Organic compound and application thereof

Abstract

The invention relates to the technical field of organic electroluminescence, in particular to an organic compound, application of the organic compound and an organic electroluminescence device containing the compound, in particular to a novel thermal activation delayed fluorescent material and an organic electroluminescence device adopting the compound as a luminescent layer luminescent dye and a sensitizer. The compound disclosed by the invention has structures shown as a formula (1), a formula (2), a formula (3), a formula (4), a formula (5) and a formula (6). The compound disclosed by the invention has the advantages that the compound has higher photoluminescence quantum efficiency and faster reverse intersystem crossing rate when being used as a luminescent dye in an OLED (Organic Light Emitting Diode) device, and can show excellent device efficiency and device service life when being used as a luminescent layer sensitizer. The invention also protects the organic light-emitting device adopting the compound with the general formula. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to the technical field of organic electroluminescence, and particularly to an organic compound, its application, and an organic electroluminescent device comprising the compound, specifically to a thermally activated delayed fluorescence material. Background Art

[0002] Organic light emitting diodes (OLEDs) are devices with a sandwich-like structure, including positive and negative electrode layers and an organic functional material layer sandwiched between the electrode layers. When a voltage is applied to the electrodes of the OLED device, positive charges are injected from the positive electrode and negative charges are injected from the negative electrode. Under the action of the electric field, the positive and negative charges migrate and meet in the organic layer to recombine and emit light. Due to the advantages of high brightness, fast response, wide viewing angle, simple process, and flexibility of OLED devices, they have attracted much attention in the fields of new display technology and new lighting technology. Currently, this technology has been widely applied to the display panels of new lighting lamps, smartphones, tablet computers and other products, and will further expand to the application fields of large-size display products such as televisions. It is a new display technology with rapid development and high technical requirements.

[0003] With the continuous advancement of OLEDs in the two major fields of lighting and display, people have paid more attention to the research of their core materials. Because an OLED device with good efficiency and long life is usually the result of the optimization of the device structure and various organic materials, this provides great opportunities and challenges for chemists to design and develop functional materials with various structures. Common functional organic materials include: hole injection materials, hole transport materials, hole blocking materials, electron injection materials, electron transport materials, electron blocking materials, as well as light-emitting host materials and light-emitting guests (dyes), etc.

[0004] In the selection of OLED luminescent materials, fluorescent materials that emit light in the singlet state have good lifetime and low price, but low efficiency; phosphorescent materials that emit light in the triplet state have high efficiency, but high price, and the lifetime problem of blue light materials has not been solved. Adachi of Kyushu University in Japan proposed a new type of organic luminescent material, namely thermally activated delayed fluorescence (TADF) materials. This type of material utilizes the separation of donors and acceptors to obtain a small singlet-triplet energy gap (ΔE ST )(<0.3 eV), so that triplet excitons can be converted into singlet excitons by reverse intersystem crossing (RISC) to emit light. Therefore, the internal quantum efficiency of the device can reach 100%.

[0005] To fabricate OLED light-emitting devices with lower driving voltages, better luminous efficiency, and longer device lifetimes, and to continuously improve the performance of OLED devices, it is necessary not only to innovate the OLED device structure and manufacturing process, but also to continuously research and innovate the optoelectronic functional materials in OLED devices to prepare functional materials with higher performance. Based on this, the OLED materials industry has been committed to developing new organic electroluminescent materials to achieve low turn-on voltages, high luminous efficiency, and better service lifetimes for devices. Summary of the Invention

[0006] To solve the above technical problems, the present invention provides an organic compound that can be applied to the field of organic electroluminescence.

[0007] This organic compound of the present invention has a structure represented by Formula (1), Formula (2), Formula (3), Formula (4), Formula (5), or Formula (6):

[0008]

[0009]

[0010] Wherein: The dashed-line content represents the part that cannot be seen from the front view angle in the three-dimensional structure of the compound molecule;

[0011] D 1 、D 2 、D 3 、D 4 、D 5 、D 6 and D 7 are each independently selected from an unsubstituted or R''' -substituted C6 - C60 aryl group or an unsubstituted or R''' -substituted C3 - C60 heteroaryl group;

[0012] The π 1 、π 2 、π 3 and π 4 in the structures of Formula (1), Formula (2), Formula (3), Formula (4), Formula (5), and Formula (6) are bridging groups, and π 1 、π 2 、π 3 and π 4 are each independently selected from an unsubstituted or R'-substituted C6 - C60 aryl group or an unsubstituted or R'-substituted C3 - C60 heteroaryl group, and at least one of π 1 、π 2 、π 3 and π 4 is a group with electron-withdrawing properties, or π 1 、π 2 、π 3and π 4 at least one of the substituents on is a group with electron-withdrawing properties;

[0013] The group with electron-withdrawing properties is selected from one or a combination of two of the following groups: cyano, isocyano, halogen, aldehyde group, carboxyl group, carbonyl group, nitro group, unsubstituted or R'-substituted xanthone, unsubstituted or R'-substituted thioxanthone, unsubstituted or R'-substituted selenoxanthone, unsubstituted or R'-substituted C3-C60 heteroaryl containing sp2 hybridized nitrogen atoms, unsubstituted or R'-substituted C3-C60 heteroaryl containing boron atoms; unsubstituted or R''-substituted C1-C10 linear alkyl, unsubstituted or R''-substituted C3-C60 heteroaryl without sp2 hybridized nitrogen atoms and boron atoms, unsubstituted or R''-substituted C6-C60 aryl;

[0014] Each of the above R''', R' is independently selected from one or a combination of two of deuterium, halogen, cyano, isocyano, aldehyde group, carboxyl group, carbonyl group, nitro group, hydroxyl group, amino group, C1-C30 linear alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C1-C30 alkoxy group, C1-C20 alkylthio group, C1-C20 alkylsilyl group, C1-C20 alkylamino group, C6-C60 aryl ether group, C3-C60 heteroaryl ether group, C6-C60 arylthioether group, C3-C60 heteroarylthioether group, C6-C60 arylsilyl group, C3-C60 heteroarylsilyl group, C2-C30 aliphatic chain hydrocarbon amino group, C4-C30 cyclic aliphatic chain hydrocarbon amino group, C6-C30 arylamino group, C3-C30 heteroarylamino group, C6-C30 aryloxy group, C6-C60 arylboron group, C6-C60 aryl, C3-C60 heteroaryl.

[0015] Each of the above R'' is independently selected from one or a combination of two of halogen, cyano, isocyano, aldehyde group, carboxyl group, carbonyl group, nitro group.

[0016] Preferably, in the above general formula, when D 1 , D 2 , D 3 , D 4 , D 5 , D 6 and D 7 are each independently connected to the corresponding π 1 , π 2 , π 3 and π 4 , it is through D 1 , D 2 , D 3 , D 4 , D 5 , D 6 or D 7The C atom or N atom on the aryl parent nucleus is independently connected to the corresponding π 1 , π 2 , π 3 or π 4 .

[0017] The innovative point of the structural design of this type of compound of the present invention is: based on the donor-acceptor (D-A) structural characteristics of traditional thermally activated delayed fluorescence materials (TADF), by introducing a central π moiety, the donor groups that could originally rotate freely are connected and locked, thereby effectively suppressing the free rotation of the peripheral donor groups, making the HOMO of the molecule mainly distributed on the peripheral donor groups, while the LUMO is mainly concentrated on the central π moiety, which further leads to a more obvious spatial separation between the HOMO and LUMO, thereby effectively reducing the singlet-triplet energy gap (ΔE ST ) of the molecule, increasing the reverse intersystem crossing rate of the molecule, realizing the efficient utilization of excitons, and improving the luminescence efficiency. And directly connecting the central π moiety through the carbon atom or nitrogen atom on the donor aromatic ring parent nucleus to lock the donor can also significantly improve the structural rigidity of the molecule, thereby effectively weakening the vibration of the molecule, suppressing the non-radiative transition and energy loss caused by the molecular vibration, reducing the relaxation degree of the excited state structure, and improving the luminescence quantum yield, color purity and stability of the molecule. In addition, such a method can also enable the molecule to have a high reverse intersystem crossing rate and luminescence quantum yield while maintaining blue light emission, thereby realizing efficient and fast blue light and deep blue light TADF materials, and then preparing efficient and stable blue light and deep blue light OLED devices, which helps the commercial application of the materials.

[0018] It should be noted that unless otherwise defined hereinafter, the meanings of all technical terms and scientific terms used herein are intended to be the same as those commonly understood by those skilled in the art. The technologies mentioned herein are intended to refer to the technologies commonly understood in the art, including those variations of the technologies that are obvious to those skilled in the art or equivalent technical substitutions. Although it is believed that the following terms are well understood by those skilled in the art, the following definitions are still set forth to better explain the present invention.

[0019] In this specification, the expression of Ca~Cb means that the group has a carbon atom number of a~b. Generally speaking, unless otherwise specified, the carbon atom number does not include the carbon atom number of the substituent. When describing C1~C30, it includes but is not limited to C1, C2, C3, C4, C3, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C22, C24, C26, C28, etc., and other numerical ranges will not be elaborated.

[0020] The terms "comprising", "including", "having", "containing", or "involving" and other variant forms thereof herein are inclusive or open-ended and do not exclude other unrecited elements or method steps.

[0021] In the present invention, for the description of chemical elements, unless otherwise specified, the concept of isotopes with the same chemical properties is usually included. For example, the description of "hydrogen" also includes the concepts of "deuterium" and "tritium" with the same chemical properties. Carbon (C) includes 12 C, 13 C, etc., which will not be elaborated herein.

[0022] The heteroatoms in the present invention usually refer to those selected from N, O, S, P, Si, and Se, preferably selected from N, O, and S.

[0023] As used herein, the terms "heterocyclic group" and "heterocycle" refer to saturated (i.e., heterocycloalkyl) or partially unsaturated (i.e., having one or more double bonds and / or triple bonds within the ring) cyclic groups in which at least one ring atom is a heteroatom selected from N, O, and S and the remaining ring atoms are C.

[0024] As used herein, the terms "(sub)aryl" and "aryl" refer to monocyclic or fused polycyclic aromatic groups of all-carbon having a conjugated π-electron system. As used herein, the terms "(sub)heteroaryl" and "heteroaryl" refer to monocyclic, bicyclic, or tricyclic aromatic ring systems. As used herein, the term "aralkyl" preferably represents an alkyl group substituted with an aryl or heteroaryl group, wherein the aryl, heteroaryl, and alkyl are as defined herein.

[0025] As used herein, the term "halo" or "halogen" group is defined to include F, Cl, Br, or I.

[0026] The term "substituted" means that one or more (e.g., one, two, three, or four) hydrogens on the specified atom are replaced by a selection from the indicated groups, provided that the normal valence of the specified atom in the current case is not exceeded and the substitution forms a stable compound. Combinations of substituents and / or variables are only permitted when such combinations form stable compounds.

[0027] If a substituent is described as "independently selected from" a group, each substituent is selected independently of the other. Thus, each substituent can be the same as or different from another (other) substituent.

[0028] As used herein, the term "one or more" means 1 or more than 1 under reasonable conditions, such as 2, 3, 4, 5, or 10.

[0029] Unless otherwise specified, as used herein, the point of attachment of a substituent can be from any suitable position of the substituent.

[0030] When the bond of a substituent is shown as passing through the bond connecting two atoms in a ring, such a substituent can be bonded to any ring-forming atom in the ring that can be substituted.

[0031] The term "about" means within ±10% of the stated value, preferably within ±5%, more preferably within ±2%.

[0032] In the structural formulas disclosed in this specification, the expression of a ring structure with a "-" drawn across it indicates that the connection site is at any position on the ring structure where bonding can occur.

[0033] The above-mentioned C6-C60 aryl and C3-C60 heteroaryl groups in the present invention, unless otherwise specified, are aromatic groups that satisfy the π-conjugated system, and both include the cases of monocyclic residues and polycyclic residues. A monocyclic residue refers to a molecule containing at least one phenyl group. When the molecule contains at least two phenyl groups, the phenyl groups are independent of each other and are connected by single bonds. Exemplarily, such as phenyl, biphenyl, terphenyl, etc.; a polycyclic residue refers to a molecule containing at least two benzene rings, but the benzene rings are not independent of each other, but are fused to each other by sharing ring edges. Exemplarily, such as naphthyl, anthryl, phenanthryl, etc.; a monocyclic heteroaryl refers to a molecule containing at least one heteroaryl group. When the molecule contains a heteroaryl group and other groups (such as aryl, heteroaryl, alkyl, etc.), the heteroaryl group and other groups are independent of each other and are connected by single bonds. Exemplarily, such as pyridine, furan, thiophene, etc.; a polycyclic heteroaryl refers to a group formed by the fusion of at least one phenyl group and at least one heteroaryl group, or by the fusion of at least two heteroaryl groups. Exemplarily, such as quinoline, isoquinoline, benzofuran, dibenzofuran, benzothiophene, dibenzothiophene, etc.

[0034] In this specification, the substituted or unsubstituted C6-C60 aryl group is preferably a C6-C30 aryl group, more preferably an aromatic ring selected from the group consisting of phenyl, naphthyl, anthryl, benzanthryl, phenanthryl, benzophenanthryl, pyrenyl, chrysenyl, perylenyl, fluoranthenyl, tetraphenyl, pentaphenyl, benzopyrenyl, biphenyl, terphenyl, triphenyl, quaterphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthryl, dihydropyrenyl, tetrahydropyrenyl, cis- or trans-indeno[1,2-b]fluorene, truxenyl, isotruxenyl, spirotruxenyl, spiroisotruxenyl. Specifically, biphenyl is selected from 2-biphenyl, 3-biphenyl, and 4-biphenyl; terphenyl includes p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl, and m-terphenyl-2-yl; the naphthyl group includes 1-naphthyl or 2-naphthyl; anthryl is selected from the group consisting of 1-anthryl, 2-anthryl, and 9-anthryl; the fluorenyl group is selected from the group consisting of 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl, and 9-fluorenyl; the pyrenyl group is selected from the group consisting of 1-pyrenyl, 2-pyrenyl, and 4-pyrenyl; tetraphenyl is selected from the group consisting of 1-tetraphenyl, 2-tetraphenyl, and 9-tetraphenyl. As a preferred example of the aromatic ring in the present invention, groups selected from the group consisting of phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, indenyl, fluorenyl and its derivatives, fluoranthenyl, triphenylene, pyrenyl, perylenyl, groups in the group consisting of and tetraphenyl. The biphenyl is selected from 2-biphenyl, 3-biphenyl, and 4-biphenyl; the terphenyl includes p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl, and m-terphenyl-2-yl; the naphthyl group includes 1-naphthyl or 2-naphthyl; the anthryl is selected from the group consisting of 1-anthryl, 2-anthryl, and 9-anthryl; the fluorenyl group is selected from the group consisting of 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl, and 9-fluorenyl; the fluorenyl derivatives are selected from the group consisting of 9,9-dimethylfluorene, 9,9-spirobifluorene, and benzofluoren; the pyrenyl group is selected from the group consisting of 1-pyrenyl, 2-pyrenyl, and 4-pyrenyl; the tetraphenyl is selected from the group consisting of 1-tetraphenyl, 2-tetraphenyl, and 9-tetraphenyl.

[0035] In this specification, the substituted or unsubstituted C6-C60 aryl group is preferably a C6-C30 aryl group, more preferably a group selected from the group consisting of phenyl, naphthyl, anthracenyl, benzanthracenyl, phenanthryl, benzophenanthryl, pyrenyl, chrysenyl, perylenyl, fluoranthenyl, tetraphenyl, pentaphenyl, benzopyrenyl, biphenyl, terphenyl, triphenyl, tetraphenyl, fluorene, spirobifluorene, dihydrophenanthryl, dihydropyrenyl, tetrahydropyrenyl, cis- or trans-indeno[1,2-b]fluorene, truxene, isotruxene, spirotruxene, spiroisotruxene. Specifically, biphenyl is selected from 2-biphenyl, 3-biphenyl and 4-biphenyl; terphenyl includes p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl and m-terphenyl-2-yl; the naphthyl group includes 1-naphthyl or 2-naphthyl; anthracenyl is selected from the group consisting of 1-anthracenyl, 2-anthracenyl and 9-anthracenyl; the fluorene group is selected from the group consisting of 1-fluorene, 2-fluorene, 3-fluorene, 4-fluorene and 9-fluorene; the pyrenyl group is selected from the group consisting of 1-pyrenyl, 2-pyrenyl and 4-pyrenyl; tetraphenyl is selected from the group consisting of 1-tetraphenyl, 2-tetraphenyl and 9-tetraphenyl. As a preferred example of the aryl group in the present invention, there may be mentioned a group selected from the group consisting of phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, indenyl, fluorene and its derivatives, fluoranthenyl, triphenylene, pyrenyl, perylenyl, a group selected from the group consisting of tetraphenyl and pentaphenyl. The biphenyl is selected from 2-biphenyl, 3-biphenyl and 4-biphenyl; the terphenyl includes p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl and m-terphenyl-2-yl; the naphthyl group includes 1-naphthyl or 2-naphthyl; the anthracenyl is selected from the group consisting of 1-anthracenyl, 2-anthracenyl and 9-anthracenyl; the fluorene group is selected from the group consisting of 1-fluorene, 2-fluorene, 3-fluorene, 4-fluorene and 9-fluorene; the fluorene derivatives are selected from the group consisting of 9,9-dimethylfluorene, 9,9-spirobifluorene and benzofluorene; the pyrenyl group is selected from the group consisting of 1-pyrenyl, 2-pyrenyl and 4-pyrenyl; the tetraphenyl is selected from the group consisting of 1-tetraphenyl, 2-tetraphenyl and 9-tetraphenyl. The C6-C60 aryl group of the present invention may also be a group formed by combining the above groups through single bonds or / and fusion.

[0036] In this specification, the substituted or unsubstituted C3-C60 heteroaryl is preferably C3-C30 heteroaryl, and can be a nitrogen-containing heteroaryl, an oxygen-containing heteroaryl, a sulfur-containing heteroaryl, etc. Specific examples include: heteroaryls formed by furyl, thienyl, pyrrolyl, pyridyl, benzofuryl, benzothienyl, isobenzofuryl, isobenzothienyl, indolyl, isoindolyl, dibenzofuryl, dibenzothienyl, carbazolyl and its derivatives, quinolinyl, isoquinolinyl, acridinyl, phenanthridinyl, benzo-5,6-quinolinyl, benzo-6,7-quinolinyl, benzo-7,8-quinolinyl, phenothiazinyl, phenazinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthimidazolyl, phenanthrimidazolyl, pyridinimidazolyl, pyrazinimidazolyl, quinoxalinimidazolyl, oxazolyl, benzoxazolyl, naphthoxazolyl, anthroxazolyl, phenanthroxazolyl, 1,2-thiazolyl, 1,3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1,5-diazaanthracenyl, 2,7-diazapyrenyl, 2,3-diazapyrenyl, 1,6-diazapyrenyl, 1,8-diazapyrenyl, 4,5-diazapyrenyl, 4,5,9,10-tetraazaperyleneyl, pyrazinyl, phenazinyl, phenothiazinyl, naphthyridinyl, azacarbazolyl, benzocarbazolyl, phenanthrolinyl, 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-tetrazinyl, 1,2,3,4-tetrazinyl, 1,2,3,5-tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazole, etc. Preferred examples of the heteroaryl in the present invention are, for example, heteroaryls of furyl, thienyl, pyrrolyl, benzofuryl, benzothienyl, isobenzofuryl, indolyl, dibenzofuryl, dibenzothienyl, carbazolyl and its derivatives, wherein the carbazolyl derivative is preferably 9-phenylcarbazole, 9-naphthylcarbazole, benzocarbazole, dibenzocarbazole or indolocarbazole.

