Organic compound and application thereof

Abstract

The invention relates to an organic compound, belongs to the technical field of organic electroluminescence, and also relates to an organic electroluminescence device adopting the organic compound. The compound provided by the invention has a structure shown in the specification. The compound disclosed by the invention is simple to prepare and relatively good in thermal stability, and when the compound is prepared and applied to an organic electroluminescent device, the transmission of carriers in the device can be improved and balanced, the voltage of the device is reduced, the luminous efficiency is improved and the service life is prolonged. # imgabs0 #

Description

Technical Field

[0001] The invention relates to an organic compound, belonging to the technical field of organic luminescent materials, and also relates to the application of the compound in an organic electroluminescent device. Background Art

[0002] Organic Light Emission Diodes (OLED) devices are an emerging display technology in recent years. They have the characteristics of high brightness, fast response, low energy consumption, wide viewing angle, flexibility, large temperature adaptability range, and simple process. They have been widely used in display panels of products such as lighting fixtures, smart phones and tablet computers, and are further expanding to large-size display products such as televisions.

[0003] OLED devices have a sandwich-like structure, including positive and negative electrodes and an organic functional material layer sandwiched between the two electrodes; when voltage is applied to the electrodes of the OLED device, electrons and holes are injected and transported to the light-emitting area and recombine there, thereby generating excitons and emitting light. The core of the OLED device is the organic functional material layer, and the common organic functional materials that constitute this material layer include: hole injection materials, hole transport materials, hole blocking materials, electron injection materials, electron transport materials, electron blocking materials, as well as luminescent host materials and luminescent guests (dyes), etc.

[0004] Common fluorescent emitters mainly emit light using singlet excitons generated when electrons and holes combine, and are still widely used in various OLED products. Some metal complexes (such as iridium complexes) can simultaneously utilize triplet excitons and singlet excitons to emit light, and are called phosphorescent emitters. Their energy conversion efficiency can be increased by up to four times compared to traditional fluorescent emitters. Thermally excited delayed fluorescence (TADF) technology promotes the transformation of triplet excitons to singlet excitons. Without the use of metal complexes, triplet excitons can still be effectively utilized to achieve higher luminescence efficiency. Thermally excited sensitized fluorescence (TASF) technology uses materials with TADF properties to sensitize the emitter through energy transfer, which can also achieve higher luminescence efficiency.

[0005] Organic hole transport materials play an important role in transferring holes injected from the anode to the light-emitting layer. Hole transport materials with excellent hole mobility are conducive to the injection balance of carriers in the device, thereby reducing the device driving voltage. On the other hand, since the excitons generated in the light-emitting layer will move to the hole transport layer, it will eventually lead to light emission at the interface between the hole transport layer and the light-emitting layer, resulting in color cast and reduced luminous efficiency. This requires an auxiliary layer, namely an electron blocking layer, between the hole transport layer and the light-emitting layer to block the migration of excitons to the hole transport layer and prevent efficiency roll-off, thereby improving luminous efficiency, delaying device attenuation, and improving device stability. Although products using OLED display technology have been commercialized, and electron blocking layer materials have also developed rapidly and their types are increasing, there are still only a handful of materials that meet the requirements of device voltage, efficiency, service life and device stability at the same time. Therefore, the development of low-voltage, high-efficiency, long-life and stable electron blocking layer materials is of vital importance to the development of OLED display technology. Summary of the invention

[0006] The present invention relates to an organic compound suitable for use as a prime material, which has a relatively shallow LUMO energy level and can be used for an electron blocking layer and / or a hole transport layer in an organic electroluminescent (EL) device. The present invention is simple to prepare, can improve and balance the transport of carriers in the device, reduce the voltage of the device, improve the luminous efficiency and enhance the service life; at the same time, the material device has good thermal stability and stable device performance.

[0007] To achieve this goal, this application adopts the following technical solutions:

[0008] One of the purposes of the present application is to provide an organic compound having a structure as shown in formula (1):

[0009]

[0010] In the general formula, ring A is selected from one of a C10-30 aryl group and a C5-C30 heteroaryl group;

[0011] L 1 ~L 3 Each is independently a single bond, a substituted or unsubstituted C6-C30 arylene group, or a substituted or unsubstituted C3-C30 heteroarylene group;

[0012] X 1 and X 2 Each independently is O or S;

[0013] Ar 1 One selected from a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C5-C60 heteroaryl group;

[0014] R 1 -R 5 Each is independently one of hydrogen, deuterium, halogen, cyano, nitro, hydroxyl, amino, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 silyl, substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted C3-C60 heteroarylamino, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl;

[0015] R 6 represents a single substituent to the maximum number of substituents allowed, R 6 Selected from hydrogen, deuterium, halogen, cyano, nitro, hydroxyl, amino, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 silyl, substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted C3-C60 heteroarylamino, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl;

[0016] The above L 1 ~L 3 ,Ar 1 , R 1 -R 5 , R 6 The substituents substituted in the above-mentioned substitution are each independently selected from at least one of halogen, C1-C20 chain alkyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C1-C10 alkoxy, carboxyl, nitro, cyano, amino, hydroxyl, mercapto, C1-C20 alkylsilyl, C1-C20 alkylamino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C60 aryl, and C3-C60 heteroaryl;

[0017] Ar 2 The attachment site on ring A is L attached to ring A 3 Ortho position of the site, Ar2 is selected from one of the following substituent groups, wherein * represents the connection site:

[0018]

[0019] It should be noted that, for the sake of convenience, the possible effects of each group / feature are described separately in the present invention, but this does not mean that these groups / features act in isolation. In fact, the reason for obtaining good performance is essentially the optimized combination of the entire molecule, which is the result of the synergistic effect between various groups and structures, rather than the effect of a single group or structure.

