A compound and use thereof

Abstract

The present application relates to a kind of compound and its application, the compound has the structure shown in formula (1), X is O or S, L is selected from one of substituted or unsubstituted C5-C60 arylene, substituted or unsubstituted C3-C60 heteroarylene, Ar is selected from one of substituted or unsubstituted C5-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, not selected from phenyl, biphenyl or cyano-substituted phenyl in-L-Ar.The compound provided by the present application can effectively improve the device efficiency when applied to OLED device, reduce driving voltage, and is a kind of electronic transmission material with good performance.

Description

Technical Field

[0001] This invention relates to the field of organic electroluminescence technology, and in particular to a compound and its applications. Background Technology

[0002] Organic light-emitting diodes (OLEDs) are a type of device with a sandwich-like structure, consisting of positive and negative electrode layers and an organic functional material layer sandwiched between them. When a voltage is applied to the electrodes of an OLED device, positive charges are injected from the positive electrode and negative charges from the negative electrode. Under the influence of an electric field, the positive and negative charges migrate, meet, and recombine within the organic layer to emit light. Due to their advantages such as high brightness, fast response, wide viewing angle, simple manufacturing process, and flexibility, OLED devices have attracted significant attention in the fields of new display and lighting technologies. Currently, this technology is widely used in display panels for new lighting fixtures, smartphones, and tablets, and its application is expected to expand further into large-size display products such as televisions. It is a rapidly developing and technologically demanding new display technology.

[0003] As OLED technology continues to advance in both lighting and display fields, research into its core materials is receiving increasing attention. This is because a high-efficiency, long-life OLED device is typically the result of an optimized combination of device structure and various organic materials. This presents chemists with both significant opportunities and challenges in designing and developing functionalized materials with diverse structures. Common functionalized organic materials include: hole injection materials, hole transport materials, hole blocking materials, electron injection materials, electron transport materials, electron blocking materials, as well as luminescent host materials and luminescent guest materials (dyes), etc.

[0004] To fabricate OLED light-emitting devices with lower driving voltages, better luminous efficiency, and longer lifespans, and to continuously improve the performance of OLED devices, innovation is needed not only in OLED device structure and fabrication processes, but also in the continuous research and innovation of optoelectronic functional materials within OLED devices to prepare functional materials with higher performance. Based on this, the OLED materials community has been committed to developing new organic electroluminescent materials to achieve devices with low start-up voltages, high luminous efficiency, and superior lifespans.

[0005] To further meet the ever-increasing demands for the photoelectric performance of OLED devices and the energy-saving requirements of mobile electronic devices, it is necessary to continuously develop new and efficient OLED materials. Among these, developing new electron transport materials with high electron injection capability and high mobility is of great significance. Summary of the Invention

[0006] The purpose of this invention is to provide a compound having high electron injection capability and high electron mobility.

[0007] To achieve this objective, the present invention adopts the following technical solution:

[0008] This invention provides a compound having the structure shown in formula (1);

[0009]

[0010] In equation (1), X is O or S;

[0011] The Ar is selected from one of substituted or unsubstituted C5-C60 aryl groups and substituted or unsubstituted C3-C60 heteroaryl groups; preferably, the Ar is selected from one of substituted or unsubstituted C5-C30 aryl groups and substituted or unsubstituted C3-C30 heteroaryl groups.

[0012] The L is selected from one of single bond, substituted or unsubstituted C5-C60 arylene, and substituted or unsubstituted C3-C60 heteroarylene; preferably, L is selected from one of single bond, substituted or unsubstituted C5-C30 arylene, and substituted or unsubstituted C3-C30 heteroarylene.

[0013] In formula (1), when X is O, the -L-Ar is not selected from phenyl, biphenyl or cyano-substituted phenyl;

[0014] The ring A represents a substituent group fused to a six-membered ring structure composed of X and P, and the ring A is selected from one of substituted or unsubstituted C6-C60 aryl and substituted or unsubstituted C3-C60 heteroaryl; preferably, the ring A is selected from one of substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl.

[0015] When the above-mentioned groups contain substituents, the substituents are selected from one or a combination of at least two of the following: halogen, cyano, carbonyl, C1-C12 chain alkyl, C3-C12 cycloalkyl, C2-C10 alkenyl, C1-C10 alkoxy or thioalkoxy, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 monocyclic aryl or fused-ring aryl, and C3-C30 monocyclic heteroaryl or fused-ring heteroaryl.

[0016] More preferably, the compound represented by formula (1) of the present invention has the structure shown in formula (1-A) or (1-B):

[0017]

[0018] In equations (1-A) and (1-B), the definitions of rings A, L, and Ar are the same as those in equation (1);

[0019] In formula (1-A), -L-Ar is not selected from phenyl, biphenyl or cyano-substituted phenyl.

[0020] More preferably, the compound represented by formula (1) of the present invention has the structure shown in formulas (1-1), (1-2), (1-3), (1-4), (1-5), (1-6), (1-7), or (1-8):

[0021]

[0022] In equations (1-1), (1-2), (1-3), (1-4), (1-5), (1-6), (1-7), and (1-8), the definition of ring A is the same as that in equation (1);

[0023] In formula (1-1), L1 is selected from one of substituted or unsubstituted C3-C60 heteroaryl groups and substituted or unsubstituted C5-C60 aryl groups, and -L-Ar is not selected from phenyl, biphenyl, or cyano-substituted phenyl groups; preferably, L1 is selected from one of substituted or unsubstituted C3-C30 heteroaryl groups and substituted or unsubstituted C5-C30 aryl groups, and -L-Ar is not selected from phenyl, biphenyl, or cyano-substituted phenyl groups;

[0024] In formula (1-2), L2 is selected from one of a single bond, a substituted or unsubstituted C3-C60 heteroaryl group, and a substituted or unsubstituted C5-C60 aryl group. Preferably, L2 is selected from one of a single bond, a substituted or unsubstituted C3-C30 heteroaryl group, and a substituted or unsubstituted C5-C30 aryl group.

