An organic electroluminescent compound and an organic electroluminescent device

Abstract

The present invention relates to an organic electroluminescent compound and an organic electroluminescent device. The organic electroluminescent compound of the present invention has a structure represented by F-L-Ar, wherein L has a structure represented by Formula 1 and F has a structure represented by Formula 2. The compound of the present invention can be used as a host material for the light-emitting layer of an organic electroluminescent device, has a significantly reduced evaporation temperature, has better thermal stability, can effectively reduce energy consumption, improve device efficiency, reduce the driving voltage of the device, and can provide better device performance.

Description

Technical Field

[0001] The present invention relates to the technical field of luminescent materials, and particularly to an organic electroluminescent compound and an organic electroluminescent device comprising the compound. Background Art

[0002] Organic electronic devices include but are not limited to the following types: organic light emitting diodes (OLEDs), organic field effect transistors (O-FETs), organic light emitting transistors (OLETs), organic photovoltaic devices (OPVs), dye-sensitized solar cells (DSSCs), organic optical detectors, organic photoreceptors, organic field effect quantum dots (OFQDs), light emitting electrochemical cells (LECs), organic laser diodes, and organic electroluminescent devices.

[0003] In 1987, Tang and Van Slyke of Eastman Kodak reported a bilayer organic electroluminescent device, which included an arylamine hole transport layer and a tris-8-hydroxyquinoline aluminum layer as 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 from the device. This invention laid the foundation for the development of modern organic light emitting diodes (OLEDs). The most advanced ones 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 the anode. Since OLEDs are a self-luminous solid-state device, they offer great potential for display and lighting applications. In addition, the inherent properties of organic materials, such as their flexibility, can make them very suitable for special applications, such as the fabrication on flexible substrates.

[0004] OLEDs can be classified into three different types according to their emission mechanisms. The OLED invented by Tang and Van Slyke is a fluorescent OLED. It only uses singlet emission. The triplets generated in the device are wasted through non-radiative decay channels. Therefore, the internal quantum efficiency (IQE) of fluorescent OLEDs is only 25%. This limitation has hindered the commercialization of OLEDs. In 1997, Forrest and Thompson reported phosphorescent OLEDs, which use triplet emission from heavy metals in complexes as emitters. Therefore, it is able to harvest both singlets and triplets, achieving 100% IQE. Due to its high efficiency, the discovery and development of phosphorescent OLEDs have 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 a small singlet-triplet gap, making it possible for excitons to return from the triplet 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 according to the form of the materials used. Small molecules refer to any organic or organometallic materials that are not polymers. As long as they have an exact structure, the molecular weight of small molecules can be very large. Dendrimers with a well-defined structure are considered small molecules. Polymer OLEDs include conjugated polymers and non-conjugated polymers with side-chain emitting groups. If post-polymerization occurs during the manufacturing process, small molecule OLEDs can turn into polymer OLEDs. There are various OLED manufacturing methods. Small molecule OLEDs are usually manufactured by vacuum thermal evaporation. Polymer OLEDs are manufactured by solution methods such as spin coating, inkjet printing, and nozzle printing. If the materials can be dissolved or dispersed in a solvent, small molecule OLEDs can also be manufactured by solution methods. The emission color of OLEDs can be achieved through the structural design of the emitting materials. OLEDs can include one or more emitting layers to achieve the desired spectrum. Green, yellow, and red OLEDs with phosphorescent materials have been successfully commercialized. Blue phosphorescent devices still have problems such as blue color unsaturation, short device lifetime, and high operating voltage. Commercial full-color OLED displays usually adopt a hybrid strategy, using blue fluorescence and phosphorescent yellow, or red and green. Currently, the rapid decrease in the efficiency of phosphorescent OLEDs at high brightness is still a problem. In addition, there is a desire for a more saturated emission spectrum, higher efficiency, and longer device lifetime.

[0005] Among the numerous host materials reported currently, there is still room for improvement. To meet the increasing demands in the industry, especially for performance requirements such as higher device efficiency, longer device lifetime, and lower driving voltage, new materials still need to be further researched and developed. Summary of the Invention

[0006] The present invention aims to provide organic electroluminescent compounds composed of Y-shaped linked aryl or heteroaryl groups, which can be used as host materials in organic electroluminescent devices. Compared with existing host material compounds, these compounds have significantly lower evaporation temperatures, higher device efficiency, and better thermal stability. They can also effectively reduce energy consumption, facilitate device fabrication, and lower device driving voltage, providing improved device performance.

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

[0008]

[0009] In Formula 1, Ring 1 and Ring 2, when they appear each time, are identical or different and are selected from a carbocycle having 5 to 18 carbon atoms, or a heterocycle having 3 to 18 carbon atoms; wherein A can be arbitrarily selected as a carbon atom or a nitrogen atom;

[0010] R X Each occurrence of the same or different means mono-, poly- or no-substitution;

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

[0012]

[0013] In Formula 2, Ring A, Ring B and Ring C are each identically or differently selected from a carbocycle having 5 to 18 carbon atoms, or a heterocarbocycle having 3 to 18 carbon atoms;

[0014] R Y Each occurrence of the same or different means mono-, poly- or no-substitution;

[0015] Y 1 , Y 2 Each occurrence is selected from NR N or CR Y ;

[0016] Ar has a structure represented by Formula 3:

[0017]

[0018] In formula 3, Z 1 To Z 5 Each occurrence is selected from NR N or CR a R b ;

[0019] In formula 1 to formula 3, R X, R Y , R N , R a and R b are the same or different each time they appear and are selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 - 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 - 20 carbon atoms, substituted or unsubstituted heteroalkyl having 1 - 20 carbon atoms, substituted or unsubstituted heterocycloalkyl having 3 - 20 carbon atoms, substituted or unsubstituted aralkyl having 7 - 30 carbon atoms, substituted or unsubstituted alkoxy having 1 - 20 carbon atoms, substituted or unsubstituted aryloxy having 6 - 30 carbon atoms, substituted or unsubstituted alkenyl having 2 - 20 carbon atoms, substituted or unsubstituted alkynyl having 2 - 20 carbon atoms, substituted or unsubstituted aryl having 6 - 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 - 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 - 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 - 20 carbon atoms, substituted or unsubstituted amino having 0 - 20 carbon atoms, acyl, carbonyl, carboxyl, ester, cyano, isocyano, hydroxyl, mercapto, sulfinyl, sulfonyl, phosphino, and combinations thereof; the substituents for the substitution are selected from hydrogen, deuterium, halogen, alkyl having 1 - 10 carbon atoms, cycloalkyl having 3 - 10 carbon atoms, aryl having 6 - 20 carbon atoms, or heteroaryl having 3 - 20 carbon atoms; adjacent substituents R X , R Y , R N , R a and R b may optionally be joined to form a ring;

[0020] "*" represents the position bonded to F and L, represents the position bonded to L and Ar.

[0021] According to some embodiments of the present invention, in Formula 1, Ring 1 and Ring 2 are each independently 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, Ring 1 and Ring 2 are each independently selected from 5 - membered carbon rings, benzene rings, naphthalene rings, 5 - membered heteroaromatic rings, 6 - membered heteroaromatic rings, benzo - 5 - membered heteroaromatic rings, or fused rings formed by a 5 - membered heteroaromatic ring and a 6 - membered heteroaromatic ring, and the heteroatoms in the heteroaromatic rings are selected from N, O, S, Se, and Si.

[0022] In some embodiments, L is selected each time it appears from the structures represented by Formulas 1 - 1 to 1 - 5:

[0023]

[0024] wherein, X1 to X 6 each occurrence is independently selected from NR N or CR X , R X as defined in formula 1;

[0025] X is each occurrence independently selected from the group consisting of O, S, Se, NR N , CR a , R b and SiR a , R b ; R N , R a and R b are as defined in formula 3.