[0020] In the present invention, the "substituted or unsubstituted" group may be substituted with one substituent or with multiple substituents. When there are multiple substituents, they may be selected from different substituents. When the same expression is involved in the present invention, it has the same meaning without special explanation, and the selection range of the substituent is as shown above and will not be repeated one by one.

[0021] In the present invention, the expression of chemical elements, unless otherwise specified, includes the concept of isotopes with the same chemical properties. For example, hydrogen (H) includes 1 H (hydrogen), 2 H (deuterium, D), 3 H (tritium, T), etc.; carbon (C) includes 12 C. 13 C, etc.

[0022] In the present invention, the heteroatom of the heteroaryl group is selected from atoms or atomic groups of N, O, S, P, B, Si or Se, preferably N, O or S.

[0023] In the present invention, the expression of a ring structure crossed by “—” indicates that the connection site is at any position on the ring structure that can form a bond.

[0024] In the present invention, the expression of Ca-Cb represents that the number of carbon atoms in the group is ab. Unless otherwise specified, the number of carbon atoms in the group generally does not include the number of carbon atoms in the substituent.

[0025] In the present invention, “each independently” means that when there are multiple subjects, they may be the same as or different from each other.

[0026] In the present invention, the halogen includes fluorine, chlorine, bromine or iodine.

[0027] In the present invention, the C6-C30 (e.g., C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28) aromatic ring includes a single aromatic ring and a condensed aromatic ring; the single aromatic ring includes a benzene ring, a biphenyl ring or a terphenyl ring, and the condensed aromatic ring means that the ring contains at least two aromatic rings, and the aromatic rings share two adjacent carbon atoms and are condensed with each other, exemplarily including but not limited to: naphthalene ring, anthracene ring, phenanthrene ring, indene ring, fluorene ring and its derivatives (9,9-dimethylfluorene ring, benzofluorene ring, etc.), fluoranthene ring, triphenylene ring, pyrene ring, perylene ring, Ring or tetracene ring, etc.

[0028] The C3-C30 (e.g., C4, C5, C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28) heteroaromatic ring includes a single heteroaromatic ring or a condensed heteroaromatic ring. The single heteroaromatic ring exemplarily includes, but is not limited to, a pyrrole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a furan ring, a thiophene ring, a carbazole ring, and the like. The fused heteroaromatic ring means that the ring structure contains at least one heteroaromatic ring and one aromatic ring (heteroaromatic ring or aromatic ring), and the two share two adjacent atoms to condense each other, and exemplary examples include but are not limited to: quinoline ring, isoquinoline ring, quinoxaline ring, quinazoline ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, isobenzothiophene ring, indole ring, dibenzofuran ring, dibenzothiophene ring, carbazole ring and its derivatives (N-phenylcarbazole ring, benzocarbazole ring, dibenzocarbazole ring, indolecarbazole ring, azacarbazole ring, etc.), acridine ring, phenothiazine ring, phenoxazine ring, hydroacridine ring, etc.

[0029] In the present invention, the C1-C20 chain alkyl group includes C1-C20 straight chain alkyl group and C1-C20 branched chain alkyl group. For example, it can be a chain alkyl group of C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17 or C18, etc.; preferably a C1-C16 chain alkyl group; more preferably a C1-C10 chain alkyl group; illustratively including but not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-octyl, n-heptyl, n-nonyl or n-decyl, etc.

[0030] In the present invention, the C2-C10 alkenyl groups can all be C2, C3, C4, C5, C6, C7, C8, C9, C10 alkenyl groups, which contain at least one C=C, illustratively including but not limited to: vinyl, propenyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, butadienyl, pentadienyl, etc.

[0031] Specific examples of the C1-C20 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17 or C18, etc.) alkoxy groups described in the present invention include monovalent groups obtained by connecting the above-mentioned chain alkyl groups to O.

[0032] In the present invention, the C3-C20 cycloalkyl group may be a cycloalkyl group of C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17 or C18, etc., illustratively including but not limited to: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, etc.

[0033] A specific example of the C1-C20 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17 or C18, etc.) alkylsilyl group is -SiH 3 A monovalent group in which at least one hydrogen in the group is replaced by the above-mentioned chain alkyl group; a specific example of the C1-C20 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17 or C18, etc.) alkylamino group is -NH 2 A monovalent group in which at least one hydrogen atom is substituted by the above-mentioned chain alkyl group.

[0034] Specific examples of the C2-C20 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17 or C18, etc.) heterocycloalkyl groups of the present invention include monovalent groups in which at least one ring C atom in the above-mentioned cycloalkyl groups is replaced by a heteroatom (e.g., O, S, N or P, etc.), including, but not limited to, epoxy, tetrahydropyrrolyl, tetrahydrofuranyl, tetrahydrothiophenyl, morpholinyl, piperidinyl, etc.

