Heterocyclic organic compound and organic electroluminescent device

Abstract

The invention relates to a heterocyclic organic compound, the heterocyclic organic compound has a structure as shown in formula (I): # imgabs0 #, and the heterocyclic organic compound disclosed by the invention can be used as a main body material to be applied to an OLED (Organic Light Emitting Diode) device, so that the luminous efficiency of the OLED is effectively improved, and the service life of the OLED is effectively prolonged.

Description

Technical Field

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

[0002] The organic electroluminescent phenomenon refers to the phenomenon of converting electrical energy into light energy by using organic substances. An organic electroluminescent element utilizing the organic electroluminescent phenomenon usually has a structure including a positive electrode, a negative electrode, and an organic functional layer therebetween. To improve the efficiency and lifespan of the organic electroluminescent element, the organic functional layer usually has a multi-layer structure, and each layer contains different organic substances. Specifically, it may include a hole injection layer, a hole transport layer, a luminescence assisting layer, a light-emitting layer, an electron transport layer, an electron injection layer, etc. In such an organic electroluminescent element, when a voltage is applied between the two electrodes, holes are injected from the positive electrode into the organic functional layer, and electrons are injected from the negative electrode into the organic functional layer. When the injected holes and electrons meet in the light-emitting layer, excitons are formed, and light is emitted when the excitons transition back to the ground state. Such an organic electroluminescent element has characteristics such as self-luminescence, high brightness, high efficiency, low driving voltage, wide viewing angle, and high contrast. It has broad development potential in the fields of smartphones, TVs, wearable devices, vehicle-mounted displays, etc.

[0003] The luminescent materials in OLED devices can be classified into two categories according to the luminescence mechanism: electrofluorescence and electrophosphorescence. Electrofluorescence is the radiative decay transition of singlet excitons, and electrophosphorescence is the light emitted when triplet excitons radiatively decay to the ground state. According to the spin quantum statistics theory, the formation probability ratio of singlet excitons and triplet excitons is 1:3; therefore, the internal quantum efficiency of electrofluorescent materials does not exceed 25%, while electrophosphorescent materials have a strong spin-orbit coupling effect and can utilize both singlet and triplet excitons, making the internal quantum efficiency of phosphorescent organic electroluminescent devices reach 100% in theory. However, phosphorescent materials have some inherent disadvantages. For example, phosphorescent emission has a relatively long lifetime, which makes triplet excitons unable to radiatively decay in time and accumulate in the light-emitting layer, resulting in strong interactions between excitons, and further leading to triplet-triplet annihilation and concentration quenching. To avoid this situation, an effective solution is to dope the phosphorescent material as a guest into a suitable host material to form a host-guest system and improve the luminescence efficiency of the device. Therefore, phosphorescent host materials play a significant role in reducing the driving voltage of the device, improving the luminescence efficiency of the device, and increasing the service life of the device.

[0004] However, at the present stage, due to the mismatching of the HOMO energy level and the LUMO energy level with the energy levels of the adjacent functional layer materials, as well as the significant difference in carrier transport, the carriers are unbalanced in the light-emitting layer, and the excitons cannot be effectively recombined in the light-emitting layer, resulting in the efficiency roll-off of the device. Therefore, it is necessary to develop new phosphorescent host materials to improve the optoelectronic performance of organic light-emitting devices. Summary of the Invention

[0005] The purpose of the present invention is to provide a heterocyclic organic compound, which can be used as a phosphorescent host material in OLED devices to effectively improve the luminous efficiency and service life of OLEDs.

[0006] To achieve the purpose of the present invention, the following technical solutions are solved:

[0007] A heterocyclic organic compound having a structure represented by the general formula (I),

[0008]

[0009] Wherein:

[0010] L 1 Is selected from a single bond, a substituted or unsubstituted aromatic group having 6-30 carbon atoms, or a substituted or unsubstituted heteroaromatic group having 5-30 ring atoms;

[0011] Ar 1 Is selected from a substituted or unsubstituted aromatic group having 6-30 carbon atoms, or a substituted or unsubstituted heteroaromatic group having 5-30 ring atoms;

[0012] R 1 、R 2 、R 3 、R 4 Are each independently selected from hydrogen, deuterium, cyano, nitro, halogen, a substituted or unsubstituted straight-chain alkyl group having 1-20 carbon atoms, a substituted or unsubstituted branched-chain alkyl group or cyclic alkyl group having 3-20 carbon atoms, a substituted or unsubstituted aromatic group having 6-30 carbon atoms, or a substituted or unsubstituted heteroaromatic group having 5-30 ring atoms;

[0013] The term "substituted or unsubstituted" means that the defined group is unsubstituted or substituted by one or more substituents R, and each occurrence of the substituent R is independently selected from deuterium, cyano, nitro, halogen, a straight-chain alkyl group having 1-20 carbon atoms, a branched-chain alkyl group or cyclic alkyl group having 3-20 carbon atoms, an aromatic group having 6-30 carbon atoms, a heteroaromatic group having 5-30 ring atoms, or a group formed by combining the above groups.

[0014] Correspondingly, the present invention also provides a phosphorescent host material, which is selected from the heterocyclic organic compounds as described above.

[0015] Correspondingly, the present invention also provides a mixture, which comprises the heterocyclic organic compound as described above and at least one other organic functional material. The other organic functional material is preferably selected from a hole injection material, a hole transport material, an electron transport material, an electron injection material, an electron blocking material, a hole blocking material, a light-emitting dopant material or a light-emitting host material.

[0016] Correspondingly, the present invention also provides an organic electronic device, which contains the heterocyclic organic compound as described above.

[0017] Compared with the prior art, the present invention has the remarkable advantage that the heterocyclic compound of the present invention is used as a host material in the OLED light-emitting layer to achieve higher luminous efficiency and device lifetime. The reason is that: in the compound structure of the present invention, On the one hand it has a large conjugated plane, making the molecule have great rigidity, thereby enhancing the stability of the compound; on the other hand, through the design of the overall molecular structure, the energy levels of the compound are optimized, and can be well matched with the energy levels of adjacent organic functional layers, thus having good charge transport performance, and further significantly improving the efficiency and lifetime of the OLED device applying the compound of the present application. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 is a schematic structural diagram of the OLED device provided by the embodiment of the present application.

[0019] Wherein, 10 is a substrate; 101 is an anode layer; 102 is a hole injection layer; 103 is a first hole transport layer; 104 is a second hole transport layer; 105 is a light-emitting layer; 106 is an electron transport layer; 107 is a cathode layer. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0020] In order to make the objectives, technical solutions and effects of the present application clearer and more definite, the present application is further described in detail below. It should be understood that the specific embodiments described herein are only used to explain the present application and are not used to limit the present application. Based on the described embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of the present invention.

[0021] As used herein, the terms "and / or", "or / and", and "and / or" include any one of two or more related listed items, as well as any and all combinations of the related listed items. The any and all combinations include combinations of any two related listed items, any more related listed items, or all related listed items. It should be noted that when at least three items are connected by at least two conjunctions selected from "and / or", "or / and", and "and / or", it should be understood that in this application, this technical solution undoubtedly includes the technical solution connected by "logical AND", and undoubtedly also includes the technical solution connected by "logical OR". For example, "A and / or B" includes three parallel solutions: A, B, and A + B. Another example, the technical solution of "A, and / or, B, and / or, C, and / or, D" includes any one of A, B, C, and D (that is, the technical solution connected by "logical OR"), and also includes any and all combinations of A, B, C, and D, that is, it includes combinations of any two or any three of A, B, C, and D, and also includes the four-item combination of A, B, C, and D (that is, the technical solution connected by "logical AND").