[0025] In equation (1-2), Y 1 Y 2 Y 3 Y 4 and Y 5 Each is independently selected from CR1 or N, and Y 1 -Y 5 At least one of them is N, and R1 is independently selected from one of hydrogen, substituted or unsubstituted C1-C12 chain alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C1-C12 chain alkoxy, halogen, cyano, nitro, hydroxyl, substituted or unsubstituted C1-C12 silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, and two adjacent R1s can be fused into a ring;

[0026] In formulas (1-3), L3 is selected from one of a single bond, a substituted or unsubstituted C3-C60 heteroaryl group, and a substituted or unsubstituted C5-C60 aryl group. Preferably, L3 is selected from one of a single bond, a substituted or unsubstituted C3-C30 heteroaryl group, and a substituted or unsubstituted C5-C30 aryl group.

[0027] In equation (1-3), Z 1 Z 2 Z 3 and Z 4 Each R2 is independently selected from CR2 or N, and R2 is independently selected from hydrogen, substituted or unsubstituted C1-C12 chain alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C1-C12 chain alkoxy, halogen, cyano, nitro, hydroxyl, substituted or unsubstituted C1-C12 silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl. Two adjacent R2s can be fused into a ring.

[0028] In formulas (1-4), L4 is selected from one of substituted or unsubstituted C6-C60 arylene or substituted or unsubstituted C3-C60 heteroarylene. Preferably, L4 is selected from one of substituted or unsubstituted C6-C30 arylene or substituted or unsubstituted C3-C30 heteroarylene.

[0029] In formulas (1-4), R is selected from H, deuterium, substituted or unsubstituted C1-C12 chain alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C1-C12 chain alkoxy, substituted or unsubstituted C3-C12 cycloalkoxy, substituted or unsubstituted C1-C12 silyl, halogen, carbonyl, cyano, hydroxyl, nitro, amino, acyl, substituted or unsubstituted C6-C60 aryl, and substituted or unsubstituted C3-C60 heteroaryl. When there are multiple Rs, adjacent Rs can be fused together. n is an integer from 1 to 5. And when L4 is a C6 arylene, R is not selected from H.

[0030] In formulas (1-5), L5 is selected from one of substituted or unsubstituted C3-C60 heteroaryl groups and substituted or unsubstituted C5-C60 aryl groups; preferably, L5 is selected from one of substituted or unsubstituted C3-C30 heteroaryl groups and substituted or unsubstituted C5-C30 aryl groups.

[0031] In formulas (1-6), L6 is selected from one of a single bond, a substituted or unsubstituted C3-C60 heteroaryl group, and a substituted or unsubstituted C5-C60 aryl group. Preferably, L6 is selected from one of a single bond, a substituted or unsubstituted C3-C30 heteroaryl group, and a substituted or unsubstituted C6-C30 aryl group.

[0032] In equation (1-6), Y 6 Y 7 Y 8 Y 9 and Y 10 Each is independently selected from CR3 or N, and Y 6 -Y 10 At least one of them is N, and R3 is independently selected from hydrogen, substituted or unsubstituted C1-C12 chain alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C1-C12 chain alkoxy, halogen, cyano, nitro, hydroxyl, substituted or unsubstituted C1-C12 silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, and two adjacent R3s can be fused into a ring;

[0033] In formulas (1-7), L7 is selected from one of a single bond, a substituted or unsubstituted C3-C60 heteroaryl group, and a substituted or unsubstituted C5-C60 aryl group. Preferably, L7 is selected from one of a single bond, a substituted or unsubstituted C3-C30 heteroaryl group, and a substituted or unsubstituted C5-C30 aryl group.

[0034] In equation (1-7), Z 5 Z 6 Z 7 and Z 8 Each of the R2 groups is independently selected from CR4 or N, and R4 is independently selected from hydrogen, substituted or unsubstituted C1-C12 chain alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C1-C12 chain alkoxy, halogen, cyano, nitro, hydroxyl, substituted or unsubstituted C1-C12 silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl. Two adjacent R2 groups can be fused together to form a ring.

[0035] In formulas (1-8), L8 is selected from one of substituted or unsubstituted C6-C60 arylene or substituted or unsubstituted C3-C60 heteroarylene. Preferably, L8 is selected from one of substituted or unsubstituted C6-C30 arylene or substituted or unsubstituted C3-C30 heteroarylene.

[0036] In formulas (1-8), R' is selected from H, deuterium, substituted or unsubstituted C1-C12 chain alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C1-C12 chain alkoxy, substituted or unsubstituted C3-C12 cycloalkoxy, substituted or unsubstituted C1-C12 silyl, halogen, carbonyl, cyano, hydroxyl, nitro, amino, acyl, substituted or unsubstituted C6-C60 aryl, and substituted or unsubstituted C3-C60 heteroaryl. When there are multiple R's, adjacent R's can be fused together. n' is an integer from 0 to 5.

[0037] When the above-mentioned groups contain substituents, the substituents are selected from one or a combination of at least two of the following: halogen, cyano, carbonyl, C1-C12 chain alkyl, C3-C12 cycloalkyl, C2-C10 alkenyl, C1-C10 alkoxy or thioalkoxy, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 monocyclic aryl or fused-ring aryl, and C3-C30 monocyclic heteroaryl or fused-ring heteroaryl.