[0037] In this specification, the substituted or unsubstituted C3-C60 heteroaryl group is preferably a C3-C30 heteroaryl group, more preferably a nitrogen-containing heteroaryl group, an oxygen-containing heteroaryl group, a sulfur-containing heteroaryl group, etc. Specific examples include: furyl, thienyl, pyrrolyl, pyridyl, benzofuryl, benzothienyl, isobenzofuryl, isobenzothienyl, indolyl, isoindolyl, dibenzofuryl, dibenzothienyl, carbazolyl and its derivatives, quinolinyl, isoquinolinyl, acridinyl, phenanthridinyl, benzo-5,6-quinolinyl, benzo-6,7-quinolinyl, benzo-7,8-quinolinyl, phenothiazinyl, phenazinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthimidazolyl, phenanthrimidazolyl, pyridinimidazolyl, pyrazinimidazolyl, quinoxalinimidazolyl, oxazolyl, benzoxazolyl, naphthoxazolyl, anthroxazolyl, phenanthroxazolyl, 1,2-thiazolyl, 1,3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1,5-diazaanthracenyl, 2,7-diazapyrenyl, 2,3-diazapyrenyl, 1,6-diazapyrenyl, 1,8-diazapyrenyl, 4,5-diazapyrenyl, 4,5,9,10-tetraazaacenaphthylenyl, pyrazinyl, phenazinyl, phenothiazinyl, naphthyridinyl, azacarbazolyl, benzocarbazolyl, phenanthrolinyl, 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-tetrazinyl, 1,2,3,4-tetrazinyl, 1,2,3,5-tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazole, etc. Preferred examples of the heteroaryl group in the present invention are, for example, furyl, thienyl, pyrrolyl, benzofuryl, benzothienyl, isobenzofuryl, indolyl, dibenzofuryl, dibenzothienyl, carbazolyl and its derivatives, wherein the carbazolyl derivative is preferably 9-phenylcarbazole, 9-naphthylcarbazole, benzocarbazole, dibenzocarbazole or indolocarbazole. The C3-C60 heteroaryl group of the present invention may also be a group formed by combining the above groups through single bonds or / and fusion.

[0038] In this specification, the concept of chain alkyl also includes straight-chain and branched-chain alkyl groups. Examples of C1-C20 chain alkyl groups include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, neopentyl, n-hexyl, neohexyl, n-heptyl, n-octyl, 2-ethylhexyl, etc. Examples of C1-C20 chain haloalkyl groups include: trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, etc.

[0039] In this specification, C3-C20 cycloalkyl includes monocyclic alkyl and polycyclic alkyl. Specific examples may be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, etc.

[0040] In this specification, alkoxy refers to a group formed by the combination of the above-mentioned linear alkyl and oxygen, or a group formed by the combination of the above-mentioned cycloalkyl and oxygen.

[0041] Examples of C1-C20 alkoxy include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, pentyloxy, isopentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, etc. Among them, methoxy, ethoxy, n-propoxy, isopropoxy, tert-butoxy, sec-butoxy, isobutoxy, and isopentyloxy are preferred, and methoxy is more preferred.

[0042] In this specification, examples of C1-C20 silyl may be silyl groups substituted by the groups exemplified in the above C1-C20 alkyl groups, that is, groups formed by substituting one, two, or three hydrogens on the above-mentioned linear alkyl or cycloalkyl-substituted silyl. Specific examples include: methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, tert-butyldimethylsilyl, tert-butyldiphenylsilyl and other groups.

[0043] Further, in the above general formula of the present invention, the electron-withdrawing group is selected from one or a combination of two of the following groups: cyano, isocyano, halogen, cyano-substituted C1-C5 linear alkyl, isocyano-substituted C1-C5 linear alkyl, halogen-substituted C1-C5 linear alkyl, cyano-substituted C6-C60 aryl, isocyano-substituted C6-C60 aryl, halogen-substituted C6-C60 aryl, cyano-substituted C3-C60 heteroaryl without sp2 hybridized nitrogen atoms and boron atoms, isocyano-substituted C3-C60 heteroaryl without sp2 hybridized nitrogen atoms and boron atoms, halogen-substituted C3-C60 heteroaryl without sp2 hybridized nitrogen atoms and boron atoms, unsubstituted or R'-substituted xanthone, unsubstituted or R'-substituted thioxanthone, unsubstituted or R'-substituted C3-C60 heteroaryl containing sp2 hybridized nitrogen atoms, unsubstituted or R'-substituted C3-C60 heteroaryl containing boron atoms; preferably, the electron-withdrawing group is selected from one or a combination of two of the following groups: cyano, isocyano, fluorine, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, triazinyl, heptazaphenanthrenyl, pyridyl, quinolinyl, isoquinolinyl, phenanthridinyl, benzo-5,6-quinolyl, benzo-6,7-quinolyl, benzo-7,8-quinolyl, fluoroboron dipyrrole, azaboron dipyrrole, pyridinoimidazolyl, pyrazinoimidazolyl, quinoxalinoimidazolyl, 1,2-thiazolyl, 1,3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1,5-diazaanthracenyl, 2,7-diazapyrenyl, 2,3-diazapyrenyl, 1,6-diazapyrenyl, 1,8-diazapyrenyl, 4,5-diazapyrenyl, 4,5,9,10-tetraazaacenaphthylenyl, pyrazinyl, naphthyridinyl, phenanthroline, 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-tetrazinyl, 1,2,3,4-tetrazinyl, 1,2,3,5-tetrazinyl, purinyl, pteridinyl, indazyl, benzothiadiazolyl, diphenylboron, dimesitylboron, dipentafluorophenylboron, di(2,4,6-triisopropylphenyl)boron, xanthone, thioxanthone, 1,3,3a 1 ,4,6,7,9-heptazaphenanthrenyl, 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthrenyl.

[0044] Still further, in the above general formula of the present invention, the D 1 , D 2 , D3 , D 4 , D 5 , D 6 and D 7 are each independently selected from unsubstituted or R'-substituted C3-C60 heteroaryl groups, wherein the heteroatoms in the heteroaryl groups are selected from at least one of N, O, S, P, Si, Se; preferably, said D 1 , D 2 , D 3 , D 4 , D 5 , D 6 and D 7 are each independently selected from unsubstituted or R'-substituted C3-C60 heteroaryl groups containing nitrogen atoms; more preferably, said D 1 , D 2 , D 3 , D 4 , D 5 , D 6 and D 7 are each independently selected from one or a combination of two of the following unsubstituted or R'-substituted groups: indolyl, isoindolyl, benzindolyl, carbazolyl, indeno[1,2-b]carbazolyl, indolo[3,2-b]carbazolyl, furo[3,2-b]carbazolyl, thieno[3,2-b]carbazolyl, carbolinyl, pyrazolyl, indazolyl, imidazolyl, acridinyl, phenazine, phenothiazine, phenoxazine;

[0045] Each R' is independently selected from one or a combination of two of deuterium, halogen, cyano, isocyano, hydroxyl, amino, C1-C10 linear alkyl, C3-C10 cycloalkyl, C7-C30 aralkyl, C1-C10 alkoxy, C2-C10 aliphatic hydrocarbon amine, C4-C10 cyclic aliphatic hydrocarbon amine, C6-C30 arylamine, C3-C30 heteroarylamine, C6-C30 aryloxy, C6-C60 arylboron, C6-C60 aryl, C3-C60 heteroaryl.

[0046] Furthermore, said D 1 , D 2 , D 3 , D 4 , D 5 , D 6 and D 7 are each independently selected from one of the following unsubstituted or R'''-substituted structures:

[0047]

[0048] * represents the attachment position of the substituent group;

[0049] Each of said R”'s independently selected from deuterium, halogen, cyano, isocyano, hydroxyl, amino, C1-C10 linear alkyl, C3-C10 cycloalkyl, C7-C30 aralkyl, C1-C10 alkoxy, C2-C10 aliphatic hydrocarbon amine group, C4-C10 cyclic aliphatic hydrocarbon amine group, C6-C30 arylamine group, C3-C30 heteroarylamine group, C6-C30 aryloxy, C6-C60 arylboron group, C6-C60 aryl, C3-C60 heteroaryl, or a combination of one or two thereof.

[0050] Preferably, the compounds of the present invention have the structures shown in Formula (2) and Formula (3):

[0051]

[0052] Wherein, D 1 , D 2 , D 3 , D 4 , D 5 are each independently selected from unsubstituted or R”'-substituted C3-C60 heteroaryl containing a nitrogen atom;

[0053] Preferably, said D 1 , D 2 , D 3 , D 4 , D 5 are each independently selected from one or a combination of two of the following groups which are unsubstituted or R”'-substituted: indolyl, isoindolyl, benzindolyl, carbazolyl, indeno[1,2-c]carbazolyl, indolo[3,2-b]carbazolyl, furo[2,3-b]carbazolyl, thieno[2,3-b]carbazolyl, carbolinyl, pyrazolyl, indazolyl, imidazolyl, acridinyl, phenazine, phenothiazine, phenoxazine;

[0054] More preferably, said D 1 , D 2 , D 3 , D 4 , D 5 are each independently selected from one or a combination of two of the following groups which are unsubstituted or R”'-substituted: carbazolyl, indolo[3,2-b]carbazolyl, furo[2,3-b]carbazolyl, thieno[2,3-b]carbazolyl, acridinyl, phenazine, phenothiazine, phenoxazine;

[0055] And each of said R”'s independently selected from deuterium, halogen, cyano, isocyano, hydroxyl, amino, C1-C10 linear alkyl, C3-C10 cycloalkyl, C7-C30 aralkyl, C1-C10 alkoxy, C2-C10 aliphatic hydrocarbon amine group, C4-C10 cyclic aliphatic hydrocarbon amine group, C6-C30 arylamine group, C3-C30 heteroarylamine group, C6-C30 aryloxy, C6-C60 arylboron group, C6-C60 aryl, C3-C60 heteroaryl, or a combination of one or two thereof.

[0056] Further, each of π1, π2, π3, and π4 is independently selected from an unsubstituted or R'-substituted aryl group having 6 to 60 carbon atoms with the same number of atoms in the parent nuclear conjugated plane, or an unsubstituted or R'-substituted heteroaryl group having 3 to 60 carbon atoms, or each of π1, π2, π3, and π4 is independently selected from an unsubstituted or R'-substituted aryl group having 6 to 60 carbon atoms with the number of atoms in the parent nuclear conjugated plane differing by 6 or less, or an unsubstituted or R'-substituted heteroaryl group having 3 to 60 carbon atoms; wherein the parent nuclear conjugated plane refers to the aryl group having 6 to 60 carbon atoms or the heteroaryl group having 3 to 60 carbon atoms after removing the substituents, and the number of atoms in the corresponding parent nuclear conjugated plane is the number of atoms of the aryl group having 6 to 60 carbon atoms or the heteroaryl group having 3 to 60 carbon atoms after removing the substituents.

[0057] Preferably, π1, π2, π3, and π4 are all electron-withdrawing groups, or the substituents on π1, π2, π3, and π4 are all electron-withdrawing groups;

[0058] Each of the above R's is independently selected from deuterium, halogen, cyano, isocyano, a linear alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, an aryl ether group having 6 to 60 carbon atoms, a heteroaryl ether group having 3 to 60 carbon atoms, an arylthioether group having 6 to 60 carbon atoms, a heteroarylthioether group having 3 to 60 carbon atoms, an arylsilyl group having 6 to 60 carbon atoms, a heteroarylsilyl group having 3 to 60 carbon atoms, an arylamino group having 6 to 30 carbon atoms, a heteroarylamino group having 3 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an arylboron group having 6 to 60 carbon atoms, an aryl group having 6 to 60 carbon atoms, a heteroaryl group having 3 to 60 carbon atoms, or a combination of one or two of them.

[0059] Furthermore, the compounds represented by the general formula (1) of the present invention can preferably include the following specific structural compounds: A-1 to A-136, B-1 to B-172, C-1 to C-72, D-1 to D-148. These compounds are only representative:

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085] The preparation process of the compounds of the present invention is simple and easy to implement, the raw materials are easily available, and it is suitable for mass production and scale-up.

[0086] In the second aspect of the present invention, the applications of the compounds represented by any one of the above general formulas are also protected. The applications are as functional materials in organic electronic devices, and the organic electronic devices include: organic light-emitting devices, optical sensors, solar cells, lighting elements, organic thin-film transistors, organic field-effect transistors, organic thin-film solar cells, information tags, electronic artificial skin sheets, sheet-type scanners or electronic papers, preferably organic light-emitting devices.

[0087] In a third aspect, the present invention also provides an organic electroluminescent device, comprising a substrate, a first electrode, a second electrode, and one or more organic layers inserted between the first electrode and the second electrode, wherein the organic layer contains a compound represented by any one of the above general formulas (1), (2), (3), (4), (5), and (6).

[0088] Specifically, an embodiment of the present invention provides an organic electroluminescent device, comprising a substrate, an anode layer, a plurality of light-emitting functional layers, and a cathode layer formed in sequence 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. 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 light-emitting layer contains the general formula compound of the present invention shown above, specifically as a light-emitting dye or a sensitizer in the light-emitting layer. When it is used as a light-emitting dye, it is characterized in that the light-emitting layer includes a host material and a light-emitting dye, and the structure of the light-emitting layer is as shown in the attached Figure 1 description.

[0089] Preferably, in this organic electroluminescent device of the present invention, the light-emitting layer includes a host material, a sensitizer, and a phosphorescent dye, and the structure of the light-emitting layer is as shown in the attached Figure 2 description.

[0090] Preferably, in this organic electroluminescent device of the present invention, the light-emitting layer includes a host material, a sensitizer, and a fluorescent dye, and the structure of the light-emitting layer is as shown in the attached Figure 3 description.

[0091] More preferably, in this organic electroluminescent device of the present invention, the light-emitting layer includes a host material, a sensitizer, a phosphorescent dye, and a fluorescent dye, and the structure of the light-emitting layer is as shown in the attached Figure 4 description.

[0092] Wherein the host material is a wide-bandgap host material, preferably a host material with TADF characteristics, more preferably an exciplex formed by mixing an electron donor material and an electron acceptor material with TADF properties, and particularly preferably an exciplex with a high quantum yield (greater than 80%);

[0093] The phosphorescent material is preferably a complex with Pt or Ir, which has phosphorescent emission, and particularly preferably a complex containing Pt atoms with a high quantum yield (greater than 80%);

[0094] The fluorescent dye has a high radiative transition rate (greater than 10 7 s -1) and traditional fluorescent dyes with high quantum yields (greater than 80%), narrow-spectrum (full width at half maximum ≤ 40 nm) fluorescent dyes, or multiple resonance thermally activated delayed fluorescence dyes.

[0095] Furthermore, it is characterized in that the doping concentration of the sensitizer is 1 wt% - 50 wt%, preferably 5 wt% - 30 wt%, and particularly preferably 5 wt% - 20 wt%;

[0096] The doping concentration of the phosphorescent dye is 1 wt% - 30 wt%, preferably 5 wt% - 30 wt%, and particularly preferably 5 wt% - 15 wt%;

[0097] The doping concentration of the fluorescent dye is 0.1 wt% - 10 wt%, preferably 0.5 wt% - 5 wt%, and particularly preferably 0.5 wt% - 3 wt%.

[0098] The advantage of the light-emitting layer structure of the organic electroluminescent device of the present invention is that: compared with the existing phosphorescent sensitization device, that is, host + phosphorescent sensitizer + fluorescent dye, a functional material is further introduced into the light-emitting layer of the device of the present invention, that is, host + sensitizer + phosphorescent dye + fluorescent dye, and the host is a double-host exciplex. The advantages of this structure are: ①. The sensitizer has a very small ΔE ST , and this property also exists in the blue light and deep blue light regions, so that the rate of reverse intersystem crossing is relatively high, which can significantly accelerate the exciton dynamics process, and while ensuring effective energy transfer, the generation of high-energy excitons is reduced, resulting in a highly efficient and stable blue light device; ②. Utilize the multiple energy transfer pathways existing in the system, including FET and DET between the sensitizer and the phosphorescent dye, FET between the sensitizer and the fluorescent dye, FET and DET between the phosphorescent dye and the fluorescent dye, and FET between the host and the sensitizer, phosphorescent dye, and fluorescent dye, etc., so as to reduce the accumulation of long-lived excitons and inhibit the energy loss and stability decline caused by the exciton annihilation process. ③. The exciplex host also has TADF properties, which can improve the exciton utilization rate, and its bipolar transport performance and stability are better than those of a general single host; ④. When the doping concentration of the sensitizer is not high, as low as 5 wt%, due to its fast upconversion rate, it can also effectively disperse and reduce the triplet exciton concentration and improve the device stability.

[0099] As shown in the specification appendix Figure 2 and appendix Figure 3 and appendix Figure 4As shown, by adding the sensitizer of the present invention to the light-emitting layer, triplet excitons can be effectively utilized and dispersed through multiple energy transfer processes. At the same time, the materials of the present invention have a fast reverse intersystem crossing rate, which can effectively accelerate the upconversion process of triplet excitons, thereby accelerating their kinetic processes, reducing the concentration of triplet excitons, and suppressing the quenching effect caused by excessive triplet exciton concentration, resulting in significant improvements in both efficiency and lifespan. Especially in the case where electroexcitation in the device generates a high proportion of initial triplet states, since it can effectively disperse and convert long-lived triplet excitons into shorter-lived phosphorescent triplet excitons or fluorescent singlet excitons, the efficiency and lifespan of related devices in high-brightness application environments are significantly improved.

[0100] The OLED device prepared with the compound of the present invention has a low turn-on voltage, high luminous efficiency, and better service life, and can meet the requirements of current panel manufacturing enterprises for high-performance materials.

[0101] Description Drawings

[0102] Figure 1 It is a schematic diagram of the light-emitting layer structure of the organic electroluminescent device in the present invention, where the light-emitting layer includes a host material and the material of the present invention as a light-emitting dye, and the energy levels of each material are only for illustration.

[0103] Figure 2 It is a schematic diagram of the light-emitting layer structure of the organic electroluminescent device in the present invention, where the light-emitting layer includes a host material, the material of the present invention as a sensitizer, and a phosphorescent dye, and the energy levels of each material are only for illustration.

[0104] Figure 3 It is a schematic diagram of the light-emitting layer structure of the organic electroluminescent device in the present invention, where the light-emitting layer includes a host material, the material of the present invention as a sensitizer, and a fluorescent dye, and the energy levels of each material are only for illustration.

[0105] Figure 4 It is a schematic diagram of the light-emitting layer structure of the organic electroluminescent device in the present invention, where the light-emitting layer includes a host material, the material of the present invention as a sensitizer, a phosphorescent dye, and a fluorescent dye, and the energy levels of each material are only for illustration.

[0106] As shown in the description drawings Figure 2 and drawings Figure 3 and drawings Figure 4As shown, by adding the sensitizer of the present invention to the light-emitting layer, triplet excitons can be effectively utilized and dispersed through multiple energy transfer processes. At the same time, the material of the present invention has a fast reverse intersystem crossing rate, which can effectively accelerate the upconversion process of triplet excitons, thereby accelerating their kinetic processes, reducing the concentration of triplet excitons, and suppressing the quenching effect caused by too high a concentration of triplet excitons, resulting in significant improvements in both efficiency and lifespan. Especially in the case of electro-excitation in the device to generate a high proportion of initial triplet states, since it can effectively disperse and convert long-lived triplet excitons into shorter-lived phosphorescent triplet excitons or fluorescent singlet excitons, the efficiency and lifespan of related devices in high-brightness application environments are significantly improved. Detailed Description of the Invention

[0107] The following will take multiple synthesis examples as illustrations to elaborate on the specific preparation methods of the above new compounds of the present invention, but the preparation methods of the present invention are not limited to these synthesis examples.