[0035] In the present invention, the C6-C60 aromatic group can be an aromatic group of C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C30, C32, C34, C36, C38, C40, C42, C44, C46, ​​C48, C50, C52, C54, C56 or C58, preferably a C6-C30 aromatic group, including a monocyclic aromatic group or a condensed ring aromatic group. The monocyclic aromatic group means that the group contains at least one phenyl group. When it contains at least two phenyl groups, the phenyl groups are connected by a single bond, and examples thereof include but are not limited to: phenyl, biphenyl, terphenyl, etc.; the condensed aromatic group means that the group contains at least two aromatic rings, and the aromatic rings share two adjacent carbon atoms and are fused to each other, and examples thereof include but are not limited to: naphthyl, anthracenyl, phenanthrenyl, indenyl, fluorenyl and its derivatives (9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, 9,9-dinaphthylfluorenyl, spirobifluorenyl, benzofluorenyl, etc.), fluoranthenyl, triphenylene, pyrenyl, peryl, The aforementioned groups include all possible connection modes thereof.

[0036] In the present invention, the C3-C60 heteroaryl group can be a heteroaryl group of C3, C4, C5, C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C30, C32, C34, C36, C38, C40, C42, C44, C46, ​​C48, C50, C52, C54, C56 or C58, preferably a C3-C30 heteroaryl group, and more preferably a C4-C20 heteroaryl group, including a monocyclic heteroaryl group or a condensed ring heteroaryl group. The monocyclic heteroaryl group means that the molecule contains 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 the other groups are connected by a single bond, exemplarily including but not limited to: furanyl, thienyl, pyrrolyl, pyridyl, etc. The fused ring heteroaryl group means a group containing at least one aromatic heterocycle and one aromatic ring (aromatic heterocycle or aromatic ring) in the molecule, and the two share two adjacent atoms that are fused to each other, including but not limited to: benzofuranyl, benzothiophenyl, isobenzofuranyl, isobenzothiophenyl, indolyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl and its derivatives (N-phenylcarbazolyl, N-naphthylcarbazolyl, benzocarbazolyl, dibenzocarbazolyl, indolcarbazolyl, azacarbazolyl, etc.), acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, hydroacridinyl, etc.; the aforementioned groups include all feasible connection modes thereof.

[0037] Specific examples of the C6-C30 (e.g., C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26 or C28, etc.) arylene group of the present invention include divalent groups obtained by removing one hydrogen atom from the above-mentioned aryl groups; specific examples of the C3-C30 (e.g., C3, C4, C5, C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26 or C28, etc.) heteroarylene group include divalent groups obtained by removing one hydrogen atom from the above-mentioned heteroaryl groups.

[0038] Specific examples of the C6-C30 (e.g., C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26 or C28, etc.) aryloxy groups of the present invention include monovalent groups obtained by connecting the above-mentioned aryl groups to O; specific examples of the C3-C30 (e.g., C3, C4, C5, C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26 or C28, etc.) heteroaryloxy groups include monovalent groups obtained by connecting the above-mentioned heteroaryl groups to O.

[0039] The C6-C60 (e.g., C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C30, C32, C34, C36, C38, C40, C42, C44, C46, ​​C48, C50, C52, C54, C56 or C58, etc.) arylamino group of the present invention, preferably C6-C30 arylamino group, is -NH 2 The monovalent group in which at least one hydrogen in the amino group is replaced by the above-mentioned aryl group includes, but is not limited to, phenylamino, methylphenylamino, naphthylamino, anthracenylamino, phenanthrenylamino, biphenylamino and the like.

[0040] The C3-C60 (e.g., C3, C4, C5, C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C30, C32, C34, C36, C38, C40, C42, C44, C46, ​​C48, C50, C52, C54, C56 or C58, etc.) heteroarylamino group of the present invention, preferably C3-C30 heteroarylamino group, is -NH 2 The monovalent group obtained by replacing at least one hydrogen in the amino group with the above-mentioned heteroaryl group includes, but is not limited to, pyridylamino, pyrimidylamino, dibenzofuranylamino and the like.

[0041] Furthermore, in the general formula (1), ring A is preferably selected from substituted or unsubstituted C10-30 aryl groups; 1 and X 2 Preferably O.

[0042] Furthermore, in the general formula (1), connected to L 3 The ring A part group on the ring has a structure shown in the following formula (a) or formula (b), wherein Ar 2 and R 6 The definition of is the same as that in formula (1), and the dotted line represents the connection site:

[0043]

[0044] Preferably, the connection to L 3 The ring A part group has a structure as shown in any one of formula (c), formula (d) or formula (e):

[0045]

[0046] More preferably, the compound of the present invention has a structure shown in any one of formula (2), formula (3) or formula (4):

[0047]

[0048] Among them, X1 and X 2 Each independently is O or S;

[0049] Ar 1 is one of a substituted or unsubstituted C10-C30 aryl group, and a substituted or unsubstituted C5-C30 heteroaryl group;

[0050] L 1 ~L 3 , R 1 -R 6 The definition of is the same as that in formula (1).

[0051] More preferably, in the above general formulas, Ar 2 One of the following substituents:

[0052]

[0053] Further preferably, in the above general formulas, the L 1 ~L 3 Each independently represents a single bond, a substituted or unsubstituted C6-C30 arylene group; preferably, the L 1 ~L 3 Each independently is a single bond or a phenylene group; more preferably, the L 1 ~L 3 For a single key.