[0022] In the present invention, when the bond where the substituent or the connection site is located passes through one or more rings, it indicates that it can be connected to any optional site in the one or more rings. For example can be represented as

[0023] In the present invention, when a plurality of substituents with the same symbol are contained on the same group, the substituents can be the same or different from each other. For example The 6 Rs on the benzene ring can be the same or different from each other.

[0024] The halogen in the present invention refers to fluorine, chlorine, bromine, and iodine.

[0025] In the present invention, "substituted or unsubstituted" means that the functional group described after this term can contain a substituent or not contain a substituent.

[0026] In the present invention, "the number of ring atoms" represents the number of atoms among the atoms constituting the ring itself of a structural compound obtained by bonding atoms into a ring (for example, a monocyclic compound, a fused-ring compound, a crosslinked compound, a carbocyclic compound, a heterocyclic compound). When the ring is substituted by a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The same applies to the "number of ring atoms" described below without special explanation. In an aromatic group, the number of ring atoms is the same as the number of carbon atoms; in a heteroaromatic group, the number of ring atoms is the number of carbon atoms plus the number of heteroatoms; for example, the number of ring atoms of a benzene ring is 6, the number of ring atoms of a naphthalene ring is 10, the number of ring atoms of quinoline is 10, the number of ring atoms of a thiophenyl group is 5, and the number of ring atoms of thiophenothiophene is 8.

[0027] In the present invention, an "aromatic group" refers to an optional functional group or substituent derived from an aromatic carbocyclic ring. The aromatic group can be a monocyclic aryl group (such as a phenyl group) or a polycyclic aryl group. In other words, the aromatic group can be a monocyclic aromatic group, a fused-ring aromatic group, two or more monocyclic aromatic groups conjugated through carbon-carbon bonds, a monocyclic aromatic group and a fused-ring aromatic group conjugated through carbon-carbon bonds, or two or more fused-ring aromatic groups conjugated through carbon-carbon bonds. That is, unless otherwise specified, two or more aromatic groups conjugated through carbon-carbon bonds can also be regarded as the aromatic groups of the present application. Preferably, the aromatic group is selected from those having 6 - 30 C atoms; further preferably, from those having 6 - 20 C atoms; further preferably, from those having 6 - 10 C atoms. The aromatic groups include but are not limited to: phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, fluoranthenyl, triphenylenyl, pyrenyl, perylenyl, tetracenyl, fluorenyl, binaphthylenyl, acenaphthylenyl, and their derivatives.

[0028] In the present invention, a "heteroaromatic group" is a heteroaromatic ring or its derivative containing 1, 2, 3, 4, 5, 6, or more heteroatoms in the ring, and the heteroatoms can be at least one of B, O, N, P, Si, Se, and S. The heteroaromatic group can be a monocyclic heteroaryl group or a polycyclic heteroaryl group. In other words, the heteroaromatic group can be a single heteroaromatic ring system or a plurality of heteroaromatic ring systems conjugated through carbon-carbon bonds, and any heteroaromatic ring system is a heteroaromatic monocyclic ring or a heteroaromatic fused-ring. Preferably, the heteroaromatic group is selected from those having 5 - 30 ring atoms; further preferably, from those having 5 - 20 ring atoms; further preferably, from those having 5 - 10 ring atoms. The heteroaromatic groups include but are not limited to: thienyl, furyl, pyrrolyl, dioxazolyl, triazolyl, imidazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, benzothienyl, benzofuryl, indolyl, pyrroloimidazolyl, pyrrolopyrrolyl, thienopyrrolyl, thienothienyl, furanopyrrolyl, furanofuryl, thienofuryl, benzisoxazolyl, benzisothiazolyl, benzimidazolyl, phthalazinyl, phenanthridinyl, peridinyl, quinazolinone, dibenzothienyl, dibenzofuryl, carbazolyl, and their derivatives.

[0029] In the present invention, the number of carbon atoms of the straight-chain alkyl group can be 1 to 30, 1 to 20, 1 to 16, 1 to 10, or 1 to 6. Non-limiting examples of the straight-chain alkyl group include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, -C 10 H 21。The number of carbon atoms in the branched alkyl group can be 3 to 30, 3 to 20, 3 to 16, 3 to 10, or 3 to 6. Non-limiting examples of the branched alkyl group include: isopropyl, a branched alkyl group having 4 C atoms, a branched alkyl group having 5 C atoms, a branched alkyl group having 6 C atoms, a branched alkyl group having 7 C atoms, a branched alkyl group having 8 C atoms, a branched alkyl group having 9 C atoms, a branched alkyl group having 10 C atoms. The number of carbon atoms in the cyclic alkyl group can be 3 to 30, 3 to 20, 3 to 16, 3 to 10, or 3 to 6. Non-limiting examples of the cyclic alkyl group include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl.

[0030] In the present invention, when the connection site is not specified in the group, it means that any optional connection site in the group can be used as the connection site.

[0031] In the present invention, "independently selected from" one or more groups means that when one or more groups appear simultaneously and in multiple places in the compound, they are all independently selected and can be the same or different.

[0032] In the process of describing the structural elements of the present invention, words such as "comprising" or "including" used in the present invention mean that the devices or materials appearing before this word cover the devices or materials listed after this word and their equivalents, without excluding other devices or materials.

[0033] In the description of the present invention, it should be understood that the orientation or positional relationship indicated by terms such as "upper", "lower", "between layers", etc. is based on the orientation or positional relationship shown in the drawings, or the orientation or positional relationship when the organic solar cell device is used in its usual placement, or the orientation or positional relationship commonly understood by those skilled in the art. It is only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be construed as a limitation to the present invention.

[0034] In the present invention, "its combination", "any combination thereof", "any combination mode thereof", "combination", etc. include all suitable combination modes of any two, any three or any three or more items in the listed groups.

[0035] In the present invention, words such as "further", "furthermore", "especially", etc. are used for descriptive purposes and represent differences in content, but should not be construed as a limitation to the protection scope of the present invention.

[0036] In the present invention, "optionally", "optional", and "option" mean having or not having, that is, any one selected from two parallel options of "having" or "not having". If "optional" appears multiple times in a technical solution, without special instructions, contradictions or mutual restrictions, each "optional" is independent.

[0037] In the present invention, among the technical features described in an open-ended manner, it includes a closed technical solution composed of the listed features, and also includes an open-ended technical solution containing the listed features.

[0038] The present invention provides a heterocyclic organic compound having a structure represented by the general formula (I):

[0039]

[0040] Wherein:

[0041] L 1 is selected from a single bond, a substituted or unsubstituted aromatic group having 6 - 30 carbon atoms, or a substituted or unsubstituted heteroaromatic group having 5 - 30 ring atoms;

[0042] Ar 1 is selected from a substituted or unsubstituted aromatic group having 6 - 30 carbon atoms, or a substituted or unsubstituted heteroaromatic group having 5 - 30 ring atoms;

[0043] R 1 、R 2 、R 3 、R 4 are independently selected from hydrogen, deuterium, cyano, nitro, halogen, a substituted or unsubstituted straight-chain alkyl group having 1 - 20 carbon atoms, a substituted or unsubstituted branched-chain alkyl group or cyclic alkyl group having 3 - 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 - 30 carbon atoms, or a substituted or unsubstituted heteroaromatic group having 5 - 30 ring atoms;

[0044] The "substituted or unsubstituted" means that the defined group is not substituted, or is substituted by one or more substituents R, and each occurrence of the substituent R is independently selected from deuterium, cyano, nitro, halogen, a straight-chain alkyl group having 1 - 20 carbon atoms, a branched-chain alkyl group or cyclic alkyl group having 3 - 20 carbon atoms, an aromatic group having 6 - 30 carbon atoms, a heteroaromatic group having 5 - 30 ring atoms, or a group formed by combining the above groups.