[0108] All kinds of chemical reagents used in the present invention, such as basic chemical raw materials like petroleum ether, ethyl acetate, sodium sulfate, toluene, tetrahydrofuran, dichloromethane, acetic acid, potassium carbonate, etc., are purchased from Shanghai Titan Scientific Co., Ltd. and Xilong Chemical Co., Ltd. The mass spectrometer used to determine the following compounds is a ZAB-HS type mass spectrometer (manufactured by Micromass UK).

[0109] The following briefly describes the synthesis method of the compounds of the present invention.

[0110] The following K-1 to K-13, M-1 to M-22, and Z-1 to Z-27 are different raw materials and reaction intermediates used in the examples:

[0111]

[0112]

[0113] Synthesis Examples

[0114] Synthesis Example 1:

[0115] Synthesis of Compound A-1

[0116]

[0117] Under a nitrogen atmosphere, the raw materials 3,6-di-tert-butyl-1-boronic acid pinacol ester-9H-carbazole (K-1) (36 mmol), 1,3,5-tribromobenzene (M-1) (10 mmol), and potassium carbonate (100 mmol) were dissolved in a mixed solution of dioxane (300 mL) and water (60 mL). Then, tetrakis(triphenylphosphine)palladium (1.5 mmol) was added, and the reaction was refluxed at 120 °C for 20 hours. After the reaction was complete, the solvent was removed by rotary evaporation, and the crude product was purified by silica gel column chromatography (the eluent was petroleum ether:dichloromethane = 1:2) to obtain intermediate compound A-1-1 with a yield of 75%, which was a white solid. Further, under a nitrogen atmosphere, intermediate compound A-1-1 (2 mmol) and 1,3,5-trifluorobenzene (Z-1) (3 mmol) were dissolved in ultra-dry N,N-dimethylformamide (150 mL). Then, solid sodium hydride (6.2 mmol) was slowly added, and the reaction was refluxed at 140 °C for 20 hours. After the reaction was complete, the solvent was removed by rotary evaporation, and the crude product was purified by silica gel column chromatography (the eluent was petroleum ether:dichloromethane = 4:1) to obtain the target product A-1 with a yield of 18%, which was a yellow solid. The MALDI-TOF-MS result showed a molecular ion peak of 981.60; the elemental analysis result: theoretical values: C, 88.03; H, 7.70; N, 4.28, experimental values: C, 88.03; H, 7.71; N, 4.28.

[0118] Synthesis Example 2:

[0119] Synthesis of Compound A-2

[0120] The synthesis method was similar to that of Synthesis Example 1, except that Z-1 was replaced with Z-2, and the yield was 17%, which was a yellow solid. The MALDI-TOF-MS result showed a molecular ion peak of 1006.59; the elemental analysis result: theoretical values: C, 87.03; H, 7.40; N, 5.56, experimental values: C, 87.03; H, 7.41; N, 5.56.

[0121] Synthesis Example 3:

[0122] Synthesis of Compound A-3

[0123] The synthesis method was similar to that of Synthesis Example 1, except that Z-1 was replaced with Z-3, and the yield was 20%, which was a yellow solid. The MALDI-TOF-MS result showed a molecular ion peak of 1049.58; the elemental analysis result: theoretical values: C, 83.47; H, 7.10; F, 5.43; N, 4.00, experimental values: C, 83.46; H, 7.10; F, 5.43; N, 4.00.

[0124] Synthesis Example 4:

[0125] Synthesis of Compound A-5

[0126] The synthesis method is similar to that of Synthesis Example 1, only replacing Z-1 with Z-4. The yield is 20%, and it is a yellow solid. The result of MALDI-TOF-MS shows that the molecular ion peak is 984.58. The result of elemental analysis shows that the theoretical values are: C, 84.11; H, 7.37; N, 8.53, and the experimental values are: C, 84.11; H, 7.38; N, 8.53.

[0127] Synthesis Example 5:

[0128] Synthesis of Compound A-8

[0129] The synthesis method is similar to that of Synthesis Example 1, only replacing Z-1 with Z-5. The yield is 21%, and it is a yellow solid. The result of MALDI-TOF-MS shows that the molecular ion peak is 1031.59. The result of elemental analysis shows that the theoretical values are: C, 86.09; H, 7.13; N, 6.78, and the experimental values are: C, 86.09; H, 7.13; N, 6.77.

[0130] Synthesis Example 6:

[0131] Synthesis of Compound A-38

[0132]

[0133] Under a nitrogen atmosphere, the raw materials 3,6-di-tert-butyl-1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (K-1) (36 mmol), 2,4,6-tribromobenzonitrile (M-2) (10 mmol), and potassium carbonate (100 mmol) were dissolved in a mixed solution of dioxane (300 mL) and water (60 mL). Then, tetrakis(triphenylphosphine)palladium(0) (1.5 mmol) was added, and the mixture was refluxed at 120 °C for 20 hours. After the reaction was complete, the solvent was removed by rotary evaporation, and the crude product was purified by silica gel column chromatography (eluent: petroleum ether:dichloromethane = 1:2) to obtain intermediate compound A-38-1 with a yield of 76%, which was a white solid. Further, under a nitrogen atmosphere, intermediate compound A-38-1 (2 mmol) and 1,3,5-trifluorobenzene (Z-1) (3 mmol) were dissolved in ultra-dry N,N-dimethylformamide (150 mL). Then, solid sodium hydride (6.2 mmol) was slowly added, and the mixture was refluxed at 140 °C for 20 hours. After the reaction was complete, the solvent was removed by rotary evaporation, and the crude product was purified by silica gel column chromatography (eluent: petroleum ether:dichloromethane = 4:1) to obtain the target product A-38 with a yield of 21%, which was a yellow solid. The result of MALDI-TOF-MS showed a molecular ion peak at 1006.59; the result of elemental analysis showed the theoretical values: C, 87.03; H, 7.40; N, 5.56, and the experimental values: C, 87.02; H, 7.41; N, 5.56.

[0134] Synthesis Example 7:

[0135] Synthesis of Compound A-44

[0136]

[0137] Under a nitrogen atmosphere, 3,6-di-tert-butyl-1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (K-1) (36 mmol), 2,4,6-tribromoisophthalonitrile (M-3) (10 mmol), and potassium carbonate (100 mmol) were dissolved in a mixed solution of dioxane (300 mL) and water (60 mL). Then, tetrakis(triphenylphosphine)palladium(0) (1.5 mmol) was added, and the mixture was refluxed at 120 °C for 20 hours. After the reaction was complete, the solvent was removed by rotary evaporation, and the crude product was purified by silica gel column chromatography (eluent: petroleum ether:dichloromethane = 1:2) to obtain intermediate compound A-44-1 as a white solid in a yield of 72%. Further, under a nitrogen atmosphere, intermediate compound A-44-1 (2 mmol) and 1,3,5-trifluorobenzene (Z-1) (3 mmol) were dissolved in ultra-dry N,N-dimethylformamide (150 mL). Then, solid sodium hydride (6.2 mmol) was slowly added, and the mixture was refluxed at 140 °C for 20 hours. After the reaction was complete, the solvent was removed by rotary evaporation, and the crude product was purified by silica gel column chromatography (eluent: petroleum ether:dichloromethane = 4:1) to obtain the target product A-44 as a yellow solid in a yield of 19%. The results of MALDI-TOF-MS showed a molecular ion peak at 1031.59; the results of elemental analysis showed the theoretical values: C, 86.09; H, 7.13; N, 6.78, and the experimental values: C, 86.08; H, 7.13; N, 6.78.

[0138] Synthesis Example 8:

[0139] Synthesis of Compound A-73

[0140] The synthesis method was similar to that of Synthesis Example 6, except that Z-1 was replaced with Z-2, and the yield was 23% as a yellow solid. The results of MALDI-TOF-MS showed a molecular ion peak at 1031.59; the results of elemental analysis showed the theoretical values: C, 86.09; H, 7.13; N, 6.78, and the experimental values: C, 86.09; H, 7.13; N, 6.75.

[0141] Synthesis Example 9:

[0142] Synthesis of Compound A-74

[0143] The synthesis method was similar to that of Synthesis Example 6, except that Z-1 was replaced with Z-2, and the yield was 16% as a yellow solid. The results of MALDI-TOF-MS showed a molecular ion peak at 1031.59; the results of elemental analysis showed the theoretical values: C, 86.09; H, 7.13; N, 6.78, and the experimental values: C, 86.09; H, 7.15; N, 6.78.

[0144] Synthesis Example 10:

[0145] Synthesis of Compound A-75

[0146] The synthesis method is similar to that of Synthesis Example 6, only replacing Z-1 with Z-3. The yield is 17%, and it is a yellow solid. The result of MALDI-TOF-MS shows that the molecular ion peak is 1074.58; the result of elemental analysis shows that the theoretical values are C, 82.65; H, 6.84; F, 5.30; N, 5.21, and the experimental values are C, 82.65; H, 6.86; F, 5.30; N, 5.22.

[0147] Synthesis Example 11:

[0148] Synthesis of Compound A-77

[0149] The synthesis method is similar to that of Synthesis Example 6, only replacing Z-1 with Z-4. The yield is 21%, and it is a yellow solid. The result of MALDI-TOF-MS shows that the molecular ion peak is 1009.58; the result of elemental analysis shows that the theoretical values are C, 83.21; H, 7.08; N, 9.70, and the experimental values are C, 83.20; H, 7.08; N, 9.71.

[0150] Synthesis Example 12:

[0151] Synthesis of Compound A-82

[0152] The synthesis method is similar to that of Synthesis Example 6, only replacing Z-1 with Z-5. The yield is 20%, and it is a yellow solid. The result of MALDI-TOF-MS shows that the molecular ion peak is 1056.58; the result of elemental analysis shows that the theoretical values are C, 85.19; H, 6.86; N, 7.95, and the experimental values are C, 85.19; H, 6.86; N, 7.96.

[0153] Synthesis Example 13:

[0154] Synthesis of Compound A-90

[0155] The synthesis method is similar to that of Synthesis Example 6, only replacing Z-1 with Z-6. The yield is 20%, and it is a yellow solid. The result of MALDI-TOF-MS shows that the molecular ion peak is 1167.56; the result of elemental analysis shows that the theoretical values are C, 78.13; H, 6.13; F, 9.76; N, 5.99, and the experimental values are C, 78.15; H, 6.13; F, 9.76; N, 5.99.

[0156] Synthesis Example 14:

[0157] Synthesis of Compound A-109

[0158] The synthesis method is similar to that of Synthesis Example 7, except that Z-1 is replaced with Z-2. The yield is 22%, and it is a yellow solid. The result of MALDI-TOF-MS shows that the molecular ion peak is 1056.58. The result of elemental analysis shows that the theoretical values are C, 85.19; H, 6.86; N, 7.95, and the experimental values are C, 85.19; H, 6.86; N, 7.96.

[0159] Synthesis Example 15:

[0160] Synthesis of Compound A-111

[0161] The synthesis method is similar to that of Synthesis Example 7, except that Z-1 is replaced with Z-3. The yield is 21%, and it is a yellow solid. The result of MALDI-TOF-MS shows that the molecular ion peak is 1099.57. The result of elemental analysis shows that the theoretical values are C, 81.86; H, 6.60; F, 5.18; N, 6.36, and the experimental values are C, 81.86; H, 6.61; F, 5.18; N, 6.36.

[0162] Synthesis Example 16:

[0163] Synthesis of Compound A-121

[0164]

[0165] Under a nitrogen atmosphere, the raw materials 3,6-di-tert-butyl-1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (K-1) (36 mmol), 2,4,6-tribromo-3-(trifluoromethyl)benzonitrile (M-4) (10 mmol), and potassium carbonate (100 mmol) were dissolved in a mixed solution of dioxane (300 mL) and water (60 mL). Then, tetrakis(triphenylphosphine)palladium (1.5 mmol) was added, and the reaction was refluxed at 120 °C for 20 hours. After the reaction was complete, the solvent was removed by rotary evaporation, and the crude product was purified by silica gel column chromatography (the eluent was petroleum ether:dichloromethane = 1:2) to obtain intermediate compound A-121-1 with a yield of 67%, which was a white solid. Further, under a nitrogen atmosphere, intermediate compound A-121-1 (2 mmol) and 1,3,5-trifluoro-2-(trifluoromethyl)benzene (Z-3) (3 mmol) were dissolved in ultra-dry N,N-dimethylformamide (150 mL). Then, sodium hydride solid (6.2 mmol) was slowly added, and the reaction was refluxed at 140 °C for 20 hours. After the reaction was complete, the solvent was removed by rotary evaporation, and the crude product was purified by silica gel column chromatography (the eluent was petroleum ether:dichloromethane = 4:1) to obtain the target product A-121 with a yield of 20%, which was a yellow solid. The result of MALDI-TOF-MS showed that the molecular ion peak was 1142.57; the result of elemental analysis showed that the theoretical values were C, 78.78; H, 6.35; F, 9.97; N, 4.90, and the experimental values were C, 78.78; H, 6.36; F, 9.98; N, 4.90.

[0166] Synthesis Example 17:

[0167] Synthesis of Compound A-129

[0168]

[0169] Under a nitrogen atmosphere, the raw materials 3,6-di-tert-butyl-1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (K-1) (36 mmol), 2,4,6-tribromophenol-1,3,5-tricarbonitrile (M-5) (10 mmol), and potassium carbonate (100 mmol) were dissolved in a mixed solution of dioxane (300 mL) and water (60 mL). Then, tetrakis(triphenylphosphine)palladium(0) (1.5 mmol) was added, and the mixture was refluxed at 120 °C for 20 hours. After the reaction was complete, the solvent was removed by rotary evaporation, and the crude product was purified by silica gel column chromatography (the eluent was petroleum ether:dichloromethane = 1:2) to obtain intermediate compound A-129-1 with a yield of 72%, which was a white solid. Further, under a nitrogen atmosphere, intermediate compound A-129-1 (2 mmol) and 2,4,6-trifluorobenzonitrile (Z-2) (3 mmol) were dissolved in ultra-dry N,N-dimethylformamide (150 mL). Then, solid sodium hydride (6.2 mmol) was slowly added, and the mixture was refluxed at 140 °C for 20 hours. After the reaction was complete, the solvent was removed by rotary evaporation, and the crude product was purified by silica gel column chromatography (the eluent was petroleum ether:dichloromethane = 4:1) to obtain the target product A-129 with a yield of 20%, which was a yellow solid. The result of MALDI-TOF-MS showed that the molecular ion peak was 1081.58; the result of elemental analysis showed that the theoretical values were C, 84.33; H, 6.61; N, 9.06, and the experimental values were C, 84.31; H, 6.61; N, 9.05.

[0170] Synthesis Example 18:

[0171] Synthesis of Compound B-2

[0172]

[0173] Under a nitrogen atmosphere, 3,6-diphenyl-1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (K-2) (36 mmol), 1,3,5-tribromobenzene (M-1) (10 mmol), and potassium carbonate (100 mmol) were dissolved in a mixed solution of dioxane (300 mL) and water (60 mL). Then, tetrakis(triphenylphosphine)palladium(0) (1.5 mmol) was added, and the mixture was refluxed at 120 °C for 20 hours. After the reaction was complete, the solvent was removed by rotary evaporation. The crude product was purified by silica gel column chromatography (eluent: petroleum ether:dichloromethane = 1:2) to obtain intermediate compound B-2-1 with a yield of 65%, which was a white solid. Further, under a nitrogen atmosphere, intermediate compound B-2-1 (2 mmol) and 2,4,6-trifluorobenzonitrile (Z-2) (3 mmol) were dissolved in ultra-dry N,N-dimethylformamide (150 mL). Then, solid sodium hydride (6.2 mmol) was slowly added, and the mixture was refluxed at 140 °C for 20 hours. After the reaction was complete, the solvent was removed by rotary evaporation. The crude product was purified by silica gel column chromatography (eluent: petroleum ether:dichloromethane = 4:1) to obtain the target product B-2 with a yield of 16%, which was a yellow solid. The result of MALDI-TOF-MS showed a molecular ion peak at 1126.40. The results of elemental analysis were as follows: theoretical values: C, 90.56; H, 4.47; N, 4.97; experimental values: C, 90.56; H, 4.46; N, 4.98.

[0174] Synthesis Example 19:

[0175] Synthesis of Compound B-3

[0176] The synthesis method was similar to that of Synthesis Example 18, except that Z-2 was replaced with Z-3. The yield was 19%, and it was a yellow solid. The result of MALDI-TOF-MS showed a molecular ion peak at 1169.40. The results of elemental analysis were as follows: theoretical values: C, 87.23; H, 4.31; F, 4.87; N, 3.59; experimental values: C, 87.23; H, 4.31; F, 4.87; N, 3.60.

[0177] Synthesis Example 20:

[0178] Synthesis of Compound B-4

[0179] The synthesis method was similar to that of Synthesis Example 18, except that Z-2 was replaced with Z-7. The yield was 19%, and it was a yellow solid. The result of MALDI-TOF-MS showed a molecular ion peak at 1126.40. The results of elemental analysis were as follows: theoretical values: C, 90.56; H, 4.47; N, 4.97; experimental values: C, 90.56; H, 4.47; N, 4.96.

[0180] Synthesis Example 21:

[0181] Synthesis of Compound B-5

[0182] The synthesis method is similar to Synthesis Example 18, only replacing Z-2 with Z-4. The yield is 21%, and it is a yellow solid. The result of MALDI-TOF-MS shows that the molecular ion peak is 1104.39. The result of elemental analysis shows that the theoretical values are: C, 88.02; H, 4.38; N, 7.60, and the experimental values are: C, 88.02; H, 4.38; N, 7.61.

[0183] Synthesis Example 22:

[0184] Synthesis of Compound B-10

[0185]

[0186] Under a nitrogen atmosphere, 1-boronic acid pinacol ester-9H-carbazole (K-3) (36 mmol), 1,3,5-tribromobenzene (M-1) (10 mmol), and potassium carbonate (100 mmol) were dissolved in a mixed solution of dioxane (300 mL) and water (60 mL). Then, tetrakis(triphenylphosphine)palladium (1.5 mmol) was added, and the reaction was refluxed at 120 °C for 20 hours. After the reaction was complete, the solvent was removed by rotary evaporation, and the crude product was purified by silica gel column chromatography (the eluent was petroleum ether:dichloromethane = 1:2) to obtain intermediate compound B-10-1 with a yield of 71%, which was a white solid. Further, under a nitrogen atmosphere, intermediate compound B-10-1 (2 mmol) and 2,4,6-trifluorobenzonitrile (Z-2) (3 mmol) were dissolved in ultra-dry N,N-dimethylformamide (150 mL). Then, solid sodium hydride (6.2 mmol) was slowly added, and the reaction was refluxed at 140 °C for 20 hours. After the reaction was complete, the solvent was removed by rotary evaporation, and the crude product was purified by silica gel column chromatography (the eluent was petroleum ether:dichloromethane = 4:1) to obtain the target product B-10 with a yield of 21%, which was a yellow solid. The result of MALDI-TOF-MS shows that the molecular ion peak is 670.22. The result of elemental analysis shows that the theoretical values are: C, 87.74; H, 3.91; N, 8.35, and the experimental values are: C, 87.75; H, 3.91; N, 8.35.

[0187] Synthesis Example 23:

[0188] Synthesis of Compound B-18

[0189] The synthesis method is similar to that of Synthesis Example 22, except that K-3 is replaced with K-4. The yield is 24%, and it is a yellow solid. The result of MALDI-TOF-MS shows that the molecular ion peak is 754.31. The result of elemental analysis shows that the theoretical values are C, 87.50; H, 5.07; N, 7.42, and the experimental values are C, 87.50; H, 5.07; N, 7.41.