[0026] Preferably, in formulas 1-1 to 1-5, R N , R a and R b each occurrence is independently selected from the group consisting of hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1-10 carbon atoms, substituted or unsubstituted cycloalkyl having 3-20 carbon atoms, substituted or unsubstituted heteroalkyl having 1-10 carbon atoms, substituted or unsubstituted heterocycloalkyl having 3-10 carbon atoms, substituted or unsubstituted aralkyl having 7-20 carbon atoms, substituted or unsubstituted alkoxy having 1-10 carbon atoms, substituted or unsubstituted aryloxy having 6-20 carbon atoms, substituted or unsubstituted alkenyl having 2-10 carbon atoms, substituted or unsubstituted alkynyl having 2-10 carbon atoms, substituted or unsubstituted aryl having 6-20 carbon atoms, substituted or unsubstituted heteroaryl having 3-20 carbon atoms, substituted or unsubstituted alkylsilyl having 3-10 carbon atoms, substituted or unsubstituted arylsilyl having 6-20 carbon atoms, substituted or unsubstituted amino having 0-10 carbon atoms, acyl, carbonyl, carboxyl, ester, cyano, isocyano, hydroxyl, mercapto, sulfinyl, sulfonyl, phosphino, and combinations thereof; the substituents for said substitution are selected from hydrogen, deuterium, halogen, alkyl having 1-10 carbon atoms, cycloalkyl having 3-10 carbon atoms, aryl having 6-20 carbon atoms, or heteroaryl having 3-20 carbon atoms; adjacent substituents R a and R b are optionally linked to form a ring;

[0027] In some preferred embodiments, L is each occurrence independently selected from the structures represented by formulas 1-1 or 1-5. In some specific embodiments, in formulas 1-1 or 1-5, X 1 to X 6 each occurrence is independently selected from CR X , and X is selected from CRa R b , R X , R a and R b The definition of is the same as above.

[0028] According to a preferred embodiment of the present invention, in Formula 1-1 to Formula 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 to 10 carbon atoms, haloalkyl having 1 to 10 carbon atoms or aryl having 6 to 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, in the compound, the structure of L is: one of the structures shown in numbers L-1 to L-39, or a structure obtained by partially or completely replacing the hydrogen in any of the structures shown in numbers L-1 to L-39 with deuterium; wherein the structures corresponding to numbers L-1 to L-39 are:

[0030]

[0031] In some embodiments, in Formula 2, Ring A, Ring B, and Ring C are each selected from a saturated or unsaturated carbocyclic ring having 5 to 18 carbon atoms, preferably a saturated or unsaturated 5-membered carbocyclic ring, or an aromatic ring having 6 to 18 carbon atoms. Preferably, Ring A, Ring B, and Ring C are each selected from a saturated or unsaturated 5-membered carbocyclic ring or a benzene ring, the same or different as each other.

[0032] In some embodiments, each occurrence of F is selected from the structures represented by Formula 2-1 to Formula 2-3:

[0033]

[0034] Among them, Y 1 To Y 12 Each occurrence is selected from NR N or CR a R b ; R N ,R a and R b The definition of is the same as that of formula 3.

[0035] Preferably, in Formula 2-1 to Formula 2-3, R N ,R a and R bis the same as or different from each occurrence and is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 10 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 10 carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 10 carbon atoms, substituted or unsubstituted heterocycloalkyl having 3 to 10 carbon atoms, substituted or unsubstituted aralkyl having 7 to 20 carbon atoms, substituted or unsubstituted alkoxy having 1 to 10 carbon atoms, substituted or unsubstituted aryloxy having 6 to 20 carbon atoms, substituted or unsubstituted alkenyl having 2 to 10 carbon atoms, substituted or unsubstituted alkynyl having 2 to 10 carbon atoms, substituted or unsubstituted aryl having 6 to 20 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 20 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 10 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 10 carbon atoms, acyl, carbonyl, carboxyl, ester, cyano, isocyano, hydroxyl, mercapto, sulfinyl, sulfonyl, phosphino, and combinations thereof. Adjacent substituents R a and R b optionally join to form a 3- to 15-membered ring, such as a benzene ring or a naphthalene ring.

[0036] In some preferred embodiments, in Formulas 2-1 to 2-3, Y 1 and Y 2 are the same as or different from each occurrence and are each independently selected from CR a R b ; the definitions of R a and R b are the same as those in Formula 3.

[0037] In some preferred embodiments, F is selected from the structure shown in Formula 2-1. Preferably, in Formula 2-1, Y 1 to Y 12 are the same as or different from each occurrence and are each independently selected from CR a R b , and the definitions of R a and R b are the same as those in Formula 3.

[0038] In some embodiments, in Formulas 2-1 to 2-3, Y 1 to Y 12 are the same as or different from each occurrence and are each independently selected from CR a R b , and the definitions of R a and R bHydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 - 20 carbon atoms, substituted or unsubstituted alkenyl having 2 - 20 carbon atoms, or substituted or unsubstituted aryl having 6 - 30 carbon atoms, wherein the substituents for substitution are selected from hydrogen, deuterium, halogen, alkyl having 1 - 10 carbon atoms, cycloalkyl having 3 - 10 carbon atoms, aryl having 6 - 20 carbon atoms, or heteroaryl having 3 - 20 carbon atoms. Preferably, R a and R b each independently is selected from hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 - 10 carbon atoms, substituted or unsubstituted alkenyl having 2 - 10 carbon atoms, or aryl having 6 - 20 carbon atoms. More preferably, R a and R b each independently is selected from hydrogen, deuterium, fluorine, chlorine, bromine, methyl, ethyl, propyl, isopropyl, tert - butyl, vinyl, propenyl, trifluoromethyl, phenyl, naphthyl, and biphenyl.

[0039] In some embodiments, the structure of F is one of the structures shown by No. F - 1 to No. F - 36, or a structure obtained by partially or fully substituting hydrogen in any of the structures shown by No. F - 1 to No. F - 36 with deuterium; wherein the structures corresponding to No. F - 1 to No. F - 36 are in sequence:

[0040]

[0041]

[0042] In some embodiments, in the compound, Ar is selected from the structures represented by Formula 3 - 1 to Formula 3 - 8 each time it appears:

[0043]

[0044] wherein, Z 1 to Z 5 each time it appears is selected from CR a R b , R a and R b are as defined in Formula 3, and adjacent substituents R a and R b can optionally be connected to form a saturated or unsaturated 3 - 15 - membered ring.

[0045] In some preferred embodiments, Ar is selected from the structure shown by Formula 3 - 1.

[0046] Preferably, in Formula 3 - 1 to Formula 3 - 8, R a and R bEach independently selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1-10 carbon atoms, substituted or unsubstituted alkenyl having 1-10 carbon atoms, substituted or unsubstituted aryl having 6-18 carbon atoms, substituted or unsubstituted heteroaryl having 3-18 carbon atoms, mercapto or hydroxy, and the substituents for the substitution are selected from deuterium, halogen, alkyl having 1-5 carbon atoms, aryl having 6-15 carbon atoms or heteroaryl having 3-15 carbon atoms.

[0047] Preferably, in Formula 3-1 to Formula 3-8, R a and R b Each 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 triazinyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolyl, mercapto, hydroxy, and the substituents for the substitution are selected from deuterium, fluorine, methyl, ethyl, isopropyl, tert-butyl, phenyl, biphenyl, naphthyl, benzofuranyl, benzothiophenyl, fluorenyl, dibenzofuranyl, dibenzothiophenyl or carbazolyl.

