,3,5-triazine was replaced with 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine. With appropriate material ratios selected, and other raw materials and steps being the same as in Synthesis Example 1, 2.86 g of yellow solid C98 was obtained, with a yield of 41%.

[0162] 1 H NMR (400MHz, CDCl3) δ=8.44–8.37(m,2H),8.22–8.17(m,2H),8.11–8.01(m,2H),8.00–7.94( m,2H),7.83(dt,J=7.2,1.3Hz,1H),7.76–7.41(m,22H),7.41–7.34(m,2H),7.37–7.28(m,2H)

[0163] MS = 763.4

[0164] Synthesis Example 3: Compound C103

[0165]

[0166] 2-Chloro-4,6-diphenyl-1,3,5-triazine was replaced with 2-chloro-4,6-diphenyl-1,3,5-triazine. A suitable material ratio was selected, and other raw materials and steps were the same as in Synthesis Example 1, yielding 2.13 g of yellow solid C103, with a yield of 30%.

[0167] 1 H NMR (400MHz, CDCl3) δ=8.45–8.37(m,2H),8.22–8.17(m,2H),8.11–7.95(m,3H),7.87–7.80(m,2H),7.76–7.66(m,4H),7. 64(dd,J=6.5,1.1Hz,2H),7.63–7.57(m,2H),7.60–7.53(m,2H),7.55–7.45(m,8H),7.40–7.33(m,2H),7.36–7.28(m,2H).

[0168] MS = 777.5.

[0169] Synthesis Example 4: Compound C107

[0170]

[0171] 2-Chloro-4,6-diphenyl-1,3,5-triazine was replaced with 2-chloro-4-(dibenzo[b,d]furan-1-yl)-6-(naphth-2-yl)-1,3,5-triazine. With appropriate material ratios selected, and other raw materials and steps being the same as in Synthesis Example 1, 3.62 g of yellow solid C107 was obtained, with a yield of 48%.

[0172] 1 H NMR (400MHz, CDCl3)δ=8.22–8.17(m,3H),8.11–7.95(m,6H),7.95–7.86(m,1H),7.86–7.80(m,3H),7.76–7.45(m,16H),7.40–7.28(m,4H)

[0173] MS = 827.9.

[0174] Synthesis Example 5: Compound C1283

[0175]

[0176] Synthesis steps:

[0177]

[0178] By replacing 1-bromo-8-chloronaphthalene with 1-chlorocarbazole, selecting an appropriate material ratio, and referring to the synthesis example 1 (see above figure) for other raw materials and steps, 2.98 g of yellow solid C1283 was obtained, with a yield of 45%.

[0179] 1 H NMR (400MHz, CDCl3) δ=8.37–8.31(m,4H),8.19(ddd,J=5.9,3.4,1.7Hz,3H),7.78–7.6 5(m,6H),7.58–7.49(m,4H),7.53–7.45(m,6H),7.48–7.35(m,4H),7.38–7.28(m,3H).

[0180] MS = 726.6.

[0181] Those skilled in the art should understand that the above preparation method is merely an exemplary example, and they can obtain other compound structures of the present invention by improving it.

[0182] Device Example 1

[0183] First, the glass substrate, which has a 120 nm thick indium tin oxide (ITO) anode, is cleaned and then treated with UV ozone and oxygen plasma. After treatment, the substrate is dried in a nitrogen-filled glove box to remove moisture, and then mounted on a substrate holder and placed in a vacuum chamber. The organic layer specified below is applied at a vacuum degree of approximately 10... -8 In the case of Torr, The deposition rate is achieved sequentially on the ITO anode via thermal vacuum. Simultaneously, the deposited compounds HT and NDP-9 are used as a hole injection layer (HIL), with a thickness of [missing information]. Compound HT is used as a hole transport layer (HTL) with a thickness of [missing information]. Compound EB is used as an electron blocking layer (EBL) with a thickness of [missing information]. Then, the compound C97 of this invention, as the main component, and the compound RD, as a dopant, are co-deposited as an emissive layer (EML) with a thickness of [thickness missing]. Compound HB was used as the hole blocking layer (HBL), with a thickness of [missing information]. On the hole-blocking layer, compound ET and 8-hydroxyquinoline-lithium (Liq) are co-deposited as an electron transport layer (ETL) with a thickness of [missing information]. Finally, vapor deposition Thick 8-hydroxyquinoline-lithium (Liq) was used as the electron injection layer (EIL) and deposited by evaporation. Aluminum was used as the cathode. The device was then transferred back to the glove box and sealed with a glass cover to complete the device.

[0184] Device Example 2

[0185] The method is the same as in Device Example 1, except that the compound C97 of the present invention is replaced by compound C98 of the present invention as the main component in the light-emitting layer (EML).

[0186] Device Example 3

[0187] The method is the same as in Device Example 1, except that the compound C103 of the present invention is used instead of the compound C97 of the present invention as the main component in the light-emitting layer (EML).

[0188] Device Example 4

[0189] The method is the same as in Device Example 1, except that the compound C107 of the present invention is used instead of the compound C97 of the present invention as the main component in the light-emitting layer (EML).

[0190] Device Example 5

[0191] The method is the same as in Device Example 1, except that the compound C1283 of the present invention is used instead of the compound C97 of the present invention as the main component in the light-emitting layer (EML).

[0192] Device Comparison Example 1

[0193] Similar to Device Example 1, except that compound A is used instead of compound C97 of the present invention as the main component in the light-emitting layer (EML).

[0194] Device Comparison Example 2

[0195] Similar to Device Example 1, except that compound B is used instead of compound C97 of the present invention as the main component in the light-emitting layer (EML).