[0190] Synthesis Example 24:

[0191] Synthesis of Compound B-26

[0192] The synthesis method is similar to that of Synthesis Example 22, except that K-3 is replaced with K-5. The yield is 20%, and it is a yellow solid. The result of MALDI-TOF-MS shows that the molecular ion peak is 1102.45. The result of elemental analysis shows that the theoretical values are C, 72.90; H, 6.76; N, 5.08; Si, 15.27, and the experimental values are C, 72.90; H, 6.76; N, 5.08; Si, 15.28.

[0193] Synthesis Example 25:

[0194] Synthesis of Compound B-34

[0195] The synthesis method is similar to that of Synthesis Example 22, except that K-3 is replaced with K-6. The yield is 16%, and it is a yellow solid. The result of MALDI-TOF-MS shows that the molecular ion peak is 1378.69. The result of elemental analysis shows that the theoretical values are C, 89.66; H, 6.28; N, 4.06, and the experimental values are C, 89.66; H, 6.28; N, 4.07.

[0196] Synthesis Example 26:

[0197] Synthesis of Compound B-57

[0198] The synthesis method is similar to that of Synthesis Example 22, except that K-3 is replaced with K-7. The yield is 18%, and it is a yellow solid. The result of MALDI-TOF-MS shows that the molecular ion peak is 988.18. The result of elemental analysis shows that the theoretical values are C, 81.35; H, 3.26; N, 5.66; S, 9.72, and the experimental values are C, 81.35; H, 3.26; N, 5.66; S, 9.73.

[0199] Synthesis Example 27:

[0200] Synthesis of Compound B-69

[0201] The synthesis method is similar to that of Synthesis Example 22, except that K-3 is replaced with K-8. The yield is 16%, and it is a yellow solid. The result of MALDI-TOF-MS shows that the molecular ion peak is 1165.39. The result of elemental analysis shows that the theoretical values are C, 87.53; H, 4.06; N, 8.41, and the experimental values are C, 87.51; H, 4.06; N, 8.41.

[0202] Synthesis Example 28:

[0203] Synthesis of Compound B-96

[0204] The synthesis method is similar to that of Synthesis Example 22, except that K-3 is replaced with K-9. The yield is 23%, and it is a yellow solid. The result of MALDI-TOF-MS shows that the molecular ion peak is 796.36. The result of elemental analysis shows that the theoretical values are C, 87.41; H, 5.56; N, 7.03, and the experimental values are C, 87.41; H, 5.56; N, 7.05.

[0205] Synthesis Example 29:

[0206] Synthesis of Compound B-99

[0207] The synthesis method is similar to that of Synthesis Example 22, except that K-3 is replaced with K-10. The yield is 20%, and it is a yellow solid. The result of MALDI-TOF-MS shows that the molecular ion peak is 1168.45. The result of elemental analysis shows that the theoretical values are C, 90.38; H, 4.83; N, 4.79, and the experimental values are C, 90.38; H, 4.83; N, 4.78.

[0208] Synthesis Example 30:

[0209] Synthesis of Compound B-106

[0210] The synthesis method is similar to that of Synthesis Example 22, except that K-3 is replaced with K-11. The yield is 21%, and it is a yellow solid. The result of MALDI-TOF-MS shows that the molecular ion peak is 868.36. The result of elemental analysis shows that the theoretical values are C, 88.45; H, 5.10; N, 6.45, and the experimental values are C, 88.45; H, 5.11; N, 6.44.

[0211] Synthesis Example 31:

[0212] Synthesis of Compound B-109

[0213]

[0214] Under a nitrogen atmosphere, the raw materials 3,6-diphenyl-1-boronic acid pinacol ester-9H-carbazole (K-2) (36 mmol), 2,4,6-tribromobenzonitrile (M-2) (10 mmol), and potassium carbonate (100 mmol) were dissolved in a mixed solution of dioxane (300 mL) and water (60 mL). Then, tetrakis(triphenylphosphine)palladium (1.5 mmol) was added, and the reaction was refluxed at 120 °C for 20 hours. After the reaction was complete, the solvent was removed by rotary evaporation. The crude product was purified by silica gel column chromatography (the eluent was petroleum ether:dichloromethane = 1:2) to obtain intermediate compound B-109-1 with a yield of 74%, which was a white solid. Further, under a nitrogen atmosphere, intermediate compound B-109-1 (2 mmol) and 2,4,6-trifluorobenzonitrile (Z-2) (3 mmol) were dissolved in ultra-dry N,N-dimethylformamide (150 mL). Then, solid sodium hydride (6.2 mmol) was slowly added, and the reaction was refluxed at 140 °C for 20 hours. After the reaction was complete, the solvent was removed by rotary evaporation. The crude product was purified by silica gel column chromatography (the eluent was petroleum ether:dichloromethane = 4:1) to obtain the target product B-109 with a yield of 22%, which was a yellow solid. The results of MALDI-TOF-MS showed that the molecular ion peak was 1151.40; the results of elemental analysis showed that the theoretical values were C, 89.64; H, 4.29; N, 6.08, and the experimental values were C, 89.64; H, 4.29; N, 6.07.

[0215] Synthesis Example 32:

[0216] Synthesis of Compound B-114

[0217] The synthesis method was similar to that of Synthesis Example 31, except that K-2 was replaced with K-3, and the yield was 15%, which was a yellow solid. The results of MALDI-TOF-MS showed that the molecular ion peak was 695.21; the results of elemental analysis showed that the theoretical values were C, 86.31; H, 3.62; N, 10.07, and the experimental values were C, 86.31; H, 3.63; N, 10.07.

[0218] Synthesis Example 33:

[0219] Synthesis of Compound B-118

[0220] The synthesis method was similar to that of Synthesis Example 31, except that K-2 was replaced with K-5, and the yield was 18%, which was a yellow solid. The results of MALDI-TOF-MS showed that the molecular ion peak was 1127.45; the results of elemental analysis showed that the theoretical values were C, 72.35; H, 6.52; N, 6.20; Si, 14.93, and the experimental values were C, 72.35; H, 6.51; N, 6.20; Si, 14.93.

[0221] Synthesis Example 34:

[0222] Synthesis of Compound B-122

[0223] The synthesis method is similar to that of Synthesis Example 31, only replacing K-2 with K-6. The yield is 15%, and it is a yellow solid. The result of MALDI-TOF-MS shows that the molecular ion peak is 1446.67; the result of elemental analysis shows that the theoretical values are: C, 86.28; H, 5.92; F, 3.94; N, 3.87, and the experimental values are: C, 86.28; H, 5.92; F, 3.94; N, 3.88.

[0224] Synthesis Example 35:

[0225] Synthesis of Compound B-137

[0226] The synthesis method is similar to that of Synthesis Example 31, only replacing K-2 with K-7. The yield is 21%, and it is a yellow solid. The result of MALDI-TOF-MS shows that the molecular ion peak is 1013.17; the result of elemental analysis shows that the theoretical values are: C, 80.53; H, 3.08; N, 6.91; S, 9.48, and the experimental values are: C, 80.53; H, 3.08; N, 6.92; S, 9.48.

[0227] Synthesis Example 36:

[0228] Synthesis of Compound B-149

[0229] The synthesis method is similar to that of Synthesis Example 31, only replacing K-2 with K-9. The yield is 20%, and it is a yellow solid. The result of MALDI-TOF-MS shows that the molecular ion peak is 821.35; the result of elemental analysis shows that the theoretical values are: C, 86.21; H, 5.27; N, 8.52, and the experimental values are: C, 86.22; H, 5.27; N, 8.51.

[0230] Synthesis Example 37:

[0231] Synthesis of Compound B-151

[0232] The synthesis method is similar to that of Synthesis Example 31, only replacing K-2 with K-10. The yield is 20%, and it is a yellow solid. The result of MALDI-TOF-MS shows that the molecular ion peak is 1193.45; the result of elemental analysis shows that the theoretical values are: C, 89.50; H, 4.64; N, 5.86, and the experimental values are: C, 89.50; H, 4.66; N, 5.86.

[0233] Synthesis Example 38:

[0234] Synthesis of Compound C-1

[0235]

[0236] Under a nitrogen atmosphere, the raw materials 3,6-di-tert-butyl-1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (K-1) (36 mmol), tribromo intermediate M-6 (10 mmol), and potassium carbonate (100 mmol) were dissolved in a mixed solution of dioxane (300 mL) and water (60 mL). Then, tetrakis(triphenylphosphine)palladium(0) (1.5 mmol) was added, and the mixture was refluxed at 120 °C for 20 hours. After the reaction was complete, the solvent was removed by rotary evaporation, and the crude product was purified by silica gel column chromatography (eluent: petroleum ether:dichloromethane = 1:2) to obtain intermediate compound C-1-1 with a yield of 73%, which was a white solid. Further, under a nitrogen atmosphere, intermediate compound C-1-1 (2 mmol) and trifluoro intermediate Z-8 (3 mmol) were dissolved in ultra-dry N,N-dimethylformamide (150 mL). Then, solid sodium hydride (6.2 mmol) was slowly added, and the mixture was refluxed at 140 °C for 20 hours. After the reaction was complete, the solvent was removed by rotary evaporation, and the crude product was purified by silica gel column chromatography (eluent: petroleum ether:dichloromethane = 4:1) to obtain the target product C-1 with a yield of 22%, which was a yellow solid. The result of MALDI-TOF-MS showed a molecular ion peak of 1365.67; the result of elemental analysis showed the theoretical values: C, 84.39; H, 6.27; B, 1.58; N, 3.08; O, 4.68, and the experimental values: C, 84.39; H, 6.28; B, 1.58; N, 3.08; O, 4.68.

[0237] Synthesis Example 39:

[0238] Synthesis of Compound C-2

[0239] The synthesis method was similar to that of Synthesis Example 38, except that M-6 was replaced with M-7, and the yield was 24%, which was a yellow solid. The result of MALDI-TOF-MS showed a molecular ion peak of 1401.73; the result of elemental analysis showed the theoretical values: C, 87.34; H, 6.61; B, 0.77; N, 3.00; O, 2.28, and the experimental values: C, 87.34; H, 6.61; B, 0.77; N, 3.01; O, 2.28.

[0240] Synthesis Example 40:

[0241] Synthesis of Compound C-5

[0242] The synthesis method is similar to Synthesis Example 38, except that M-6 is replaced with M-8. The yield is 21%, and it is a yellow solid. The result of MALDI-TOF-MS shows that the molecular ion peak is 1482.76. The result of elemental analysis shows that the theoretical values are: C, 85.00; H, 6.45; B, 0.73; N, 5.66; O, 2.16, and the experimental values are: C, 85.00; H, 6.45; B, 0.73; N, 5.67; O, 2.16.

[0243] Synthesis Example 41:

[0244] Synthesis of Compound C-9

[0245]

[0246] Under a nitrogen atmosphere, the raw materials 3,6-di-tert-butyl-1-boronic acid pinacol ester-9H-carbazole (K-1) (36 mmol), tribromo intermediate M-9 (10 mmol), and potassium carbonate (100 mmol) were dissolved in a mixed solution of dioxane (300 mL) and water (60 mL). Then, tetrakis(triphenylphosphine)palladium (1.5 mmol) was added, and the reaction was refluxed at 120 °C for 20 hours. After the reaction was complete, the solvent was removed by rotary evaporation, and the crude product was purified by silica gel column chromatography (the eluent was petroleum ether:dichloromethane = 1:2) to obtain intermediate compound C-9-1 with a yield of 70%, which was a white solid. Further, under a nitrogen atmosphere, intermediate compound C-9-1 (2 mmol) and trichloro intermediate Z-9 (3 mmol) were dissolved in ultra-dry N,N-dimethylformamide (150 mL). Then, solid sodium hydride (6.2 mmol) was slowly added, and the reaction was refluxed at 140 °C for 20 hours. After the reaction was complete, the solvent was removed by rotary evaporation, and the crude product was purified by silica gel column chromatography (the eluent was petroleum ether:dichloromethane = 4:1) to obtain the target product C-9 with a yield of 18%, which was a yellow solid. The result of MALDI-TOF-MS shows that the molecular ion peak is 1226.64. The result of elemental analysis shows that the theoretical values are: C, 82.19; H, 6.40; N, 11.41, and the experimental values are: C, 82.20; H, 6.40; N, 11.41.

[0247] Synthesis Example 42:

[0248] Synthesis of Compound C-11

[0249] The synthesis method is similar to Synthesis Example 41, except that M-9 is replaced with M-8. The yield is 21%, and it is a yellow solid. The result of MALDI-TOF-MS shows that the molecular ion peak is 1385.72. The result of elemental analysis shows that the theoretical values are: C, 80.55; H, 6.32; N, 13.13, and the experimental values are: C, 80.55; H, 6.32; N, 13.14.

[0250] Synthesis Example 43:

[0251] Synthesis of Compound C-26

[0252] The synthesis method is similar to that of Synthesis Example 1, only replacing Z-1 with Z-10. The yield is 20%, and it is a yellow solid. The result of MALDI-TOF-MS shows that the molecular ion peak is 1006.59; the result of elemental analysis shows that the theoretical values are C, 87.03; H, 7.40; N, 5.56, and the experimental values are C, 87.03; H, 7.40; N, 5.57.

[0253] Synthesis Example 44:

[0254] Synthesis of Compound C-31

[0255]

[0256] Under a nitrogen atmosphere, the raw materials 3,6-di-tert-butyl-1-boronic acid pinacol ester-9H-carbazole (K-1) (36 mmol), 1,2,3-tribromobenzene (M-10) (10 mmol), and potassium carbonate (100 mmol) were dissolved in a mixed solution of dioxane (300 mL) and water (60 mL), and then tetrakis(triphenylphosphine)palladium (1.5 mmol) was added. The reaction was refluxed at 120 °C for 20 hours. After the reaction was complete, the solvent was removed by rotary evaporation, and the crude product was purified by silica gel column chromatography (the eluent was petroleum ether:dichloromethane = 1:2) to obtain the intermediate compound C-31-1 with a yield of 75% and it was a white solid. Further, under a nitrogen atmosphere, the intermediate compound C-31-1 (2 mmol) and 2,3,4-trifluorobenzonitrile (Z-11) (3 mmol) were dissolved in ultra-dry N,N-dimethylformamide (150 mL), and then solid sodium hydride (6.2 mmol) was slowly added. The reaction was refluxed at 140 °C for 20 hours. After the reaction was complete, the solvent was removed by rotary evaporation, and the crude product was purified by silica gel column chromatography (the eluent was petroleum ether:dichloromethane = 4:1) to obtain the target product C-31 with a yield of 22% and it was a yellow solid. The result of MALDI-TOF-MS shows that the molecular ion peak is 1006.59; the result of elemental analysis shows that the theoretical values are C, 87.03; H, 7.40; N, 5.56, and the experimental values are C, 87.02; H, 7.40; N, 5.56.

[0257] Synthesis Example 45:

[0258] Synthesis of Compound C-38

[0259] The synthesis method is similar to that of Synthesis Example 44, except that M-10 is replaced by M-11 and Z-11 is replaced by Z-12. The yield is 19%, and it is a yellow solid. The result of MALDI-TOF-MS shows that the molecular ion peak is 1049.58. The result of elemental analysis shows that the theoretical values are C, 83.47; H, 7.10; F, 5.43; N, 4.00, and the experimental values are C, 83.47; H, 7.10; F, 5.43; N, 4.01.

[0260] Synthesis Example 46:

[0261] Synthesis of Compound C-42

[0262] The synthesis method is similar to that of Synthesis Example 44, except that M-10 is replaced by M-2 and Z-11 is replaced by Z-10. The yield is 18%, and it is a yellow solid. The result of MALDI-TOF-MS shows that the molecular ion peak is 1031.59. The result of elemental analysis shows that the theoretical values are C, 86.09; H, 7.13; N, 6.78, and the experimental values are C, 86.09; H, 7.14; N, 6.78.

[0263] Synthesis Example 47:

[0264] Synthesis of Compound C-56

[0265] The synthesis method is similar to that of Synthesis Example 44, except that M-10 is replaced by M-12 and Z-11 is replaced by Z-13. The yield is 21%, and it is a yellow solid. The result of MALDI-TOF-MS shows that the molecular ion peak is 1074.58. The result of elemental analysis shows that the theoretical values are C, 82.65; H, 6.84; F, 5.30; N, 5.21, and the experimental values are C, 82.65; H, 6.85; F, 5.30; N, 5.21.

[0266] Synthesis Example 48:

[0267] Synthesis of Compound C-60

[0268] The synthesis method is similar to that of Synthesis Example 44, except that M-10 is replaced by M-13 and Z-11 is replaced by Z-14. The yield is 21%, and it is a yellow solid. The result of MALDI-TOF-MS shows that the molecular ion peak is 1031.59. The result of elemental analysis shows that the theoretical values are C, 86.09; H, 7.13; N, 6.78, and the experimental values are C, 86.09; H, 7.14; N, 6.78.

[0269] Synthesis Example 49:

[0270] Synthesis of Compound C-71

[0271] The synthesis method is similar to Synthesis Example 44, except that Z-11 is replaced with Z-15. The yield is 23%, and it is a yellow solid. The result of MALDI-TOF-MS shows that the molecular ion peak is 1074.58. The result of elemental analysis shows that the theoretical values are: C, 82.65; H, 6.84; F, 5.30; N, 5.21, and the experimental values are: C, 82.65; H, 6.84; F, 5.31; N, 5.21.

[0272] Synthesis Example 50:

[0273] Synthesis of Compound D-1

[0274]

[0275] Under a nitrogen atmosphere, the raw materials 3,6-di-tert-butyl-1-boronic acid pinacol ester-9H-carbazole (K-1) (24 mmol), 1,3-dibromobenzene (M-14) (10 mmol), and potassium carbonate (50 mmol) were dissolved in a mixed solution of dioxane (200 mL) and water (40 mL). Then, tetrakis(triphenylphosphine)palladium (1.5 mmol) was added, and the mixture was refluxed at 120 °C for 20 hours. After the reaction was complete, the solvent was removed by rotary evaporation, and the crude product was purified by silica gel column chromatography (the eluent was petroleum ether:dichloromethane = 1:2) to obtain the intermediate compound D-1-1 with a yield of 66% as a white solid. Further, under a nitrogen atmosphere, the intermediate compound D-1-1 (2 mmol) and 2,6-difluorobenzonitrile (Z-16) (3 mmol) were dissolved in ultra-dry N,N-dimethylformamide (150 mL). Then, solid sodium hydride (4.2 mmol) was slowly added, and the mixture was refluxed at 140 °C for 20 hours. After the reaction was complete, the solvent was removed by rotary evaporation, and the crude product was purified by silica gel column chromatography (the eluent was petroleum ether:dichloromethane = 4:1) to obtain the target product D-1 with a yield of 18% as a yellow solid. The result of MALDI-TOF-MS shows that the molecular ion peak is 731.42. The result of elemental analysis shows that the theoretical values are: C, 86.96; H, 7.30; N, 5.74, and the experimental values are: C, 86.96; H, 7.31; N, 5.73.