[0038] More preferably, in formulas (1), (1-1), (1-2), (1-3), (1-4), (1-5), (1-6), (1-7), and (1-8), ring A is selected from the following substituted or unsubstituted groups:

[0039]

[0040] When the above-mentioned groups contain substituents, the substituents are selected from one or a combination of at least two of the following: halogen, cyano, carbonyl, C1-C12 chain alkyl, C3-C12 cycloalkyl, C2-C10 alkenyl, C1-C10 alkoxy or thioalkoxy, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 monocyclic aryl or fused-ring aryl, and C3-C30 monocyclic heteroaryl or fused-ring heteroaryl.

[0041] More preferably, R1, R2, R3, R4, R, and R' are each independently selected from hydrogen or the following substituents: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, phenyl, naphthyl, anthracene, benzo[a]anthrayl, phenanthrene, benzo[a]phenanthrene, pyrene, pyrene, peryl, fluoranyl, tetraphenyl, pentaphenyl, benzo[a]pyrene, biphenyl, amphyl, triphenyl Biphenyl, triphenyl, tetraphenyl, fluorenyl, spirodifluorenyl, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis or trans indofluorenyl, trimenyl, isotrimeric indoyl, spirotrimeric indoyl, spiroisotrimeric indoyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thiopheneyl, benzothiopheneyl, isobenzothiopheneyl, dibenzothiopheneyl, pyrroleyl, isoindoleyl, carbazoleyl, indocarbazoleyl, pyridyl, quinolinyl, isoquinolinyl, acridineyl, phenanthridineyl, benzo-5,6-quinolinyl, benzo-6,7-quinolinyl, benzo-7,8-quinolinyl, pyrazolyl, indazoleyl, imidazoyl, benzimidazolyl, naphtho Imidazolyl, phenanthreneimidazolyl, pyridiniumimidazolyl, pyraziniumimidazolyl, quinoxaliniumimidazolyl, oxazolyl, benzoxoxazolyl, naphthoxoxazolyl, anthraquinoneiumimidazolyl, phenanthreneiumimidazolyl, 1,2-thiazolyl, 1,3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1,5-diazaanthrayl, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperyl, pyrazinyl, phenazinyl, phenthiazinyl, naphridinyl, azacarbazolyl, benzocarbazolyl, phenanthrene One of the following groups: pyrrolidyl, 1,2,3-triazolyl, 1,2,4-triazolyl, benzotriazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, tetrazolyl, 1,2,4,5-tetraazinyl, 1,2,3,4-tetraazinyl, 1,2,3,5-tetraazinyl, purine, pteridinyl, indazyl, benzothiadiazolyl, or a combination thereof.

[0042] Furthermore, the compounds described in the general formula of this invention can preferably include the following specific structural compounds, which are merely representative examples:

[0043]

[0044]

[0045]

[0046]

[0047]

[0048] As another aspect of the invention, the application of the compound described above in an organic electroluminescent device is also provided. Specifically, its application as an electron transport layer material in an organic electroluminescent device is preferred.

[0049] As another aspect of the present invention, an organic electroluminescent device is also provided, comprising a first electrode, a second electrode, and one or more light-emitting functional layers inserted between the first electrode and the second electrode, wherein the light-emitting functional layer contains a compound of the general formula of the present invention as shown in any of the above formulas (1), (1-A), (1-B), (1-1), (1-2), (1-3), (1-4), (1-5), (1-6), (1-7), and (1-8), or contains a compound as shown in the various specific structural formulas described above.

[0050] Specifically, one embodiment of the present invention provides an organic electroluminescent device, including a substrate, and a first electrode, a plurality of light-emitting functional layers, and a second electrode sequentially formed on the substrate; the light-emitting functional layers include a hole transport region, a light-emitting layer, and an electron transport region, wherein the hole transport region is formed on the anode layer, the cathode layer is formed on the electron transport region, and the light-emitting layer is located between the hole transport region and the electron transport region; wherein the electron transport region includes an electron transport layer, and the electron transport layer contains a compound of the general formula of the present invention shown in any one of the above formulas (1), (1-A), (1-B), (1-1), (1-2), (1-3), (1-4), (1-5), (1-6), (1-7), and (1-8), or contains a compound shown in the various specific structural formulas described above.

[0051] OLED devices prepared using the compounds of this invention have low start-up voltage, high luminous efficiency, and better lifespan, which can meet the current requirements of panel manufacturers for high-performance materials.

[0052] Specifically, one embodiment of the present invention provides an organic electroluminescent device, including a substrate, and an anode layer, a plurality of light-emitting functional layers and a cathode layer sequentially formed on the substrate; the light-emitting functional layers include a hole injection layer, a hole transport layer, a light-emitting layer and an electron transport layer, wherein the hole injection layer is formed on the anode layer, the hole transport layer is formed on the hole injection layer, the cathode layer is formed on the electron transport layer, and the light-emitting layer is located between the hole transport layer and the electron transport layer; wherein the electron transport layer contains a compound of the general formula of the present invention shown in formula (1) above.

[0053] More specifically, organic electroluminescent devices will be described in detail.

[0054] An OLED includes a first electrode and a second electrode, and an organic material layer located between the electrodes. This organic material layer can be further divided into multiple regions. For example, the organic material layer may include a hole transport region, a light-emitting layer, and an electron transport region.

[0055] In specific embodiments, a substrate can be used below the first electrode or above the second electrode. The substrate is typically made of glass or polymer material with excellent mechanical strength, thermal stability, water resistance, and transparency. Furthermore, thin-film transistors (TFTs) can also be incorporated into the substrate used for displays.

[0056] The first electrode can be formed by sputtering or depositing the material to be used as the first electrode on a substrate. When the first electrode is used as the anode, transparent conductive oxide materials such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), and zinc oxide (ZnO) and any combination thereof can be used. When the first electrode is used as the cathode, metals or alloys such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), and magnesium-silver (Mg-Ag) and any combination thereof can be used.

