An organic compound and use thereof

Abstract

This invention relates to an organic compound and its applications, the compound having the structure shown in the following formula. The compound provided by this invention employs two triazine groups as electron-withdrawing groups on the benzene ring of the parent nucleus of general formula (1), causing a red shift in the compound's luminescence. Simultaneously, D1 employs a benzocarbazole-type donor group, which, while lowering the excited state energy level of the compound, enhances the compound's rigidity, improves luminescence efficiency, and improves the compound's carrier transport performance. When the compound of this invention is used in organic electroluminescent devices, particularly as a light-emitting layer material, it ensures that the device achieves excellent results with high luminescence efficiency and low start-up voltage.

Description

Technical Field

[0001] This invention relates to an organic compound, the application of such organic compound, and an organic electroluminescent device using such organic compound, belonging to the field of electroluminescence technology. Background Technology

[0002] In recent years, optoelectronic devices based on organic materials have become increasingly popular. The inherent flexibility of organic materials makes them ideal for fabrication on flexible substrates, allowing for the design and production of aesthetically pleasing and stylish optoelectronic products, offering unparalleled advantages over inorganic materials. Examples of such organic optoelectronic devices include organic light-emitting diodes (OLEDs), organic field-effect transistors, organic photovoltaic cells, and organic sensors. OLEDs, in particular, have developed rapidly and have already achieved commercial success in the information display field. OLEDs can provide highly saturated red, green, and blue colors, and full-color displays made with them do not require an additional backlight, offering advantages such as vibrant colors, thinness, and flexibility.

[0003] The core of an OLED device is a thin-film structure containing various organic functional materials. Common functionalized organic materials include: hole injection materials, hole transport materials, hole blocking materials, electron injection materials, electron transport materials, electron blocking materials, as well as light-emitting host materials and light-emitting guest materials (dyes). When an electric current is applied, electrons and holes are injected and transported to the light-emitting region, where they recombine, thereby generating excitons and emitting light.

[0004] Various organic materials have been developed and combined with unique device structures to improve carrier mobility, regulate carrier balance, break through electroluminescence efficiency barriers, and delay device decay. For quantum mechanical reasons, common fluorescent emitters primarily utilize singlet excitons generated when electrons and empty blood combine to emit light, and are still widely used in various OLED products. Some metal complexes, such as iridium complexes, can simultaneously utilize triplet and singlet excitons for light emission, and are called phosphorescent emitters, with energy conversion efficiencies up to four times higher than traditional fluorescent emitters. Thermally excited delayed fluorescence (TADF) technology promotes the transition from triplet to singlet excitons, achieving high luminescence efficiency without the use of metal complexes, while still effectively utilizing triplet excitons. Thermally excited sensitized fluorescence (TASF) technology uses materials with TADF properties to sensitize the emitter through energy transfer, also achieving high luminescence efficiency.

[0005] As OLED products gradually enter the market, people have increasingly higher requirements for their performance. Current OLED materials and device structures cannot fully solve the problems related to efficiency, lifespan, and cost of OLED products. Through careful consideration and continuous experimentation, the researchers of this invention have discovered an ingenious molecular design scheme, which is described in detail below. The compounds disclosed in this invention are highly suitable for application in OLEDs and for improving device performance. Summary of the Invention

[0006] To address the problems of the prior art, this invention provides a class of organic compounds that can be used in organic electroluminescent devices, meeting the photoelectric performance and operating voltage requirements of OLED devices.

[0007] This invention provides an organic compound with the structure shown in formula (1):

[0008]

[0009] In equation (1), Ar 1 Ar 2 Ar 3 Ar 4 Each is independently selected from one of substituted or unsubstituted C6-C30 aryl groups and substituted or unsubstituted C3-C30 heteroaryl groups;

[0010] R is independently selected from one of 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 C6-C60 heteroarylamino, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C3-C30 heteroaryloxy, substituted or unsubstituted C6-C60 aryl, and substituted or unsubstituted C3-C60 heteroaryl, wherein R is independently cyclically connected to or not cyclically connected to the connected benzene ring;

[0011] n is an integer from 0 to 2, m is an integer from 2 to 4, and m+n≤4;

[0012] D 1 For groups as shown in formula (2):

[0013]

[0014] In formula (2), ring A and ring B represent groups fused to the connected benzene ring, and ring A and ring B are independently selected from one of substituted or unsubstituted C6-C60 aromatic rings and substituted or unsubstituted C3-C60 heteroaromatic rings.