[0276] Synthesis Example 51:

[0277] Synthesis of Compound D-5

[0278]

[0279] Under a nitrogen atmosphere, the raw materials 3,6-di-tert-butyl-1-boronic acid pinacol ester-9H-carbazole (K-1) (48 mmol), 1,2,4,5-tetrabromobenzene (M-15) (10 mmol), and potassium carbonate (150 mmol) were dissolved in a mixed solution of dioxane (400 mL) and water (80 mL), and then tetrakis(triphenylphosphine)palladium (1.5 mmol) was added. The reaction was refluxed at 120 °C for 20 hours. After the reaction was complete, the solvent was removed by rotary evaporation, and the crude product was purified by silica gel column chromatography (the eluent was petroleum ether:dichloromethane = 1:2) to obtain intermediate compound D-5-1 with a yield of 71% as a white solid. Further, under a nitrogen atmosphere, intermediate compound D-5-1 (2 mmol) and 2,3,5,6-tetrafluorobenzonitrile (Z-17) (3 mmol) were dissolved in ultra-dry N,N-dimethylformamide (150 mL), and then solid sodium hydride (8.2 mmol) was slowly added. The reaction was refluxed at 140 °C for 20 hours. After the reaction was complete, the solvent was removed by rotary evaporation, and the crude product was purified by silica gel column chromatography (the eluent was petroleum ether:dichloromethane = 4:1) to obtain the target product D-5 with a yield of 21% as a yellow solid. The result of MALDI-TOF-MS showed a molecular ion peak at 1281.76; the result of elemental analysis showed the theoretical values: C, 87.08; H, 7.46; N, 5.46, and the experimental values: C, 87.08; H, 7.47; N, 5.46.

[0280] Synthesis Example 52:

[0281] Synthesis of Compound D-8

[0282]

[0283] Under a nitrogen atmosphere, 3,6-di-tert-butyl-1-boronic acid pinacol ester-9H-carbazole (K-1) (60 mmol), 1,2,3,4,5-pentabromobenzene (M-16) (10 mmol), and potassium carbonate (200 mmol) were dissolved in a mixed solution of dioxane (500 mL) and water (100 mL). Then, tetrakis(triphenylphosphine)palladium (1.5 mmol) was added, and the reaction was refluxed at 120 °C for 20 hours. After the reaction was complete, the solvent was removed by rotary evaporation. The crude product was purified by silica gel column chromatography (the eluent was petroleum ether:dichloromethane = 1:2) to obtain intermediate compound D-8-1 with a yield of 72%, which was a white solid. Further, under a nitrogen atmosphere, intermediate compound D-8-1 (2 mmol) and 2,3,4,5,6-pentafluorobenzonitrile (Z-18) (3 mmol) were dissolved in ultra-dry N,N-dimethylformamide (150 mL). Then, solid sodium hydride (10.2 mmol) was slowly added, and the reaction was refluxed at 140 °C for 20 hours. After the reaction was complete, the solvent was removed by rotary evaporation. The crude product was purified by silica gel column chromatography (the eluent was petroleum ether:dichloromethane = 4:1) to obtain the target product D-8 with a yield of 20%, which was a yellow solid. The result of MALDI-TOF-MS, molecular ion peak: 1556.93; the result of elemental analysis, theoretical values: C, 87.10; H, 7.50; N, 5.39, experimental values: C, 87.11; H, 7.50; N, 5.39.

[0284] Synthesis Example 53:

[0285] Synthesis of Compound D-13

[0286] The synthesis method was similar to that of Synthesis Example 51, only replacing Z-17 with Z-19, with a yield of 24%, which was a yellow solid. The result of MALDI-TOF-MS, molecular ion peak: 1324.75; the result of elemental analysis, theoretical values: C, 84.25; H, 7.22; F, 4.30; N, 4.23, experimental values: C, 84.25; H, 7.22; F, 4.30; N, 4.22.

[0287] Synthesis Example 54:

[0288] Synthesis of Compound D-20

[0289] The synthesis method was similar to that of Synthesis Example 52, only replacing Z-18 with Z-20, with a yield of 25%, which was a yellow solid. The result of MALDI-TOF-MS, molecular ion peak: 1556.93; the result of elemental analysis, theoretical values: C, 87.10; H, 7.50; N, 5.39, experimental values: C, 87.10; H, 7.51; N, 5.39.

[0290] Synthesis Example 55:

[0291] Synthesis of Compound D-23

[0292] The synthesis method is similar to that of Synthesis Example 51, only replacing Z-17 with Z-21. The yield is 18%, and it is a yellow solid. The result of MALDI-TOF-MS shows that the molecular ion peak is 1487.84. The result of elemental analysis: theoretical values: C, 86.31; H, 7.11; N, 6.58, experimental values: C, 86.31; H, 7.11; N, 6.57.

[0293] Synthesis Example 56:

[0294] Synthesis of Compound D-25

[0295] The synthesis method is similar to that of Synthesis Example 50, only replacing K-1 with K-9. The yield is 16%, and it is a yellow solid. The result of MALDI-TOF-MS shows that the molecular ion peak is 591.27. The result of elemental analysis: theoretical values: C, 87.28; H, 5.62; N, 7.10, experimental values: C, 87.28; H, 5.62; N, 7.11.

[0296] Synthesis Example 57:

[0297] Synthesis of Compound D-31

[0298] The synthesis method is similar to that of Synthesis Example 50, only replacing M-14 with M-17 and Z-16 with Z-22. The yield is 20%, and it is a yellow solid. The result of MALDI-TOF-MS shows that the molecular ion peak is 933.48. The result of elemental analysis: theoretical values: C, 86.14; H, 6.37; N, 7.50, experimental values: C, 86.14; H, 6.38; N, 7.50.

[0299] Synthesis Example 58:

[0300] Synthesis of Compound D-35

[0301] The synthesis method is similar to that of Synthesis Example 50, only replacing Z-16 with Z-23 and changing the equivalent of intermediate compound D-1-1 to 9 mmol. The yield is 20%, and it is a yellow solid. The result of MALDI-TOF-MS shows that the molecular ion peak is 1460.83. The result of elemental analysis: theoretical values: C, 87.08; H, 7.17; N, 5.75, experimental values: C, 87.08; H, 7.17; N, 5.76.

[0302] Synthesis Example 59:

[0303] Synthesis of Compound D-37

[0304] The synthesis method is similar to Synthesis Example 50, except that Z-16 is replaced with Z-24 and the equivalent of intermediate compound D-1-1 is changed to 9 mmol. The yield is 20%, and it is a yellow solid. The result of MALDI-TOF-MS shows that the molecular ion peak is 1416.81. The result of elemental analysis shows that the theoretical values are C, 83.01; H, 7.11; N, 9.88, and the experimental values are C, 83.02; H, 7.11; N, 9.88.

[0305] Synthesis Example 60:

[0306] Synthesis of Compound D-42

[0307]

[0308] Under a nitrogen atmosphere, raw material K-12 (24 mmol), 1,3-dibromobenzonitrile (M-18) (10 mmol), and sodium tert-butoxide (50 mmol) were dissolved in toluene (200 mL) solution, and then bis(tri-tert-butylphosphine)palladium (1.5 mmol) was added. The mixture was refluxed at 100 °C for 20 hours. After the reaction was complete, the solvent was removed by rotary evaporation, and the crude product was purified by silica gel column chromatography (the eluent was petroleum ether:dichloromethane = 1:2) to obtain intermediate compound D-42-1 with a yield of 68%, which was a white solid. Further, under a nitrogen atmosphere, intermediate compound D-42-1 (2 mmol) and 2,6-difluorobenzonitrile (Z-16) (3 mmol) were dissolved in ultra-dry N,N-dimethylformamide (150 mL), and then solid sodium hydride (4.2 mmol) was slowly added. The mixture was refluxed at 140 °C for 20 hours. After the reaction was complete, the solvent was removed by rotary evaporation, and the crude product was purified by silica gel column chromatography (the eluent was petroleum ether:dichloromethane = 4:1) to obtain the target product D-42 with a yield of 18%, which was a yellow solid. The result of MALDI-TOF-MS shows that the molecular ion peak is 710.22. The result of elemental analysis shows that the theoretical values are C, 84.49; H, 3.69; N, 11.82, and the experimental values are C, 84.49; H, 3.68; N, 11.83.

[0309] Synthesis Example 61:

[0310] Synthesis of Compound D-57

[0311]

[0312] Under a nitrogen atmosphere, the raw materials K-13 (24 mmol), 1,3-dibromobenzene (M-14) (10 mmol), and sodium tert-butoxide (50 mmol) were dissolved in toluene (200 mL) solution. Then, bis(tri-tert-butylphosphine)palladium(0) (1.5 mmol) was added, and the mixture was refluxed at 100 °C for 20 hours. After the reaction was complete, the solvent was removed by rotary evaporation. The crude product was purified by silica gel column chromatography (eluent: petroleum ether:dichloromethane = 1:2) to obtain intermediate compound D-57-1 with a yield of 77%, which was a white solid. Further, under a nitrogen atmosphere, intermediate compound D-57-1 (2 mmol) and difluoro intermediate Z-22 (3 mmol) were dissolved in ultra-dry N,N-dimethylformamide (150 mL). Then, solid sodium hydride (4.2 mmol) was slowly added, and the mixture was refluxed at 140 °C for 20 hours. After the reaction was complete, the solvent was removed by rotary evaporation. The crude product was purified by silica gel column chromatography (eluent: petroleum ether:dichloromethane = 4:1) to obtain the target product D-57 with a yield of 20%, which was a yellow solid. The results of MALDI-TOF-MS showed a molecular ion peak of 786.25. The results of elemental analysis showed a theoretical value of C, 85.48; H, 3.84; N, 10.68, and an experimental value of C, 85.48; H, 3.85; N, 10.68.

[0313] Synthesis Example 62:

[0314] Synthesis of Compound D-61

[0315] The synthesis method was similar to that of Synthesis Example 61, except that Z-22 was replaced with Z-23 and the equivalent of intermediate compound D-57-1 was changed to 9 mmol. The yield was 20%, and it was a yellow solid. The results of MALDI-TOF-MS showed a molecular ion peak of 1368.44. The results of elemental analysis showed a theoretical value of C, 85.95; H, 3.83; N, 10.23, and an experimental value of C, 85.96; H, 3.83; N, 10.23.

[0316] Synthesis Example 63:

[0317] Synthesis of Compound D-69

[0318] The synthesis method was similar to that of Synthesis Example 60, except that Z-16 was replaced with Z-25. The yield was 17%, and it was a yellow solid. The results of MALDI-TOF-MS showed a molecular ion peak of 710.22. The results of elemental analysis showed a theoretical value of C, 84.49; H, 3.69; N, 11.82, and an experimental value of C, 84.49; H, 3.68; N, 11.83.

[0319] Synthesis Example 64:

[0320] Synthesis of Compound D-77

[0321] The synthesis method is similar to that of Synthesis Example 50, only replacing M-14 with M-19. The yield is 18%, and it is a yellow solid. The result of MALDI-TOF-MS shows that the molecular ion peak is 756.42. The result of elemental analysis: theoretical values are C, 85.68; H, 6.92; N, 7.40, and experimental values are C, 85.68; H, 6.92; N, 7.41.

[0322] Synthesis Example 65:

[0323] Synthesis of Compound D-81

[0324] The synthesis method is similar to that of Synthesis Example 51, only replacing M-15 with M-20. The yield is 20%, and it is a yellow solid. The result of MALDI-TOF-MS shows that the molecular ion peak is 1306.75. The result of elemental analysis: theoretical values are C, 86.33; H, 7.24; N, 6.43, and experimental values are C, 86.31; H, 7.24; N, 6.43.

[0325] Synthesis Example 66:

[0326] Synthesis of Compound D-101

[0327] The synthesis method is similar to that of Synthesis Example 64, only replacing K-1 with K-9. The yield is 21%, and it is a yellow solid. The result of MALDI-TOF-MS shows that the molecular ion peak is 616.26. The result of elemental analysis: theoretical values are C, 85.69; H, 5.23; N, 9.08, and experimental values are C, 85.68; H, 5.23; N, 9.08.

[0328] Synthesis Example 67:

[0329] Synthesis of Compound D-134

[0330] The synthesis method is similar to that of Synthesis Example 50, only replacing M-14 with M-21 and Z-16 with Z-26. The yield is 18%, and it is a yellow solid. The result of MALDI-TOF-MS shows that the molecular ion peak is 928.50. The result of elemental analysis: theoretical values are C, 86.60; H, 6.94; N, 3.01; O, 3.44, and experimental values are C, 86.62; H, 6.94; N, 3.01; O, 3.42.

[0331] Synthesis Example 68:

[0332] Synthesis of Compound D-136

[0333] The synthesis method was similar to Synthesis Example 51, except that M-15 was replaced with M-22 and Z-17 was replaced with Z-27. The yield was 21%, and it was a yellow solid. The result of MALDI-TOF-MS showed that the molecular ion peak was 1492.77. The result of elemental analysis showed that the theoretical values were C, 85.22; H, 6.75; N, 3.75; O, 4.28, and the experimental values were C, 85.22; H, 6.77; N, 3.75; O, 4.26.

[0334] The technical effects and advantages of the present invention will be demonstrated and verified by specifically applying the compounds of the present invention to organic electroluminescent devices to test their actual performance in use.

[0335] An organic electroluminescent device includes an anode, a cathode, and an organic material layer located between the two electrodes. The organic material can be further divided into multiple regions. For example, the organic material layer can include a hole transport region, a light-emitting layer, and an electron transport region.

[0336] The material of the anode can be an oxide transparent conductive material such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), zinc oxide (ZnO), etc., and any combination thereof. The material of the cathode can be a metal or alloy such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), etc., and any combination thereof.

[0337] 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 multi-layer structure including at least one of a hole injection layer (HIL), a hole transport layer (HTL), and an electron blocking layer (EBL).

[0338] The material of the hole transport region can be selected from, but not limited to, phthalocyanine derivatives such as CuPc, conductive polymers, or polymers containing conductive dopants such as poly(phenylene vinylene), 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, etc.

[0339] The light-emitting layer includes light-emitting dyes (i.e., dopants) that can emit spectra of different wavelengths, and may also include a host material at the same time. The light-emitting layer can be a monochromatic light-emitting layer that emits a single color such as red, green, or blue. Monochromatic light-emitting layers of multiple different colors can be arranged in a planar pattern according to a pixel pattern, or stacked together to form a color light-emitting layer. When light-emitting layers of different colors are stacked together, they can be separated from each other or connected to each other. The light-emitting layer can also be a single color light-emitting layer that can simultaneously emit different colors such as red, green, and blue.

[0340] 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. The electron transport region can also be a multi-layer structure including at least one of an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL).

[0341] In an embodiment of the present invention, the preparation process of the organic electroluminescent device is as follows: The material of the present invention is used as the light-emitting dye in the light-emitting layer. The light-emitting layer includes a host and a light-emitting dye, and the structure of the light-emitting layer is as shown in the Figure 1 specification appendix.

[0342] An anode, a hole transport layer, an organic light-emitting layer, an electron transport layer, and a cathode are sequentially deposited on a substrate, and then encapsulated. Among them, when preparing the organic light-emitting layer, the organic light-emitting layer is formed by co-evaporation of an electron donor-type material source, an electron acceptor-type material source, and the TADF material source of the present invention.

[0343] Specifically, it includes the following steps:

[0344] 1. Ultrasonically treat the glass plate coated with the anode material in a commercial cleaning agent, rinse it in deionized water, ultrasonically remove oil in an acetone:ethanol mixed solvent, bake it in a clean environment until all moisture is completely removed, clean it with ultraviolet light and ozone, and bombard the surface with a low-energy cation beam;

[0345] 2. Place the above glass plate with the anode in a vacuum chamber, evacuate to 1×10 -5 ~9×10 -3 Pa, and vacuum-evaporate a hole injection material on the above anode layer film to form a hole injection layer, with an evaporation rate of 0.1-0.5 nm / s;

[0346] 3. Vacuum-evaporate a hole transport material on the hole injection layer to form a hole transport layer, with an evaporation rate of 0.1-0.5 nm / s,

[0347] 4. Vacuum deposit the organic light-emitting layer of the device on top of the hole transport layer. The organic light-emitting layer material includes a host material and the compound of the present invention as a dye. Using the method of co-evaporation from multiple sources, adjust the evaporation rate of the host material and the evaporation rate of the luminescent dye so that the luminescent dye reaches a preset doping ratio;

[0348] 5. Vacuum deposit the electron transport material of the device on top of the organic light-emitting layer to form an electron transport layer, and its evaporation rate is 0.1 - 0.5 nm / s;

[0349] 6. Vacuum deposit LiF as the electron injection layer on the electron transport layer at a rate of 0.1 - 0.5 nm / s, and vacuum deposit an Al layer as the cathode of the device at a rate of 0.5 - 1 nm / s.

[0350] The embodiment of the present invention also provides a display device, and the display device includes the organic electroluminescent device provided as above. The display device can specifically be a display device such as an OLED display, as well as any product or component with a display function including the display device, such as a television, digital camera, mobile phone, tablet computer, etc. The advantages of the display device compared with the prior art are the same as those of the above organic electroluminescent device, and will not be elaborated here.

[0351] The following further introduces the organic electroluminescent device of the present invention through specific embodiments.

[0352] In the following embodiments of the present invention, the OLED includes an anode / hole injection layer / hole transport layer / first exciton blocking layer / luminescent layer / second exciton blocking layer / electron transport layer / electron injection layer / cathode stacked in sequence. Among them, the anode is ITO; the hole injection layer is HATCN; the hole transport layer is NPB; the first exciton blocking layer is TCTA; the host materials of the luminescent layer are SiCzCz and SiTrzCz 2 The formed exciplex, with a mass ratio of 1:1 between the two, and doping the thermally activated delayed fluorescence material of the present invention as the luminescent dye, with a doping mass percentage concentration of 20 wt%; the second exciton blocking layer is DCzPm; the electron transport layer is co-evaporated with DPyPA; the electron injection layer is LiF; the cathode is Al.

[0353]

[0354] The structure of the comparative compound is:

[0355]

[0356] Example 1

[0357] The glass plate coated with the ITO transparent conductive layer is ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in an acetone:ethanol mixed solvent, baked in a clean environment until all moisture is completely removed, cleaned with ultraviolet light and ozone, and the surface is bombarded with a low-energy cation beam;

[0358] HATCN is vacuum-evaporated on the ITO transparent conductive layer as the hole injection layer of the device, with an evaporation rate of 0.1 nm / s and a total film thickness of 5 nm;

[0359] NPB is vacuum-evaporated on the hole injection layer as the hole transport layer of the device, with an evaporation rate of 0.1 nm / s and a total film thickness of 30 nm;

[0360] TCTA is vacuum-evaporated on the hole transport layer as the first exciton blocking layer, with an evaporation rate of 0.1 nm / s and a total film thickness of 10 nm;

[0361] The light-emitting layer of the device is vacuum-evaporated on the first exciton blocking layer. The light-emitting layer of the present invention includes a host material and a light-emitting dye. The host materials are SiCzCz and SiTrzCz 2 The formed exciplex, with a mass ratio of 1:1 between the two, and the thermally activated delayed fluorescence material A-1 of the present invention is used as the light-emitting dye. The evaporation rate of the above host materials is adjusted to 0.1 nm / s, that is, SiCzCz and SiTrzCz 2 are 0.05 nm / s respectively, and the evaporation rate of the light-emitting dye is set at 20 wt% of the host evaporation rate. The total film thickness of the light-emitting layer is 30 nm;

[0362] DCzPm is vacuum-evaporated on the light-emitting layer as the second exciton blocking layer of the device, with an evaporation rate of 0.1 nm / s and a total film thickness of 10 nm;

[0363] DPyPA is vacuum-evaporated on the second exciton blocking layer as the electron transport material of the device, with an evaporation rate of 0.1 nm / s and a total film thickness of 30 nm;

[0364] A 0.5-nm-thick LiF is vacuum-evaporated on the electron transport layer as the electron injection layer, and a 150-nm-thick Al layer is used as the cathode of the device.