[0048] In some embodiments, the structure of Ar is: one of the structures shown by Ar-1 to Ar-108, or a structure obtained by partially or completely substituting hydrogen in any of the structures shown by Ar-1 to Ar-108 with deuterium; wherein, the structures corresponding to Ar-1 to Ar-108 are in sequence:

[0049]

[0050]

[0051]

[0052]

[0053] In some preferred embodiments, in the above Formula 1 to Formula 3, Formula 1-1 to Formula 1-5, Formula 2-1 to 2-3 and Formula 3-1 to 3-8, R X 、R Y 、R N 、R a and R bis the same as or different from each occurrence and is selected from the group consisting of hydrogen, deuterium, halogen, substituted or unsubstituted heteroalkyl having 1-20 carbon atoms, substituted or unsubstituted heterocycloalkyl having 3-20 carbon atoms, substituted or unsubstituted aralkyl having 7-30 carbon atoms, substituted or unsubstituted alkoxy having 1-20 carbon atoms, substituted or unsubstituted aryloxy having 6-30 carbon atoms, substituted or unsubstituted alkenyl having 2-20 carbon atoms, substituted or unsubstituted aryl having 6-30 carbon atoms, substituted or unsubstituted heteroaryl having 3-30 carbon atoms, substituted or unsubstituted amino having 0-20 carbon atoms, acyl, carbonyl, carboxyl, ester, cyano, isocyano, hydroxyl, mercapto, sulfinyl, sulfonyl, phosphino, and combinations thereof. Preferably, R X 、R Y 、R N 、R a and R b are at least one selected from deuterium, substituted or unsubstituted aryl having 6-30 carbon atoms, substituted or unsubstituted heteroaryl having 3-30 carbon atoms. More preferably, R X 、R Y 、R N 、R a and R b are at least one selected from deuterium, phenyl, biphenyl, naphthyl or pyridyl.

[0054] In some embodiments, the compound has the structure of F-L-Ar, where F is selected from the group consisting of the structures shown by F-1 to F-36, L is selected from the group consisting of the structures shown by L-1 to L-39, and Ar is selected from the group consisting of the structures shown by Ar-1 to Ar-108; optionally, the hydrogen in the structures shown by F-1 to F-36, the structures shown by L-1 to L-39, and the structures shown by Ar-1 to Ar-108 is partially or completely replaced by deuterium.

[0055] In some specific embodiments, the compound is selected from the following structures: the structures corresponding to Compound No. C1 to Compound No. C891, and the structures obtained by partially or completely replacing the hydrogen in any of the structures corresponding to Compound No. C1 to Compound No. C891 with deuterium; the structures shown by Compound No. C1 to Compound No. C891 have the structure of F-L-Ar, where F, L, and Ar respectively correspond to the structures selected from Table 1 below.

[0056] Table 1

[0057]

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068] In a second aspect, the present invention provides the use of the above-mentioned organic electroluminescent compound in the preparation of an organic electroluminescent device.

[0069] Preferably, the compound is used as a host material for the light-emitting layer in the organic electroluminescent device.

[0070] In a third aspect, the present invention provides an organic electroluminescent device, comprising a light-emitting layer, wherein the host material of the light-emitting layer contains the organic electroluminescent compound described in the first aspect of the present invention.

[0071] Preferably, the organic electroluminescent device includes an anode, a cathode, and a light-emitting layer disposed between the anode and the cathode. In some embodiments, the light-emitting layer further includes a dopant. In some embodiments, the dopant included in the organic electroluminescent device of the present invention can be at least one phosphorescent or fluorescent dopant, preferably a phosphorescent dopant. The phosphorescent dopant material is not particularly limited, but can preferably be selected from metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu), and platinum (Pt), more preferably from ortho-metalated complex compounds of iridium (Ir), osmium (Os), copper (Cu), and platinum (Pt), and even more preferably ortho-metalated iridium complex compounds. 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%, and more preferably 2 wt% to 8 wt%.

[0072] Preferably, the organic electroluminescent device further includes one or more of 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.

[0073] In a fourth aspect, the present invention provides a display component / device, which includes 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.

[0074] The beneficial effects of the present invention are as follows: The novel organic electroluminescent compound disclosed in the present invention, which is bonded by an aryl or heteroaryl group with a "Y" shape, can be used as a host material in an electroluminescent device. The compounds designed in this way connect the hole transport unit and the electron transport unit through a "Y" shape, endowing these compound molecules with a special spatial structure, bringing unexpected effects, making this novel compound have a significantly reduced evaporation temperature, effectively improving the device efficiency, having better thermal stability, effectively reducing energy consumption, being beneficial to the device manufacturing process, and also being able to provide better device performance. Description of the Drawings

[0075] Figure 1 It is a schematic diagram of an organic light-emitting device in a specific embodiment of the present invention.

[0076] Figure 2 It is a schematic diagram of an organic light-emitting device in another specific embodiment of the present invention.

[0077] The reference numerals are as follows:

[0078] 100, the first organic light-emitting device; 101, the substrate; 102, the encapsulation layer; 110, the anode; 120, the hole injection layer; 130, the hole transport layer; 140, the electron blocking layer; 150, the light-emitting layer; 160, the hole blocking layer; 170, the electron transport layer; 180, the electron injection layer; 190, the cathode; 200, the second organic light-emitting device. Detailed Embodiments

[0079] OLEDs can be fabricated on various substrates, such as glass, plastic, and metal. Figure 1 Schematically and non-limitingly shows the first organic light-emitting device 100. The figures are not necessarily drawn to scale, and some layer structures in the figures can also be omitted as needed. The device 100 can 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. The device 100 can be fabricated by sequentially depositing the described layers. The properties and functions of each layer and exemplary materials are described in more detail in columns 6-10 of US Patent No. 7,279,704B2, and the entire content of the above patent is incorporated herein by reference.

[0080] Each of these layers has more instances. For example, U.S. Patent No. 5,844,363, incorporated herein by reference in its entirety, discloses a flexible and transparent substrate-anode combination. 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, incorporated herein by reference in its entirety. Examples of host materials are disclosed in U.S. Patent No. 6,303,238, issued to Thompson et al., 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, incorporated herein by reference in its entirety. U.S. Patents Nos. 5,703,436 and 5,707,745, incorporated herein by reference in their entireties, disclose examples of cathodes that include a composite cathode having a thin layer of a metal such as Mg:Ag and an overlying 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, incorporated herein by reference in their entireties. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004 / 0174H6, incorporated herein by reference in its entirety. A description of the protective layer can be found in U.S. Patent Application Publication No. 2004 / 0174H6, incorporated herein by reference in its entirety.

[0081] The above-described layered structure is provided by way of non-limiting examples. The function of the OLED can be achieved by combining the various layers described above, or some layers can be completely omitted. It can 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 can include several sub-layers. For example, the light-emitting layer can have two different light-emitting materials to achieve a desired emission spectrum.

[0082] In one embodiment, the OLED can be described as having an "organic layer" disposed between the cathode and the anode. The organic layer can include one or more layers.

[0083] The OLED also requires a encapsulation layer, as Figure 2 Schematically and non-limitingly shows a second organic light-emitting device 200, which is Figure 1In contrast, a encapsulation layer 102 may also be included on the cathode 190 to prevent harmful substances from the environment, such as moisture and oxygen. Any material capable of providing an encapsulation function 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 US7,968,146B2, the entire content of which is incorporated herein by reference.

[0084] Devices manufactured in accordance with embodiments of the present invention can be incorporated into a variety of consumer products having one or more electronic component modules (or units) with the device. 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, smart phones, tablet computers, phablets, wearable devices, smart watches, laptop computers, digital cameras, portable video cameras, viewfinders, microdisplays, 3-D displays, vehicle displays, and taillights.

[0085] The materials and structures described herein can also be used in other organic electronic devices listed above.

[0086] As used herein, "top" means furthest from the substrate, and "bottom" means closest to the substrate. In the case where a first layer is described as "disposed" "on" a second layer, the first layer is disposed further from the substrate. Unless it is specified that the first layer "contacts" the second layer, other layers may exist between the first and second layers. For example, even though there are various organic layers between the cathode and the anode, the cathode can still be described as "disposed on" the anode.