[0045] Further, each occurrence of the substituent R is independently selected from deuterium, cyano, nitro, halogen, a straight-chain alkyl group having 1 to 10 carbon atoms, a branched-chain alkyl group or a cyclic alkyl group having 3 to 10 carbon atoms, an aromatic group having 6 to 20 carbon atoms, a heteroaromatic group having 5 to 20 ring atoms, or a group formed by combining the above groups.

[0046] In one embodiment, the R 1 , R 2 , R 3 , R 4 are independently selected from hydrogen, deuterium, cyano, nitro, halogen, a substituted or unsubstituted straight-chain alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted branched-chain alkyl group or a cyclic alkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms.

[0047] Further, the heterocyclic organic compound has a structure represented by General Formula (II-1), General Formula (II-2), or General Formula (II-3):

[0048]

[0049] Wherein:

[0050] In General Formula (II-2), R 2 , R 4 are selected from deuterium, cyano, nitro, halogen, a substituted or unsubstituted straight-chain alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted branched-chain alkyl group or a cyclic alkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms;

[0051] In General Formula (II-3), R 1 , R 3 are selected from deuterium, cyano, nitro, halogen, a substituted or unsubstituted straight-chain alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted branched-chain alkyl group or a cyclic alkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms.

[0052] In one embodiment, the is selected from any one of the following structures:

[0053]

[0054] Wherein: * represents a connection site.

[0055] In one embodiment, the L1 Selected from a single bond, an aromatic group having 6 - 30 carbon atoms, or a heteroaromatic group having 5 - 30 ring atoms.

[0056] Specifically, the L 1 Is selected from a single bond, phenyl, biphenyl, pyridyl, or naphthyl.

[0057] In one embodiment, the Ar 1 Is selected from any one of the following groups:

[0058]

[0059] Wherein:

[0060] Each occurrence of X is independently selected from C, CR 5 Or N;

[0061] Each occurrence of Y is independently selected from O, S or CR 6 R 7 ;

[0062] R 5 、R 6 、R 7 Are selected from hydrogen, deuterium, cyano, nitro, halogen, a straight-chain alkyl group having 1 - 10 carbon atoms, a branched-chain alkyl group or a cyclic alkyl group having 3 - 10 carbon atoms, an aromatic group having 6 - 20 carbon atoms, or a heteroaromatic group having 5 - 20 ring atoms, or a group formed by combining the above groups;

[0063] When X is a connection site, X is selected from C;

[0064] * represents the connection site.

[0065] In a specific embodiment, the R 6 、R 7 Each occurrence is independently selected from methyl or phenyl.

[0066] Furthermore, Ar 1 Is selected from any one of the following groups:

[0067]

[0068] In a specific embodiment, the R 5 Each occurrence is independently selected from hydrogen, deuterium, cyano, nitro, halogen, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, methyl substituted with one or more deuteriums, ethyl substituted with one or more deuteriums, propyl substituted with one or more deuteriums, isopropyl substituted with one or more deuteriums, butyl substituted with one or more deuteriums, tert-butyl substituted with one or more deuteriums, phenyl, biphenyl, naphthyl, phenanthryl, triphenylenyl, pyridyl, carbazolyl, substituted with one or more R* Substituted phenyl, substituted by one or more R * Substituted biphenyl, substituted by one or more R * Substituted naphthyl, substituted by one or more R * substituted phenoxy, replaced by one or more R * substituted triphenylene, carbazolyl substituted with one or more R*, or * Substituted pyridyl; said R * Each occurrence is independently selected from deuterium, cyano, nitro, halogen, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, methyl substituted with one or more deuteriums, ethyl substituted with one or more deuteriums, propyl substituted with one or more deuteriums, isopropyl substituted with one or more deuteriums, butyl substituted with one or more deuteriums, tert-butyl substituted with one or more deuteriums.

[0069] In one embodiment, R in the general formula (II-2) 2 , R 4 is selected from deuterium, cyano, nitro, halogen, a straight-chain alkyl group having 1 to 10 carbon atoms which may be substituted by deuterium, a branched-chain alkyl group or a cyclic alkyl group having 3 to 10 carbon atoms which may be substituted by deuterium, or any of the following groups:

[0070]

[0071] Wherein: X and Y have the same meanings as described above.

[0072] Specifically, R in the general formula (II-2) 2 , R 4 Selected from deuterium, cyano, nitro, halogen, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, deuterated methyl or any of the following groups:

[0073]

[0074] The R 5 The meaning is the same as above.

[0075] In one embodiment, R in the general formula (II-3) 1 , R 3 is selected from deuterium, cyano, nitro, halogen, a straight-chain alkyl group having 1 to 10 carbon atoms which may be substituted by deuterium, a branched-chain alkyl group or a cyclic alkyl group having 3 to 10 carbon atoms which may be substituted by deuterium, or any of the following groups:

[0076]

[0077] Wherein: X and Y have the same meanings as described above.

[0078] Specifically, R described in general formula (II-3) 1 and R 3 are selected from deuterium, cyano, nitro, halogen, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, deuterated methyl or any one of the following groups:

[0079]

[0080] The meaning of R 5 is the same as described above.

[0081] In a specific embodiment, the heterocyclic organic compound according to the present invention is selected from any one of the following structures, but not limited thereto:

[0082]

[0083]

[0084]

[0085]

[0086]

[0087] Furthermore, the present invention relates to a phosphorescent host material, and the phosphorescent host material is selected from the heterocyclic organic compounds described above.

[0088] The present invention also provides a mixture, which contains the heterocyclic organic compound described above and at least one other organic functional material. Preferably, the other organic functional material is preferably selected from a hole injection material, a hole transport material, an electron transport material, an electron injection material, an electron blocking material, a hole blocking material, a light-emitting guest material or a light-emitting host material. Preferably, the other organic functional material is selected from a light-emitting host material or a light-emitting guest material. More preferably, the other organic functional material is selected from a phosphorescent light-emitting guest material.

[0089] The present invention further relates to an organic electronic device, and the organic electronic device contains the heterocyclic organic compound described above. The organic electronic device according to the present invention may be selected from, but not limited to, an organic light-emitting diode (OLED), an organic photovoltaic cell, an organic field effect transistor, an organic laser, an organic spintronic device, an organic sensor, an organic plasmon emission diode, etc., and is particularly preferably an OLED.

[0090] Furthermore, the organic electronic device includes an anode, a cathode, and a functional layer located between the anode and the cathode, and the functional layer contains the heterocyclic organic compound described above.

[0091] In a specific embodiment, the organic electronic device according to the present invention includes an anode layer, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a cathode layer stacked in sequence from bottom to top; the light-emitting layer contains the heterocyclic organic compound as described above.

[0092] In some embodiments, the organic electronic device further includes a substrate. The substrate can be located on the side of the anode away from the light-emitting layer or on the side of the cathode away from the light-emitting layer. The substrate can be opaque or transparent. The substrate can also be rigid or flexible. For example, the material of the substrate can be plastic, metal, semiconductor wafer, or glass. Preferably, the substrate has a smooth surface, and a substrate without surface defects is a particularly ideal choice. In a preferred embodiment, the substrate is glass, poly(ethylene terephthalate) (PET), or poly(ethylene 2,6-naphthalate) (PEN).

[0093] The material of the anode can be an anode material known in the art for organic electronic devices, such as a conductive metal, a conductive metal oxide, or a conductive polymer. As an example, the material of the anode can be selected from, but not limited to, at least one of Al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, and aluminum-doped zinc oxide (AZO). Other suitable anode materials are known, and those of ordinary skill in the art can easily select and use them.

[0094] The material of the cathode can be a cathode material known in the art for organic electronic devices, such as a conductive metal or a conductive metal oxide. As an example, the material of the cathode can be selected from, but not limited to, at least one of Al, Au, Ag, Ca, Ba, Mg, LiF / Al, MgAg alloy, BaF2 / Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, and ITO. The cathode material can be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), etc.