[0365] Examples 2 to 68 are all the same as the preparation method of Example 1, except that the light-emitting dye in the light-emitting layer is respectively replaced by the compounds involved in the synthesis examples of the present invention instead of the compound A-1 of the present invention. Comparative Examples 1-6 are all the same as the preparation method of Example 1, except that the light-emitting dye in the light-emitting layer is respectively replaced by the above comparative compounds instead of the compound A-1 of the present invention.

[0366] The performance of the organic light-emitting devices prepared in the above embodiments is shown in Table 1 below.

[0367] Table 1:

[0368]

[0369]

[0370]

[0371] As can be seen from Table 1 above, when the compound of the present invention is used as a luminescent dye in the light-emitting layer of an organic light-emitting device, when the required brightness is 1000 cd / m 2 ², the driving voltage is as low as 5 V or less, the current efficiency is as high as more than 50 cd / A, and the T90 life is greater than 300 h. The performance is much superior to that of Comparative Examples 1-6.

[0372] The reason for the analysis is that compared with Comparative Materials 1-4, based on the donor-acceptor (D-A) structural characteristics of traditional thermally activated delayed fluorescence materials (TADF), this type of compound of the present invention connects and locks the originally freely rotatable donor group by introducing a central π moiety, thereby effectively suppressing the free rotation of the peripheral donor group, making the HOMO of the molecule mainly distributed on the peripheral donor group, while the LUMO is mainly concentrated on the central π moiety, and then resulting in a more obvious spatial separation between the HOMO and the LUMO, thereby effectively reducing the singlet-triplet energy gap (ΔE ST ) of the molecule, increasing the reverse intersystem crossing rate of the molecule, realizing the efficient utilization of excitons, and improving the luminescence efficiency. And directly connecting the central π moiety through the carbon atom or nitrogen atom on the donor aromatic ring parent nucleus to lock the donor can also significantly improve the structural rigidity of the molecule, thereby effectively weakening the vibration of the molecule, suppressing the non-radiative transition and energy loss caused by the molecular vibration, reducing the relaxation degree of the excited state structure, and improving the luminescence quantum yield, color purity and stability of the molecule. In addition, such a method can also enable the molecule to have a high reverse intersystem crossing rate and luminescence quantum yield while maintaining blue light emission, thereby realizing efficient and fast blue light and deep blue light TADF materials, and then preparing highly efficient and stable blue light and deep blue light OLED devices, which is helpful for the commercial application of the materials.

[0373] Compared with Comparative Material 5, the emission peak of the molecule is around 400 nm, the emission band gap is relatively large, the driving voltage is very high, and the singlet-triplet energy gap (ΔE ST) It is very large, and it is difficult to improve the luminescence efficiency of the molecule through the reverse intersystem crossing process. Moreover, the peripheral linking group is a flexible chain fragment, and the rigidity of the molecule is poor, resulting in an increase in non-radiative transitions caused by molecular vibrations. Therefore, the efficiency and lifespan are very poor. In contrast, the peripheral linking group of Comparative Material 6 does not participate in the luminescence process of the molecule. The luminescence of the molecule mainly comes from the transition of the CT state between D and A in the middle, which is essentially different from the material invented by this institute. At the same time, the peripheral linking group also has a certain degree of flexibility and poor rigidity. The photoluminescence quantum yield of the molecule is only 35%, and the connecting part is directly connected through oxygen atoms and nitrogen atoms, resulting in poor stability, and thus the efficiency and lifespan of the device are poor.

[0374] The above experimental data show that the organic material of the present invention, as a luminescent dye for organic electroluminescent devices, is an organic luminescent functional material with good performance and is expected to be popularized for commercial applications.

[0375] In the embodiments of the present invention, the preparation process of the organic electroluminescent device is as follows: The material of the present invention is used as a sensitizer in the light-emitting layer. The light-emitting layer includes a host material, a sensitizer, and a phosphorescent dye. The structure of the light-emitting layer is as shown in the attached Figure 2 description.

[0376] The anode, hole transport layer, organic light-emitting layer, electron transport layer, and cathode are sequentially deposited on the substrate and then encapsulated. Among them, when preparing the organic light-emitting layer, the organic light-emitting layer is formed by co-evaporating an electron donor-type material source, an electron acceptor-type material source, the TADF material source of the present invention, and a phosphorescent dye source.

[0377] Specifically, it includes the following steps:

[0378] 1. Ultrasonically treat the glass plate coated with the anode material in a commercial cleaning agent, rinse it in deionized water, ultrasonically degrease it in a mixed solvent of acetone:ethanol, bake it in a clean environment until all moisture is completely removed, clean it with ultraviolet light and ozone, and bombard the surface with a low-energy cation beam;

[0379] 2. Place the above glass plate with the anode in a vacuum chamber, evacuate to 1×10 -5 ~9×10 -3 Pa, and vacuum deposit a hole injection material on the above anode layer film to form a hole injection layer, with an evaporation rate of 0.1 - 0.5 nm / s;

[0380] 3. Vacuum deposit a hole transport material on the hole injection layer to form a hole transport layer, with an evaporation rate of 0.1 - 0.5 nm / s,

[0381] 4. Vacuum deposit the organic light-emitting layer of the device on top of the hole transport layer. The organic light-emitting layer material includes a host material, the compound of the present invention as a sensitizer, and a phosphorescent dye. Using the method of co-evaporation from multiple sources, adjust the evaporation rate of the host material, the evaporation rate of the sensitizer, and the evaporation rate of the phosphorescent dye so that the sensitizer and the phosphorescent dye reach a preset doping ratio;

[0382] 5. Vacuum deposit the electron transport material of the device on top of the organic light-emitting layer to form an electron transport layer, and its evaporation rate is 0.1 - 0.5 nm / s;

[0383] 6. Vacuum deposit LiF as the electron injection layer on the electron transport layer at a rate of 0.1 - 0.5 nm / s, and vacuum deposit an Al layer as the cathode of the device at a rate of 0.5 - 1 nm / s.

[0384] The embodiment of the present invention also provides a display device, and the display device includes the organic electroluminescent device provided as above. The display device can specifically be a display device such as an OLED display, as well as any product or component with a display function including the display device, such as a television, a digital camera, a mobile phone, a tablet computer, etc. The display device has the same advantages as the above-mentioned organic electroluminescent device over the prior art, and will not be elaborated here.

[0385] The following further introduces the organic electroluminescent device of the present invention through specific embodiments.

[0386] In the following embodiments of the present invention, the OLED includes an anode / hole injection layer / hole transport layer / first exciton blocking layer / light-emitting layer / second exciton blocking layer / electron transport layer / electron injection layer / cathode stacked in sequence. Among them, the anode is ITO; the hole injection layer is HATCN; the hole transport layer is NPB; the first exciton blocking layer is TCTA; the host materials of the light-emitting layer are SiCzCz and SiTrzCz 2 The formed exciplex, with a mass ratio of 1:1 between the two, the sensitizer is the material of the present invention, and the doping mass percentage concentration is 5 wt%; the phosphorescent dye is PtON-TBBI, and the doping mass percentage concentration is 10 wt%; the second exciton blocking layer is DCzPm; the electron transport layer is DPyPA co-evaporated; the electron injection layer is LiF; the cathode is Al.

[0387]

[0388]

[0389] The structure of the comparative compound is:

[0390]

[0391] Example 69

[0392] The glass plate coated with the ITO transparent conductive layer is ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in an acetone:ethanol mixed solvent, baked in a clean environment until all moisture is removed, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam on the surface;

[0393] HATCN is vacuum-evaporated on the ITO transparent conductive layer as the hole injection layer of the device, with an evaporation rate of 0.1 nm / s and a total evaporation film thickness of 5 nm;

[0394] NPB is vacuum-evaporated on the hole injection layer as the hole transport layer of the device, with an evaporation rate of 0.1 nm / s and a total evaporation film thickness of 30 nm;

[0395] TCTA is vacuum-evaporated on the hole transport layer as the first exciton blocking layer, with an evaporation rate of 0.1 nm / s and a total evaporation film thickness of 10 nm;

[0396] The light-emitting layer of the device is vacuum-evaporated on the first exciton blocking layer. The light-emitting layer of the present invention includes a host material, a sensitizer, and a phosphorescent dye. The host materials are SiCzCz and SiTrzCz 2 The formed exciplex, with a mass ratio of 1:1 between the two. The sensitizer is the material of the present invention, with a doping mass percentage concentration of 5 wt%. The phosphorescent dye is PtON-TBBI, with a doping mass percentage concentration of 10 wt%. The thermally activated delayed fluorescence material A-1 of the present invention is used as the sensitizer. The evaporation rate of the above host materials is adjusted to 0.1 nm / s, that is, SiCzCz and SiTrzCz 2 are 0.05 nm / s respectively. The evaporation rate of the sensitizer A-1 in the light-emitting layer is set at a 5 wt% ratio of the host evaporation rate, and the evaporation rate of the phosphorescent dye PtON-TBBI in the light-emitting layer is set at a 10 wt% ratio of the host evaporation rate. The total evaporation film thickness of the light-emitting layer is 30 nm;

[0397] DCzPm is vacuum-evaporated on the light-emitting layer as the second exciton blocking layer of the device, with an evaporation rate of 0.1 nm / s and a total evaporation film thickness of 10 nm;

[0398] DPyPA is vacuum-evaporated on the second exciton blocking layer as the electron transport material of the device, with an evaporation rate of 0.1 nm / s and a total evaporation film thickness of 30 nm;

[0399] LiF with a thickness of 0.5 nm is vacuum-evaporated on the electron transport layer as the electron injection layer, and an Al layer with a thickness of 150 nm is used as the cathode of the device.

[0400] Examples 70 to 136 are the same as the preparation method of Example 69, except that the sensitizer in the light-emitting layer is replaced by the compounds involved in the synthesis examples of the present invention instead of Compound A-1 of the present invention. Comparative Examples 7-12 are the same as the preparation method of Example 69, except that the sensitizer in the light-emitting layer is replaced by the above-mentioned comparative compounds instead of Compound A-1 of the present invention. Comparative Example 13 is without a sensitizer, and the light-emitting layer is only the host and the phosphorescent dye PtON-TBBI.

[0401] The performance of the organic electroluminescent devices prepared in the above examples is shown in Table 2 below.

[0402] Table 2:

[0403]

[0404]

[0405] As can be seen from Table 2 above, when the compound of the present invention is used as the sensitizer in the light-emitting layer of an organic electroluminescent device, when the required brightness is 1000 cd / m 2 , the driving voltage is as low as 5 V or less, the current efficiency is as high as more than 60 cd / A, and the T90 life is greater than 400 h. The performance is much superior to that of Comparative Examples 7-13.

[0406] The reason for the analysis is that compared with Comparative Materials 1-4, based on the donor-acceptor (D-A) structural characteristics of traditional thermally activated delayed fluorescence materials (TADF), this type of compound of the present invention connects and locks the originally freely rotatable donor groups by introducing a central π moiety, thereby effectively suppressing the free rotation of the peripheral donor groups, making the HOMO of the molecule mainly distributed on the peripheral donor groups, while the LUMO is mainly concentrated on the central π moiety, and then resulting in a more obvious spatial separation between the HOMO and the LUMO, thereby effectively reducing the singlet-triplet energy gap (ΔE ST ) of the molecule, increasing the reverse intersystem crossing rate of the molecule, realizing the efficient utilization of excitons, and improving the luminescence efficiency. And directly connecting the central π moiety through the carbon atom or nitrogen atom on the donor aromatic ring parent nucleus to lock the donor can also significantly improve the structural rigidity of the molecule, thereby effectively weakening the vibration of the molecule, suppressing the non-radiative transition and energy loss caused by the molecular vibration, reducing the relaxation degree of the excited state structure, and improving the luminescence quantum yield, color purity and stability of the molecule. In addition, such a method can also enable the molecule to have a high reverse intersystem crossing rate and luminescence quantum yield while maintaining blue light emission, thereby realizing efficient and fast blue light and deep blue light TADF materials, and then preparing highly efficient and stable blue light and deep blue light OLED devices, which is helpful for the commercial application of the materials.

[0407] Compared with Comparative Material 5, the emission peak of the molecule is around 400 nm, with a relatively large emission band gap, a very high driving voltage, and a large singlet-triplet energy gap (ΔE ST ). It is difficult to improve the luminescence efficiency of the molecule through the reverse intersystem crossing process. Moreover, the peripheral linking group is a flexible chain fragment, resulting in poor rigidity of the molecule, which exacerbates the non-radiative transition caused by molecular vibration. Therefore, the efficiency and lifetime are very poor. In contrast, the peripheral linking group of Comparative Material 6 does not participate in the luminescence process of the molecule. The luminescence of the molecule mainly comes from the transition of the CT state between the middle D and A, which is essentially different from the material invented by this institute. At the same time, the peripheral linking group also has a certain degree of flexibility and poor rigidity. The photoluminescence quantum yield of the molecule is only 35%, and the connecting part is directly connected through oxygen and nitrogen atoms, resulting in poor stability, thus making the efficiency and lifetime of the device poor.

[0408] Compared with Comparative Example 13, after adding the sensitizer of the present invention to the light-emitting layer, the driving voltage decreases, and both the current efficiency and lifetime are significantly improved. The reason is that the light-emitting layer structure of the organic electroluminescent device of the present invention can utilize multiple energy transfer pathways existing in the system to reduce the accumulation of long-lived excitons, thereby suppressing the energy loss and stability degradation caused by the exciton annihilation process. As shown in the attached Figure 2 drawing of the specification, by adding the sensitizer of the present invention to the light-emitting layer, excitons and dispersed triplet excitons can be effectively utilized through multiple energy transfer processes. At the same time, the material of the present invention has a fast reverse intersystem crossing rate, which can effectively accelerate the up-conversion process of triplet excitons, thereby accelerating its kinetic process, reducing the concentration of triplet excitons, and suppressing the quenching effect caused by too high a concentration of triplet excitons, resulting in a significant improvement in both efficiency and lifetime. Especially in the case where a high proportion of initial triplets are generated by electroexcitation in the device, since it can effectively disperse and convert long-lived triplet excitons into shorter-lived phosphorescent triplet excitons or fluorescent singlet excitons, the efficiency and lifetime of related devices in high-brightness application environments are significantly improved.

[0409] The above experimental data show that the organic material of the present invention as a sensitizer for organic electroluminescent devices is an organic luminescent functional material with good performance and is expected to be popularized for commercial applications.

[0410] In the examples of the present invention, the preparation process of the organic electroluminescent device is as follows: The material of the present invention is used as a sensitizer in the light-emitting layer, and the light-emitting layer includes a host material, a sensitizer, and a fluorescent dye. The structure of the light-emitting layer is as shown in the attached Figure 3 drawing of the specification.

[0411] An anode, a hole transport layer, an organic light-emitting layer, an electron transport layer, and a cathode are sequentially deposited on a substrate and then encapsulated. Among them, when preparing the organic light-emitting layer, the organic light-emitting layer is formed by co-evaporating an electron donor-type material source, an electron acceptor-type material source, the TADF material source of the present invention, and a fluorescent dye source.

[0412] Specifically, it includes the following steps:

[0413] 1. Ultrasonically treat the glass plate coated with the anode material in a commercial cleaning agent, rinse it in deionized water, ultrasonically degrease it in an acetone:ethanol mixed solvent, bake it in a clean environment until all moisture is completely removed, clean it with ultraviolet light and ozone, and bombard the surface with a low-energy cation beam;

[0414] 2. Place the glass plate with the anode in a vacuum chamber, evacuate it to 1×10 -5 ~9×10 -3 Pa, and vacuum deposit a hole injection material on the anode layer film to form a hole injection layer, with an evaporation rate of 0.1 - 0.5 nm / s;

[0415] 3. Vacuum deposit a hole transport material on the hole injection layer to form a hole transport layer, with an evaporation rate of 0.1 - 0.5 nm / s,

[0416] 4. Vacuum deposit the organic light-emitting layer of the device on the hole transport layer. The organic light-emitting layer material includes a host material, the compound of the present invention as a sensitizer, and a fluorescent dye. Using the multi-source co-evaporation method, adjust the evaporation rates of the host material, the sensitizer, and the fluorescent dye so that the sensitizer and the fluorescent dye reach a preset doping ratio;

[0417] 5. Vacuum deposit the electron transport material of the device on the organic light-emitting layer, with an evaporation rate of 0.1 - 0.5 nm / s;

[0418] 6. Vacuum deposit LiF as an electron injection layer on the electron transport layer at a rate of 0.1 - 0.5 nm / s, and vacuum deposit an Al layer as the cathode of the device at a rate of 0.5 - 1 nm / s.

[0419] An embodiment of the present invention also provides a display device, and the display device includes the organic electroluminescent device provided as above. The display device can specifically be a display device such as an OLED display, as well as any product or component with a display function including this display device, such as a television, a digital camera, a mobile phone, a tablet computer, etc. The advantages of this display device compared with the prior art are the same as those of the above organic electroluminescent device, and will not be elaborated here.

[0420] The organic electroluminescent device of the present invention is further introduced below through specific embodiments.

[0421] In the following embodiments of the present invention, the OLED includes an anode / hole injection layer / hole transport layer / first exciton blocking layer / light-emitting layer / second exciton blocking layer / electron transport layer / electron injection layer / cathode stacked in sequence. Among them, the anode is ITO; the hole injection layer is HATCN; the hole transport layer is NPB; the first exciton blocking layer is TCTA; the host materials of the light-emitting layer are SiCzCz and SiTrzCz 2 The formed exciplex, with a mass ratio of 1:1 between the two, the sensitizer is the material of the present invention, with a doping mass percentage concentration of 20 wt%, the fluorescent dye is B-N-S or BD, with a doping mass percentage concentration of 1 wt%; the second exciton blocking layer is DCzPm; the electron transport layer is co-evaporated with DPyPA; the electron injection layer is LiF; the cathode is Al.

[0422]

[0423] The structure of the comparative compound is:

[0424]

[0425]

[0426] Example 137

[0427] The glass plate coated with the ITO transparent conductive layer is ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone:ethanol, baked in a clean environment until all moisture is removed, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam on the surface;

[0428] HATCN is vacuum-evaporated on the ITO transparent conductive layer as the hole injection layer of the device, with an evaporation rate of 0.1 nm / s and a total evaporation film thickness of 5 nm;

[0429] NPB is vacuum-evaporated on the hole injection layer as the hole transport layer of the device, with an evaporation rate of 0.1 nm / s and a total evaporation film thickness of 30 nm;

[0430] TCTA is vacuum-evaporated on the hole transport layer as the first exciton blocking layer, with an evaporation rate of 0.1 nm / s and a total evaporation film thickness of 10 nm;

[0431] The light-emitting layer of the device is vacuum-evaporated on the first exciton blocking layer. The light-emitting layer of the present invention includes host materials, a sensitizer, and a fluorescent dye. The host materials are SiCzCz and SiTrzCz 2The formed exciplex has a mass ratio of 1:1 between the two. The sensitizer is the material of the present invention, with a doping mass percentage concentration of 20 wt%. The fluorescent dye is B-N-S, with a doping mass percentage concentration of 1 wt%. The thermally activated delayed fluorescence material A-1 of the present invention is used as the sensitizer. The evaporation rate of the above-mentioned host material is adjusted to 0.1 nm / s, that is, SiCzCz and SiTrzCz 2 are 0.05 nm / s respectively. The evaporation rate of the sensitizer A-1 in the light-emitting layer is set at 20 wt% of the host evaporation rate, and the evaporation rate of the fluorescent dye B-N-S in the light-emitting layer is set at 1 wt% of the host evaporation rate. The total evaporation film thickness of the light-emitting layer is 30 nm;

[0432] On top of the light-emitting layer, DCzPm is vacuum-evaporated as the second exciton blocking layer of the device, with an evaporation rate of 0.1 nm / s and a total evaporation film thickness of 10 nm;

[0433] On top of the second exciton blocking layer, DPyPA is vacuum-evaporated as the electron transport material of the device, with an evaporation rate of 0.1 nm / s and a total evaporation film thickness of 30 nm;

[0434] On the electron transport layer, LiF with a thickness of 0.5 nm is vacuum-evaporated as the electron injection layer, and an Al layer with a thickness of 150 nm is used as the cathode of the device.