[0015] The substituents in ring A and ring B are each independently selected from at least one of halogen, unsubstituted or R'-substituted C1-C20 chain alkyl, unsubstituted or R'-substituted C3-C20 cycloalkyl, unsubstituted or R'-substituted C1-C20 alkoxy, unsubstituted or R'-substituted C1-C20 silyl, cyano, nitro, hydroxy, amino, unsubstituted or R'-substituted C6-C30 arylamino, unsubstituted or R'-substituted C3-C30 heteroarylamino, unsubstituted or R'-substituted C6-C30 aryloxy, unsubstituted or R'-substituted C3-C30 heteroaryloxy, unsubstituted or R'-substituted C6-C60 aryl, and unsubstituted or R'-substituted C3-C60 heteroaryl; the substituents in ring A and ring B are each independently unconnected, or at least two adjacent substituents are connected to form a ring;

[0016] a and b are independent integers from 0 to 2, and a + b ≥ 1;

[0017] * indicates the location of the bond that the group is attached to;

[0018] The above Ar 1 Ar 2 Ar 3 Ar 4 The substituents R and R' mentioned in the text are each independently selected from one or a combination of at least two of the following: halogen, cyano, nitro, hydroxyl, amino, C1-C20 chain alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 silyl, C6-C60 arylamino, C3-C60 heteroarylamino, C6-C60 aryl, and C3-C60 heteroaryl.

[0019] More preferably, the general formula compound of the present invention has a structure as shown in formula (3) or formula (4):

[0020]

[0021] In equations (3) and (4), R and D 1 m, n, Ar 1 Ar 2 Ar 3 Ar 4 The definitions are the same as in equation (1);

[0022] More preferably, the general formula compound of the invention has a structure as shown in formula (3).

[0023] In equations (1), (3), and (4), preferably, m = 2;

[0024] Preferably, m = 2, and D 1 The structures are the same.

[0025] More preferably, the general formula compounds of the present invention have a structure as shown in any of formulas (5) to (11):

[0026]

[0027] In equations (5) to (11), Ar 1 Ar 2 Ar 3 Ar 4 The definition is the same as in formula (1), where D1 and D2 independently represent groups as shown in formula (2).

[0028] In equations (1) to (11), D 1 D1 and D2 are groups as shown in formula (2), preferably, in formula (2), a+b is 1 or a+b is 2;

[0029] Further preferred, a is 0 and b is 1; or preferred, a is 0 and b is 2; or preferred, a is 1 and b is 1.

[0030] More preferably, a is 1 and b is 1.

[0031] In formulas (1) to (11) of the present invention, Ar is preferred. 1 Ar 2 Ar 3 Ar 4 Each is independently selected from substituted or unsubstituted C6–C30 aryl groups; more preferably, Ar 1 Ar 2 Ar 3 Ar 4 Each is independently selected from C6 to C30 aryl groups; further preferred, Ar 1 Ar 2 Ar 3 Ar 4 Each is independently selected from substituted or unsubstituted phenyl groups; most preferably, Ar 1 Ar 2 Ar 3 Ar 4 Each is independently selected from phenyl.

[0032] Ar 1 Ar 2 Ar 3 Ar 4The substituents described herein are each independently selected from one of halogen, cyano, C1-C10 chain alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C1-C10 silyl, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryl, and C3-C30 heteroaryl; preferably, the substituents described herein are each independently selected from one of C1-C10 alkyl, C3-C10 cycloalkyl, and C1-C10 alkoxy.

[0033] Further preferably, the general formula compound of the present invention has a structure represented by formula (5) or formula (7); most preferably, the general formula compound of the present invention has a structure represented by formula (5).

[0034] In the general formula of the present invention, preferably in formula (2), ring A and ring B are each independently selected from one of C6-C60 aromatic rings and C3-C60 heteroaromatic rings; more preferably, ring A and ring B are each independently selected from C6-C60 aromatic rings; more preferably, ring A and ring B are each independently selected from benzene rings.

[0035] In the general formula compounds of the present invention, formula (2) is selected from the following groups, substituted or unsubstituted, wherein * represents the bond position of the group:

[0036]

[0037] When substituents are present on each of the above groups, the substituents are independently selected from one or a combination of at least two of the following: C1-C10 chain alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C1-C10 silyl, C6-C30 aryl, and C3-C30 heteroaryl.

[0038] Preferably, formula (2) is selected from the following groups, either substituted or unsubstituted:

[0039]

[0040] Preferably, formula (2) is selected from the following groups, either substituted or unsubstituted:

[0041]

[0042] In this specification, the "substituted or unsubstituted" group can replace one substituent or multiple substituents. When there are multiple substituents, they can be selected from different substituents. When the same expression is used in this invention, they all have the same meaning, and the selection range of substituents is as shown above and will not be repeated one by one.