[0087] As used herein, "solution processable" means capable of being dissolved, dispersed, or transported in a liquid medium in the form of a solution or suspension and / or deposited from a liquid medium.

[0088] When a ligand is believed to directly contribute to the photosensitive properties of an emissive material, the ligand can be referred to as "photosensitive". When a ligand is believed not to contribute to the photosensitive properties of an emissive material, the ligand can be referred to as "auxiliary", but an auxiliary ligand can modify the properties of a photosensitive ligand.

[0089] It is believed that the internal quantum efficiency (IQE) of a fluorescent OLED can exceed the 25% spin statistical limit by delayed fluorescence. Delayed fluorescence can generally be divided into two types, namely p-type delayed fluorescence and E-type delayed fluorescence. P-type delayed fluorescence is generated by triplet-triplet annihilation (TTA).

[0090] On the other hand, E-type delayed fluorescence does not rely on the collision of two triplets, but rather on the conversion between the triplet state and the singlet excited state. Compounds capable of generating E-type delayed fluorescence need to have an extremely small singlet-triplet gap for the energy state conversion. Thermal energy can activate the transition from the triplet state back to the singlet state. This type of delayed fluorescence is also known as thermally activated delayed fluorescence (TADF). A remarkable feature of TADF is that the delayed component increases with increasing temperature. If the rate of reverse intersystem crossing (RISC) is fast enough to minimize the non-radiative decay from the triplet state, the fraction of singlet excited state re-population can reach 75%. The total singlet fraction can be 100%, far exceeding the 25% of the spin statistics of electro-generated excitons.

[0091] The characteristics of E-type delayed fluorescence can be found in exciplex systems or single compounds. Without being bound by theory, it is believed that E-type delayed fluorescence requires the luminescent material to have a small singlet-triplet energy gap (ΔE S-T ). Organic non-metal-containing donor-acceptor luminescent materials may be able to achieve this. The emission of these materials is usually characterized as donor-acceptor charge transfer (CT) type emission. The spatial separation of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) in these donor-acceptor type compounds usually results in a small ΔE S-T . These states can include CT states. Generally, donor-acceptor luminescent materials are constructed by connecting an electron donor moiety (such as an amino or carbazole derivative) to an electron acceptor moiety (such as an N-containing six-membered aromatic ring).

[0092] Definition of substituent terms

[0093] Halogen or halide - as used herein, includes fluorine, chlorine, bromine, and iodine.

[0094] Alkyl - as used herein, includes straight-chain and branched-chain alkyls. The alkyl can be an alkyl having 1 to 20 carbon atoms, preferably an alkyl having 1 to 12 carbon atoms, more preferably an alkyl having 1 to 6 carbon atoms. Examples of alkyls include methyl, ethyl, propyl, isopropyl, 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-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, neopentyl, 1-methylpentyl, 2-methylpentyl, 1-pentylhexyl, 1-butylpentyl, 1-heptyloctyl, 3-methylpentyl. Additionally, the alkyl can be optionally substituted. Among the above, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, and n-hexyl are preferred. Additionally, the alkyl can be optionally substituted.

[0095] Cycloalkyl - as used herein, cycloalkyl includes cyclic alkyl groups. The cycloalkyl can be a cycloalkyl having 3 to 20 ring carbon atoms, preferably a cycloalkyl having 4 to 10 carbon atoms. Examples of cycloalkyl 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. Additionally, the cycloalkyl can be optionally substituted.

[0096] Heteroalkyl - as used herein, heteroalkyl is formed by replacing one or more carbons in an alkyl chain with heteroatoms selected from the group consisting of nitrogen atom, oxygen atom, sulfur atom, selenium atom, phosphorus atom, silicon atom, germanium atom, and boron atom. The heteroalkyl can be a heteroalkyl having 1 to 20 carbon atoms, preferably a heteroalkyl having 1 to 10 carbon atoms, more preferably a heteroalkyl having 1 to 6 carbon atoms. Examples of heteroalkyl include methoxymethyl, ethoxymethyl, ethoxyethyl, methylthiomethyl, ethylthiomethyl, ethylthioethyl, methoxymethoxymethyl, ethoxymethoxymethyl, ethoxyethoxyethyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, mercaptomethyl, mercaptoethyl, mercaptopropyl, aminomethyl, aminoethyl, aminopropyl, dimethylaminomethyl, trimethylsilyl, dimethylethylsilyl, dimethylisopropylsilyl, tert - butyldimethylsilyl, triethylsilyl, triisopropylsilyl, trimethylsilylmethyl, trimethylsilylethyl, trimethylsilylisopropyl. Additionally, the heteroalkyl can be optionally substituted.

[0097] Alkenyl - as used herein, encompasses straight - chain, branched - chain, and cyclic olefin groups. The alkenyl can be an alkenyl having 2 to 20 carbon atoms, preferably an alkenyl having 2 to 10 carbon atoms. Examples of alkenyl include vinyl, propenyl, 1 - butenyl, 2 - butenyl, 3 - butenyl, 1,3 - butadienyl, 1 - methylvinyl, styryl, 2,2 - diphenylethylenyl, 1,2 - diphenylethylenyl, 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, cycloheptatrienyl, cyclooctenyl, cyclooctatetraenyl, and norbornenyl. Additionally, the alkenyl can be optionally substituted.

[0098] Alkynyl - As used herein, it encompasses straight-chain alkynyl. The alkynyl can be an alkynyl having 2 to 20 carbon atoms, preferably an alkynyl having 2 to 10 carbon atoms. Examples of alkynyl include ethynyl, propynyl, propargyl, 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, phenylacetylenyl, phenylpropargyl, etc. Among the above, ethynyl, propynyl, propargyl, butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, phenylacetylenyl are preferred. Additionally, the alkynyl can be optionally substituted.

[0099] Aryl or aromatic group - As used herein, non-fused and fused systems are considered. The aryl can be an aryl having 6 to 30 carbon atoms, preferably an aryl having 6 to 20 carbon atoms, more preferably an aryl having 6 to 12 carbon atoms. Examples of aryl include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthyl, anthracenyl, phenalenyl, phenanthrenyl, fluorenyl, pyrenyl, yl, perylenyl, and azulyl, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorenyl, and naphthyl. Additionally, the aryl can be optionally substituted. Examples of non-fused aryl include phenyl, 2-biphenylyl, 3-biphenylyl, 4-biphenylyl, 4-p-terphenyllyl, 3-p-terphenyllyl, 2-p-terphenyllyl, 4-m-terphenyllyl, 3-m-terphenyllyl, 2-m-terphenyllyl, o-tolyl, m-tolyl, p-tolyl, p-(2-phenylpropyl)phenyl, 4'-methylbiphenylyl, 4''-tert-butyl-4-p-terphenyllyl, o-cumyl, m-cumyl, p-cumyl, 2,3-dimethylphenyl, 3,4-dimethylphenyl, 2,5-dimethylphenyl, mesityl, and m-tetraphenylyl. Additionally, the aryl can be optionally substituted.

[0100] Heterocyclic group or heterocycle - As used herein, non-aromatic cyclic groups are considered. The non-aromatic heterocyclic group includes saturated heterocyclic groups having 3 - 20 ring atoms and unsaturated non-aromatic heterocyclic groups having 3 - 20 ring atoms, where at least one ring atom is selected from the group consisting of nitrogen atom, oxygen atom, sulfur atom, selenium atom, silicon atom, phosphorus atom, germanium atom, and boron atom. Preferred non-aromatic heterocyclic groups are those having 3 to 7 ring atoms, which include at least one heteroatom such as nitrogen, oxygen, silicon, or sulfur. Examples of non-aromatic heterocyclic groups include oxiranyl, oxetanyl, tetrahydrofuranyl, tetrahydropyranyl, dioxolanyl, dioxanyl, aziridinyl, dihydropyrrolyl, tetrahydropyrrolyl, piperidinyl, oxazolidinyl, morpholinyl, piperazinyl, oxepinyl, thiepinyl, azepinyl, and tetrahydrothienyl. Additionally, the heterocyclic group can be optionally substituted.