[0054] More preferably, in the above general formulas, Ar 1 One of the following substituted or unsubstituted groups, Ar 1 The substituents substituted in the above-mentioned are each independently selected from one of halogen, C1-C20 chain alkyl, and C3-C20 cycloalkyl:

[0055]

[0056] More preferably, in the above general formulas, R 1 -R 5 are each independently one of hydrogen, deuterium, C1-C10 chain alkyl, C3-C10 cycloalkyl, C6-C30 aryl, and C3-C30 heteroaryl; preferably, R 5 For hydrogen.

[0057] More preferably, in the above general formulas, R 6 is selected from one of methyl, ethyl, isopropyl, tert-butyl, isopentyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuran, substituted or unsubstituted dibenzothiophene, and substituted or unsubstituted carbazolyl;

[0058] R 6 The substituents are each independently selected from one of halogen, C1-C20 chain alkyl, C3-C20 cycloalkyl, and C6-C60 aryl.

[0059] More preferably, the organic compound of the present invention has a structure shown in any one of the following P1-P456:

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079] As another aspect of the present invention, there is also provided a use of the compound as described above in an organic electroluminescent device, in particular, preferably as an electron blocking layer material and / or a hole transport layer material in the organic electroluminescent device.

[0080] As another aspect of the present invention, an organic electroluminescent device is provided, comprising a first electrode, a second electrode and one or more light-emitting functional layers inserted between the first electrode and the second electrode, wherein the light-emitting functional layer contains at least one compound of the general formula as described above, or contains at least one compound of P1-P456 as described above.

[0081] The specific reasons why the above compounds of the present invention have excellent performance as electron blocking materials and / or hole transport materials are not yet clear, but it is speculated that the reasons may be as follows:

[0082] The organic compound provided in the present application has a structure as shown in formula (1), wherein a specific

[0083]

[0084] The structural unit is a parent core, which ensures that the compound of the present invention has better electron blocking performance and effectively prevents electrons and triplet excitons from leaking to the hole transport layer. At the same time, the structure also has better thermodynamic stability, thereby improving the service life of the device. Further, setting Ar 2 The group is connected to the ortho position of the C atom to which the N aromatic amine is connected on the ring A, which is conducive to improving the mobility, achieving a better balance between hole injection and migration, making the molecular spatial structure more compact, the film stacking morphology better, and having better stability and film-forming properties.

[0085] The ring A structure designed in the compound structure of the present invention can ensure that the conjugated structure of the molecule is extended, the π-π interaction between molecules is enhanced, and the quenching caused by the leakage of electrons and excitons in the light-emitting layer to the hole transport layer can be effectively blocked, thereby effectively improving the device life. 2 For some specific groups of C6 and above aryl groups or C5 and above heteroaryl groups, compared with other structures, when substituted at the ortho position, their steric hindrance is greater, the molecular structure is more distorted, and the HOMO-LUMO electron cloud overlap is reduced, so that their LUMO energy level is improved, thereby increasing the electron blocking and hole transport capabilities of the molecule.

[0086] It should be noted that, for the sake of convenience, the possible effects of each group / feature are described separately in this application, but this does not mean that these groups / features act in isolation. In fact, the reason for obtaining good performance is essentially the optimized combination of the entire molecule, which is the result of the synergistic effect between the various groups, rather than the effect of a single group. BRIEF DESCRIPTION OF THE DRAWINGS

[0087] Figure 1 This is a graph showing the 48h thermal stability test results of Example 13 of the present invention. DETAILED DESCRIPTION

[0088] Synthesis Example

[0089] The technical solution of the present application is further described below through specific implementation methods. Those skilled in the art should understand that the embodiments are only to help understand the present application and should not be regarded as specific limitations of the present application.

[0090] In the present application, the representative synthesis route of the organic compound having the structure shown in formula (1) is as follows:

[0091]

[0092] Wherein, each symbol has the same meaning as in formula (1); Pd 2 (dba) 3 represents tris(dibenzylacetone)dipalladium(0), IPr.HCl represents 1,3-bis(2,6-diisopropylphenyl)imidazolium chloride, NaOBu-t represents sodium tert-butoxide, (t-Bu) 3 P represents tri-tert-butylphosphine.

[0093] The preparation of the organic compound described in the present application includes the above method, but is not limited to the above method. The organic compound represented by formula (1) synthesized by other methods by those skilled in the art also belongs to the protection scope of the present application.

[0094] More specifically, the following synthesis examples of the present application provide a specific synthesis method of the organic compound, and the solvents and reagents used in the following synthesis examples can all be purchased or customized from the chemical product market. In addition, those skilled in the art can also synthesize by other known methods.

[0095] The mass spectrometry data in the following synthesis examples were obtained by testing with a ZAB-HS mass spectrometer manufactured by Micromass, UK.

[0096] Synthesis example 1

[0097] Synthesis of compound P4

[0098]

[0099] In a 1000 mL single-mouth bottle, add 10 g M1, 11.14 g 2-bromo-9,9′-dimethylfluorene, and 0.37 g tris(dibenzylacetone)dipalladium(0)Pd 2 (dba) 3, 0.35g 1,3-bis(2,6-diisopropylphenyl)imidazolium chloride IPr.HCl, 11.75g ​​sodium tert-butoxide NaOBu-t, 200mL toluene, vacuum and replace with nitrogen 3 times, heat the reaction to 90°C for 5h. After the reaction is complete, stop the reaction. Cool to room temperature, separate the reaction solution, purify the organic phase twice with silica gel column, concentrate the organic phase, add methanol and reflux and stir for 1h, filter to obtain light yellow powder P4-1, and then recrystallize with ethyl acetate to obtain 16.0g of white pure product.