[0435] Examples 138 to 204 are all prepared in the same way as Example 137, except that the sensitizer in the light-emitting layer is replaced by the compounds involved in the synthesis examples of the present invention instead of the compound A-1 of the present invention. Comparative Examples 14-19 are all prepared in the same way as Example 137, except that the sensitizer in the light-emitting layer is replaced by the above-mentioned comparative compounds instead of the compound A-1 of the present invention. Comparative Example 20 is without a sensitizer, and the light-emitting layer only contains the host and the fluorescent dye B-N-S.

[0436] Example 205

[0437] The glass plate coated with the ITO transparent conductive layer is ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone:ethanol, baked in a clean environment until all moisture is removed, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam on the surface;

[0438] On top of the ITO transparent conductive layer, HATCN is vacuum-evaporated as the hole injection layer of the device, with an evaporation rate of 0.1 nm / s and a total evaporation film thickness of 5 nm;

[0439] On top of the hole injection layer, NPB is vacuum-evaporated as the hole transport layer of the device, with an evaporation rate of 0.1 nm / s and a total evaporation film thickness of 30 nm;

[0440] Vacuum deposit TCTA as the first exciton blocking layer on the hole transport layer, with a deposition rate of 0.1 nm / s and a total deposited film thickness of 10 nm;

[0441] Vacuum deposit the light-emitting layer of the device above the first exciton blocking layer. The light-emitting layer of the present invention includes a host material, a sensitizer, and a fluorescent dye. The host materials are SiCzCz and SiTrzCz 2 The formed exciplex, with a mass ratio of the two of 1:1. The sensitizer is the material of the present invention, with a doping mass percentage concentration of 20 wt%. The fluorescent dye is BD, with a doping mass percentage concentration of 1 wt%. Use the thermally activated delayed fluorescence material A-1 of the present invention as the sensitizer. Adjust the deposition rate of the above host materials to 0.1 nm / s, that is, SiCzCz and SiTrzCz 2 are 0.05 nm / s respectively. Adjust the deposition rate of the sensitizer A-1 in the light-emitting layer to be set at 20 wt% of the host deposition rate, and adjust the deposition rate of the fluorescent dye BD in the light-emitting layer to be set at 1 wt% of the host deposition rate. The total deposited film thickness of the light-emitting layer is 30 nm;

[0442] Vacuum deposit DCzPm as the second exciton blocking layer of the device above the light-emitting layer, with a deposition rate of 0.1 nm / s and a total deposited film thickness of 10 nm;

[0443] Vacuum deposit DPyPA as the electron transport material of the device above the second exciton blocking layer, with a deposition rate of 0.1 nm / s and a total deposited film thickness of 30 nm;

[0444] Vacuum deposit LiF with a thickness of 0.5 nm as the electron injection layer and an Al layer with a thickness of 150 nm as the cathode of the device on the electron transport layer.

[0445] Examples 206 to 272 are all prepared in the same way as Example 205, except that the sensitizer in the light-emitting layer is respectively replaced by the compounds involved in the synthesis examples of the present invention. Comparative Examples 21-26 are all prepared in the same way as Example 205, except that the sensitizer in the light-emitting layer is respectively replaced by the above comparative compounds. Comparative Example 27 is without a sensitizer, and the light-emitting layer only contains the host and the fluorescent dye BD.

[0446] The performance of the organic electroluminescent devices prepared in the above respective examples is shown in Table 3 below.

[0447] Table 3:

[0448]

[0449]

[0450]

[0451]

[0452] As can be seen from Table 3 above, when the compound of the present invention is used as a sensitizer in the light-emitting layer of an organic electroluminescent device, when the required brightness is 1000 cd / m 2 , the driving voltage is as low as 5 V or less, the current efficiency is as high as over 60 cd / A, and the T90 life is greater than 400 h. The performance is much superior compared with Comparative Examples 14-27.

[0453] The reason for the analysis is that, compared with Comparative Materials 1-4, this type of compound of the present invention, based on the donor-acceptor (D-A) structural characteristics of traditional thermally activated delayed fluorescence materials (TADF), by introducing a central π moiety, connects and locks the donor groups that could originally rotate freely, thereby effectively suppressing the free rotation of the peripheral donor groups, making the HOMO of the molecule mainly distributed on the peripheral donor groups, while the LUMO is mainly concentrated on the central π moiety, and then resulting in a more obvious spatial separation between the HOMO and the LUMO, thus effectively reducing the singlet-triplet energy gap (ΔE ST ), increasing the reverse intersystem crossing rate of the molecule, realizing the efficient utilization of excitons, and improving the light-emitting efficiency. And directly connecting to the central π moiety through the carbon atoms or nitrogen atoms on the donor aromatic ring parent nucleus to lock the donor can also significantly improve the structural rigidity of the molecule, thereby effectively weakening the vibration of the molecule, suppressing the non-radiative transition and energy loss caused by the molecular vibration, reducing the relaxation degree of the excited state structure, and improving the luminescence quantum yield, color purity and stability of the molecule. In addition, such a method can also enable the molecule to have a high reverse intersystem crossing rate and luminescence quantum yield while maintaining blue light emission, thus realizing highly efficient and fast blue and deep blue TADF materials, and then preparing highly efficient and stable blue and deep blue OLED devices, which contributes to the commercial application of the materials.

[0454] While compared with Comparative Material 5, the emission peak of the molecule is around 400 nm, the emission band gap is relatively large, the driving voltage is very high, and the singlet-triplet energy gap (ΔE ST)It is very large, and it is difficult to improve the luminescence efficiency of the molecule through the reverse intersystem crossing process. Moreover, the peripheral linking group is a flexible chain fragment, and the rigidity of the molecule is poor, which intensifies the non-radiative transition caused by molecular vibration. Therefore, the efficiency and lifespan are very poor. In contrast, the peripheral linking group of Comparative Material 6 does not participate in the luminescence process of the molecule. The luminescence of the molecule mainly comes from the transition of the CT state between D and A in the middle. There are essential differences between the materials invented by this institute. At the same time, the peripheral linking group also has a certain degree of flexibility and poor rigidity. The photoluminescence quantum yield of the molecule is only 35%. Moreover, the connecting part is directly connected through oxygen atoms and nitrogen atoms, and the stability is poor, resulting in poor efficiency and lifespan of the device.

[0455] Compared with Comparative Examples 20 and 27, after adding the sensitizer of the present invention to the light-emitting layer, the driving voltage is reduced, and both the current efficiency and lifespan are significantly improved. The reason for the analysis is that the light-emitting layer structure of the organic electroluminescent device of the present invention can utilize multiple energy transfer pathways existing in the system to reduce the accumulation of long-lived excitons, thereby suppressing the energy loss and stability decline caused by the exciton annihilation process. As shown in the attached Figure 3 specification. As shown, by adding the sensitizer of the present invention to the light-emitting layer, excitons and dispersed triplet excitons can be effectively utilized through multiple energy transfer processes. At the same time, the material of the present invention has a fast reverse intersystem crossing rate, which can effectively accelerate the upconversion process of triplet excitons, thereby accelerating its kinetic process, reducing the concentration of triplet excitons, and suppressing the quenching effect caused by too high a concentration of triplet excitons, resulting in a significant improvement in both efficiency and lifespan. Especially in the case where a high proportion of initial triplets are generated by electroexcitation in the device, since it can effectively disperse and convert long-lived triplet excitons into shorter-lived phosphorescent triplet excitons or fluorescent singlet excitons, the efficiency and lifespan of related devices in high-brightness application environments are significantly improved.

[0456] The above experimental data show that the organic material of the present invention as a sensitizer for organic electroluminescent devices is an organic light-emitting functional material with good performance and is expected to be promoted for commercial applications.

[0457] In the examples of the present invention, the preparation process of the organic electroluminescent device is as follows: The material of the present invention is used as a sensitizer in the light-emitting layer. The light-emitting layer includes a host material, a sensitizer, a phosphorescent dye, and a fluorescent dye. The structure of the light-emitting layer is as shown in the attached Figure 4 specification.

[0458] An anode, a hole transport layer, an organic light-emitting layer, an electron transport layer, and a cathode are sequentially deposited on the substrate and then encapsulated. Among them, when preparing the organic light-emitting layer, the organic light-emitting layer is formed by co-evaporation of an electron donor-type material source, an electron acceptor-type material source, the TADF material source of the present invention, a phosphorescent dye source, and a fluorescent dye source.

[0459] Specifically, it includes the following steps:

[0460] 1. Ultrasonically treat the glass plate coated with the anode material in a commercial cleaning agent, rinse it in deionized water, ultrasonically remove oil in an acetone:ethanol mixed solvent, bake it in a clean environment until all moisture is completely removed, clean it with ultraviolet light and ozone, and bombard the surface with a low-energy cation beam;

[0461] 2. Place the glass plate with the anode above in a vacuum chamber, evacuate to 1×10 -5 ~9×10 -3 Pa, and vacuum deposit a hole injection material on the above anode layer film to form a hole injection layer, with a deposition rate of 0.1 - 0.5 nm / s;

[0462] 3. Vacuum deposit a hole transport material on the hole injection layer to form a hole transport layer, with a deposition rate of 0.1 - 0.5 nm / s,

[0463] 4. Vacuum deposit the organic light-emitting layer of the device on the hole transport layer. The organic light-emitting layer material includes a host material and the compound of the present invention as a sensitizer, a phosphorescent dye, and a fluorescent dye. Using the method of co-evaporation from multiple sources, adjust the deposition rates of the host material, the sensitizer, the phosphorescent dye, and the fluorescent dye so that the sensitizer, the phosphorescent dye, and the fluorescent dye reach a preset doping ratio;

[0464] 5. Vacuum deposit the electron transport material of the device on the organic light-emitting layer to form an electron transport layer, with a deposition rate of 0.1 - 0.5 nm / s;

[0465] 6. Vacuum deposit LiF as an electron injection layer on the electron transport layer at a rate of 0.1 - 0.5 nm / s, and vacuum deposit an Al layer as the cathode of the device at a rate of 0.5 - 1 nm / s.

[0466] The embodiment of the present invention also provides a display device, and the display device includes the organic electroluminescent device provided as above. The display device can specifically be a display device such as an OLED display, and any product or component with a display function including the display device, such as a TV, a digital camera, a mobile phone, a tablet computer, etc. The advantages of the display device compared with the prior art are the same as those of the above organic electroluminescent device, and will not be elaborated here.

[0467] The following further introduces the organic electroluminescent device of the present invention through specific embodiments.

[0468] In the following embodiments of the present invention, the OLED includes an anode / hole injection layer / hole transport layer / first exciton blocking layer / light-emitting layer / second exciton blocking layer / electron transport layer / electron injection layer / cathode stacked in sequence. Among them, the anode is ITO; the hole injection layer is HATCN; the hole transport layer is NPB; the first exciton blocking layer is TCTA; the host materials of the light-emitting layer are SiCzCz and SiTrzCz 2 The formed exciplex, with a mass ratio of the two of 1:1, the sensitizer is the material of the present invention, with a doping mass percentage concentration of 5 wt%, the phosphorescent dye is PtON-TBBI, with a doping mass percentage concentration of 10 wt%, the fluorescent dye is B-N-S or BD, with a doping mass percentage concentration of 1 wt%; the second exciton blocking layer is DCzPm; the electron transport layer is co-evaporated with DPyPA; the electron injection layer is LiF; the cathode is Al.

[0469]

[0470]

[0471] The structure of the comparative compound is:

[0472]

[0473] Example 273

[0474] The glass plate coated with the ITO transparent conductive layer is ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in an acetone:ethanol mixed solvent, baked in a clean environment until all moisture is completely removed, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam on the surface;

[0475] HATCN is vacuum-evaporated on the ITO transparent conductive layer as the hole injection layer of the device, with an evaporation rate of 0.1 nm / s and a total evaporation film thickness of 5 nm;

[0476] NPB is vacuum-evaporated on the hole injection layer as the hole transport layer of the device, with an evaporation rate of 0.1 nm / s and a total evaporation film thickness of 30 nm;

[0477] TCTA is vacuum-evaporated on the hole transport layer as the first exciton blocking layer, with an evaporation rate of 0.1 nm / s and a total evaporation film thickness of 10 nm;

[0478] The light-emitting layer of the device is vacuum-evaporated on the first exciton blocking layer. The light-emitting layer of the present invention includes host materials, a sensitizer, a phosphorescent dye, and a fluorescent dye. The host materials are SiCzCz and SiTrzCz 2The formed exciplex has a mass ratio of 1:1 between the two. The sensitizer is the material of the present invention, with a doping mass percentage concentration of 5 wt%. The phosphorescent dye is PtON-TBBI, with a doping mass percentage concentration of 10 wt%. The fluorescent dye is B-N-S, with a doping mass percentage concentration of 1 wt%. The thermally activated delayed fluorescence material A-1 of the present invention is used as the sensitizer. The evaporation rate of the above host material is adjusted to 0.1 nm / s, that is, SiCzCz and SiTrzCz 2 are 0.05 nm / s respectively. The evaporation rate of the sensitizer A-1 in the light-emitting layer is set at 5 wt% of the host evaporation rate. The evaporation rate of the phosphorescent dye PtON-TBBI in the light-emitting layer is set at 10 wt% of the host evaporation rate. The evaporation rate of the fluorescent dye B-N-S in the light-emitting layer is set at 1 wt% of the host evaporation rate. The total film thickness of the evaporated light-emitting layer is 30 nm;

[0479] On top of the light-emitting layer, DCzPm is vacuum-evaporated as the second exciton blocking layer of the device, with an evaporation rate of 0.1 nm / s and a total film thickness of 10 nm;

[0480] On top of the second exciton blocking layer, DPyPA is vacuum-evaporated as the electron transport material of the device, with an evaporation rate of 0.1 nm / s and a total film thickness of 30 nm;

[0481] On the electron transport layer, LiF with a thickness of 0.5 nm is vacuum-evaporated as the electron injection layer, and an Al layer with a thickness of 150 nm is used as the cathode of the device.

[0482] Examples 274 to 340 are all prepared in the same way as Example 273, except that the sensitizer in the light-emitting layer is replaced by the compounds involved in the synthesis examples of the present invention instead of the compound A-1 of the present invention. Comparative Examples 28-33 are all prepared in the same way as Example 273, except that the sensitizer in the light-emitting layer is replaced by the above comparative compounds instead of the compound A-1 of the present invention. Comparative Example 34 is without a sensitizer, and the light-emitting layer only contains the host, the phosphorescent dye, and the fluorescent dye B-N-S.

[0483] Example 341

[0484] The glass plate coated with the ITO transparent conductive layer is ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in an acetone:ethanol mixed solvent, baked in a clean environment until all moisture is completely removed, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam on the surface;

[0485] On top of the ITO transparent conductive layer, HATCN is vacuum-evaporated as the hole injection layer of the device, with an evaporation rate of 0.1 nm / s and a total film thickness of 5 nm;

[0486] On top of the hole injection layer, NPB is vacuum-evaporated as the hole transport layer of the device at an evaporation rate of 0.1 nm / s and a total evaporation film thickness of 30 nm;

[0487] On the hole transport layer, TCTA is vacuum-evaporated as the first exciton blocking layer at an evaporation rate of 0.1 nm / s and a total evaporation film thickness of 10 nm;

[0488] On top of the first exciton blocking layer, the light-emitting layer of the device is vacuum-evaporated. The light-emitting layer of the present invention includes a host material, a sensitizer, a phosphorescent dye, and a fluorescent dye. The host materials are SiCzCz and SiTrzCz 2 The formed exciplex, with a mass ratio of the two of 1:1. The sensitizer is the material of the present invention, with a doping mass percentage concentration of 5 wt%. The phosphorescent dye is PtON-TBBI, with a doping mass percentage concentration of 10 wt%. The fluorescent dye is BD, with a doping mass percentage concentration of 1 wt%. The thermally activated delayed fluorescence material A-1 of the present invention is used as the sensitizer. The evaporation rate of the above host materials is adjusted to 0.1 nm / s, that is, SiCzCz and SiTrzCz 2 are 0.05 nm / s respectively. The evaporation rate of the sensitizer A-1 in the light-emitting layer is set at a ratio of 5 wt% of the host evaporation rate. The evaporation rate of the phosphorescent dye PtON-TBBI in the light-emitting layer is set at a ratio of 10 wt% of the host evaporation rate. The evaporation rate of the fluorescent dye BD in the light-emitting layer is set at a ratio of 1 wt% of the host evaporation rate. The total evaporation film thickness of the light-emitting layer is 30 nm;

[0489] On top of the light-emitting layer, DCzPm is vacuum-evaporated as the second exciton blocking layer of the device at an evaporation rate of 0.1 nm / s and a total evaporation film thickness of 10 nm;

[0490] On top of the second exciton blocking layer, DPyPA is vacuum-evaporated as the electron transport material of the device at an evaporation rate of 0.1 nm / s and a total evaporation film thickness of 30 nm;

[0491] On the electron transport layer, LiF with a thickness of 0.5 nm is vacuum-evaporated as the electron injection layer, and an Al layer with a thickness of 150 nm is used as the cathode of the device.

[0492] Examples 342 to 408 are all prepared in the same manner as Example 341, except that the sensitizer in the light-emitting layer is replaced by the compounds involved in the synthetic examples of the present invention instead of Compound A-1 of the present invention. Comparative Examples 35-40 are all prepared in the same manner as Example 341, except that the sensitizer in the light-emitting layer is replaced by the above-mentioned comparative compounds instead of Compound A-1 of the present invention. Comparative Example 41 is without a sensitizer, and the light-emitting layer consists only of a host, a phosphorescent dye, and a fluorescent dye BD.

[0493] The performance of the organic electroluminescent devices prepared in the above respective examples is shown in Table 4 below.

[0494] Table 4:

[0495]

[0496]

[0497]

[0498]

[0499] As can be seen from Table 4 above, when the compounds of the present invention are used as sensitizers in the light-emitting layer of organic electroluminescent devices, when the required brightness is 1000 cd / m 2 ², the driving voltage is as low as 5 V or less, the current efficiency is as high as more than 70 cd / A, and the T90 life is greater than 500 h. The performance is much superior compared with Comparative Examples 28-41.

[0500] The reason for the analysis is that, compared with Comparative Materials 1-4, based on the donor-acceptor type (D-A) structural characteristics of traditional thermally activated delayed fluorescence materials (TADF), by introducing a central π moiety, the donor groups that could originally rotate freely are connected and locked, thus effectively suppressing the free rotation of the peripheral donor groups, making the HOMO of the molecule mainly distributed on the peripheral donor groups, while the LUMO is mainly concentrated on the central π moiety, and further resulting in a more obvious spatial separation between HOMO and LUMO, thereby effectively reducing the singlet-triplet energy gap (ΔE ST) to increase the reverse intersystem crossing rate of the molecule, achieve efficient utilization of excitons, and improve the luminescence efficiency. And by directly connecting the carbon atom or nitrogen atom on the donor aromatic ring parent nucleus to the central π part, and then locking the donor, the structural rigidity of the molecule can be significantly improved, thereby effectively weakening the vibration of the molecule, suppressing non-radiative transitions and energy losses caused by molecular vibration, reducing the relaxation degree of the excited state structure, and improving the luminescence quantum yield, color purity and stability of the molecule. In addition, such a method can also enable the molecule to have a high reverse intersystem crossing rate and luminescence quantum yield while maintaining blue light emission, so as to achieve efficient and fast blue light and deep blue light TADF materials, and then prepare efficient and stable blue light and deep blue light OLED devices, which is helpful for the commercial application of the materials.