[0101] Heteroaryl - As used herein, it can include non - fused and fused heteroaromatic groups containing 1 to 5 heteroatoms, where at least one heteroatom is selected from the group consisting of nitrogen atom, oxygen atom, sulfur atom, selenium atom, silicon atom, phosphorus atom, germanium atom and boron atom. Isoaryl also refers to heteroaryl. The heteroaryl can be a heteroaryl having 3 to 30 carbon atoms, preferably a heteroaryl having 3 to 20 carbon atoms, more preferably a heteroaryl having 3 to 12 carbon atoms. Suitable heteroaryls include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridoindole, pyrrolopyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indenoazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, benzofuranopyridine, furanodipyridine, benzothiophenopyridine, thiophenodipyridine, benzoselenophenopyridine, selenophenodipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2 - azaborolane, 1,3 - azaborolane, 1,4 - azaborolane, borazole and their nitrogen - containing analogs. Additionally, the heteroaryl can be optionally substituted.

[0102] Alkoxy - As used herein, it is represented by - O - alkyl, - O - cycloalkyl, - O - heteroalkyl or - O - heterocycloalkyl. Examples and preferred examples of alkyl, cycloalkyl, heteroalkyl and heterocycloalkyl are the same as those described above. The alkoxy can be an alkoxy having 1 to 20 carbon atoms, preferably an alkoxy having 1 to 6 carbon atoms. Examples of alkoxy include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, tetrahydrofuryloxy, tetrahydropyranyloxy, methoxypropyloxy, ethoxyethyloxy, methoxymethyloxy and ethoxymethyloxy. Additionally, the alkoxy can be optionally substituted.

[0103] Aryloxy - As used herein, it is represented by - O - aryl or - O - heteroaryl. Examples and preferred examples of aryl and heteroaryl are the same as those described above. The aryloxy can be an aryloxy having 6 to 30 carbon atoms, preferably an aryloxy having 6 - 20 carbon atoms. Examples of aryloxy include phenoxy and biphenyloxy. Additionally, the aryloxy can be optionally substituted.

[0104] Aralkyl - As used herein, it encompasses alkyl substituted by an aryl. The aralkyl can be an aralkyl having 7 to 30 carbon atoms, preferably an aralkyl having 7 to 20 carbon atoms, more preferably an aralkyl having 7 to 13 carbon atoms. Examples of aralkyl 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, 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 aralkyl can be optionally substituted.

[0105] Alkylsilyl - As used herein, it encompasses silyl substituted by an alkyl. The alkylsilyl can be an alkylsilyl having 3 - 20 carbon atoms, preferably an alkylsilyl having 3 to 10 carbon atoms. Examples of alkylsilyl include trimethylsilyl, triethylsilyl, methyldiethylsilyl, ethyldimethylsilyl, tripropylsilyl, tributylsilyl, triisopropylsilyl, methyldiisopropylsilyl, dimethylisopropylsilyl, tri-tert-butylsilyl, triisobutylsilyl, dimethyl-tert-butylsilyl, methyl-di-tert-butylsilyl. Additionally, the alkylsilyl can be optionally substituted.

[0106] Arylsilyl - As used herein, it encompasses silyl substituted by at least one aryl. The arylsilyl can be an arylsilyl having 6 - 30 carbon atoms, preferably an arylsilyl having 8 to 20 carbon atoms. Examples of arylsilyl include triphenylsilyl, phenyldibiphenylsilyl, diphenylbiphenylsilyl, phenyldiethylsilyl, diphenylethylsilyl, phenyldimethylsilyl, diphenylmethylsilyl, phenyldiisopropylsilyl, diphenylisopropylsilyl, diphenylbutylsilyl, diphenylisobutylsilyl, diphenyl-tert-butylsilyl, tri-tert-butylsilyl, dimethyl-tert-butylsilyl, methyl-di-tert-butylsilyl. Additionally, the arylsilyl can be optionally substituted.

[0107] In terms such as azadibenzofuran and azadibenzothiophene, the term "aza" means that one or more C-H groups in the corresponding aromatic moiety are replaced by nitrogen atoms. For example, azatriphenylene includes dibenzo[f,h]quinoline, dibenzo[f,h]quinoline and other analogs having two or more nitrogens in the ring system. Those of ordinary skill in the art can readily envision other nitrogen analogs of the above-described aza derivatives, and all such analogs are determined to be included within the terms described herein.

[0108] In the present disclosure, unless otherwise defined, when any one of the terms consisting of the following group is used: substituted alkyl, substituted cycloalkyl, substituted heteroalkyl, substituted heterocyclic group, substituted aralkyl, substituted alkoxy, substituted aryloxy, substituted alkenyl, substituted alkynyl, substituted aryl, substituted heteroaryl, substituted alkylsilyl, substituted arylsilyl, substituted amino, substituted acyl, substituted carbonyl, substituted carboxyl group, substituted ester group, substituted sulfinyl, substituted sulfonyl, substituted phosphino, it means that any one of the groups alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, alkenyl, aryl, heteroaryl, alkylsilyl, arylsilyl, amino, acyl, carbonyl, carboxyl group, ester group, sulfinyl, sulfonyl and phosphino can be substituted by one or more selected from deuterium, halogen, unsubstituted alkyl having 1-20 carbon atoms, unsubstituted cycloalkyl having 3-20 ring carbon atoms, unsubstituted heteroalkyl having 1-20 carbon atoms, unsubstituted heterocyclic group having 3-20 ring atoms, unsubstituted aralkyl having 7-30 carbon atoms, unsubstituted alkoxy having 1-20 carbon atoms, unsubstituted aryloxy having 6-30 carbon atoms, unsubstituted alkenyl having 2-20 carbon atoms, unsubstituted alkynyl having 2-20 carbon atoms, unsubstituted aryl having 6-30 carbon atoms, unsubstituted heteroaryl having 3-30 carbon atoms, unsubstituted alkylsilyl having 3-20 carbon atoms, unsubstituted arylsilyl having 6-20 carbon atoms, unsubstituted amino having 0-20 carbon atoms, acyl, carbonyl, carboxyl group, ester group, cyano, isocyano, hydroxy, mercapto, sulfinyl, sulfonyl, phosphino and combinations thereof.

[0109] It should be understood that when a molecular moiety is described as a substituent or otherwise attached to another moiety, its name can be written according to whether it is a moiety (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or according to whether it is the entire molecule (such as benzene, naphthalene, dibenzofuran). As used herein, these different ways of specifying a substituent or a linking moiety are considered equivalent.

[0110] In the compounds mentioned in the present disclosure, hydrogen atoms can be partially or fully replaced by deuterium. Other atoms such as carbon and nitrogen can also be replaced by their other stable isotopes. Due to enhancing the efficiency and stability of the device, the replacement of other stable isotopes in the compounds may be preferred.

[0111] In the compounds mentioned in the present disclosure, multiple substitution refers to the range including double substitution up to the maximum available substitution. When a certain substituent in the compounds mentioned in the present disclosure indicates multiple substitution (including disubstitution, trisubstitution, tetrasubstitution, etc.), it means that the substituent can exist at multiple available substitution positions on its connecting structure, and the substituent existing at multiple available substitution positions can be of the same structure or different structures.