[0095] The hole injection layer has the functions of reducing the surface roughness of ITO, reducing internal defects in the device, and reducing the hole injection barrier. The material of the hole injection layer can be a material known in the art for hole injection layers, such as, but not limited to, HAT-CN, F4-TCQN, 1-TNATA, 2-TNATA, m-MTDATA, PEDOT:PSS, MoO3, AgO, etc.

[0096] The hole transport layer has the function of improving the hole transport efficiency in the device and blocking electrons in the light-emitting layer. The materials of the hole transport layer can be those known in the art for hole transport layer materials. For example, they can be selected from aromatic amine organic compounds, including but not limited to NPB, CBP, TFB, TCTA, TAPC, TPD, Spiro-TAD, TDATA, etc.

[0097] The light-emitting layer may include a host material and a guest material. The host material includes the heterocyclic organic compound as described above. The guest material is selected from metal complexes, preferably Ir-based metal complexes. Generally, the doping ratio of the guest material is 0.01% - 20%, preferably 0.1% - 15%, and more preferably 1% - 10%.

[0098] The electron transport layer can play a role in promoting electron transport. The electron transport material is a material that advantageously receives electrons from the cathode and transports the electrons to the light-emitting layer, and a material with high electron mobility is suitable. The electron transport layer may include compounds containing heterocycles, such as pyridine derivatives, pyrimidine derivatives, triazine derivatives, benzimidazole derivatives, etc.

[0099] The electron injection layer serves to reduce the electron injection barrier between the cathode and the organic layer and enables effective injection of electrons into the organic layer. The materials of the electron injection layer include but are not limited to the materials described below, such as metals, metal compounds, metal oxides, etc. Specific examples may include lithium (Li), lithium fluoride (LiF), lithium 8-hydroxyquinolate (LiQ), cesium fluoride (CsF), lithium oxide (Li 2 O), cesium carbonate (Cs 2 CO 3 ), etc., but are not limited thereto.

[0100] The present invention also relates to an electronic device comprising the organic electronic device. The present invention relates to the application of the electroluminescent device in various electronic devices. The electronic device can be but is not limited to a display device, a lighting device, a light source, a sensor, etc. The present invention will be specifically described below through specific examples of compound preparation and device effect experiments. The following examples are only partial examples of the present invention and do not limit the present invention.

[0101] Synthesis Example of Heterocyclic Organic Compound

[0102] The present invention has no particular limitation on the sources of the raw materials used in the following various reactions. Commercially available product raw materials can be used or obtained by the preparation methods well known to those skilled in the art. The present invention has no special limitation on the following reactions, and conventional reactions well known to those skilled in the art can be used.

[0103] Synthesis Example 1: Synthesis of Compound (2)

[0104]

[0105] Synthesis of compound 1-3:

[0106] Accurately weigh compound 1-1 (20.62g, 100mmol), 1-2 (32.02g, 100mmol), bis(dibenzylideneacetone)palladium (2.83g, 5mmol), sodium tert-butoxide (28.83g, 300mmol), add them to a 1000mL three-necked flask, add 350mL toluene, replace nitrogen three times, inject 10% tri-tert-butylphosphonium toluene solution (20ml, 10mmol), heat to 80℃ and react for 8h. After the reaction is completed, cool to room temperature, add water to quench the reaction, extract three times with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, concentrate in vacuo, slurry the residue with petroleum ether, and filter to finally obtain about 27.35g of compound 1-3, yield: 61.3%, MS: 445.96.

[0107] Synthesis of compound (2)

[0108] Accurately weigh compound 1-3 (4.46 g, 10 mmol), compound 3-bromobiphenyl (2.56 g, 11 mmol), bis(dibenzylideneacetone)palladium (0.28 g, 0.5 mmol), sodium tert-butoxide (2.88 g, 30 mmol), add them to a 100 mL three-necked flask, add 60 mL toluene, replace nitrogen three times, inject 10% tri-tert-butylphosphonium toluene solution (2 ml, 1 mmol), heat to 80 ° C and react for 8 hours. After the reaction is completed, cool to room temperature, add water to quench the reaction, extract with ethyl acetate three times, combine the organic phases, dry with anhydrous sodium sulfate, concentrate in vacuo, slurry the residue with petroleum ether, and filter to finally obtain about 4.30 g of compound (2), yield: 71.9%, MS: 597.48.

[0109] Synthesis Example 2: Synthesis of Compound (12)

[0110]

[0111] Compound 1-3 (4.46 g, 10 mmol), compound 2-1 (3.14 g, 11 mmol), bis(dibenzylideneacetone)palladium (0.28 g, 0.5 mmol), sodium tert-butoxide (2.88 g, 30 mmol) were accurately weighed and added to a 100 mL three-necked flask in sequence, and 60 mL of toluene was added, nitrogen was replaced three times, and then 10% tri-tert-butylphosphonium toluene solution (2 ml, 1 mmol) was injected, and the mixture was heated to 80°C for 8 h. After the reaction was completed, the mixture was cooled to room temperature, water was added to quench the reaction, and the mixture was extracted three times with ethyl acetate. The organic phases were combined, dried with anhydrous sodium sulfate, and concentrated in vacuo. The residue was slurried with petroleum ether and filtered to finally obtain about 4.05 g of compound (12), with a yield of 62.3% and MS of 649.87.

[0112] Synthesis Example 3: Synthesis of Compound (14)

[0113]

[0114] Compound 1-3 (4.46 g, 10 mmol), 2-bromodibenzothiophene (2.89 g, 11 mmol), bis(dibenzylideneacetone)palladium (0.28 g, 0.5 mmol), sodium tert-butoxide (2.88 g, 30 mmol) were accurately weighed and added to a 100 mL three-necked flask in sequence, and 60 mL of toluene was added, nitrogen was replaced three times, and then 10% tri-tert-butylphosphonium toluene solution (2 ml, 1 mmol) was injected, and the mixture was heated to 80°C for 8 h. After the reaction was completed, the mixture was cooled to room temperature, water was added to quench the reaction, and the mixture was extracted three times with ethyl acetate. The organic phases were combined, dried with anhydrous sodium sulfate, and concentrated in vacuo. The residue was slurried with petroleum ether and filtered to finally obtain about 5.24 g of compound (14), with a yield of 83.4% and MS of 628.06.

[0115] Synthesis Example 4: Synthesis of Compound (19)

[0116]

[0117] Compound 1-1 (2.06 g, 10 mmol), compound 1-2 (7.04 g, 22 mmol), bis(dibenzylideneacetone)palladium (0.45 g, 0.8 mmol), sodium tert-butoxide (4.32 g, 45 mmol) were accurately weighed and added to a 100 mL three-necked flask in sequence. 60 mL of toluene was added, nitrogen was replaced three times, and then 10% tri-tert-butylphosphonium toluene solution (3.2 ml, 1.6 mmol) was injected and heated to 80°C for 8 h. After the reaction was completed, it was cooled to room temperature, water was added to quench the reaction, and it was extracted with ethyl acetate three times. The organic phases were combined, dried over anhydrous sodium sulfate, and concentrated in vacuo. The residue was slurried with petroleum ether and filtered to finally obtain about 5.33 g of compound (19), with a yield of 77.8% and MS of 684.86.