[0196] Device Comparison Example 3

[0197] Similar to Device Example 1, except that compound C is used instead of compound C97 of the present invention as the main component in the light-emitting layer (EML).

[0198] During the experiment, the vapor deposition temperature of the compound materials C97, C98, C103, C107, and C1283 of the present invention was significantly lower than that of compound A, compound B, and compound C. The specific values ​​are shown in Table 2.

[0199] Table 2 Comparison of Evaporation Temperatures

[0200] Material Number Evaporation temperature / ℃ C97 168 C98 176 C103 179 C107 182 C1283 170 Compound A 224 Compound B 215 Compound C 231

[0201] The detailed device layer structure and thickness are shown in Table 3 below. The layers used are made of more than one material, and are obtained by doping different compounds in the weight ratios specified herein.

[0202] Table 3 Device structures of the device embodiments and comparative examples

[0203]

[0204]

[0205] The material structure used in the device is shown below:

[0206]

[0207] Table 4 lists the values ​​at 10 mA / cm 2 Under the conditions, the measured current efficiency (CE) and maximum wavelength (λ) max ) and external quantum efficiency (EQE). To better illustrate the data comparison, the CE and EQE data of Comparative Example 2 were set to 100%. The CE and EQE data of Examples 1, 2, 3, 4, 5, Comparative Example 1 and Comparative Example 3 were all converted relative to the corresponding data of Comparative Example 2. The relevant data and conversion results are shown in Table 4.

[0208] Table 4

[0209]

[0210] discuss:

[0211] As shown in Table 4, the maximum wavelength of the comparative examples and the embodiments remained essentially unchanged. At 10 mA / cm² 2 The EQE of Examples 1, 2, 3, 4, and 5, measured at current densities, was increased by 9%, 6%, 3%, 5%, and 4%, respectively, compared to the EQE of Comparative Example 1; the CE of Examples 1, 2, 3, 4, and 5 was increased by 11%, 7%, 2%, 5%, and 6%, respectively, compared to Comparative Example 1; at 10 mA / cm 2 The EQE of Examples 1, 2, 3, 4, and 5, measured at current densities, was 12%, 9%, 6%, 8%, and 7% higher than that of Comparative Example 3, respectively; the CE of Examples 1, 2, 3, 4, and 5 was 13%, 9%, 4%, 7%, and 8% higher than that of Comparative Example 3, respectively, showing a significant improvement; at 10 mA / cm 2 The EQE of Examples 1, 2, 3, 4 and 5 measured at current density were 19%, 16%, 13%, 15% and 14% higher than that of Comparative Example 2, respectively; the CE of Examples 1, 2, 3, 4 and 5 were 18%, 14%, 9%, 12% and 13% higher than that of Comparative Example 2, respectively, with more significant improvements.

[0212] The above data demonstrates that the devices of the present invention exhibit superior luminous efficiency compared to the comparative examples. Specifically, the compounds of the present invention, which are formed by connecting hole transport units with fused macrocyclic structures of naphthalene or carbazole at double α-positions and electron transport units with triazine or similar structures, exhibit different device performance compared to comparative examples A, B, and C due to the altered connecting segments. Unexpectedly, this results in excellent device performance, achieving higher current efficiency and external quantum efficiency, and significantly improving device performance. This demonstrates the unique advantages of the compounds of the present invention.

[0213] It should be understood that the various embodiments described herein are merely examples and are not intended to limit the scope of the invention. Therefore, as will be apparent to those skilled in the art, the claimed invention may include variations of the specific embodiments and preferred embodiments described herein. Many of the materials and structures described herein can be substituted with other materials and structures without departing from the spirit of the invention. It should be understood that various theories regarding why the invention works are not intended to be limiting.

Claims

1. An organic electroluminescent compound having a structure represented by FL-Ar, wherein L is selected from the structures numbered L-1 to L-3 or L-38, or L is selected from the structure obtained by partially or completely replacing hydrogen in any of the structures numbered L-1 to L-3 or L-38 with deuterium: F is selected from the structures shown in F-1, F-73 to F-85, F-142 or F-143, or F is selected from the structures obtained by partially or completely replacing hydrogen with deuterium in any of the structures shown in F-1, F-73 to F-85, F-142 or F-143: Ar is selected from the structures shown in Ar-97 to Ar-108, or Ar is selected from the structures obtained by partially or completely replacing hydrogen with deuterium in any of the structures shown in Ar-97 to Ar-108:

2. The compound according to claim 1, characterized in that, The hydrogen in the compound is partially or completely replaced by deuterium.

3. The compound according to any one of claims 1-2, characterized in that, The compound is selected from compounds numbered C97 to C108, C180 to C192, C249 to C250, C1283, C1381 to C1391, C1463 to C1475, and C1532 to C1533, or the structure obtained by partially or completely replacing hydrogen with deuterium in any structure corresponding to compounds numbered C97 to C108, C180 to C192, C249 to C250, C1283, C1381 to C1391, C1463 to C1475, and C1532 to C153.

4. The use of the compound according to any one of claims 1-3 in the preparation of organic electroluminescent devices.

5. The application according to claim 4, characterized in that, The compound is used as the host material for the light-emitting layer in organic electroluminescent devices.

6. An electroluminescent device, comprising a light-emitting layer, wherein the bulk material of the light-emitting layer contains a compound according to any one of claims 1-3.

7. The electroluminescent device according to claim 6, characterized in that, The device includes an anode, a cathode, and a light-emitting layer disposed between the anode and the cathode.

8. The electroluminescent device according to claim 6, characterized in that, The organic electroluminescent device further includes one or more of the following: a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer.

9. A display component comprising the electroluminescent device according to any one of claims 6-8.

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