[0043] In this specification, the expression "Ca-Cb" represents that the group has a carbon atom number of a to b. Generally in this specification, unless otherwise specified, "independently of each other" means that when the subject has multiple ones, they can be the same or different from each other.

[0044] The heteroatoms in this specification usually refer to atoms or atomic groups selected from N, O, S, P, Si, and Se, preferably selected from N, O, S.

[0045] In this specification, for the description of chemical elements, unless otherwise specified, it usually includes the concept of isotopes with the same chemical properties. For example, the description of "hydrogen (H)" also includes 1 H (protium or H), 2 H (deuterium or D); carbon (C) includes 12 C, 13 C, etc., which will not be elaborated here.

[0046] In this specification, examples of halogens include: fluorine, chlorine, bromine, iodine, etc.

[0047] In this specification, unless otherwise specified, aryl and heteroaryl both include monocyclic and fused-ring cases.

[0048] In this specification, the substituted or unsubstituted C6-C60 aryl includes monocyclic aryl and fused-ring aryl, preferably C6-C30 aryl, and more preferably C6-C20 aryl. The so-called monocyclic aryl means that the molecule contains 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. Specifically, the biphenyl includes 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 fused-ring aryl means that the molecule contains at least two aromatic rings, and the aromatic rings are not independent of each other but are fused together by sharing two adjacent carbon atoms. Exemplarily, such as: naphthyl, anthryl, phenanthryl, indenyl, fluorenyl, fluoranthenyl, triphenylenyl, pyrenyl, perylenyl, Naphthyl, 2-naphthyl, and their derivatives are used. The naphthyl group includes 1-naphthyl or 2-naphthyl; the anthraceneyl group is selected from 1-anthrayl, 2-anthrayl, and 9-anthrayl; the fluorenyl group is selected from 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl, and 9-fluorenyl; the pyreneyl group is selected from 1-pyrene, 2-pyrene, and 4-pyrene; and the 2-tetraphenyl group is selected from 1-2 ... The fluorene derivative group is selected from 9,9-dimethylfluorenyl, 9,9-diethylfluorenyl, 9,9-dipropylfluorenyl, 9,9-dibutylfluorenyl, 9,9-dipentylfluorenyl, 9,9-dihexylfluorenyl, 9,9-diphenylfluorenyl, 9,9-dinaphthylfluorenyl, 9,9'-spirodifluorenyl, and benzo[a]fluorenyl.

[0049] The C3-C60 heteroaryl groups mentioned in this specification include monocyclic heteroaryl groups and fused-ring heteroaryl groups, preferably C3-C30 heteroaryl groups, more preferably C4-C20 heteroaryl groups, and even more preferably C5-C12 heteroaryl groups. A monocyclic heteroaryl group refers to a molecule containing at least one heteroaryl group. When a molecule contains one heteroaryl group and other groups (such as aryl, heteroaryl, alkyl, etc.), the heteroaryl group and the other groups are independent of each other and connected by a single bond. Examples of monocyclic heteroaryl groups include furanyl, thiophene, pyrrole, and pyridinyl. A fused-ring heteroaryl group refers to a molecule containing at least one aromatic heterocycle and an aromatic ring (aromatic heterocycle or aromatic ring), where the two are not independent of each other but share a group consisting of two adjacent atoms fused together. Examples of fused-ring heteroaryl groups include: benzofuranyl, benzothiophenyl, isobenzofuranyl, indolyl, dibenzofuranyl, dibenzothiophenyl, carbazoyl, acridineyl, isobenzofuranyl, isobenzothiophenyl, benzocarbazoyl, azircarbazoyl, phenothiazinyl, phenothiazinyl, 9-phenylcarbazoyl, 9-naphthylcarbazoyl, dibenzocarbazoyl, indolocarbazoyl, etc.

[0050] Examples of C6-C30 arylamino groups mentioned in this invention include phenylamino, methylphenylamino, naphthylamino, anthraceneylamino, phenanthreneamino, and biphenylamino.

[0051] Examples of C3-C30 heteroaryl amino groups mentioned in this invention include pyridinylamino, pyrimidinylamino, and dibenzofuranylamino.

[0052] Unless otherwise specified, the chain alkyl groups mentioned in this invention include straight-chain alkyl groups and branched-chain alkyl groups. Specifically, substituted or unsubstituted C1-C30 chain alkyl groups are preferably substituted or unsubstituted C1-C16 chain alkyl groups, and more preferably substituted or unsubstituted C1-C10 chain alkyl groups. Examples of substituted or unsubstituted C1-C10 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.