[0057] Organic material layers can be formed on electrodes using methods such as vacuum thermal evaporation, spin coating, and printing. The compounds used as organic material layers can be small organic molecules, large organic molecules, polymers, and combinations thereof.

[0058] The hole transport region is located between the anode and the light-emitting layer. The hole transport region can be a single-layer hole transport layer (HTL), including a single-layer hole transport layer containing only one compound and a single-layer hole transport layer containing multiple compounds. The hole transport region can also be a multilayer structure including at least one of a hole injection layer (HIL), a hole transport layer (HTL), and an electron blocking layer (EBL).

[0059] The material for the hole transport region may be selected from, but is not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or polymers containing conductive dopants such as polyphenylene ethylene, polyaniline / dodecylbenzenesulfonic acid (Pani / DBSA), poly(3,4-ethylenedioxythiophene) / poly(4-styrenesulfonate) (PEDOT / PSS), polyaniline / camphorsulfonic acid (Pani / CSA), polyaniline / poly(4-styrenesulfonate) (Pani / PSS), aromatic amine derivatives as shown in HT-1 to HT-34 below; or any combination thereof.

[0060]

[0061]

[0062] The hole injection layer is located between the anode and the hole transport layer. The hole injection layer can be a single compound material or a combination of multiple compounds. For example, the hole injection layer can be one or more compounds of HT-1 to HT-34 described above, or one or more compounds of HI-1 to HI-3 described below; it can also be one or more compounds of HT-1 to HT-34 doped with one or more compounds of HI-1 to HI-3 described below.

[0063]

[0064] The emissive layer includes luminescent dyes (i.e., dopants) that can emit different wavelengths of light, and may also include a host material. The emissive layer can be a monochromatic emissive layer emitting a single color such as red, green, or blue. Multiple monochromatic emissive layers of different colors can be arranged in a planar pattern according to pixel design, or they can be stacked together to form a colored emissive layer. When different colored emissive layers are stacked together, they can be separated from each other or connected to each other. The emissive layer can also be a single colored emissive layer that can simultaneously emit different colors such as red, green, and blue.

[0065] Depending on the technology used, the light-emitting layer material can be various, including fluorescent electroluminescent materials, phosphorescent electroluminescent materials, and thermally activated delayed fluorescence materials. An OLED device can employ a single light-emitting technology or a combination of different technologies. These different light-emitting materials, categorized by technology, can emit light of the same color or different colors.

[0066] In one aspect of the invention, the light-emitting layer employs fluorescent electroluminescence technology. The fluorescent host material of the light-emitting layer may be selected from, but is not limited to, one or more combinations of BFH-1 to BFH-17 listed below.

[0067]

[0068] In one aspect of the invention, the light-emitting layer employs fluorescent electroluminescence technology. The fluorescent dopant of the light-emitting layer may be selected from, but not limited to, one or more combinations of BFD-1 to BFD-12 listed below.

[0069]

[0070]

[0071] In one aspect of the invention, the light-emitting layer employs phosphorescent photoluminescence technology. The main material of the light-emitting layer is selected from, but not limited to, one or more combinations of GPH-1 to GPH-80.

[0072]

[0073]

[0074]

[0075]

[0076] In one aspect of the invention, the light-emitting layer employs phosphorescent photoluminescence technology. The phosphorescent dopant of the light-emitting layer may be selected from, but not limited to, one or more combinations of GPD-1 to GPD-47 listed below.

[0077]

[0078]

[0079]

[0080] Where D represents deuterium.

[0081] In one aspect of the invention, the light-emitting layer employs phosphorescent photoluminescence technology. The phosphorescent dopant of the light-emitting layer may be selected from, but not limited to, one or more combinations of RPD-1 to RPD-28 listed below.

[0082]

[0083]

[0084] In one aspect of the invention, the light-emitting layer employs phosphorescent photoluminescence technology. The phosphorescent dopant of the light-emitting layer may be selected from, but not limited to, one or more combinations of YPD-1 to YPD-11 listed below.

[0085]

[0086] The organic electroluminescent device of the present invention includes an electron transport region between a light-emitting layer and a cathode. The electron transport region can be a single-layer electron transport layer (ETL), including a single-layer electron transport layer containing only one compound and a single-layer electron transport layer containing multiple compounds. Alternatively, the electron transport region can be a multilayer structure including at least one of an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL).

[0087] The electron transport region can also be formed by applying the compound of the present invention to a multilayer structure including at least one of an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL). Of course, the material of the electron transport region can also be combined with one or more of ET-1 to ET-57 listed below.

[0088]

[0089]

[0090]

[0091]

[0092] The device may also include an electron injection layer located between the electron transport layer and the cathode, wherein the electron injection layer material includes, but is not limited to, one or more combinations of the following:

[0093] Liq, LiF, NaCl, CsF, Li2O, Cs2CO3, BaO, Na, Li, Ca.

[0094] The specific reasons for the superior performance of the compounds of the present invention are not yet clear, but it is speculated that the reasons may be as follows:

[0095] The general formula compounds of this invention employ novel phosphorus-oxygen-deficient groups bridged with electron-deficient groups via aryl or heteroaryl groups to form novel compounds. Compared to commonly used single oxazole, thiazole, imidazole, triazole, or triazine structures in the prior art, the compounds of this invention exhibit relatively stronger electron-deficient properties, thus facilitating electron injection. Simultaneously, the molecular structure of the compounds of this invention possesses greater planar conjugation, thereby improving electron mobility. These two structural characteristics enable the molecule as a whole to exhibit excellent electron injection and migration performance. Therefore, when the compounds of this invention are used as electron transport layer materials in organic electroluminescent devices, they can effectively improve the electron injection and migration efficiency in the device, thereby ensuring that the device achieves excellent results with high luminous efficiency and low start-up voltage.