[0100] P4-1: m / z theoretical value: 437; m / z measured value: 438.

[0101] In a 1000mL single-mouth bottle, add 16.0g P4-1, 11.54g 2-bromodibenzodioxin, and 0.67g Pd 2 (dba) 3 , 0.3 g tri-tert-butylphosphine (t-Bu) 3 P, 10.54g sodium tert-butoxide and 300mL toluene were added, and the mixture was vacuumed and replaced with nitrogen three times. The reaction temperature was raised to 110°C for 8h. After the reaction was completed, the reaction was stopped. The reaction solution was cooled to room temperature, and the organic phase was separated. The organic phase was purified by silica gel column twice, and the organic phase was concentrated. Methanol was added and refluxed for 1h. The light yellow powder P4 was obtained by suction filtration, and then recrystallized from toluene / ethanol three times to obtain 19.8g of a white pure product.

[0102] Organic compound P4: m / z theoretical value: 619; m / z measured value: 620.

[0103] Synthesis example 2-21

[0104] The process route of Synthesis Example 2-21 is the same as that of Synthesis Example 1, except that the raw materials are different. The raw materials, target products and result characterization data are shown in Table 1.

[0105] Table 1

[0106]

[0107]

[0108]

[0109]

[0110]

[0111] Device Embodiment

[0112] Implementation

[0113] OLED includes a first electrode, a second electrode, and an organic material layer between the electrodes. The organic material layer can be 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.

[0114] In a specific embodiment, a substrate may be used below the first electrode or above the second electrode. The substrate is a glass or polymer material with excellent mechanical strength, thermal stability, water resistance, and transparency. In addition, a thin film transistor (TFT) may also be provided on the substrate used as a display.

[0115] The first electrode can be formed by sputtering or depositing a material used as the first electrode on the substrate. When the first electrode is used as an anode, indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO 2 ), zinc oxide (ZnO) and other oxide transparent conductive materials and any combination thereof. When the first electrode is used as a cathode, metals or alloys such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), ytterbium (Yb), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag) and the like and any combination thereof can be used.

[0116] The organic material layer can be formed on the electrode by vacuum thermal evaporation, spin coating, printing, etc. The compound used as the organic material layer can be organic small molecules, organic macromolecules and polymers, and combinations thereof.

[0117] The hole transport region is located between the anode and the light-emitting layer. The hole transport region can be a single-layer hole transport layer (HTL), including a single-layer hole transport layer containing only one compound and a single-layer hole transport layer containing multiple compounds. The hole transport region can also be a multilayer structure including at least one layer of a hole injection layer (HIL), a hole transport layer (HTL), and an electron blocking layer (EBL); wherein the HIL is located between the anode and the HTL, and the EBL is located between the HTL and the light-emitting layer.

[0118] The material of the hole transport layer can be selected from, but not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or polymers containing conductive dopants such as polyphenylene ethylene, polyaniline / dodecylbenzenesulfonic acid (Pani / DBSA), poly(3,4-ethylenedioxythiophene) / poly(4-styrenesulfonate) (PEDOT / PSS), polyaniline / camphorsulfonic acid (Pani / CSA), polyaniline / poly(4-styrenesulfonate) (Pani / PSS), aromatic amine derivatives such as the compounds shown in HT-1 to HT-51 below, compounds P1-P456 shown in the present invention; or any combination thereof.

[0119]

[0120]

[0121]

[0122] The hole injection layer is located between the anode and the hole transport layer. The hole injection layer can be a single compound material or a combination of multiple compounds. For example, the hole injection layer can use one or more compounds of HT-1 to HT-51 above, or one or more compounds of HI-1 to HI-3 below; or one or more compounds of HT-1 to HT-51 can be doped with one or more compounds of HI-1 to HI-3 below.

[0123]

[0124] The light-emitting layer includes a light-emitting dye (i.e., dopant) that can emit light of different wavelength spectra, and may also include a host material (Host). The light-emitting layer may be a monochrome light-emitting layer that emits a single color such as red, green, and blue. A plurality of monochrome light-emitting layers of different colors may be arranged in a plane according to a pixel pattern, or may be stacked together to form a color light-emitting layer. When light-emitting layers of different colors are stacked together, they may be separated from each other or may be connected to each other. The light-emitting layer may also be a single color light-emitting layer that can simultaneously emit different colors such as red, green, and blue.

[0125] According to different technologies, the light-emitting layer material can be made of different materials such as fluorescent electroluminescent materials, phosphorescent electroluminescent materials, and thermally activated delayed fluorescent materials. In an OLED device, a single light-emitting technology can be used, or a combination of multiple different light-emitting technologies can be used. These different light-emitting materials classified by technology can emit light of the same color or different colors.

[0126] In one aspect of the present invention, the light-emitting layer adopts fluorescent electroluminescence technology. The fluorescent host material of the light-emitting layer can be selected from, but not limited to, one or more combinations of BFH-1 to BFH-17 listed below.