[0053] In this invention, the cycloalkyl group includes monocycloalkyl and polycycloalkyl; wherein, monocycloalkyl refers to an alkyl group containing a single ring structure; polycycloalkyl refers to a structure composed of two or more cycloalkyl groups sharing one or more carbon atoms on a ring; examples of C3-C20 cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, etc.

[0054] In this specification, the substituted or unsubstituted C1-C20 alkoxy group is preferably a substituted or unsubstituted C1-C10 alkoxy group. Examples of C1-C10 alkoxy groups include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, pentooxy, isopentoxy, hexoxy, heptoxy, octoxy, nonoxy, decoxy, undecoxy, dodecoxy, etc., with methoxy, ethoxy, n-propoxy, isopropoxy, tert-butoxy, sec-butoxy, isobutoxy, isopentoxy, and more preferably methoxy.

[0055] In this specification, the substituted or unsubstituted C1-C20 silanes and the substituted or unsubstituted C1-C10 silanes are examples of silanes substituted with groups listed in the above C1-C10 silanes, specifically including: methylsilane, dimethylsilane, trimethylsilane, ethylsilane, diethylsilane, triethylsilane, tert-butyldimethylsilane, tert-butyldiphenylsilane, etc.

[0056] In this invention, the D1 group in the general formula of the compound adopts a benzocarbazole-type donor group, which, while lowering the excited state energy level of the compound, can enhance the rigidity of the compound, improve luminescence efficiency, and improve the charge carrier transport performance. The two substituted triazine groups in the parent core structure are not connected at ortho positions on the central benzene ring of the parent core, and the Ar group among the two triazine groups is most preferably phenyl. When the compound of this invention is used in organic electroluminescent devices, especially as a light-emitting layer material, it can ensure that the device achieves excellent results with high luminescence efficiency and low start-up voltage. Fusing two aryl groups can lower the excited state energy level of the molecule, which is more beneficial for redshift of emission compared to the structure fused with one aryl group, and is also more conducive to charge carrier transport, thus reducing the device voltage.

[0057] Furthermore, the organic compounds of the present invention may preferably be compounds with the specific structures shown below. These compounds are merely representative and do not limit the scope of the present invention.

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070] As another aspect of the present invention, the application of the compound described above in an organic electroluminescent device is also provided. Specifically, it is preferably used as a light-emitting layer material in an organic electroluminescent device.

[0071] In addition, the preparation process of the compound of the present invention is simple and easy, the raw materials are readily available, it is suitable for mass production and scale-up, and it is very suitable for industrial applications.

[0072] The compounds of this invention possess excellent luminescent properties, capable of providing triplet excitons to achieve high luminescent efficiency. Furthermore, due to their excellent carrier transport efficiency, they are suitable for use as luminescent dyes, particularly as red luminescent dyes. Of course, the compounds of this invention can also act as sensitizers, working together with the host material and dye to achieve a good luminescent layer. Applications include, but are not limited to, organic electroluminescent 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 paper, preferably organic electroluminescent devices.

[0073] The present invention also provides an organic electroluminescent device, the organic electroluminescent device comprising a first electrode, a second electrode, and at least one or more light-emitting functional layers inserted between the first electrode and the second electrode, wherein the light-emitting functional layers contain at least one compound described in the present invention.

[0074] The organic electroluminescent device of the present invention has a structure consistent with existing devices, for example including an anode layer, multiple light-emitting functional layers and a cathode layer; the multiple light-emitting functional layers include at least a light-emitting layer, wherein the light-emitting layer contains the above-mentioned organic compound of the present invention.

[0075] OLED devices prepared using the compounds of this invention have low start-up voltage, high luminous efficiency, and better lifespan, which can meet the current requirements of panel and display manufacturers for high-performance materials. Detailed Implementation

[0076] The technical solution of the present invention will be further described in more detail below. Those skilled in the art should understand that the embodiments described are merely illustrative of the invention and should not be considered as specific limitations thereof.

[0077] Method for obtaining the compound of the present invention

[0078] The compounds represented by general formula (1) of this invention can be obtained by known methods, such as by known organic synthesis methods. An exemplary synthetic route is given below, but those skilled in the art can also obtain them by other known methods.

[0079] Synthesis process

[0080] Synthesis Example 1: Synthesis of Compound Y1

[0081]

[0082] Synthesis of intermediate Y1-1:

[0083] At room temperature, add A (50g, 248mmol), B (165.9g, 620mmol), tetraphenylphosphine palladium (1.8g, 4.96mmol), and potassium carbonate (137g, 991mmol) to a 2L single-necked flask, along with Dioxane / H2O (900ml / 300ml). Purge with nitrogen for protection, heat to 80°C, and react for 4 hours.