[0096] In addition, the preparation process of the compounds of the present invention is simple and easy to implement, the raw materials are readily available, and it is suitable for mass production scale-up. Detailed Implementation

[0097] The specific preparation methods of the novel compounds of the present invention will be described in detail below using several synthetic examples, but the preparation methods of the present invention are not limited to these synthetic examples. Obtaining the compound is not limited to the synthetic methods and raw materials used in the present invention; those skilled in the art can also select other methods or routes to obtain the novel compounds proposed in the present invention. Compounds for which synthetic methods are not mentioned in the present invention are all raw material products obtained through commercial means, or self-prepared using these raw material products according to known methods.

[0098] All the chemical reagents used in the following synthesis examples, such as ethyl acetate, sodium sulfate, toluene, tetrahydrofuran, dichloromethane, acetic acid, and potassium carbonate, were purchased from Shanghai Titan Technology Co., Ltd. and Xilong Chemical Co., Ltd. The mass spectrometer used to determine the following compounds was a ZAB-HS type mass spectrometer (manufactured by Micromass, UK).

[0099] The synthetic route for the compounds represented by the general formula of this invention is as follows:

[0100]

[0101] The first step involves reacting 1-bromo-2-iodoaryl or heteroaryl compound M-1 with diphenylphosphine under Pd(PPh3)4 catalysis to generate intermediate M-2. The second step involves reacting intermediate M-2 with bromoacetophenone compound M-3 in toluene solvent under heating to generate intermediate M-4. The third step, following the previous step, involves adding potassium tert-butoxide to the reaction system and reacting at room temperature for 1 hour to generate the corresponding phosphorus ylide intermediate M-5. The fourth step, following the third step, involves adding Pd(PPh3)4 to the above reaction system and reacting under reflux in toluene for 4 hours under Pd(PPh3)4 catalysis to generate intermediate M-6 via a cyclization reaction. The fifth step involves reacting intermediate M-6 with NaOH to generate intermediate M-7. The sixth step involves reacting intermediate M-7 with pinacol diboronate to generate intermediate M-8. The seventh step involves reacting intermediate M-8 with various aryl and heteroaryl halides via a Suzuki coupling reaction to generate the final product Cx.

[0102] Synthesis Example 1:

[0103] Synthesis of compound C1

[0104]

[0105] (1) Preparation of compound 1-1

[0106] In a flask, o-iodobromobenzene (310 g, 1.1 mol), diphenylphosphine (185 g, 1 mol), and triethylamine (121 g, 1.2 mol) were dissolved in 1.5 L of acetonitrile. After purging with nitrogen, Pd(PPh3)4 (11.5 g, 10 mmol) was added. After the addition was complete, nitrogen was purged three times, and the mixture was heated under reflux with stirring for 6 hours. The reaction was confirmed by TLC. The mixture was cooled to room temperature, and the reaction was quenched with water. The mixture was extracted with dichloromethane, and the organic phase was dried over anhydrous sodium sulfate and purified by column chromatography to give compound 1-1 (309 g, 91%).

[0107] (2) Preparation of compounds 1-4

[0108] Compound 1-1 (306 g, 0.9 mol) and 4-chloro-bromoacetophenone (232 g, 1 mol) were added to a flask containing 5 L of toluene. The mixture was purged with nitrogen three times and heated to 90 °C for 3 hours with stirring to generate intermediate compound 1-2. The reaction was cooled to room temperature, and potassium tert-butoxide (168 g, 1.5 mol) was added, followed by stirring for another hour to obtain intermediate compound 1-3. Pd(PPh3)4 (57.5 g, 50 mmol) was added to the above reaction system. After the addition was complete, the mixture was refluxed under nitrogen for 4 hours, precipitating a solid. TLC analysis confirmed the reaction was complete. The mixture was cooled to room temperature, and toluene solvent was removed by rotary evaporation under reduced pressure. Water and dichloromethane were added, and the mixture was separated. The organic phase was dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation under reduced pressure. The resulting solid was washed with toluene and petroleum ether, respectively, to obtain compound 1-4 (381 g, 86%).

[0109] (3) Preparation of compounds 1-5

[0110] Compounds 1-4 (369 g, 750 mmol) were dissolved in a flask containing 7.5 L of dichloromethane. The mixture was cooled to -10 °C and maintained at -10 °C to 0 °C. NaOH (10 M, 450 mL) was added dropwise. After the addition was complete, the reaction was allowed to proceed for 30 minutes, and then 750 mL of water was added. The mixture was separated into two phases. The aqueous phase was extracted twice with dichloromethane. The combined dichloromethane phases were dried over anhydrous sodium sulfate and purified by column chromatography to give compounds 1-5 (211 g, 80%).

[0111] (4) Preparation of compounds 1-6

[0112] Compounds 1-5 (176 g, 500 mmol), pinacol diborate (190 g, 750 mmol), and potassium acetate (147 g, 1.5 mol) were added to a flask containing 1,4-dioxane (3 L). After purging with nitrogen at room temperature, palladium acetate (2.24 mg, 10 mmol) and SPhos (8.2 g, 20 mmol) were added. The mixture was stirred and refluxed for 12 hours, with the reaction endpoint monitored by TLC. 1,4-dioxane was removed by rotary evaporation. The mixture was separated by adding water and dichloromethane. The organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, and purified by column chromatography to give compounds 1-6 (200 g, 90% yield).