[0118] Synthesis Example 5: Synthesis of Compound (26)

[0119]

[0120] Synthesis of compound 5-2:

[0121] Accurately weigh compound 1-1 (20.62g, 100mmol), compound 5-1 (27.57g, 100mmol), palladium acetate (1.12g, 5mmol), X-Phos (4.77g, 10mmol), sodium tert-butoxide (28.83g, 300mmol), add them to a 1000mL three-necked flask in sequence, add 500mL toluene, replace nitrogen three times, heat to 80°C and react for 8h. After the reaction is completed, cool to room temperature, add water to quench the reaction, extract with ethyl acetate three times, combine the organic phases, dry with anhydrous sodium sulfate, concentrate in vacuo, and purify the residue by column chromatography to finally obtain about 29.02g of compound 5-2, yield: 65.1%, MS: 445.72.

[0122] Synthesis of compound (26):

[0123] Compound 5-2 (4.45 g, 10 mmol), 2-bromonaphthalene (2.28 g, 11 mmol), bis(dibenzylideneacetone)palladium (0.28 g, 0.5 mmol), sodium tert-butoxide (2.88 g, 30 mmol) were accurately weighed and added to a 250 mL three-necked flask in sequence. 80 mL of toluene was added, nitrogen was replaced three times, and then 10% tri-tert-butylphosphonium toluene solution (2 ml, 1 mmol) was injected, and the mixture was heated to 80°C for 8 h. After the reaction was completed, the mixture was cooled to room temperature, water was added to quench the reaction, and the mixture was extracted three times with ethyl acetate. The organic phases were combined, dried with anhydrous sodium sulfate, and concentrated in vacuo. The residue was slurried with petroleum ether and filtered to finally obtain about 4.56 g of compound (26), with a yield of 79.8% and MS of 571.74.

[0124] Synthesis Example 6: Synthesis of Compound (30)

[0125]

[0126] Accurately weigh compound 5-2 (4.45 g, 10 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (2.94 g, 11 mmol), palladium acetate (0.11 g, 0.5 mmol), X-Phos (0.47 g, 1.0 mmol), sodium tert-butoxide (2.88 g, 30 mmol), and successively add them to a 100 mL three-necked flask. Add 60 mL of toluene, displace nitrogen three times, and heat to 80 °C for reaction for 8 h. After the reaction is completed, cool to room temperature, quench the reaction with water, extract three times with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, concentrate in vacuo, slurry the residue with petroleum ether, filter by suction, and finally obtain about 4.49 g of compound (30), yield: 66.4%, MS: 676.59.

[0127] Synthesis Example 7: Synthesis of Compound (31)

[0128]

[0129] Synthesis of Compound 7-1:

[0130] Accurately weigh compound 5-1 (5.5 g, 20 mmol), 4-chlorophenylboronic acid (3.44 g, 22 mmol), palladium acetate (0.22 g, 1.0 mmol), S-Phos (0.82 g, 2 mmol), potassium carbonate (8.30 g, 60 mmol), and successively add them to a 500 mL three-necked flask. Add 160 mL of dioxane and 20 mL of water, displace nitrogen three times, and heat to 90 °C for reaction for 8 h. After the reaction is completed, cool to room temperature, quench the reaction with water, extract three times with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, concentrate in vacuo, slurry the residue with petroleum ether, filter by suction, and finally obtain about 5.46 g of compound 7-1, yield: 77.6%, MS: 352.01.

[0131] Synthesis of Compound 7-2:

[0132] Accurately weigh compound 1-1 (3.09 g, 15 mmol), compound 7-1 (5.28 g, 15 mmol), palladium acetate (0.17 g, 0.75 mmol), X-Phos (0.72 g, 1.5 mmol), sodium tert-butoxide (4.32 g, 45 mmol), and successively add them to a 100 mL three-necked flask. Add 48 mL of dioxane and 6 mL of water, displace nitrogen three times, and heat to 90 °C for reaction for 8 h. After the reaction is completed, cool to room temperature, quench the reaction with water, extract three times with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, concentrate in vacuo, slurry the residue with petroleum ether, filter by suction, and finally obtain about 5.53 g of compound 7-2, yield: 70.7%, MS: 521.81.

[0133] Synthesis of compound (31):

[0134] Compound 7-2 (5.22 g, 10 mmol), bromobenzene (1.73 g, 11 mmol), bis(dibenzylideneacetone)palladium (0.28 g, 0.5 mmol), sodium tert-butoxide (2.88 g, 30 mmol) were accurately weighed and added to a 250 mL three-necked flask in sequence. 80 mL of toluene was added, nitrogen was replaced three times, and then 10% tri-tert-butylphosphonium toluene solution (2 ml, 1 mmol) was injected, and the mixture was heated to 80°C for 8 h. After the reaction was completed, the mixture was cooled to room temperature, water was added to quench the reaction, and the mixture was extracted three times with ethyl acetate. The organic phases were combined, dried with anhydrous sodium sulfate, and concentrated in vacuo. The residue was slurried with petroleum ether and filtered to finally obtain about 4.58 g of compound (31), with a yield of 76.5% and MS of 598.14.

[0135] Synthesis Example 8: Synthesis of Compound (33)

[0136]

[0137] Compound 5-2 (4.45 g, 10 mmol), 9-(4-bromophenyl)carbazole (3.54 g, 11 mmol), bis(dibenzylideneacetone)palladium (0.28 g, 0.5 mmol), sodium tert-butoxide (2.88 g, 30 mmol) were accurately weighed and added to a 250 mL three-necked flask in sequence. 90 mL of toluene was added, nitrogen was replaced three times, and then 10% tri-tert-butylphosphonium toluene solution (2 ml, 1 mmol) was injected, and the mixture was heated to 80°C for 8 h. After the reaction was completed, the mixture was cooled to room temperature, water was added to quench the reaction, and the mixture was extracted three times with ethyl acetate. The organic phases were combined, dried with anhydrous sodium sulfate, and concentrated in vacuo. The residue was slurried with petroleum ether and filtered to finally obtain about 6.03 g of compound (33), with a yield of 87.8% and MS of 686.85.

[0138] Synthesis Example 9: Synthesis of Compound (51)

[0139]

[0140] Compound 5-2 (4.45 g, 10 mmol), compound 9-1 (3.92 g, 11 mmol), palladium acetate (0.11 g, 0.5 mmol), X-Phos (0.47 g, 1.0 mmol), sodium tert-butoxide (2.88 g, 30 mmol) were accurately weighed and added to a 250 mL three-necked flask in sequence, and 80 mL of toluene was added, nitrogen was replaced three times, and the mixture was heated to 80°C for 8 h. After the reaction was completed, the mixture was cooled to room temperature, water was added to quench the reaction, and the mixture was extracted three times with ethyl acetate. The organic phases were combined, dried with anhydrous sodium sulfate, and concentrated in vacuo. The residue was slurried with petroleum ether and filtered to finally obtain about 5.88 g of compound (51), with a yield of 76.8% and MS of 766.12.

[0141] Synthesis Example 10: Synthesis of Compound (64)

[0142]

[0143] Synthesis of compound 10-2:

[0144] Accurately weigh compound 10-1 (21.84g, 60mmol), compound 1-2 (19.21g, 60mmol), bis(dibenzylideneacetone)palladium (1.68g, 3.0mmol), sodium tert-butoxide (17.28g, 180mmol), add them to a 1000mL three-necked flask, add 480mL toluene, replace nitrogen three times, inject 10% tri-tert-butylphosphonium toluene solution (12ml, 6mmol), heat to 80℃ and react for 4h. After the reaction is completed, cool to room temperature, add water to quench the reaction, extract with ethyl acetate three times, combine the organic phases, dry with anhydrous sodium sulfate, concentrate in vacuo, and purify the residue by column chromatography to finally obtain about 16.38g of compound 10-2, with a yield of 45.2% and MS of 603.07.