[0084] The reaction was stopped, the temperature was lowered, and column chromatography was performed. 128 g of a white solid was obtained, with a yield of 89.5%. Mass spectrometry analysis determined the molecular ion mass to be 576.9 (theoretical value: 576.6).

[0085] Synthesis of compound Y1:

[0086] At room temperature, Y1-1 (5g, 8.6mmol), C (5.8g, 21.6mmol), cesium carbonate (11.3g, 34.7mmol), and DMF (200ml) were added to a 500ml single-necked flask. Nitrogen was used for purging and protection, and the temperature was raised to 100 degrees Celsius. The reaction was carried out for 16 hours.

[0087] The reaction was stopped, the reaction solution was injected into water, ammonium chloride solid was added, the mixture was stirred, the solid was filtered, and column chromatography was performed. 6.7 g of a red solid was obtained. The molecular ion mass determined by mass spectrometry was 1071.6 (theoretical value: 1071.2).

[0088] Synthesis Example 2: Synthesis of compound Y17:

[0089]

[0090] At room temperature, Y1-1 (5g, 8.6mmol), C (5.8g, 21.6mmol), cesium carbonate (11.3g, 34.7mmol), and DMF (200ml) were added to a 500ml single-necked flask. Nitrogen was used for purging and protection, and the temperature was raised to 100 degrees Celsius. The reaction was carried out for 16 hours.

[0091] The reaction was stopped, the reaction solution was injected into water, ammonium chloride solid was added, the mixture was stirred, the solid was filtered, and column chromatography was performed. 7.2 g of a red solid was obtained. The molecular ion mass determined by mass spectrometry was 1071.6 (theoretical value: 1071.2).

[0092] Synthesis Example 3: Synthesis of Compound Y21:

[0093]

[0094] Synthesis of intermediate Y21-1:

[0095] At room temperature, Y1-1 (5g, 8.6mmol), D (2.78g, 10.4mmol), potassium carbonate (1.8g, 13.01mmol), and DMF (150ml) were added to a 500ml single-necked flask. Nitrogen was used for purging and protection, and the temperature was raised to 45 degrees Celsius. The reaction was carried out for 6 hours.

[0096] The reaction was stopped, the temperature was lowered, the reaction solution was injected into water, ammonium chloride solid was added, the mixture was stirred, the solid was filtered, and column chromatography was performed. 4.1 g of a yellow solid was obtained. The molecular ion mass determined by mass spectrometry was 824.3 (theoretical value: 823.9).

[0097] Synthesis of compound Y21:

[0098] At room temperature, Y21-1 (4 g, 4.85 mmol), F (2.31 g, 7.28 mmol), cesium carbonate (3.16 g, 9.71 mmol), and DMF (150 ml) were added to a 500 ml single-necked flask. Nitrogen was used for purging and protection, and the temperature was raised to 100 degrees Celsius. The reaction was carried out for 16 hours.

[0099] The reaction was stopped, the temperature was lowered, the reaction solution was injected into water, ammonium chloride solid was added, the mixture was stirred, the solid was filtered, and column chromatography was performed. 4.3 g of a red solid was obtained. The molecular ion mass determined by mass spectrometry was 1121.8 (theoretical value: 1121.3).

[0100] Synthesis Example 4: Synthesis of compound Y41:

[0101]

[0102] At room temperature, Y1-1 (5g, 8.6mmol), F (6.88g, 21.68mmol), cesium carbonate (11.3g, 34.7mmol), and DMF (200ml) were added to a 500ml single-necked flask. Nitrogen was used for purging and protection, and the temperature was raised to 100 degrees Celsius. The reaction was carried out for 16 hours.

[0103] The reaction was stopped, the reaction solution was injected into water, ammonium chloride solid was added, the mixture was stirred, the solid was filtered, and column chromatography was performed. 8.6 g of a red solid was obtained. The molecular ion mass determined by mass spectrometry was 1173.5 (theoretical value: 1173.3).

[0104] Synthesis Example 5: Synthesis of compound Y162:

[0105]

[0106] Synthesis of intermediate Y126-1:

[0107] At room temperature, Y1-1 (5g, 8.6mmol), F (3.44g, 10.8mmol), potassium carbonate (1.8g, 10.3mmol), and DMF (200ml) were added to a 500ml single-necked flask. Nitrogen was used for purging and protection, and the temperature was raised to 100 degrees Celsius. The reaction was carried out for 16 hours.

[0108] The reaction was stopped, the reaction solution was injected into water, ammonium chloride solid was added, the mixture was stirred, the solid was filtered, and column chromatography was performed. 4.3 g of a yellow solid was obtained. The molecular ion mass determined by mass spectrometry was 873.8 (theoretical value: 873.3).