[0113] (5) Preparation of compound C1

[0114] Compounds 1-6 (8.0 g, 18 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (4.8 g, 18 mmol), potassium carbonate (7.45 g, 54 mmol), and pd(dppf)Cl2 (132 mg, 0.18 mmol) were added to a flask containing 100 mL tetrahydrofuran and 25 mL water. The mixture was purged with nitrogen and refluxed under nitrogen atmosphere for 10 hours. TLC showed complete reaction. The precipitated solid was filtered, washed with water and ethanol, dried, and purified by column chromatography to give compound C1 (8.5 g, 86% yield). Calculated molecular weight: 549.16, measured C / Z: 549.2.

[0115] Synthesis Example 2:

[0116] Synthesis of compound C16

[0117]

[0118] Compound C16 was synthesized using a method similar to that of compound C1, except that the starting material o-iodobromobenzene was replaced with 1-bromo-2-iodonaphthalene, and the starting material 4-chlorobromoacetophenone was replaced with 3-chlorobromoacetophenone. The calculated molecular weight of the resulting compound C16 was 599.18, and the measured C / Z ratio was 599.2.

[0119] Synthesis Example 3:

[0120] Synthesis of compound C33

[0121]

[0122] Compound C33 was synthesized using a method similar to that of compound C1, except that the starting material o-iodobromobenzene was replaced with 1-bromo-2-iodothiophene, and 2-chloro-4,6-diphenyl-1,3,5-triazine was replaced with 2-chloro-4-phenylquinazoline. The calculated molecular weight of compound C33 was 528.11, and the measured C / Z ratio was 528.1.

[0123] Synthesis Example 4:

[0124] Synthesis of compound C75

[0125]

[0126] (1) Preparation of compounds 4-6

[0127] The synthesis of compounds 4-6 was carried out using a similar method to that of compounds 1-6, except that the starting material 4-chlorobromoacetophenone was replaced with 5-chloro-2-bromothiophene acetophenone.

[0128] (2) Preparation of compounds 4-7

[0129] Compound 2-bromo-5-iodothiophene (28.8 g, 100 mmol), 4-cyanobenzonic acid (14.7 g, 100 mmol), potassium carbonate (41.4 g, 300 mmol), and pd(dppf)Cl2 (732 mg, 1 mmol) were added to a flask containing 500 mL tetrahydrofuran and 100 mL water. The mixture was heated under nitrogen atmosphere and refluxed for 8 hours. TLC showed that the reaction was complete. After cooling to room temperature, the mixture was separated into aqueous and organic phases. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and evaporated under reduced pressure to obtain the crude product. The crude product was purified by column chromatography to obtain compound 4-7 (18.4 g, 76%).

[0130] (3) Preparation of compound C75

[0131] Compounds 4-6 (8.1 g, 18 mmol), 4-7 (2.6 g, 18 mmol), and potassium carbonate (7.45 g, 54 mmol) were added to a flask containing 1,4-dioxane:water (150 mL: 50 mL). After purging with nitrogen under stirring at room temperature, Pd₂(dba)₃ (329 mg, 0.36 mmol) and Sphos (295 mg, 0.72 mmol) were added. The mixture was then heated under reflux for 15 hours with stirring under nitrogen atmosphere, and TLC showed complete reaction. The precipitated white solid was filtered. Recrystallization after column chromatography gave a white solid, compound C75 (7.1 g, 78% yield). Calculated molecular weight: 507.05, Measured C / Z: 507.1.

[0132] Synthesis Example 5:

[0133] Synthesis of compound C92

[0134]

[0135] Compound C92 was synthesized using a method similar to that of compound C1, except that the starting material o-iodobromobenzene was replaced with 3-bromo-4-iodopyridine, and the starting material 4-chlorobromoacetophenone was replaced with 4-chlorobromothioacetophenone. The calculated molecular weight of the obtained compound C92 was 566.13, and the measured C / Z ratio was 566.1.

[0136] Device Example 1

[0137] This embodiment of the device provides a method for fabricating an organic electroluminescent device, as detailed below:

[0138] The glass plate coated with the ITO transparent conductive layer was ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in a acetone:ethanol mixed solvent, baked in a clean environment until all moisture was removed, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam.

[0139] The glass substrate with the anode was placed in a vacuum chamber and evacuated until the pressure was less than 10. -5 Pa, using a multi-source co-evaporation method, HI-3 was vacuum-deposited as a hole injection layer on the above-mentioned anodic layer film at a deposition rate of 0.1 nm / s and a total film thickness of 10 nm.

[0140] HT-4 was vacuum-deposited on top of the hole injection layer as the first hole transport layer of the device at a deposition rate of 0.1 nm / s and a total film thickness of 40 nm.

[0141] HT-14 was vacuum-deposited on top of the first hole transport layer as the second hole transport layer of the device at a deposition rate of 0.1 nm / s and a total film thickness of 10 nm.

[0142] The light-emitting layer of the device is vacuum-deposited on the second hole transport layer. The light-emitting layer includes a host material and a dye material. Using a multi-source co-evaporation method, the evaporation rate of the host material BFH-4 is adjusted to 0.1 nm / s, the evaporation rate of the dye BFD-4 is set to 5%, and the total evaporation film thickness is 20 nm.

[0143] ET-17 was vacuum-deposited on top of the light-emitting layer as a hole-blocking layer for the device at a deposition rate of 0.1 nm / s and a total film thickness of 5 nm.

[0144] An electron transport layer was deposited on top of the hole blocking layer using a multi-source co-evaporation method. The evaporation rate of compound C1 was adjusted to 0.1 nm / s and set to be 100% of the evaporation rate of ET-57. The total film thickness was 23 nm.

[0145] A 1 nm thick LiF layer was vacuum-deposited on the electron transport layer (ETL) as an electron injection layer, and an 80 nm thick Al layer was used as the cathode of the device.

[0146] The only difference between Device Examples 2-5 and Device Example 1 is that the electron transport layer material is replaced by the compound C1 of the present invention with the compounds C16, C33, C75 and C92 of the present invention, respectively, as detailed in Table 1 below.