[0127]

[0128] In one aspect of the present invention, the light-emitting layer adopts fluorescent electroluminescence technology. The fluorescent dopant of the light-emitting layer can be selected from, but not limited to, one or more combinations of BFD-1 to BFD-24 listed below.

[0129]

[0130]

[0131]

[0132] In one aspect of the present invention, the light-emitting layer adopts phosphorescent electroluminescence technology, and the main material of the light-emitting layer is selected from, but not limited to, one or more combinations of PH-1 to PH-85.

[0133]

[0134]

[0135]

[0136]

[0137] In one aspect of the present invention, the light-emitting layer adopts phosphorescent electroluminescence technology. The phosphorescent dopant of the light-emitting layer can be selected from, but not limited to, one or more combinations of GPD-1 to GPD-47 listed below.

[0138]

[0139]

[0140]

[0141] In one aspect of the present invention, the light-emitting layer adopts phosphorescent electroluminescence technology. The phosphorescent dopant of the light-emitting layer can be selected from, but not limited to, one or more combinations of RPD-1 to RPD-28 listed below.

[0142]

[0143]

[0144] In one aspect of the present invention, the light-emitting layer adopts phosphorescent electroluminescence technology. The phosphorescent dopant of the light-emitting layer can be selected from, but not limited to, one or more combinations of YPD-1 to YPD-11 listed below.

[0145]

[0146] In one aspect of the present invention, the light-emitting layer adopts the technology of thermally activated delayed fluorescence luminescence. The main material of the light-emitting layer is selected from, but not limited to, one or more combinations of the above PH-1 to PH-85.

[0147] In one aspect of the present invention, the light-emitting layer adopts the technology of thermally activated delayed fluorescence luminescence. The fluorescent dopant of the light-emitting layer can be selected from, but not limited to, one or more combinations of TDE1-TDE37 listed below.

[0148]

[0149]

[0150]

[0151] In one aspect of the present invention, an electron blocking layer (EBL) is located between the hole transport layer and the light emitting layer. The electron blocking layer may be, but not limited to, one or more compounds of HT-1 to HT-51 described above, or one or more compounds of PH-47 to PH-77 described above, or one or more compounds of P1 to P456 of the present invention; or a mixture of, but not limited to, one or more compounds of HT-1 to HT-51 and one or more compounds of PH-47 to PH-77 and one or more compounds of P1 to P456 of the present invention.

[0152] The OLED organic material layer may further include an electron transport region between the light emitting layer and the cathode. The electron transport region may 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 may also be a multilayer structure including at least one layer of an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL).

[0153] In one aspect of the present invention, the electron transport layer material can be selected from, but not limited to, one or more combinations of ET-1 to ET-73 listed below.

[0154]

[0155]

[0156]

[0157]

[0158] In one aspect of the present invention, a hole blocking layer (HBL) is located between the electron transport layer and the light emitting layer. The hole blocking layer may be, but not limited to, one or more compounds of ET-1 to ET-73, or one or more compounds of PH-1 to PH-46; or a mixture of one or more compounds of ET-1 to ET-73 and one or more compounds of PH-1 to PH-46.

[0159] The device may further include an electron injection layer located between the electron transport layer and the cathode. Materials for the electron injection layer include, but are not limited to, one or more combinations of the following.

[0160] LiQ,LiF,NaCl,CsF,Li 2 O,Cs 2 CO 3 ,BaO,Na,Li,Ca,Mg,Yb.

[0161] The preparation process of the organic electroluminescent device in this embodiment is as follows:

[0162] Example 1: Green organic electroluminescent device

[0163] The preparation method of the organic electroluminescent device is as follows: a glass plate coated with an 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 the water is completely removed, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam; the glass substrate with the anode is placed in a vacuum chamber, and the vacuum is evacuated to less than 1×10 -5 Pa, on the above-mentioned anode layer film, 10nm of the compound HT-4:HI-3 (97 / 3, w / w) mixture is vacuum thermally deposited in sequence as a hole injection layer, 60nm of the compound HT-4 is used as a hole transport layer, 35nm of the organic compound P28 provided in the present application is used as an electron blocking layer; 40nm of the compound PH-61:PH-3:GPD-12 (100:100:20, w / w) ternary mixture is used as a light-emitting layer; 5nm of ET-23 is used as a hole blocking layer, 25nm of the compound ET-69:ET-57 (50 / 50, w / w) mixture is used as an electron transport layer, 1nm of LiF is used as an electron injection layer, and 150nm of metal aluminum is used as a cathode; the total evaporation rate of all organic layers and LiF is controlled at 0.1nm / s, and the evaporation rate of the metal electrode is controlled at 1nm / s.

[0164] Embodiment 2-6

[0165] An organic electroluminescent device, which is different from Example 1 only in that the electron blocking layer material organic compound P28 is replaced by P209, P238, P309, P417, or P446.

[0166] Comparative Examples 1-6

[0167] An organic electroluminescent device, which is different from Example 1 only in that the electron blocking layer material organic compound P28 is replaced by CCP-2, CCP-3, or CCP-6.