[0501] Compared with the comparative material 5, the emission peak of the molecule is around 400 nm, the emission band gap is large, the driving voltage is very high, and the singlet-triplet energy gap (ΔE ST ) is very large, making it difficult to improve the luminescence efficiency of the molecule through the reverse intersystem crossing process. Moreover, the peripheral linking group is a flexible chain segment, and the rigidity of the molecule is poor, resulting in an increase in non-radiative transitions caused by molecular vibration, so the efficiency and lifetime are very poor. For the comparative material 6, the peripheral linking group does not participate in the luminescence process of the molecule, and the luminescence of the molecule mainly comes from the transition of the CT state between the middle D and A. There is an essential difference between the materials invented by this institute. At the same time, the peripheral linking group also has a certain degree of flexibility and poor rigidity. The photoluminescence quantum yield of the molecule is only 35%, and the connecting part is directly connected through oxygen atoms and nitrogen atoms, with poor stability, resulting in poor efficiency and lifetime of the device.

[0502] At the same time, compared with the existing phosphorescent sensitization device in the luminescent layer structure of the organic electroluminescent device of the present invention, that is, host + phosphorescent sensitizer + fluorescent dye, a functional material is further introduced into the luminescent layer of the device of the present invention, that is, host + sensitizer + phosphorescent dye + fluorescent dye, and the host is a double-host exciplex. The advantages of this structure are as follows: ① The sensitizer has a very small ΔE STMoreover, this property also exists in the blue and deep blue light regions, resulting in a relatively high rate of reverse intersystem crossing, which can significantly accelerate the exciton dynamics process. While ensuring effective energy transfer, the generation of high-energy excitons is reduced, leading to a highly efficient and stable blue light device. ② By utilizing multiple energy transfer pathways existing in the system, including FET and DET between the sensitizer and the phosphorescent dye, FET between the sensitizer and the fluorescent dye, FET and DET between the phosphorescent dye and the fluorescent dye, and FET between the host and the sensitizer, phosphorescent dye, and fluorescent dye, etc., the accumulation of long-lived excitons is reduced, and the energy loss and stability degradation caused by the exciton annihilation process are inhibited. ③ The exciplex host also has TADF properties, which can improve the exciton utilization rate, and its bipolar transport performance and stability are better compared to general single hosts. ④ When the doping concentration of the sensitizer is not high, as low as 5 wt%, due to its fast upconversion rate, it can also effectively disperse and reduce the concentration of triplet excitons, improving the device stability.

[0503] Compared with Comparative Examples 34 and 41, after adding the sensitizer of the present invention to the light-emitting layer, the driving voltage is reduced, and both the current efficiency and the lifetime are significantly improved. The reason is that the light-emitting layer structure of the organic electroluminescent device of the present invention can utilize multiple energy transfer pathways existing in the system to reduce the accumulation of long-lived excitons, thereby inhibiting the energy loss and stability degradation caused by the exciton annihilation process. As shown in the Figure 4 specification appendix, by adding the sensitizer of the present invention to the light-emitting layer, excitons can be effectively utilized and triplet excitons can be dispersed through multiple energy transfer processes. At the same time, the material of the present invention has a fast reverse intersystem crossing rate, which can effectively accelerate the upconversion process of triplet excitons, thereby accelerating its dynamics process, reducing the concentration of triplet excitons, and inhibiting the quenching effect caused by too high a concentration of triplet excitons, resulting in a significant improvement in both efficiency and lifetime. Especially in the case where a high proportion of initial triplets are generated by electroexcitation in the device, since it can effectively disperse and convert long-lived triplet excitons into shorter-lived phosphorescent triplet excitons or fluorescent singlet excitons, the efficiency and lifetime of related devices in high-brightness application environments are significantly improved.

[0504] The above experimental data show that the organic material of the present invention as a sensitizer for organic electroluminescent devices is an organic light-emitting functional material with good performance and is expected to be promoted for commercial applications.

[0505] Although the present invention has been described in conjunction with the embodiments, the present invention is not limited to the above embodiments. It should be understood that under the guidance of the inventive concept of the present invention, those skilled in the art can make various modifications and improvements, and the appended claims define the scope of the present invention.

[0506] Obviously, the above embodiments are merely examples given for clear illustration and not limitations on the implementation manners. For those of ordinary skill in the art, other different forms of changes or alterations can be made based on the above description, and the obvious changes or alterations derived therefrom are still within the protection scope of the present invention.

[0507] In summary, the above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. An organic compound having a structure represented by formula (1), formula (2), formula (3), formula (4), formula (5) or formula (6): Wherein: The dashed content represents the part that cannot be seen from the front view angle in the three-dimensional structure of the compound molecule; D 1 、 D 2 、 D 3 、 D 4 、 D 5 、 D 6 and D 7 are each independently selected from an unsubstituted or R”'-substituted C6-C60 aryl group or an unsubstituted or R”'-substituted C3-C60 heteroaryl group; The π at the structural centers of Formula (1), Formula (2), Formula (3), Formula (4), Formula (5) and Formula (6)) 1 , π 2 , π 3 and π 4 are bridging groups, and π 1 , π 2 , π 3 and π 4 are each independently selected from an unsubstituted or R'-substituted C6-C60 aryl group and an unsubstituted or R'-substituted C3-C60 heteroaryl group, and at least one of π 1 , π 2 , π 3 and π 4 is a group with electron-withdrawing properties, or at least one of the substituents on π 1 , π 2 , π 3 and π 4 is a group with electron-withdrawing properties; The group with electron-withdrawing property is selected from one or a combination of two of the following groups: cyano group, isocyano group, halogen, aldehyde group, carboxyl group, carbonyl group, nitro group, unsubstituted or R'-substituted xanthone, unsubstituted or R'-substituted thioxanthone, unsubstituted or R'-substituted selenoxanthone, unsubstituted or R'-substituted C3-C60 heteroaryl containing sp 2 hybridized nitrogen atom, unsubstituted or R'-substituted C3-C60 heteroaryl containing boron atom, unsubstituted or R''-substituted C1-C10 linear alkyl group, unsubstituted or R''-substituted C3-C60 heteroaryl without sp 2 hybridized nitrogen atom and boron atom, unsubstituted or R''-substituted C6-C60 aryl group; Each of said R''' and R' independently is selected from one or a combination of two of deuterium, halogen, cyano, isocyano, aldehyde group, carboxyl group, carbonyl group, nitro group, hydroxyl group, amino group, C1-C30 linear alkyl group, C2-C20 alkenyl group, C2-C20 alkynyl group, C3-C20 cycloalkyl group, C1-C30 alkoxy group, C1-C20 alkylthio group, C1-C20 alkylsilyl group, C1-C20 alkylamino group, C6-C60 aryl ether group, C3-C60 heteroaryl ether group, C6-C60 arylthioether group, C3-C60 heteroarylthioether group, C6-C60 arylsilyl group, C3-C60 heteroarylsilyl group, C2-C30 aliphatic chain hydrocarbon amino group, C4-C30 cyclic aliphatic chain hydrocarbon amino group, C6-C30 arylamino group, C3-C30 heteroarylamino group, C6-C30 aryloxy group, C6-C60 arylboron group, C6-C60 aryl group, C3-C60 heteroaryl group; Each of said R'' independently is selected from one or a combination of two of halogen, cyano, isocyano, aldehyde group, carboxyl group, carbonyl group, nitro group.

2. The organic compound according to claim 1, Characterized in that Said D 1 、D 2 、D 3 、D 4 、D 5 、D 6 and D 7 each independently connects with the corresponding π 1 、π 2 、π 3 and π 4 When connected, through the C atom or N atom on the aryl mother nucleus in D 1 、D 2 、D 3 、D 4 、D 5 、D 6 or D 7 each independently connects with the corresponding π 1 、π 2 、π 3 or π 4 respectively.

3. The organic compound according to claim 1, Characterized in that The electron-withdrawing group is selected from one or a combination of two of the following groups: cyano, isocyano, halogen, cyano-substituted C1-C5 linear alkyl group, isocyano-substituted C1-C5 linear alkyl group, halogen-substituted C1-C5 linear alkyl group, cyano-substituted C6-C60 aryl group, isocyano-substituted C6-C60 aryl group, halogen-substituted C6-C60 aryl group, cyano-substituted C3-C60 heteroaryl group without sp2 hybridized nitrogen atom and boron atom, isocyano-substituted C3-C60 heteroaryl group without sp2 hybridized nitrogen atom and boron atom, halogen-substituted C3-C60 heteroaryl group without sp2 hybridized nitrogen atom and boron atom, unsubstituted or R'-substituted xanthone, unsubstituted or R'-substituted thioxanthone, unsubstituted or R'-substituted C3-C60 heteroaryl group with sp2 hybridized nitrogen atom, unsubstituted or R'-substituted C3-C60 heteroaryl group with boron atom; More preferably, the electron-withdrawing group is selected from one or a combination of two of the following groups: cyano, isocyano, fluorine, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, triazinyl, heptazaphenanthrenyl, pyridyl, quinolinyl, isoquinolinyl, phenanthridinyl, benzo-5,6-quinolyl, benzo-6,7-quinolyl, benzo-7,8-quinolyl, fluoroboron dipyrrole, azaboron dipyrrole, pyridinylimidazolyl, pyrazinylimidazolyl, quinoxalinylimidazolyl, 1,2-thiazolyl, 1,3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1,5-diazaanthracenyl, 2,7-diazapyrenyl, 2,3-diazapyrenyl, 1,6-diazapyrenyl, 1,8-diazapyrenyl, 4,5-diazapyrenyl, 4,5,9,10-tetraazaperopyrenyl, pyrazinyl, naphthyridinyl, phenanthroline, 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-tetrazinyl, 1,2,3,4-tetrazinyl, 1,2,3,5-tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazolyl, diphenylboron, dimesitylboron, dipentafluorophenylboron, bis(2,4,6-triisopropylphenyl)boron, xanthenone, thioxanthenone, 1,3,3a 1 ,4,6,7,9-heptazaphenanthrenyl, 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracenyl.

4. The organic compound according to claim 1, Characterized in that Said D 1 、D 2 、D 3 、D 4 、D 5 、D 6 and D 7 are each independently selected from unsubstituted or R'-substituted C3-C60 heteroaryl, and the heteroatoms in the heteroaryl are selected from at least one of N, O, S, P, Si, Se; Preferably, the D 1 , D 2 , D 3 , D 4 , D 5 , D 6 and D 7 are each independently selected from unsubstituted or R'-substituted C3-C60 heteroaryl containing a nitrogen atom; More preferably, the D 1 , D 2 , D 3 , D 4 , D 5 , D 6 and D 7 are each independently selected from one or a combination of two of the following unsubstituted or R'-substituted groups: indolyl, isoindolyl, benzindolyl, carbazolyl, indeno[1,2-b]carbazolyl, indolo[3,2-b]carbazolyl, furo[3,2-b]carbazolyl, thieno[3,2-b]carbazolyl, carbolinyl, pyrazolyl, indazolyl, imidazolyl, acridinyl, phenazine, phenothiazine, phenoxazine; Each of said R' independently is selected from one or a combination of two of deuterium, halogen, cyano, isocyano, hydroxyl group, amino group, C1-C10 linear alkyl group, C3-C10 cycloalkyl group, C7-C30 aralkyl group, C1-C10 alkoxy group, C2-C10 aliphatic chain hydrocarbon amino group, C4-C10 cyclic aliphatic chain hydrocarbon amino group, C6-C30 arylamino group, C3-C30 heteroarylamino group, C6-C30 aryloxy group, C6-C60 arylboron group, C6-C60 aryl group, C3-C60 heteroaryl group.

5. The organic compound according to claim 1, It is characterized in that Said D 1 、D 2 、D 3 、D 4 、D 5 、D 6 and D 7 are each independently selected from one of the following unsubstituted or R''' - substituted structures: * represents the attachment bond position of the substituent group; Each of said R''' is independently selected from deuterium, halogen, cyano, isocyano, hydroxyl, amino, C1-C10 linear alkyl, C3-C10 cycloalkyl, C7-C30 aralkyl, C1-C10 alkoxy, C2-C10 aliphatic hydrocarbon amine group, C4-C10 cyclic aliphatic hydrocarbon amine group, C6-C30 arylamine group, C3-C30 heteroarylamine group, C6-C30 aryloxy, C6-C60 arylboron group, C6-C60 aryl, C3-C60 heteroaryl, or a combination of one or two of them.

6. The organic compound according to claim 1 has the structures shown in Formula (2) and Formula (3): Wherein, D 1 、D 2 、D 3 、D 4 、D 5 are each independently selected from unsubstituted or R‴-substituted C3-C60 heteroaryl containing a nitrogen atom; Preferably, the D 1 , D 2 , D 3 , D 4 , D 5 are each independently selected from one or a combination of two of the following groups which are unsubstituted or substituted by R''': indolyl, isoindolyl, benzindolyl, carbazolyl, indeno[1,2-b]carbazolyl, indolocarbazolyl, furo[3,2-b]carbazolyl, thieno[3,2-b]carbazolyl, carbolinyl, pyrazolyl, indazolyl, imidazolyl, acridinyl, phenazine, phenothiazine, phenoxazine; More preferably, the D 1 , D 2 , D 3 , D 4 , D 5 are each independently selected from one or a combination of two of the following groups which are unsubstituted or substituted by R''': carbazolyl, indolocarbazolyl, furocarbazolyl, thiophenocarbazolyl, acridinyl, phenazine, phenothiazine, phenoxazine; And each of said R''' is independently selected from deuterium, halogen, cyano, isocyano, hydroxyl, amino, C1-C10 linear alkyl, C3-C10 cycloalkyl, C7-C30 aralkyl, C1-C10 alkoxy, C2-C10 aliphatic hydrocarbon amine group, C4-C10 cyclic aliphatic hydrocarbon amine group, C6-C30 arylamine group, C3-C30 heteroarylamine group, C6-C30 aryloxy, C6-C60 arylboron group, C6-C60 aryl, C3-C60 heteroaryl, or a combination of one or two of them.

7. The organic compound according to claim 1 or 6, It is characterized in that Said π 1 , π 2 , π 3 and π 4 are each independently selected from an unsubstituted or R'-substituted aryl group having 6 to 60 carbon atoms or a heteroaryl group having 3 to 60 carbon atoms in the conjugated plane of the parent nucleus, or π 1 , π 2 , π 3 and π 4 are each independently selected from an unsubstituted or R'-substituted aryl group having 6 to 60 carbon atoms or a heteroaryl group having 3 to 60 carbon atoms in the conjugated plane of the parent nucleus, with the number of atoms in the conjugated plane of the parent nucleus differing by 6 or less; Preferably, π 1 , π 2 , π 3 and π 4 are all electron-withdrawing groups, or the substituents on π 1 , π 2 , π 3 and π 4 are all electron-withdrawing groups; Each of the above-mentioned R' is independently selected from deuterium, halogen, cyano, isocyano, C1-C30 linear alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C1-C30 alkoxy, C1-C20 alkylthio, C1-C20 alkylsilyl, C6-C60 aryl ether group, C3-C60 heteroaryl ether group, C6-C60 arylthioether group, C3-C60 heteroarylthioether group, C6-C60 arylsilyl group, C3-C60 heteroarylsilyl group, C6-C30 arylamine group, C3-C30 heteroarylamine group, C6-C30 aryloxy, C6-C60 arylboron group, C6-C60 aryl, C3-C60 heteroaryl, or a combination of one or two of them.

8. The compound according to claim 1 is selected from the following specific structural compounds:

9. The application of the compound according to any one of claims 1-8, wherein the application is as a functional material in an organic electronic device, and the organic electronic device is selected from an organic light-emitting device, an optical sensor, a solar cell, a lighting element, an organic thin-film transistor, an organic field-effect transistor, an information tag, an electronic artificial skin sheet, a sheet-type scanner, or an electronic paper; Preferably, the application of the organic compound is as a light-emitting dye or a sensitizer in an organic light-emitting device; More preferably, the application of the organic compound is as a sensitizer in an organic light-emitting device.

10. An organic light-emitting device, comprising a first electrode layer, a second electrode layer, and one or more light-emitting functional layers inserted between the first electrode layer and the second electrode layer, wherein the light-emitting functional layer contains the compound according to any one of claims 1-8; Further, the light-emitting functional layer includes a hole transport region, a light-emitting layer, and an electron transport region. The hole transport region is formed on the first electrode layer, the second electrode 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 light-emitting layer contains the compound according to any one of claims 1-8.

11. An organic electroluminescent device, comprising a first electrode layer, a second electrode layer, and one or more light-emitting functional layers inserted between the first electrode layer and the second electrode layer, wherein the light-emitting functional layer includes a host material and a sensitizer material; characterized in that, the sensitizer material is the compound according to any one of claims 1-8, and the doping concentration of the sensitizer material in the light-emitting functional layer is 1 wt% - 50 wt%; preferably, the doping concentration of the sensitizer material in the light-emitting functional layer is 5 wt% - 30 wt%; the host material is a wide-bandgap host material.

12. The organic electroluminescent device according to claim 11, characterized in that, the light-emitting functional layer further includes a first light-emitting dye, the first light-emitting dye is a phosphorescent dye, and the doping concentration of the phosphorescent dye in the light-emitting functional layer is 1 wt% - 30 wt%; preferably, the doping concentration of the phosphorescent material in the light-emitting functional layer is 5 wt% - 30 wt%.

13. The organic electroluminescent device according to claim 12, characterized in that, the light-emitting functional layer further includes a second light-emitting dye, the second light-emitting dye is a fluorescent dye, and the doping concentration of the fluorescent dye in the light-emitting functional layer is 0.1 wt% - 10 wt%; preferably, the doping concentration of the fluorescent dye in the light-emitting functional layer is 0.5 wt% - 5 wt%.

14. The organic electroluminescent device according to claim 11, characterized in that, the light-emitting functional layer further includes a first light-emitting dye, the first light-emitting dye is a fluorescent dye, and the doping concentration of the fluorescent dye in the light-emitting functional layer is 0.1 wt% - 10 wt%; preferably, the doping concentration of the fluorescent dye in the light-emitting functional layer is 0.5 wt% - 5 wt%.

15. The organic electroluminescent device according to any one of claims 11-14, characterized in that, the host material is a host material with TADF characteristics; preferably, the host material is an exciplex formed by mixing an electron donor material and an electron acceptor material with TADF properties; more preferably, the host material is an exciplex with a quantum yield greater than 80%.

16. The organic electroluminescent device according to claim 12, characterized in that, the first light-emitting dye is a Pt metal complex or an Ir metal complex; preferably, the first light-emitting dye is a Pt metal complex with a quantum yield greater than 80%.

17. The organic electroluminescent device according to claim 13 or 14, characterized in that, The fluorescent dye has a radiative transition rate greater than 10 7 s -1 and a fluorescent dye with a quantum yield greater than 80%, or the fluorescent dye is a fluorescent dye with a full width at half maximum ≤ 40 nm, or the fluorescent dye is a multiple resonance type thermally activated delayed fluorescence dye.

18. The organic electroluminescent device according to claim 13, characterized in that, The doping concentration of the sensitizer material in the light-emitting functional layer is 5 wt% - 20 wt%; The doping concentration of the phosphorescent material in the light-emitting functional layer is 5 wt% - 15 wt%; the doping concentration of the fluorescent dye in the light-emitting functional layer is 0.5 wt% - 3 wt%.

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