[0109] Synthesis of compound Y126:

[0110] At room temperature, Y126-1 (4 g, 4.58 mmol), G (2.12 g, 6.87 mmol), cesium carbonate (2.98 g, 9.15 mmol), and DMF (200 ml) were added to a 500 ml single-necked flask. Nitrogen was used for purging and protection, and the temperature was raised to 100 degrees Celsius. The reaction was carried out for 16 hours.

[0111] The reaction was stopped, the reaction solution was injected into water, ammonium chloride solid was added, the mixture was stirred, the solid was filtered, and column chromatography was performed. 3.7 g of a yellow solid was obtained. The molecular ion mass determined by mass spectrometry was 1163.8 (theoretical value: 1167.3).

[0112] Synthesis Example 6: Synthesis of compound Y313:

[0113]

[0114] Synthesis of intermediate Y216-1:

[0115] At room temperature, W (50g, 248mmol), B (165.9g, 620mmol), tetraphenylphosphine palladium (1.8g, 4.96mmol), and potassium carbonate (137g, 991mmol), along with Dioxane / H2O (900ml / 300ml), were added to a 2L single-necked flask. The flask was purged with nitrogen for protection, heated to 80°C, and reacted for 4 hours.

[0116] The reaction was stopped, the temperature was lowered, and column chromatography was performed. 101 g of a white solid was obtained, with a yield of 70.6%. Mass spectrometry analysis determined the molecular ion mass to be 576.9 (theoretical value: 576.6).

[0117] Synthesis of compound Y216:

[0118] At room temperature, Y216-1 (5g, 8.6mmol), C (5.8g, 21.6mmol), cesium carbonate (11.3g, 34.7mmol), and DMF (200ml) were added to a 500ml single-necked flask. Nitrogen was used for purging and protection, and the temperature was raised to 100 degrees Celsius. The reaction was carried out for 16 hours.

[0119] The reaction was stopped, the reaction solution was injected into water, ammonium chloride solid was added, the mixture was stirred, the solid was filtered, and column chromatography was performed. 8.2 g of a red solid was obtained. The molecular ion mass determined by mass spectrometry was 1170.9 (theoretical value: 1170.4).

[0120] Device Examples

[0121] Implementation

[0122] An OLED includes a first electrode and a second electrode, and an organic material layer located between the electrodes. This organic material layer can be further divided into multiple regions. For example, the organic material layer may include a hole transport region, a light-emitting layer, and an electron transport region.

[0123] In specific embodiments, a substrate can be used below the first electrode or above the second electrode. The substrate is typically made of glass or polymer material with excellent mechanical strength, thermal stability, water resistance, and transparency. Furthermore, thin-film transistors (TFTs) can also be incorporated into the substrate used for displays.

[0124] The first electrode can be formed by sputtering or depositing the material to be used as the first electrode on a substrate. When the first electrode is used as the anode, it can be a transparent conductive oxide material such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), zinc oxide (ZnO), or any combination thereof. When the first electrode is used as the cathode, it can be a metal or alloy such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), ytterbium (Yb), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), or any combination thereof.

[0125] Organic material layers can be formed on electrodes using methods such as vacuum thermal evaporation, spin coating, and printing. The compounds used as organic material layers can be small organic molecules, large organic molecules, polymers, and combinations thereof.

[0126] The hole transport region is located between the anode and the emissive layer. The hole transport region can be a single-layer hole transport layer (HTL), including single-layer hole transport layers containing only one compound and single-layer hole transport layers containing multiple compounds. Alternatively, the hole transport region can be a multilayer structure including at least one of a hole injection layer (HIL), a hole transport layer (HTL), and an electron blocking layer (EBL); wherein the HIL is located between the anode and the HTL, and the EBL is located between the HTL and the emissive layer.

[0127] The material for the hole transport region may be selected from, but is not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or polymers containing conductive dopants such as polyphenylene ethylene, polyaniline / dodecylbenzenesulfonic acid (Pani / DBSA), poly(3,4-ethylenedioxythiophene) / poly(4-styrenesulfonate) (PEDOT / PSS), polyaniline / camphorsulfonic acid (Pani / CSA), polyaniline / poly(4-styrenesulfonate) (Pani / PSS), aromatic amine derivatives as shown in HT-1 to HT-51 below; or any combination thereof.