[0145] Synthesis of compound 10-3:

[0146] Accurately weigh compound 10-2 (12.06g, 20mmol), 3-bromobiphenyl (7.0g, 30mmol), bis(dibenzylideneacetone)palladium (0.56g, 1.0mmol), sodium tert-butoxide (5.76g, 60mmol), add them to a 500mL three-necked flask, add 200mL toluene, replace nitrogen three times, inject 10% tri-tert-butylphosphonium toluene solution (4ml, 2mmol), heat to 80℃ for 4h. After the reaction is completed, cool to room temperature, add water to quench the reaction, extract with ethyl acetate three times, combine the organic phases, dry with anhydrous sodium sulfate, concentrate in vacuo, and purify the residue by column chromatography to finally obtain about 8.67g of compound 10-3, yield: 57.4%, MS: 755.54.

[0147] Synthesis of Compound (64):

[0148] Accurately weigh Compound 10-3 (7.56 g, 10 mmol), 1,3-bis(diphenylphosphinopropane)nickel dichloride (0.54 g, 1 mmol), and 80 ml of anhydrous tetrahydrofuran, add them to a 250 ml three-necked flask, displace nitrogen three times, then cool the reaction system to -78 °C, dropwise add 2.5 M tert-butyllithium (10 ml, 25 mmol). After the addition is complete, warm the reaction system to -50 °C and keep it warm for 3 h while monitoring the reaction. After confirming the reaction is complete, add 10 ml of methanol to the reaction system to quench the reaction. After the reaction is completed, warm it to room temperature, add water, extract three times with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, concentrate in vacuo, and purify the residue by column chromatography to finally obtain about 4.53 g of Compound (64), yield: 63.8%, MS: 709.68.

[0149] Synthesis Example 11: Synthesis of Compound (74)

[0150]

[0151] Synthesis of Compound 11-2:

[0152] Accurately weigh Compound 10-1 (7.28 g, 20 mmol), 11-1 (12.72 g, 60 mmol), palladium acetate (0.44 g, 2 mmol), S-Phos (0.84 g, 4 mmol), and potassium carbonate (8.60 g, 120 mmol), and add them successively to a 500 mL three-necked flask. Add 200 mL of dioxane and 50 ml of water, displace nitrogen three times, and heat to 90 °C for reaction for 8 h. After the reaction is completed, cool it to room temperature, quench the reaction with water, extract three times with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, concentrate in vacuo, and purify the residue by column chromatography to finally obtain about 8.74 g of Compound 11-2, yield: 81.1%, MS: 538.47.

[0153] Synthesis of Compound 11-3:

[0154] Accurately weigh compound 11-2 (5.38 g, 10 mmol), bromobenzene (1.57 g, 10 mmol), bis(dibenzylideneacetone)palladium (0.28 g, 0.5 mmol), sodium tert-butoxide (2.88 g, 30 mmol), add them to a 100 mL three-necked flask, add 50 mL toluene, replace nitrogen three times, inject 10% tri-tert-butylphosphonium toluene solution (2 ml, 1 mmol), heat to 80 ° C for 8 h. After the reaction is completed, cool to room temperature, add water to quench the reaction, extract with ethyl acetate three times, combine the organic phases, dry with anhydrous sodium sulfate, concentrate in vacuo, slurry the residue with petroleum ether, and filter to finally obtain about 4.48 g of compound 11-3, yield: 72.9%, MS: 614.84.

[0155]

[0156] Synthesis of compound 11-4:

[0157] Accurately weigh compound 1-2 (6.40 g, 20 mmol), 4-chlorophenylboronic acid (3.44 g, 22 mmol), palladium acetate (0.22 g, 1.0 mmol), S-Phos (0.82 g, 2 mmol), potassium carbonate (8.30 g, 60 mmol), add them to a 250 mL three-necked flask, add 80 mL of dioxane, 20 ml of water, replace nitrogen three times, heat at 90 ° C for 8 hours. After the reaction is completed, cool to room temperature, add water to quench the reaction, extract with ethyl acetate three times, combine the organic phases, dry with anhydrous sodium sulfate, concentrate in vacuo, slurry the residue with petroleum ether, and filter to finally obtain about 5.52 g of compound 11-4, yield: 78.4%, MS: 352.01. Synthesis of compound (74):

[0158] Compound 11-4 (1.76 g, 5 mmol), compound 11-3 (3.07 g, 5 mmol), palladium acetate (0.06 g, 0.25 mmol), X-Phos (0.24 g, 0.5 mmol), sodium tert-butoxide (1.44 g, 15 mmol) were accurately weighed and added to a 100 mL three-necked flask in sequence, and 50 mL of toluene was added, and the nitrogen was replaced three times, and the mixture was heated to 90°C for 8 h. After the reaction was completed, the mixture was cooled to room temperature, and water was added to quench the reaction. The mixture was extracted three times with ethyl acetate, the organic phases were combined, dried with anhydrous sodium sulfate, and concentrated in vacuo. The residue was slurried with petroleum ether and filtered to finally obtain about 4.07 g of compound (74), with a yield of 87.5% and MS of 930.21.

[0159] Synthesis Example 12: Synthesis of Compound (80)

[0160]

[0161] Synthesis of compound 12-1:

[0162] Accurately weigh compound 10-1 (7.28g, 20mmol), phenylboronic acid (6.10g, 50mmol), palladium acetate (0.44g, 12mmol), S-Phos (0.84g, 4mmol), potassium carbonate (4.60g, 120mmol), add to a 500mL three-necked flask in sequence, add 200mL dioxane, 50ml water, replace nitrogen three times, heat to 90°C and react for 8h. After the reaction is completed, cool to room temperature, add water to quench the reaction, extract with ethyl acetate three times, combine the organic phases, dry with anhydrous sodium sulfate, concentrate in vacuo, slurry the residue with petroleum ether, filter, and finally obtain about 5.94g of compound 12-1, yield: 82.8%, MS: 358.57.

[0163] Synthesis of compound 12-2:

[0164] Accurately weigh compound 12-1 (3.59 g, 10 mmol), 2-bromonaphthalene (2.78 g, 11 mmol), bis(dibenzylideneacetone)palladium (0.28 g, 0.5 mmol), sodium tert-butoxide (2.88 g, 30 mmol), add them to a 100 mL three-necked flask, add 50 mL toluene, replace nitrogen three times, inject 10% tri-tert-butylphosphonium toluene solution (2 ml, 1 mmol), heat to 80 ° C for 8 h. After the reaction is completed, cool to room temperature, add water to quench the reaction, extract with ethyl acetate three times, combine the organic phases, dry with anhydrous sodium sulfate, concentrate in vacuo, slurry the residue with petroleum ether, and filter to finally obtain about 3.80 g of compound 12-2, yield: 78.4%, MS: 484.66.

[0165] Synthesis of compound (80):

[0166] Compound 12-2 (2.42 g, 5 mmol), compound 5-1 (1.38 g, 5 mmol), palladium acetate (0.055 g, 0.25 mmol), X-Phos (0.235 g, 0.5 mmol), sodium tert-butoxide (1.44 g, 15 mmol) were accurately weighed and added to a 100 mL three-necked flask in sequence, and 50 mL of toluene was added, nitrogen was replaced three times, and the mixture was heated at 90°C for 8 h. After the reaction was completed, the mixture was cooled to room temperature, water was added to quench the reaction, and the mixture was extracted three times with ethyl acetate. The organic phases were combined, dried with anhydrous sodium sulfate, and concentrated in vacuo. The residue was slurried with petroleum ether and filtered to finally obtain about 3.05 g of compound (80), with a yield of 84.3% and MS of 723.82.