[0112] In the compounds mentioned in the present disclosure, unless explicitly defined, for example, adjacent substituents can optionally be connected to form a ring, adjacent substituents in the compounds cannot be connected to form a ring. In the compounds mentioned in the present disclosure, adjacent substituents can optionally be connected to form a ring, which includes both the case where adjacent substituents can be connected to form a ring and the case where adjacent substituents are not connected to form a ring. When adjacent substituents can optionally be connected to form a ring, the formed ring can be a monocyclic or polycyclic ring, and an alicyclic, heteroalicyclic, aromatic or heteroaromatic ring. In this expression, 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.

[0113] The expression that adjacent substituents can optionally be connected to form a ring is also intended to be considered as referring to two substituents bonded to the same carbon atom being connected to each other by a chemical bond to form a ring, which can be exemplified by the following formula:

[0114]

[0115] The expression that adjacent substituents can optionally be connected to form a ring is also intended to be considered as referring to two substituents bonded to carbon atoms directly bonded to each other being connected to each other by a chemical bond to form a ring, which can be exemplified by the following formula:

[0116]

[0117] In addition, the expression that adjacent substituents can optionally be connected to form a ring is also intended to be considered as referring to the case where, when one of the two substituents bonded to carbon atoms directly bonded to each other represents hydrogen, the second substituent is bonded to the position where the hydrogen atom is bonded, thereby forming a ring. This is exemplified by the following formula:

[0118]

[0119] The materials for specific layers in the organic light-emitting devices described in the present invention can be used in combination with various other materials present in the devices. The combinations of these materials are described in detail in paragraphs 0132 - 0161 of US Patent Application US2016 / 0359122M, the entire content of which is incorporated herein by reference. The materials described or mentioned therein are non-limiting examples of materials that can be used in combination with the compounds disclosed herein, and those skilled in the art can easily consult the literature to identify other materials that can be used in combination.

[0120] The materials described herein as being useful for specific layers in organic light-emitting devices can be used in combination with a variety of other materials present in the devices. For example, the compounds disclosed herein can be combined with a variety of hosts, transport layers, blocking layers, injection layers, electrodes, and other layers that may be present. The combinations of these materials are described in detail in paragraphs 0080 - 0101 of US Patent Application US2015 / 0349273M, the entire content of which is incorporated herein by reference. The materials described or mentioned therein are non-limiting examples of materials that can be used in combination with the compounds disclosed herein, and those skilled in the art can easily consult the literature to identify other materials that can be used in combination.

[0121] 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 received from commercial sources. The synthesized products were subjected to structure confirmation and property testing using one or more conventional devices in the art (including but not limited to Agilent's liquid chromatograph, liquid chromatography-mass spectrometry, gas chromatography-mass spectrometry, differential scanning calorimeter, fluorescence spectrophotometer, electrochemical workstation, sublimator, etc.) by methods well-known to those skilled in the art. In the examples of devices, the properties of the devices were also tested using conventional devices in the art (including but not limited to the evaporation coater produced by Nanjing Microelectronics Institute, the optical testing system and lifetime testing system produced by Suzhou Fosida, the ellipsometer produced by Wuhan Yiguang Technology Co., Ltd., etc.) by methods well-known to those skilled in the art. Since those skilled in the art are aware of the relevant content such as the use of the above devices and testing methods and can obtain the inherent data of the samples determinately and without interference, the above relevant content will not be elaborated further in this patent.

[0122] Examples of material synthesis:

[0123] The preparation method of the compounds of the present invention is not limited. Typically but not restrictively, the following compounds are taken as examples, and their synthetic routes and preparation methods are as follows:

[0124] Synthesis Example 1: Synthesis of Compound C97

[0125] Synthesis of Intermediate 1:

[0126]

[0127] Under a nitrogen atmosphere, 2-nitro-1-naphthol (18.9 g, 0.1 mol), dimethylaminopyridine (1.22 g, 0.01 mol), and 200 mL of dichloromethane were placed in a three-necked flask. The temperature was rapidly lowered, and triethylamine (12.14 g, 0.12 mol) was added dropwise at 0 °C. After stirring at a controlled temperature for half an hour, trifluoromethanesulfonic anhydride (33.85 g, 0.12 mo1) was slowly added dropwise, and the reaction was carried out at room temperature for 6 hours. It was extracted with dichloromethane and water, and the organic phase was desolvated. Purification by column chromatography gave Compound 1 (28.5 g, yield 89%).

[0128] Synthesis of Intermediate 2:

[0129]

[0130] Under a nitrogen atmosphere, Compound 1 (32.1 g, 0.1 mol), 2-bromophenylboronic acid (24.1 g, 0.12 mol), tetrakis(triphenylphosphine)palladium (5.78 g, 5 mmol), sodium carbonate (26.5 g, 0.25 mol), 300 mL of toluene, 150 mL of ethanol, and 150 mL of water were added to a three-necked flask. The mixture was refluxed at 110 °C for 12 hours. The organic layer was extracted with ethyl acetate and water, dried over magnesium sulfate, and desolvated. Purification by column chromatography gave Compound 2 (30.84 g, yield 94%).

[0131] Synthesis of Intermediate 3:

[0132]

[0133] Under a nitrogen atmosphere, Compound 2 (32.8 g, 0.1 mo), 2-aminophenylboronic acid pinacol ester (26.3 g, 0.12 mol), tetrakis(triphenylphosphine)palladium (5.78 g, 5 mmol), potassium carbonate (34.55 g, 0.25 mo1), 300 mL of toluene, 150 mL of ethanol, and 150 mL of water were placed in a three-necked flask, and the mixture was refluxed for 12 hours. The organic layer was extracted with ethyl acetate and water, and the organic phase was dried over magnesium sulfate and desolvated. Purification by column chromatography gave Compound 3 (26.89 g, yield 79%).

[0134] Synthesis of Intermediate 4:

[0135]

[0136] Compound 3 (34 g, 0.1 mol), 350 mL of acetic acid, and 35 mL of sulfuric acid were placed in a single-necked flask. While controlling the temperature at 0 °C, sodium nitrite (8.97 g, 0.13 mol) was slowly added dropwise. After the addition was complete, the mixture was stirred for 2 hours. After the reaction was completed, the product was added dropwise to water, and a large amount of solid precipitated. The solid was filtered and purified by column chromatography to obtain product 4 (3.88 g, yield 12%).

[0137] Synthesis of intermediate 5:

[0138]

[0139] Under a nitrogen atmosphere, compound 4 (3.23 g, 10 mmol), triphenylphosphine (13.1 g, 50 mmol), and 35 mL of o-dichlorobenzene were placed in a three-necked flask and refluxed for 12 hours. After the reaction was completed, o-dichlorobenzene was removed by distillation under reduced pressure, and the mixture was extracted with ethyl acetate and water. The organic layer was dried over magnesium sulfate. The organic phase was concentrated by evaporation and purified by column chromatography to obtain compound 5 (1.16 g, yield 40%).

[0140] Synthesis of intermediate 6:

[0141]

[0142] In a 250 mL dry three-necked flask, 1-bromo-8-chloronaphthalene (5 g, 20.66 mmol), bis(pinacolato)diboron (6.3 g, 24.79 mmol), potassium acetate (4.05 g, 41.32 mmol), Pd(dppf)Cl2 (0.190 g, 0.26 mmol) were added. Nitrogen was purged three times, and 50 mL of 1,4-dioxane was added to the reaction flask. The reaction was carried out for 12 h. The reaction mixture was extracted with ethyl acetate and water, concentrated by evaporation, slurried with heptane for 2 h and then filtered to obtain intermediate 6 (4.4 g, yield 73.8%).

[0143] Synthesis of intermediate 7:

[0144]

[0145] Under nitrogen, 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 palladium tetrakis(triphenylphosphine) (0.9 g, 0.8 mmol) were successively added to a three-necked flask. Dioxane (50 mL) and water (25 mL) were added, and the temperature was controlled at about 110 °C for reaction for 12 hours. After cooling to room temperature, the reaction mixture was extracted with ethyl acetate and water. The organic phase was washed with water until neutral, dried and concentrated by evaporation, slurried with heptane for 2 h and then filtered to obtain white intermediate 7 (3.7 g, yield 52%).