[0128]

[0129]

[0130]

[0131] The hole injection layer is located between the anode and the hole transport layer. The hole injection layer can be a single compound material or a combination of multiple compounds. For example, the hole injection layer can be one or more compounds of HT-1 to HT-51 mentioned above, or one or more compounds of HI-1 to HI-3 mentioned below; it can also be one or more compounds of HT-1 to HT-51 doped with one or more compounds of HI-1 to HI-3 mentioned below.

[0132]

[0133] In one aspect of the invention, the light-emitting layer employs a thermally activated delayed fluorescence emission technique. 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.

[0134]

[0135]

[0136]

[0137]

[0138] In this invention, the light-emitting layer dopant is one or more of the TADF materials represented by general formula (1).

[0139] In this invention, the TADF material represented by general formula (1) can not only be used as a luminescent material, but also as a sensitizer for fluorescent dyes. That is, in addition to the main material, the luminescent layer also includes dopant one and dopant two. Dopant one is selected from one or more combinations of the TADF materials represented by general formula (1).

[0140] Dopant 2 may be selected from, but is not limited to, one or more combinations listed below;

[0141]

[0142]

[0143] 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 employ, but is 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 a mixture of one or more compounds of HT-1 to HT-51 and one or more compounds of PH-47 to PH-77 may be employed.

[0144] The OLED organic material layer may also include an electron transport region between the light-emitting layer and the cathode. The electron transport region can be a single-layer electron transport layer (ETL), including single-layer electron transport layers containing only one compound and single-layer electron transport layers containing multiple compounds. Alternatively, the electron transport region can be a multilayer structure including at least one of an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL).

[0145] In one aspect of the present invention, the electron transport layer material may be selected from, but not limited to, one or more combinations of ET-1 to ET-73 listed below.

[0146]

[0147]

[0148]

[0149]

[0150] 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 employ, but is 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 may be employed.

[0151] The device may also include an electron injection layer located between the electron transport layer and the cathode, and the electron injection layer material includes, but is not limited to, one or more combinations of the following.

[0152] LiQ, LiF, NaCl, CsF, Li2O, Cs2CO3, BaO, Na, Li, Ca, Mg, Yb.

[0153] The fabrication process of the organic electroluminescent device in this embodiment is as follows:

[0154] The fabrication process of the thermally activated delayed fluorescence device in Example 1 is as follows:

[0155] The glass plate coated with the ITO transparent conductive layer was ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in a acetone:ethanol mixed solvent, baked in a clean environment until all moisture was removed, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam.

[0156] The glass substrate with the anode was placed in a vacuum chamber and evacuated to a vacuum level of <1×10⁻⁶. -5 Pa, on the aforementioned anolyte film, a 10 nm HT-4:HI-3 (97 / 3, w / w) mixture was vacuum thermally deposited as a hole injection layer, a 60 nm HT-4 compound as a hole transport layer, and a 5 nm HT-51 compound as an electron blocking layer; a 40 nm PH54:Y1 (100:40, w / w) binary mixture was deposited as a light-emitting layer; a 5 nm PH-28 compound was deposited as a hole blocking layer; a 25 nm ET-69:ET-57 (50 / 50, w / w) compound as an electron transport layer; a 1 nm LiF compound as an electron injection layer; and a 150 nm aluminum alloy as a cathode. The total deposition rate of all organic layers and LiF was controlled at 0.1 nm / s, and the deposition rate of the metal electrode was controlled at 1 nm / s.

[0157] The preparation process of Device Examples 2-12 and Comparative Examples 1-4 is the same as that of Device Example 1, except that Y1 in the light-emitting layer is replaced with the compounds listed in Table 2.

[0158] The organic electroluminescent devices prepared by the above process were subjected to the following performance measurements:

[0159] Under the same brightness, the driving voltage, emission peak, and external quantum efficiency of the organic electroluminescent devices prepared in Examples 1-12 and Comparative Examples 1-3 were measured using a digital source meter and luminance meter. Specifically, the emission peak of the device was measured by testing the fluorescence emission spectrum; the voltage was increased at a rate of 0.1V per second, and the measurement was performed when the brightness of the organic electroluminescent device reached 10000 cd / m². 2 The voltage at that time is the driving voltage; the external quantum efficiency of the organic electroluminescent device is determined using an integrating sphere.

[0160] The structural formulas of the comparative compounds in this invention are as follows, wherein the preparation methods of compounds K1 and K2 are described in WO2018237385A, the preparation method of compound K3 is described in WO2020111586A, and the preparation method of compound K4 is described in CN107935915A.

[0161]

[0162]

[0163] The performance of thermally activated delayed fluorescence devices is shown in Table 2 below:

[0164]

[0165]

[0166] Device Example 13 is the same as Device Example 1, except that the light-emitting layer is a 40nm ternary mixture of compound PH54:Y1:RD20 (100:40:1, w / w / w), while the other functional layers remain unchanged.