[0168]

[0169] The organic electroluminescent devices provided in the above-mentioned Examples 1-6 and Comparative Examples 1-3 were subjected to the following performance tests: at the same brightness, the driving voltage and current efficiency of the organic electroluminescent devices were measured using a digital source meter and a brightness meter. Specifically, the voltage was increased at a rate of 0.1 V per second, and the brightness of the organic electroluminescent device was measured when it reached 10000 cd / m 2 The voltage at which the light is on is the driving voltage, and the current density at this time is measured at the same time; the ratio of brightness to current density is the current efficiency; the life test of LT97 is as follows: use a brightness meter at 10000cd / m 2 At the same brightness, the current is kept constant and the brightness of the organic electroluminescent device is measured to drop to 9700cd / m 2 The LT97 life of comparative example 1 is set to 1, and the LT97 life of other compounds are all relative values ​​to that of comparative example 1. The test results are shown in Table 2 below.

[0170] Table 2:

[0171]

[0172]

[0173] Example 7: Red organic electroluminescent device

[0174] The preparation method of the organic electroluminescent device is as follows: a glass plate coated with an 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 the water is completely removed, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam; the glass substrate with the anode is placed in a vacuum chamber, and the vacuum is evacuated to less than 1×10 -5 Pa, on the above-mentioned anode layer film, 10nm of the compound HT-4:HI-3 (97 / 3, w / w) mixture is vacuum thermally deposited in sequence as a hole injection layer, 60nm of the compound HT-4 as a hole transport layer, 60nm of the organic compound P4 provided in the present application as an electron blocking layer; 40nm of the compound PH-34:RPD-8 (97 / 3, w / w) binary mixture is used as a light-emitting layer; 5nm of ET-23 is used as a hole blocking layer, 25nm of the compound ET-46:ET-57 (50 / 50, w / w) mixture is used as an electron transport layer, 0.5nm of LiF is used as an electron injection layer, and 150nm of metal aluminum is used as a cathode; the total evaporation rate of all organic layers and LiF is controlled at 0.1nm / s, and the evaporation rate of the metal electrode is controlled at 1nm / s.

[0175] Embodiment 8-13

[0176] An organic electroluminescent device, which is different from Example 7 only in that the electron blocking layer material organic compound P4 is replaced by P64, P78, P111, P146, P374, or P434.

[0177] Comparative Examples 4-6

[0178] An organic electroluminescent device, which is different from Example 7 only in that the electron blocking layer material organic compound P4 is replaced by CCP-1, CCP-4, or CCP-5.

[0179] The organic electroluminescent devices provided in the above-mentioned Examples 7-13 and Comparative Examples 4-6 were subjected to the following performance tests: at the same brightness, the driving voltage and current efficiency of the organic electroluminescent devices were measured using a digital source meter and a brightness meter. Specifically, the voltage was increased at a rate of 0.1 V per second, and the brightness of the organic electroluminescent device was measured when it reached 3000 cd / m 2 The voltage at which the light is on is the driving voltage, and the current density at this time is measured at the same time; the ratio of brightness to current density is the current efficiency; the life test of LT97 is as follows: use a brightness meter at 3000cd / m 2 At the same brightness, the current is kept constant and the brightness of the organic electroluminescent device is measured to drop to 2910cd / m 2 The LT97 life of the comparative example 4 is set to 1, and the LT97 life of the other compounds are all relative values ​​to that of the comparative example 4. The test results are shown in Table 3 below.

[0180] Table 3:

[0181]

[0182]

[0183] Compared with CCP-1, the ring A of compound P4 is a meta-biphenyl structure, so that the conjugated structure of the molecule is extended, and the π-π interaction between molecules and molecules is enhanced, and the excitons in the electron and the light-emitting layer can be effectively blocked from leaking to the hole transport layer to cause the quenching, so the current efficiency of compound P4 is high and the life span is long.Compound P434 is compared with CCP-4 and CCP-5, and their three compounds all have Ar2 in the N ortho position to be phenyl substituted, but CCP-4 and CCP-5 have phenyl substituted in the O ortho position, and compound P434 has phenyl substituted in the O meta position, and from the structural comparison, when it is substituted in the meta position, the molecular torsion angle is larger, and its steric hindrance is larger, and the molecular structure is more distorted, and the HOMO-LUMO electron cloud overlaps and decreases, so that its LUMO energy level is promoted, so as to increase the electron blocking and hole transport ability of the molecule.

[0184] The above results show that the novel organic material of the present invention can be used in organic electroluminescent devices to effectively reduce the starting and ending voltage, improve the current efficiency, and enhance the device life, and is an electron blocking material with good performance.

[0185] Example 13: 48h thermal stability test

[0186] The thermal stability experiment of the materials of Example 7 and Comparative Examples 4-6 was conducted: the samples were sealed in a vacuum glass tube and placed in a muffle furnace and heated continuously at 280°C to 320°C for 48 hours. The HPLC purity of the test materials before and after heating was determined (based on the compounds P4, CCP-1, CCP-4, and CCP-5 of the present invention). The results are shown in the attached manual. Figure 1 .based on Figure 1 As a result, the difference between comparative example CCP-1 and the compound P4 of embodiment is that the ring A connected on its N of the compound P4 of embodiment is biphenyl, so that the P4 molecular conjugated structure is extended, and the π-π interaction between molecules is enhanced, and the molecular structure is relatively stable, and its thermal stability is relatively high. Although the ring A connected on its N of compound CCP-4 is biphenyl, it has phenyl substitution in the ortho position of O, and the molecular torsion angle is relatively small, and the molecular equilibrium stability is poor, and its molecular structure is easily destroyed in a high temperature environment, and its thermal stability is relatively poor. In addition, N, biphenyl and Ar2 of aromatic amine structure are respectively connected to the adjacent positions of benzene ring, and the rigid stereostructure of molecule can be effectively adjusted when there is substitution in the meta position of O, and the LUMO energy level is shallow, effectively improving the thermal stability of molecule.