[0147] Device Comparison Examples 1-4

[0148] The difference from Device Example 1 is that the electron transport layer material is replaced by the compound C1 of the present invention with compounds D-1, D-2, D-3 and D-4 in the prior art.

[0149]

[0150] Performance testing:

[0151] Under the same brightness, the driving voltage and current efficiency of the organic electroluminescent devices prepared in Examples 1-5 and Comparative Examples 1-4 were measured using a Photo Research PR 750 radiometer, an ST-86LA luminance meter (Beijing Normal University Optoelectronic Instrument Factory), and a Keithley 4200 testing system. Specifically, the voltage was increased at a rate of 0.1V per second, and the driving voltage and current efficiency were measured when the brightness of the organic electroluminescent device reached 1000 cd / m². 2 The voltage at that time is the driving voltage, and the current density at that time is measured simultaneously; the ratio of brightness to current density is the current efficiency.

[0152] The performance test results are shown in Table 1 below.

[0153] Table 1:

[0154]

[0155] As shown in Table 1, when the material schemes and fabrication processes of other functional layers in the organic electroluminescent device structure are exactly the same, compared with the comparative examples, the organic electroluminescent devices prepared in Examples 1-5 of the present invention have higher current efficiency and lower driving voltage. In Examples 1-5, the device current efficiency is 8.51-9.05 cd / A and the device driving voltage is 3.89-4.05 V.

[0156] The device prepared in Comparative Example 1 had a driving voltage of 4.37V and a current efficiency of 8.16cd / A; the device prepared in Comparative Example 2 had a driving voltage of 5.16V and a current efficiency of 6.85cd / A; the device prepared in Comparative Example 3 had a driving voltage of 5.33V and a current efficiency of 6.47cd / A; and the device prepared in Comparative Example 4 had a driving voltage of 4.51V and a current efficiency of 7.74cd / A. The devices prepared in Comparative Examples 1 to 4 all showed slightly inferior performance compared to the devices prepared in Examples 1-5 of this invention. The presumably, this is because the novel compound constructed in this invention, with an aryl or heteroaryl bridging link between the electron-deficient phosphorus group and the electron-deficient group at the 3-position, has a better molecular dipole moment than the comparative example molecules. This facilitates molecular stacking and the formation of a denser molecular film, thus resulting in stronger electron transport capabilities. Although the comparative example D-4 molecule also contains an electron-deficient structure similar to that of the present invention, its low molecular weight and low glass transition temperature result in poor thermal stability of the solid film used in the device, thus exhibiting relatively inferior optoelectronic performance.

[0157] Experiments have shown that the novel compounds constructed by bridging the phosphorus oxygen electron-deficient group at the 3-position with the electron-deficient group via aryl or heteroaryl groups in the compounds of this invention have good electron injection and migration properties when used as electron transport materials, thereby enabling the devices to have high current efficiency and low driving voltage.

[0158] The experimental data above show that the novel organic material of this invention, as an electron transport material for organic electroluminescent devices, is a high-performance organic light-emitting functional material with broad application prospects.

[0159] The present invention has been illustrated with the above embodiments to explain the detailed method of the present invention. However, the present invention is not limited to the detailed method described above, that is, it does not mean that the present invention must rely on the detailed method described above to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A compound of the general formula (1-A) or (1-B): ###0001### (1-A) (1-B) wherein: -L-Ar is not selected from a biphenyl group; -L is selected from one of a substituted or unsubstituted C5-C60 arylene group, a substituted or unsubstituted C3-C60 heteroarylene group; -Ar is selected from one of a substituted or unsubstituted C5-C60 aryl group, a substituted or unsubstituted C3-C60 heteroaryl group; -ring A represents a substituted group fused to a six-membered ring structure consisting of X and P, ring A is selected from one of a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C3-C60 heteroaryl group; and -when the above groups have substituents, the substituents are selected from one or a combination of at least two of a halogen, a cyano group, a carbonyl group, a C1-C12 chain alkyl group, a C3-C12 cyclic alkyl group, a C2-C10 alkenyl group, a C1-C10 alkoxyl or thioalkoxyl group, a C6-C30 arylamino group, a C3-C30 heteroarylamino group, a C6-C30 monocyclic or fused ring aryl group, a C3-C30 monocyclic or fused ring heteroaryl group.

2. The compound according to claim 1, wherein: -ring A is selected from one of a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group; -Ar is selected from one of a substituted or unsubstituted C5-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group; -L is selected from one of a substituted or unsubstituted C5-C30 arylene group, a substituted or unsubstituted C3-C30 heteroarylene group.