[0167] The preparation process of devices 14-24 and comparative examples 5-8 is the same as that of device 13, except that Y1 in the light-emitting layer is replaced with the compounds listed in Table 3.

[0168] The organic electroluminescent devices prepared by the above process were subjected to the following performance measurements:

[0169] At the same brightness, the driving voltage and external quantum efficiency of the organic electroluminescent devices prepared in Examples 13-24 and Comparative Examples 5-8 were measured using a digital source meter and a luminance meter. Specifically, the voltage was increased at a rate of 0.1 V per second, and the driving voltage and external quantum efficiency of the organic electroluminescent devices were measured when the brightness reached 10000 cd / m². 2 The voltage at that time is the driving voltage; the external quantum efficiency of the organic electroluminescent device is determined using an integrating sphere.

[0170] The performance of thermally activated sensitized delayed fluorescence devices is shown in Table 3 below:

[0171]

[0172]

[0173] As shown in Table 2, when the compound of the present invention is used as the luminescent dye, the operating voltage is lower and the light color is redder compared with the comparative compound. This may be due to the increased conjugation of the compound of the present invention, which leads to a red shift in the emission, and at the same time, it is beneficial to the transport of charge carriers. As shown in Table 3, when the compound of the present invention is used as the sensitizer, the device efficiency is higher. This may be due to the greater overlap between the emission spectrum of the compound of the present invention and the absorption spectrum of the dye, resulting in more complete energy transfer.

[0174] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above descriptions are merely specific 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 principles of the present invention should be included within the protection scope of the present invention.

Claims

1. An organic compound having the structure shown in formula (1): In equation (1), Ar 1 Ar 2 Ar 3 Ar 4 Each is independently selected from C6~C30 aryl groups; R is independently selected from C1-C20 chain alkyl groups; n is 0 or 1, m is an integer from 2 to 4, and m+n≤4; D 1 For groups as shown in formula (2): In formula (2), ring A and ring B represent groups fused to the connected benzene ring, and ring A and ring B are independently selected from substituted or unsubstituted benzene rings. The substituents in ring A and ring B are each independently selected from C1-C20 chain alkyl groups; a and b are independent integers from 0 to 2, and a + b ≥ 1; The position of the bond that the representative group is attached to.

2. The compound according to claim 1, characterized in that, It has a structure as shown in equation (3) or equation (4): In equations (3) and (4), R and D 1 m, n, Ar 1 Ar 2 Ar 3 Ar 4 The definitions are the same as in equation (1).

3. The compound according to claim 1 or 2, characterized in that, m=2。 4. The compound according to claim 1 or 2, characterized in that, m=2, and D 1 The structures are the same.

5. The compound according to claim 1, characterized in that, It has a structure as shown in any of equations (5) to (11): In equations (5) to (11), Ar 1 Ar 2 Ar 3 Ar 4 The definition is the same as in formula (1), where D1 and D2 independently represent groups as shown in formula (2).

6. The compound according to claim 1, characterized in that, It has a structure as represented by equation (5) or equation (7).

7. The compound according to claim 1 or 2, characterized in that, D 1 D1 and D2 are groups as shown in formula (2), where a+b is 2.

8. The compound according to claim 1 or 2, characterized in that, a = 0, b = 2; or a = 1, b = 1.

9. The compound according to claim 1 or 2, characterized in that, a is 1, b is 1.

10. The compound according to claim 1 or 2, characterized in that, Ar 1 Ar 2 Ar 3 Ar 4 Each is independently selected from phenyl.

11. The compound according to claim 1, characterized in that, In equation (2), ring A and ring B are independently selected from benzene rings.

12. The compound according to claim 1, characterized in that, Formula (2) is selected from the following groups, wherein The position of the bond connecting the representative group: 。 13. The compound according to claim 1, characterized in that, Formula (2) is selected from the following groups: 。 14. A compound, characterized in that, The compound has the structure shown below: 。 15. The use of the organic compound of any one of claims 1-14 as a functional material in an organic electronic device, wherein the organic electronic device is selected from organic electroluminescent devices, optical sensors, solar cells, organic thin-film transistors, organic field-effect transistors, information tags, electronic artificial skin sheets, sheet-type scanners, or electronic paper; The organic compound is used as a light-emitting layer material in organic electroluminescent devices.

16. The application according to claim 15, used as a luminescent dye in the luminescent layer of an organic electroluminescent device.

17. 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, wherein the light-emitting functional layer comprises 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 wherein the light-emitting layer contains an organic compound as described in any one of claims 1-14.

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