[0167] Synthesis Example 13: Synthesis of Compound (90)

[0168]

[0169] Synthesis of Compound 13-2:

[0170] Accurately weigh Compound 13-1 (10.92 g, 30 mmol), phenylboronic acid (9.15 g, 75 mmol), palladium acetate (0.66 g, 3 mmol), S-Phos (1.26 g, 6 mmol), and potassium carbonate (12.90 g, 180 mmol). Add them successively to a 500 mL three-necked flask, then add 300 mL of dioxane and 25 mL of water. Replace nitrogen three times, and heat to 90 °C for reaction for 8 h. After the reaction is completed, cool to room temperature, quench the reaction with water, extract three times with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, concentrate under vacuum, slurry the residue with petroleum ether, filter by suction. Finally, about 9.19 g of Compound 13-2 is obtained, with a yield of 85.4%, MS: 358.57.

[0171] Synthesis of Compound 13-3:

[0172] Accurately weigh Compound 13-2 (7.18 g, 20 mmol), 4-bromobiphenyl (4.66 g, 20 mmol), bis(dibenzylideneacetone)palladium (0.56 g, 1.0 mmol), and sodium tert-butoxide (5.76 g, 60 mmol). Add them successively to a 250 mL three-necked flask, then add 100 mL of toluene. Replace nitrogen three times, then inject 10% tris(tert-butylphosphine)toluene solution (4 mL, 2 mmol), and heat to 80 °C for reaction for 8 h. After the reaction is completed, cool to room temperature, quench the reaction with water, extract three times with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, concentrate under vacuum, slurry the residue with petroleum ether, filter by suction. Finally, about 8.2 g of Compound 13-3 is obtained, with a yield of 80.3%, MS: 510.52.

[0173] Synthesis of Compound (90):

[0174] Accurately weigh Compound 13-3 (5.10 g, 10 mmol), Compound 1-2 (3.20 g, 10 mmol), bis(dibenzylideneacetone)palladium (0.28 g, 0.5 mmol), and sodium tert-butoxide (2.88 g, 30 mmol). Add them successively to a 250 mL three-necked flask, then add 100 mL of toluene. Replace nitrogen three times, then inject 10% tris(tert-butylphosphine)toluene solution (2 mL, 1 mmol), and heat to 80 °C for reaction for 8 h. After the reaction is completed, cool to room temperature, quench the reaction with water, extract three times with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, concentrate under vacuum, slurry the residue with petroleum ether, filter by suction. Finally, about 6.53 g of Compound (90) is obtained, with a yield of 87.0%, MS: 750.22.

[0175] Synthesis Example 14: Synthesis of Compound (109)

[0176]

[0177] Synthesis of compound 14-2:

[0178] Accurately weigh compound 13-1 (10.92g, 30mmol), compound 14-1 (17.10g, 75mmol), palladium acetate (0.66g, 3mmol), S-Phos (1.26g, 6mmol), potassium carbonate (12.90g, 180mmol), add them to a 1000mL three-necked flask, add 300mL dioxane, 75ml water, replace nitrogen three times, heat to 90°C and react for 8h. After the reaction is completed, cool to room temperature, add water to quench the reaction, extract with ethyl acetate three times, combine the organic phases, dry with anhydrous sodium sulfate, concentrate in vacuo, slurry the residue with petroleum ether, filter, and finally obtain about 12.84g of compound 14-2, yield: 75.0%, MS: 570.69.

[0179] Synthesis of compound 14-3:

[0180] Accurately weigh compound 14-2 (11.41 g, 20 mmol), 4-tert-butyl bromobenzene (4.26 g, 20 mmol), bis(dibenzylideneacetone) palladium (0.56 g, 1.0 mmol), sodium tert-butoxide (5.76 g, 60 mmol), add them to a 500 mL three-necked flask, add 200 mL toluene, replace nitrogen three times, inject 10% tri-tert-butylphosphonium toluene solution (4 ml, 2 mmol), heat to 80 ° C for 8 h. After the reaction is completed, cool to room temperature, add water to quench the reaction, extract with ethyl acetate three times, combine the organic phases, dry with anhydrous sodium sulfate, concentrate in vacuo, slurry the residue with petroleum ether, and filter to finally obtain about 11.26 g of compound 14-3, yield: 80.1%, MS: 702.61.

[0181] Synthesis of compound (109):

[0182] Accurately weigh Compound 14-3 (7.02 g, 10 mmol), Compound 5-1 (2.75 g, 10 mmol), palladium acetate (0.11 g, 0.5 mmol), X-Phos (0.47 g, 1.0 mmol), and sodium tert-butoxide (2.88 g, 30 mmol), and successively add them to a 250 mL three-necked flask. Add 100 mL of toluene, displace nitrogen three times, and heat at 90 °C for 8 h. After the reaction is completed, cool to room temperature, quench the reaction with water, extract three times with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, concentrate under vacuum, slurry the residue with petroleum ether, filter by suction, and finally obtain about 7.38 g of Compound (109), yield: 78.3%, MS: 942.37.

[0183] Device Example

[0184] The OLED device structure provided by the present invention is as follows: ITO / HI-1 (10 nm) / HT-1 (60 nm) / HT-2 (5 nm) / Host material: EM-1 (35 nm) / ET-1:LiQ (5:5, 30 nm) / LiQ (1 nm) / Al (100 nm). Specifically as Figure 1 shown.

[0185] The preparation steps of the OLED-1 device are as follows:

[0186] Step a, cleaning of the ITO conductive glass substrate: Clean the ITO conductive glass successively with chloroform, ketone, and isopropanol, and then perform ultraviolet ozone treatment;

[0187] Step b, preparation of the hole injection layer: Transfer the cleaned conductive glass substrate to a nitrogen glove box, and under high vacuum (1×10 -6 mbar) conditions, vacuum deposit the organic compound HI-1 on the ITO substrate to form a hole injection layer, and the deposition thickness is 10 nm.

[0188] Step c, preparation of the first hole transport layer: Vacuum deposit the organic compound HT-1 on the hole injection layer to form a hole transport layer, and the deposition thickness is 60 nm.

[0189] Step d, preparation of the second hole transport layer: Vacuum deposit the organic compound HT-2 on the first hole transport layer to form a second hole transport layer, and the deposition thickness is 5 nm.

[0190] Step e, preparation of the light-emitting layer: Vacuum deposit the host material and the guest material EM-1 on the second hole transport layer to form a light-emitting layer, and the deposition thickness is 35 nm; wherein the host material includes a first host material and a second host material, the first host material is selected from Compound (2), the second host material is selected from Compound H-1, and the mass ratio of Compound (2):Compound H-1:EM-1 is 48:48:4.

[0191] Step f, Preparation of electron transport layer: Evaporate ET-1 and LiQ in vacuum on the light-emitting layer to form the electron transport layer. Specifically, in a vacuum chamber, place the electron transport material ETM-1 and LiQ in different evaporation crucibles, and co-deposit ETM-1 and LiQ at a weight ratio of 5:5 under a high vacuum environment (1×10 -6 mbar) to obtain the electron transport layer, with an evaporation thickness of 30 nm.

[0192] Step g, Preparation of cathode layer: Evaporate LiQ / Al (1 nm / 100 nm) in vacuum on the electron transport layer as the cathode layer;

[0193] Step h, Encapsulation: Encapsulate the device with ultraviolet curable resin in a nitrogen glove box.

[0194] Among them, the chemical structural formulas of HI-1, HT-1, HT-2, EM-1, and ET-1 are as follows:

[0195]

[0196] Fabrication of OLED-2 to OLED-14 devices:

[0197] The fabrication methods of OLED-2 to OLED-14 devices are the same as that of OLED-1, and the difference lies in: the selection of the first host material in the light-emitting layer is different. Specifically, replace the first host material compound (2) in the light-emitting layer of OLED-1 with compound (12), compound (14), compound (19), compound (26), compound (30), compound (31), compound (33), compound (51), compound (64), compound (74), compound (80), compound (90), and compound (109) respectively. See Table 1 for details.