[0146] Synthesis of C97:

[0147]

[0148] Under a nitrogen atmosphere, intermediate 7 (3.42 g, 8.68 mmol), intermediate 5 (2.66 g, 9.12 mmol), (dibenzylideneacetone)dipalladium (0.46 g, 0.8 mmol), sodium tert-butoxide (1.25 g, 13.02 mmol), tri-tert-butylphosphine tetrafluoroborate (5.036 g, 17.36 mmol), and toluene (70 mL) were added sequentially to a three-necked flask. The reaction was controlled at about 200 ° C. for 18 hours, then cooled to room temperature, and ethyl acetate and water were added to extract the reaction solution. The organic phase was desolvated and column chromatography was performed to obtain a bright yellow solid C97 (1.7 g, yield 31%).

[0149] 1 HNMR (400MHz, CDCl3) δ=8.45–8.36(m,4H),8.11–7.97(m,5H),7.89(d,J=5.5Hz,2H),7.83(d ,J=1.3Hz,1H),7.74(dd,J=7.3,1.1Hz,1H),7.68–7.42(m,14H),7.37(dd,J=7.3,6.4Hz,1H).

[0150] MS=648.5

[0151] Synthesis Example 2: Compound C98

[0152]

[0153] 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine, and the appropriate material ratio was selected. Other raw materials and steps were the same as those in Synthesis Example 1 to obtain 3.02 g of yellow solid C98 with a yield of 48%.

[0154] 1 HNMR (400MHz, CDCl3) δ=8.44–8.37(m,2H),8.11–7.94(m,6H),7.89(ddd,J=7.4,5.5,3.3Hz, 2H),7.83(dt,J=7.0,1.3Hz,2H),7.77–7.55(m,8H),7.55–7.41(m,10H),7.41–7.34(m,2H).

[0155] MS=724.7

[0156] Synthesis Example 3: Compound C103

[0157]

[0158] Replace 2-chloro-4,6-diphenyl-1,3,5-triazine with 2-chloro-4-(dibenzo[b,d]furan-1-yl)-6-phenyl-1,3,5-triazine, select an appropriate material ratio, and keep other raw materials and steps the same as in Synthesis Example 1 to obtain 2.1 g of yellow solid C103 with a yield of 33%.

[0159] 1 HNMR(400MHz, CDCl3) δ=8.45–8.37(m,2H),8.09(dd,J=9.0,1.7Hz,2H),8.06–8.01(m,2H),8.01–7.95(m,2H),7.89(ddd,J=7.4,5.5,3.3Hz,2H),7.83(ddd,J=8.6,3.6,1.3Hz,2H),7.74(dd,J=7.3,1.1Hz,1H),7.68–7.55(m,6H),7.55–

[0160] 7.43(m,9H),7.40–7.30(m,2H).

[0161] MS=738.8

[0162] Synthesis Example 4: Compound C107

[0163]

[0164] Replace 2-chloro-4,6-diphenyl-1,3,5-triazine with 2-chloro-4-(dibenzo[b,d]furan-1-yl)-6-(naphthalen-2-yl)-1,3,5-triazine, select an appropriate material ratio, and keep other raw materials and steps the same as in Synthesis Example 1 to obtain 2.81 g of yellow solid C107 with a yield of 41%.

[0165] 1 HNMR(400MHz, CDCl3) δ=8.87(t,J=1.9Hz,1H),8.36(dd,J=9.9,1.9Hz,1H),8.11–7.95(m,8H),7.89(ddd,J=7.5,5.5,3.2Hz,3H),7.83(ddd,J=8.6,3.6,1.3Hz,2H),7.74(dd,J=7.3,1.1Hz,1H),7.68–7.43(m,14H),7.37(dd,J=7.3,6.4Hz,1H),7.33(td,J=8.9,1.3Hz,1H).

[0166] MS=788.9

[0167] Synthesis Example 5: Compound C748

[0168]

[0169] Synthesis steps:

[0170]

[0171] Using 1-chlorocarbazole to replace 1-bromo-8-chloronaphthalene, selecting an appropriate material ratio, and referring to Synthesis Example 1 (see the figure above) for other raw materials and steps, 1.25 g of yellow solid C748 was obtained with a yield of 21%.

[0172] 1 HNMR (400 MHz, CDCl3) δ = 8.39–8.30 (m, 4H), 8.19 (dd, J = 7.9, 1.3 Hz, 1H), 8.13 (dd, J = 6.5, 1.2 Hz, 1H), 8.09 (d, J = 8.2 Hz, 1H), 8.02–7.96 (m, 2H), 7.89 (ddd, J = 7.4, 5.5, 3.3 Hz, 2H), 7.78–7.71 (m, 3H), 7.67–7.59 (m, 3H), 7.55–7.49 (m, 1H), 7.51 (s, 1H), 7.52–7.42 (m, 8H), 7.41 (dd, J = 6.6, 5.7 Hz, 1H), 7.37–7.28 (m, 1H).

[0173] MS = 687.6

[0174] Those skilled in the art should be aware that the above preparation method is only an exemplary example, and those skilled in the art can obtain other compound structures of the present invention by improving it.

[0175] Device Example 1

[0176] First, clean the glass substrate, which has an indium tin oxide (ITO) anode with a thickness of 120 nm, and then treat it with UV ozone and oxygen plasma. After treatment, dry the substrate in a nitrogen-filled glove box to remove moisture, and then mount the substrate on a substrate holder and load it into a vacuum chamber. The following specified organic layers are deposited on the ITO anode by thermal vacuum in sequence at a rate of about 10 -8 Torr Compound HT and NDP-9 are co-evaporated as the hole injection layer (HIL) with a thickness of Compound HT is used as the hole transport layer (HTL) with a thickness of Compound EB is used as the electron blocking layer (EBL) with a thickness of Then, the compound C97 of the present invention as the host and the compound RD as the dopant are co-evaporated and used as the emitting layer (EML) with a thickness of The compound HB is used as the hole blocking layer (HBL) with a thickness of On the hole blocking layer, the compound ET and lithium 8-hydroxyquinoline (Liq) are co-evaporated as the electron transport layer (ETL) with a thickness of Finally, Lithium 8-hydroxyquinoline (Liq) with a thickness of is evaporated as the electron injection layer (EIL), and Aluminum of is evaporated as the cathode. Then, the device is transferred back to the glove box and encapsulated with a glass cover to complete the device.

[0177] Device Example 2

[0178] The implementation of Device Example 2 is the same as that of Device Example 1, except that the compound C98 of the present invention is used instead of the compound C97 of the present invention as the host in the emitting layer (EML).

[0179] Device Example 3

[0180] The implementation of Device Example 3 is the same as that of 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 host in the emitting layer (EML).

[0181] Device Example 4

[0182] The implementation of Device Example 4 is the same as that of 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 host in the emitting layer (EML).

[0183] Device Example 5

[0184] The implementation of Device Example 5 is the same as that of Device Example 1, except that the compound C748 of the present invention is used instead of the compound C97 of the present invention as the host in the emitting layer (EML).

[0185] Device Comparative Example 1

[0186] The implementation of Device Comparative Example 1 is the same as that of Device Example 1, except that the compound A is used instead of the compound C97 of the present invention as the host in the emitting layer (EML).

[0187] Device Comparative Example 2

[0188] The implementation of Device Comparative Example 2 is the same as that of Device Example 1, except that the compound B is used instead of the compound C97 of the present invention as the host in the emitting layer (EML).