3. The compound according to claim 1, having a structure of formula (1-1), (1-2), (1-3), (1-4), (1-5), (1-6), (1-7) or (1-8): ###0002### (1-1) (1-2) (1-3) (1-4) (1-5) (1-6) (1-7) (1-8) wherein: -the definition of ring A is the same as in formula (1-A) and (1-B); -L1 is selected from one of a substituted or unsubstituted C3-C60 heteroarylene group, a substituted or unsubstituted C5-C60 arylene group; -L2 is selected from one of a substituted or unsubstituted C3-C60 heteroarylene group, a substituted or unsubstituted C5-C60 arylene group; -L3 is selected from one of a substituted or unsubstituted C3-C60 heteroarylene group, a substituted or unsubstituted C5-C60 arylene group. ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ In formula (1-2), the Y 1 , Y 2 , Y 3 , Y 4 and Y 5 are each independently selected from CR1or N, and Y 1 -Y 5 at least one of which is N, R1is independently selected from one of hydrogen, C1-C12 linear alkyl, C3-C12 cyclic alkyl, halogen, cyano, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryl, C3-C30 heteroaryl; ​ In formula (1-3), the Z 1 , Z 2 , Z 3 and Z 4 are each independently selected from CR2or N, R2is independently selected from one of hydrogen, C1-C12chain alkyl, C3-C12cycloalkyl, halogen, cyano, C6-C30aryl amino, C3-C30heteroaryl amino, C6-C30aryl, C3-C30heteroaryl; In formula (1-4), L4 is selected from one of substituted or unsubstituted C6-C60 arylene, substituted or unsubstituted C3-C60 heteroarylene; In formula (1-4), R is selected from one of H, C1-C12 chain alkyl, C3-C12 cyclic alkyl, halogen, cyano, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryl, C3-C30 heteroaryl; n is an integer of 1-5; and when L4 is C6 arylene, R is not selected from H; In formula (1-5), L5 is selected from one of substituted or unsubstituted C3-C60 heteroarylene, substituted or unsubstituted C5-C60 arylene; In formula (1-6), L6 is selected from one of single bond, substituted or unsubstituted C3-C60 heteroarylene, substituted or unsubstituted C5-C60 arylene; In formula (1-6), the Y 6 , Y 7 , Y 8 , Y 9 and Y 10 are each independently selected from CR3or N, and Y 6 -Y 10 at least one of which is N, R3is independently selected from one of hydrogen, C1-C12 linear alkyl, C3-C12 cyclic alkyl, halogen, cyano, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryl, C3-C30 heteroaryl; In formula (1-7), L7 is selected from one of single bond, substituted or unsubstituted C3-C60 heteroarylene, substituted or unsubstituted C5-C60 arylene; In formula (1-7), the Z 5 , Z 6 , Z 7 and Z 8 are each independently selected from CR4or N, R4is independently selected from one of hydrogen, C1-C12chain alkyl, C3-C12cycloalkyl, halogen, cyano, C6-C30aryl amino, C3-C30heteroaryl amino, C6-C30aryl, C3-C30heteroaryl; In formula (1-8), L8 is selected from one of substituted or unsubstituted C6-C60 arylene, substituted or unsubstituted C3-C60 heteroarylene; In formula (1-8), R' is selected from one of H, C1-C12 chain alkyl, C3-C12 cyclic alkyl, halogen, cyano, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryl, C3-C30 heteroaryl; n' is an integer of 0-5; When the above group has a substituent, the substituent is selected from one or a combination of at least two of halogen, cyano, carbonyl, C1-C12 chain alkyl, C3-C12 cyclic alkyl, C2-C10 alkenyl, C1-C10 alkoxy or thioalkoxy, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 monocyclic aryl or fused ring aryl, C3-C30 monocyclic heteroaryl or fused ring heteroaryl.

4. The compound of claim 3, wherein: In formula (1-1), L1 is selected from one of substituted or unsubstituted C3-C30 heteroarylene, substituted or unsubstituted C5-C30 arylene; In formula (1-3), L3 is selected from one of substituted or unsubstituted C3-C30 heteroarylene, substituted or unsubstituted C5-C30 arylene; In formula (1-4), L4 is selected from one of substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C3-C30 heteroarylene; In formula (1-5), L5 is selected from one of substituted or unsubstituted C3-C30 heteroarylene, substituted or unsubstituted C5-C30 arylene; In formula (1-6), L6 is selected from one of single bond, substituted or unsubstituted C3-C30 heteroarylene, substituted or unsubstituted C6-C30 arylene; In formula (1-7), L7 is selected from one of single bond, substituted or unsubstituted C3-C30 heteroarylene, substituted or unsubstituted C5-C30 arylene; In formula (1-8), the L8is selected from one of substituted or unsubstituted C6-C30arylene, substituted or unsubstituted C3-C30heteroarylene; When the above group has a substituent, the substituent is selected from one or a combination of at least two of halogen, cyano, carbonyl, C1-C12chain alkyl, C3-C12cycloalkyl, C2-C10alkenyl, C1-C10alkoxy or thioalkoxy, C6-C30aryl amino, C3-C30heteroaryl amino, C6-C30monocyclic or condensed aryl, C3-C30monocyclic or condensed heteroaryl.

5. The compound according to any one of claims 1 to 4, wherein the ring A is selected from the following groups, which are substituted or unsubstituted: When the above group has a substituent, the substituent is selected from one or a combination of at least two of halogen, cyano, carbonyl, C1-C12chain alkyl, C3-C12cycloalkyl, C2-C10alkenyl, C1-C10alkoxy or thioalkoxy, C6-C30aryl amino, C3-C30heteroaryl amino, C6-C30monocyclic or condensed aryl, C3-C30monocyclic or condensed heteroaryl.

6. The compound according to claim 1, having the following structure:

7. Use of a compound according to any one of claims 1 to 6 as a functional material in an organic electronic device, including an organic electroluminescent device, an optical sensor, a solar cell, a lighting element, an organic thin film transistor, an organic field effect transistor, an organic thin film solar cell, an information tag, an electronic artificial skin sheet, a sheet-type scanner, or an electronic paper.

8. Use of a compound according to claim 7 as an electron transport material in an organic electroluminescent device.

9. An organic electroluminescent device comprising a first electrode, a second electrode, and one or more light-emitting functional layers interposed between the first electrode and the second electrode, wherein the light-emitting functional layers contain a compound according to any one of claims 1 to 6.

10. The organic electroluminescent device according to claim 9, wherein the light-emitting functional layer comprises a hole-transporting zone, a light-emitting zone, and an electron-transporting zone, the hole-transporting zone is formed on the anode layer, the cathode layer is formed on the electron-transporting zone, and the light-emitting zone is between the hole-transporting zone and the electron-transporting zone; wherein, The electron transport region includes an electron transport layer containing a compound according to any one of claims 1 to 6.

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