[0198] Fabrication of OLED-Ref device:

[0199] The fabrication method of OLED-Ref device is the same as that of OLED-1, and the difference lies in: the selection of the first host material in the light-emitting layer is different. Specifically, replace the host material compound (2) in the light-emitting layer of OLED-1 with compound (Ref).

[0200]

[0201] Characterize the current-voltage (J-V) characteristics of OLED-1 to OLED-14 and OLED-Ref devices, and record important parameters such as luminous efficiency and lifetime at the same time, as shown in Table 1. Among them, the luminous efficiency is at a current density of 10 mA / cm 2The relative value obtained at that time, and the lifetime (LT95) is the time it takes for the device brightness to decrease from the initial 1000 nits to 95% under a constant current.

[0202] Table 1

[0203]

[0204] As can be seen from Table 1, when the heterocyclic compound described in the present invention is used as the host material in the OLED light-emitting layer, compared with OLED-ref, both the luminous efficiency and the lifetime are significantly improved. The reason is that: by introducing On the one hand it has a large conjugated plane, making the molecule have great rigidity, thus enhancing the stability of the compound; on the other hand, through the design of the molecular structure, the energy levels of the compound are optimized, which can be well matched with the energy levels of adjacent organic functional layers, thus having good charge transport performance, and further significantly improving the efficiency and lifetime of the OLED device applying the compound of the present application.

[0205] The technical features of the above-described embodiments can be combined arbitrarily. For the sake of brevity of description, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, it should be considered as the scope described in this specification.

[0206] The above-described embodiments only represent several implementation manners of the present application. Their descriptions are relatively specific and detailed, but they should not be construed as limiting the scope of the patent application. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present application, several modifications and improvements can still be made, and these all belong to the protection scope of the present application. Therefore, the protection scope of the patent of the present application should be subject to the appended claims.

Claims

1. A heterocyclic organic compound, characterized in that: The heterocyclic organic compound has a structure as shown in general formula (I), in: L1 is selected from a single bond, a substituted or unsubstituted aromatic group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms; Ar1 is selected from a substituted or unsubstituted aromatic group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms; R1, R2, R3, and R4 are independently selected from hydrogen, deuterium, cyano, nitro, halogen, substituted or unsubstituted straight-chain alkyl having 1 to 20 carbon atoms, substituted or unsubstituted branched or cyclic alkyl having 3 to 20 carbon atoms, substituted or unsubstituted aromatic group having 6 to 30 carbon atoms, or substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms; The term "substituted or unsubstituted" means that the defined group is not substituted or is substituted by one or more substituents R, wherein each occurrence of the substituent R is independently selected from deuterium, cyano, nitro, halogen, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched-chain alkyl group or a cyclic alkyl group having 3 to 20 carbon atoms, an aromatic group having 6 to 30 carbon atoms, a heteroaromatic group having 5 to 30 ring atoms, or a group formed by a combination of the above groups.

2. The heterocyclic organic compound according to claim 1, characterized in that: The heterocyclic organic compound has a structure as shown in general formula (II-1), general formula (II-2) or general formula (II-3): in: In the general formula (II-2), R2 and R4 are selected from deuterium, cyano, nitro, halogen, substituted or unsubstituted straight-chain alkyl having 1 to 10 carbon atoms, substituted or unsubstituted branched alkyl or cyclic alkyl having 3 to 10 carbon atoms, substituted or unsubstituted aromatic group having 6 to 20 carbon atoms, or substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms; In the general formula (II-3), R1 and R3 are selected from deuterium, cyano, nitro, halogen, substituted or unsubstituted straight-chain alkyl groups having 1 to 10 carbon atoms, substituted or unsubstituted branched alkyl groups or cyclic alkyl groups having 3 to 10 carbon atoms, substituted or unsubstituted aromatic groups having 6 to 20 carbon atoms, or substituted or unsubstituted heteroaromatic groups having 5 to 20 ring atoms.

3. The heterocyclic organic compound according to claim 1 or 2, characterized in that: Said Select from any of the following structures: Where: * represents the connection site.

4. The heterocyclic organic compound according to claim 1 or 2, characterized in that: The L1 is selected from a single bond, a phenyl group, a biphenyl group, a pyridyl group, or a naphthyl group.

5. The heterocyclic organic compound according to claim 1 or 2, characterized in that: The Ar1 is selected from any of the following groups: in: Each occurrence of X is independently selected from C, CR5 or N; Each occurrence of Y is independently selected from O, S or CR6R7; R5, R6, and R7 are selected from hydrogen, deuterium, cyano, nitro, halogen, a straight-chain alkyl group having 1 to 10 carbon atoms, a branched alkyl group or a cyclic alkyl group having 3 to 10 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a heteroaromatic group having 5 to 20 ring atoms, or a group formed by a combination of the above groups; When X is a linking site, X is selected from C; * indicates the attachment site.

6. The heterocyclic organic compound according to claim 5, characterized in that: Each occurrence of R5 is independently selected from hydrogen, deuterium, cyano, nitro, halogen, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, methyl substituted with one or more deuterium, ethyl substituted with one or more deuterium, propyl substituted with one or more deuterium, isopropyl substituted with one or more deuterium, butyl substituted with one or more deuterium, tert-butyl substituted with one or more deuterium, phenyl, biphenyl, naphthyl, phenanthrenyl, triphenylene, pyridyl, carbazolyl, substituted with one or more R * Substituted phenyl, substituted by one or more R * Substituted biphenyl, substituted by one or more R * Substituted naphthyl, substituted by one or more R * substituted phenoxy, replaced by one or more R * substituted triphenylene, carbazolyl substituted with one or more R*, or * Substituted pyridyl; said R * Each occurrence is independently selected from deuterium, cyano, nitro, halogen, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, methyl substituted with one or more deuteriums, ethyl substituted with one or more deuteriums, propyl substituted with one or more deuteriums, isopropyl substituted with one or more deuteriums, butyl substituted with one or more deuteriums, tert-butyl substituted with one or more deuteriums.

7. The heterocyclic organic compound according to claim 2, characterized in that: In the general formula (II-2), R2 and R4 are selected from deuterium, cyano, nitro, halogen, a straight-chain alkyl group having 1 to 10 carbon atoms which is substituted or not substituted by deuterium, a branched alkyl group or a cyclic alkyl group having 3 to 10 carbon atoms which is substituted or not substituted by deuterium, or any of the following groups: And / or, in the general formula (II-3), R1 and R3 are selected from deuterium, cyano, nitro, halogen, a straight-chain alkyl group having 1 to 10 carbon atoms which is substituted or not substituted by deuterium, a branched alkyl group or a cyclic alkyl group having 3 to 10 carbon atoms which is substituted or not substituted by deuterium, or any of the following groups: in: Each occurrence of X is independently selected from CR5 or N; Each occurrence of Y is independently selected from O, S or CR6R7; R5, R6, and R7 are selected from hydrogen, deuterium, cyano, nitro, halogen, a straight-chain alkyl group having 1 to 10 carbon atoms, a branched alkyl group or a cyclic alkyl group having 3 to 10 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a heteroaromatic group having 5 to 20 ring atoms, or a group formed by a combination of the above groups; * indicates the attachment site.

8. The heterocyclic organic compound according to claim 1, characterized in that: The heterocyclic organic compound is selected from any of the following structures:

9. A mixture, characterized in that: The mixture comprises a heterocyclic organic compound as described in any one of claims 1 to 8, and at least another organic functional material, wherein the another organic functional material is preferably selected from hole injection materials, hole transport materials, electron transport materials, electron injection materials, electron blocking materials, hole blocking materials, luminescent guest materials or luminescent host materials.

10. An organic electronic device, characterized in that: The organic electronic device comprises the heterocyclic organic compound according to any one of claims 1 to 8, or the mixture according to claim 9.

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