[0187] 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 concept of the present invention, those skilled in the art may make various modifications and improvements. The appended claims summarize the scope of the present invention.

Claims

1. An organic compound, characterized in that It has the structure shown in the following formula (1): In the general formula, ring A is selected from one of a C10-30 aryl group and a C5-C30 heteroaryl group; L 1 ~L 3 Each is independently a single bond, a substituted or unsubstituted C6-C30 arylene group, or a substituted or unsubstituted C3-C30 heteroarylene group; X1 and X2 are each independently O or S; Ar 1 One selected from a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C5-C60 heteroaryl group; R 1 -R 5 Each is independently one of hydrogen, deuterium, halogen, cyano, nitro, hydroxyl, amino, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 silyl, substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted C3-C60 heteroarylamino, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl; R 6 represents a single substituent to the maximum number of substituents allowed, R 6 Selected from hydrogen, deuterium, halogen, cyano, nitro, hydroxyl, amino, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 silyl, substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted C3-C60 heteroarylamino, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl; The above L 1 ~L 3 ,Ar 1 , R 1 -R 5 , R 6 The substituents substituted in the above-mentioned substitution are each independently selected from at least one of halogen, C1-C20 chain alkyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C1-C10 alkoxy, carboxyl, nitro, cyano, amino, hydroxyl, mercapto, C1-C20 alkylsilyl, C1-C20 alkylamino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C60 aryl, and C3-C60 heteroaryl; Ar 2 The attachment site on ring A is L attached to ring A 3 Ortho position of the site, Ar2 is selected from one of the following substituent groups, wherein "—*" represents the connection site:

2. The organic compound according to claim 1, characterized in that The ring A is selected from substituted or unsubstituted C10-30 aryl groups; The X1 and X2 are O.

3. The organic compound according to claim 1, characterized in that The connection to L 3 The ring A part group on the ring has a structure shown in the following formula (a) or formula (b), wherein Ar 2 and R 6 The definition of is the same as that in formula (1), and the dotted line represents the connection site: Preferably, the connection to L 3 The ring A part group has a structure as shown in any one of formula (c), formula (d) or formula (e):

4. The organic compound according to claim 1, characterized in that It has a structure as shown in any of the following formulas (2), (3) or (4): Wherein, X1 and X2 are each independently O or S; Ar 1 is one of a substituted or unsubstituted C10-C30 aryl group, a substituted or unsubstituted C5-C30 heteroaryl group; L 1 ~L 3 , R 1 -R 6 The definition of is the same as that in formula (1).

5. The organic compound according to claim 1 or 4, characterized in that The Ar 2 One of the following substituent groups:

6. The organic compound according to claim 1 or 4, characterized in that The L 1 ~L 3 Each is independently a single bond, a substituted or unsubstituted C6-C30 arylene group; Preferably, the L 1 ~L 3 Each is independently a single bond or a phenylene group; More preferably, the L 1 ~L 3 For a single key.

7. The organic compound according to claim 1 or 4, characterized in that Ar 1 One of the following substituted or unsubstituted groups, Ar 1 The substituents substituted in the above-mentioned are each independently selected from one of halogen, C1-C20 chain alkyl, and C3-C20 cycloalkyl:

8. The organic compound according to claim 1 or 4, characterized in that R 1 -R 5 Each is independently one of hydrogen, deuterium, C1-C10 chain alkyl, C3-C10 cycloalkyl, C6-C30 aryl, and C3-C30 heteroaryl; Preferably, R 5 For hydrogen.

9. The organic compound according to claim 1 or 4, characterized in that R 6 is selected from one of methyl, ethyl, isopropyl, tert-butyl, isopentyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuran, substituted or unsubstituted dibenzothiophene, and substituted or unsubstituted carbazolyl; R 6 The substituents are each independently selected from one of halogen, C1-C20 chain alkyl, C3-C20 cycloalkyl, and C6-C60 aryl.

10. The organic compound according to claim 1, characterized in that Selected from the following compounds:

11. Use of the organic compound according to any one of claims 1 to 10, wherein the use is as a functional material in an organic electronic device, wherein the organic electronic device is selected from an organic electroluminescent 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 organic compound is used as an electron blocking layer material and / or a hole transport layer material in an organic electroluminescent device.

12. An organic electroluminescent device, comprising a first electrode, a second electrode and one or more light-emitting functional layers inserted between the first electrode and the second electrode, characterized in that: The light-emitting functional layer contains the organic compound according to any one of claims 1 to 10; Preferably, the light-emitting functional layer includes an electron blocking layer and at least one of a hole injection layer, a hole transport layer, a light-emitting layer, and an electron transport layer, and the electron blocking layer and / or the hole transport layer contains the organic compound described in any one of claims 1 to 10.

13. An electronic device having a display screen or a display panel, characterized in that: The display screen or display panel adopts the organic electroluminescent device according to claim 12.

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