[0189] Device Comparative Example 3

[0190] The implementation of Device Comparative Example 3 is the same as that of Device Example 1, except that Compound C is used instead of the compound C97 of the present invention as the host in the emission layer (EML).

[0191] During the experiment, the evaporation temperatures of compounds C97, C98, C103, C107, and C748 were significantly lower than those of compounds A, B, and C. The specific readings are shown in Table 2.

[0192] Table 2 Comparison of evaporation temperatures of materials

[0193] Material Number Evaporation Temperature / °C C97 181 C98 179 C103 187 C107 194 C748 180 Compound A 224 Compound B 215 Compound C 231

[0194] The detailed device layer structure and thickness are shown in Table 3 below. For the layers where more than one material is used, they are doped with different compounds in the recorded weight ratios.

[0195] Table 3 Device structures of device examples and comparative examples

[0196]

[0197] The material structures used in the device are as follows:

[0198]

[0199] Table 4 lists the current efficiency (CE), maximum wavelength (λ 2 ) and external quantum efficiency (EQE) measured under the condition of 10 mA / cm max . In order to better show the data comparison, the CE and EQE data of Comparative Example 2 are set to 100% respectively. The CE and EQE data of Example 1, Example 2, Example 3, Example 4, Example 5, Comparative Example 1, and Comparative Example 3 are all converted relative to the corresponding data of Comparative Example 2. The relevant data and conversion results are shown in Table 4.

[0200] Table 4 Device data

[0201]

[0202] Discussion:

[0203] As shown in Table 4, the maximum wavelengths of the comparative examples and examples basically remain unchanged. The EQEs of Examples 1, 2, 3, 4, and 5 measured at a current density of 10 mA / cm 2 are increased by 5%, 3%, 2%, 1%, and 4% respectively compared with the EQE of Comparative Example 1; the CEs of Examples 1, 2, 3, 4, and 5 are increased by 9%, 7%, 2%, 6%, and 8% respectively compared with Comparative Example 1; at 10 mA / cm 2The EQEs of Examples 1, 2, 3, 4, and 5 measured at the current density were increased by 8%, 6%, 5%, 4%, and 7% respectively compared to that of Comparative Example 3; the CEs of Examples 1, 2, 3, 4, and 5 were increased by 11%, 9%, 4%, 8%, and 10% respectively compared to that of Comparative Example 3, and the improvement was obvious; at 10 mA / cm 2 The EQEs of Examples 1, 2, 3, 4, and 5 measured at the current density were increased by 15%, 13%, 12%, 11%, and 14% respectively compared to that of Comparative Example 2; the CEs of Examples 1, 2, 3, 4, and 5 were increased by 16%, 14%, 9%, 13%, and 15% respectively compared to that of Comparative Example 2, and the improvement was even more obvious; the data indicate that the Examples have more excellent luminous efficiency compared to the Comparative Examples, that is, the compound of the present invention formed by connecting a hole transport unit with a naphthalene or carbazole-linked fused macrocyclic structure at the double α-position and an electron transport unit with a triazine and its similar structure, compared to Comparative Example Compounds A, B, and C, due to the change of the connecting fragment, results in different device performances from those of Compounds A, B, and C, and unexpectedly brings excellent device effects, enabling the device to obtain higher current efficiency and external quantum efficiency, and there is a significant improvement in device performance. This proves the unique advantages of the compound of the present invention.

[0204] It should be understood that the various embodiments described herein are only examples and are not intended to limit the scope of the present invention. Therefore, as will be obvious to those skilled in the art, the claimed invention may include variations of the specific and preferred embodiments described herein. Many of the materials and structures described herein may be replaced with other materials and structures without departing from the spirit of the present invention.

Claims

1. An organic electroluminescent compound having a structure represented by F-L-Ar, wherein, L has a structure represented by Formula 1-1 or Formula 1-5: In Formula 1-1 and Formula 1-5, X 1 to X 6 are each independently selected from CR X , X is selected from CR a R b , R X , R a and R b are each independently selected from the group consisting of: hydrogen, deuterium, fluorine, chlorine, bromine, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, trifluoromethyl, phenyl, naphthyl, and biphenyl; F has a structure represented by Formula 2-1, or a structure obtained by partially or completely replacing hydrogen in the structure represented by Formula 2-1 with deuterium: In Formula 2-1, Y 1 to Y 12 is the same as or different from each other each time it appears and is independently selected from CR a R b R a and R b each independently selected from hydrogen, deuterium, fluorine, chlorine, bromine, methyl, ethyl, propyl, isopropyl, tert-butyl, trifluoromethyl, phenyl, naphthyl and biphenyl; Ar has a structure represented by Formula 3-1: In Formula 3-1, Z 2 and Z 4 are each independently selected from CR a R b , R a and R b are each 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 triazinyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolyl, mercapto, hydroxyl, and the substituents for the substitution are selected from deuterium, fluorine, methyl, ethyl, isopropyl, tert-butyl, phenyl, biphenyl, naphthyl, benzofuranyl, benzothiophenyl, fluorenyl, dibenzofuranyl, dibenzothiophenyl or carbazolyl; "*" indicates the position bonded to F and L, indicating the position bonded to L and Ar.

2. The compound according to claim 1, wherein L is selected from the structures shown by L-1, L-2, L-3, L-38, or a structure obtained by partially or completely replacing hydrogen in the structures shown by L-1, L-2, L-3, L-38 with deuterium:

3. The compound according to claim 2, characterized in that, F is selected from the structures shown by F-1, F-5 to F-11, or a structure obtained by partially or completely replacing hydrogen in the structures shown by F-1, F-5 to F-11 with deuterium:

4. The compound according to claim 1, wherein, In Formula 3-1, Z 2 and Z 4 each independently selected from CR a R b , R a and R b each independently selected from the group consisting of: substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted triazinyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolyl, and the substituents for the substitution are selected from deuterium, fluorine, methyl, ethyl, isopropyl, tert-butyl, phenyl, biphenyl, naphthyl, benzofuranyl, benzothiophenyl, fluorenyl, dibenzofuranyl, dibenzothiophenyl or carbazolyl.

5. The compound according to claim 3, wherein Ar is selected from the structures shown by Ar-97 to Ar-108, or a structure obtained by partially or completely replacing hydrogen in the structures shown by Ar-97 to Ar-108 with deuterium:

6. The compound according to claim 5, wherein F is selected from the group consisting of the structures shown by F-1, F-5 to F-11, L is selected from the group consisting of the structures shown by L-1, L-2, L-3, L-38, and Ar is selected from the group consisting of the structures shown by Ar-97 to Ar-108; optionally, hydrogen in the compound is partially or completely replaced by deuterium.

7. The compound according to claim 5, characterized in that, The compound is selected from the compounds corresponding to C97 to C108, C112 to C118, C716, C717, C748, C846 to C856, C860 to C866 below, or a compound obtained by partially or completely replacing hydrogen in any of the compounds corresponding to C97 to C108, C112 to C118, C716, C717, C748, C846 to C856, C860 to C866 with deuterium; in the compounds C97 to C108, C112 to C118, C716, C717, C748, C846 to C856, C860 to C866, F, L, and Ar respectively correspond to the following structures: 。 8. Use of the compound according to any one of claims 1-7 in the preparation of an organic electroluminescent device.

9. The application according to claim 8, characterized in that, The compound is used as a host material for the light-emitting layer in an organic electroluminescent device.

10. An electroluminescent device, comprising a light-emitting layer, wherein the host material of the light-emitting layer contains the compound according to any one of claims 1-7.

11. The electroluminescent device according to claim 10, wherein, The device includes an anode, a cathode, and a light-emitting layer disposed between the anode and the cathode.

12. The electroluminescent device according to claim 10, wherein The organic electroluminescent device further includes one or more of 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.

13. A display component, which comprises the electroluminescent device according to any one of claims 10-12.

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