Compound containing triazine and carbazoloindole structures and organic electroluminescent device

Abstract

The invention discloses a compound containing triazine and carbazoloindole structures and an organic electroluminescent device, and belongs to the technical field of semiconductors. The structure of the compound containing the triazine and the carbazolo indole structure is shown as a general formula (1) or a general formula (2): # imgabs0, and the compound containing the triazine and the carbazolo indole structure is applied to a light-emitting layer of an organic light-emitting device. Meanwhile, the voltage of the device is reduced, and the efficiency of the device is improved.

Description

Technical Field

[0001] The invention relates to the field of semiconductor technology, in particular to a compound containing triazine and carbazole indole structure and an organic electroluminescent device. Background Art

[0002] Organic light emitting diodes (OLEDs) are like sandwich structures, including electrode material layers and organic functional materials sandwiched between different electrode film layers. Various functional materials are superimposed on each other according to their uses to form organic light emitting diodes. As a current device, when voltage is applied to the electrodes at both ends of the organic light emitting diode and the electric field acts on the positive and negative charges in the organic layer functional material film layer, the positive and negative charges are further compounded in the light emitting layer, generating organic light emitting diodes.

[0003] There may be a hole transport region between the anode and the light-emitting layer of the organic electroluminescent device, and there may be an electron transport region between the light-emitting layer and the cathode. Holes from the anode may migrate to the light-emitting layer through the hole transport region, and electrons from the cathode may migrate to the light-emitting layer through the electron transport region, and the holes and electrons may recombine in the light-emitting layer to generate excitons.

[0004] The light-emitting layer is composed of a main material and a doping material. The doping material is dispersed in the main material. The main material is divided into a single main material and a double main material. The single main material is usually composed of a single compound, and the double main material is composed of an N-type (electron type) material and a P-type (hole type) material. The doping material is divided into a fluorescent material and a phosphorescent material. The phosphorescent material mainly relies on the spin coupling effect of heavy metal atoms to realize the direct energy transition from the triplet state to the ground state, and theoretically can achieve an internal quantum yield of 100%.

[0005] Nevertheless, there is still a need for improvement in device voltage, current efficiency and life of triplet phosphorescent organic electroluminescent devices. The performance of the host material in the light-emitting layer usually affects the above-mentioned key performances of the organic electroluminescent device to a large extent. According to the prior art, the host material, especially the compounds of N-type host and bipolar host, usually contain triazine groups, and when the existing triazine derivatives are used as host materials, there is a need for improvement in device voltage, current efficiency and device life. Summary of the invention

[0006] In view of the above problems existing in the prior art, the present invention provides a compound containing triazine and carbazole indole structure and an organic electroluminescent device. The compound containing triazine and carbazole indole structure is used as the main material of the light-emitting layer of the organic electroluminescent device, which can achieve lower voltage, significantly improve the device efficiency, and greatly extend the device life.

[0007] The technical solution of the present invention is: a compound containing triazine and carbazole indole structure, wherein the structure of the compound containing triazine and carbazole indole structure is shown in general formula (1) or general formula (2):

[0008]

[0009] In the general formula (1) and the general formula (2), X represents S or O;

[0010] A2 and A3 independently represent substituted or unsubstituted phenyl groups, hydrogen atoms;

[0011] A4 and A5 are independently represented by substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, cyano, or hydrogen atom, wherein the number of hydrogen atoms represented by A4 and A5 is 0 or 1, i.e., A4 and A5 are not simultaneously represented by hydrogen atoms;

[0012] The hydrogen atoms in the triazine and carbazole indole structure-containing compound may be partially or completely deuterated;

[0013] The substituent for substituting the above substitutable group may be selected from a F atom and a cyano group.

[0014] Furthermore, the structure of the compound containing triazine and carbazole indole structure is selected from the following structural formula:

[0015]

[0016] In general formula-2a to general formula-2h,

[0017] A2 and A3 are independently represented by phenyl or hydrogen atom;

[0018] A4 and A5 independently represent phenyl, biphenyl, cyano, or hydrogen atom, wherein the number of hydrogen atoms represented by A4 and A5 is 0 or 1.

[0019] The hydrogen atoms in the triazine and carbazole indole structure-containing compound may be partially or completely deuterated.

[0020] Furthermore, the structure of the compound containing triazine and carbazole indole structure is selected from the following structural formula:

[0021]

[0022] Wherein, X represents S or O;

[0023] A2 and A3 independently represent substituted or unsubstituted phenyl groups, hydrogen atoms;

[0024] A4 and A5 independently represent substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, cyano, or hydrogen atom, wherein A4 and A5 represent that the number of hydrogen atoms is 0 or 1;

[0025] The hydrogen atoms in the triazine and carbazole indole structure-containing compound may be partially or completely deuterated;

[0026] The substituent for substituting the above substitutable group may be selected from a F atom and a cyano group.

[0027] Furthermore, the structure of the compound containing triazine and carbazole indole structure is selected from the following structural formula:

[0028]

[0029] Wherein, X represents S or O;

[0030] A2 and A3 independently represent substituted or unsubstituted phenyl groups, hydrogen atoms;

[0031] A4 and A5 independently represent substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, cyano, or hydrogen atom, wherein A4 and A5 represent that the number of hydrogen atoms is 0 or 1;

[0032] The hydrogen atoms in the triazine and carbazole indole structure-containing compound may be partially or completely deuterated;

[0033] The substituent for substituting the above substitutable group may be selected from a F atom and a cyano group.

[0034] Furthermore, the compound containing triazine and carbazole indole structure is selected from any one of the following structures:

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

[0041] The invention also discloses an organic electroluminescent device, comprising a cathode, an anode and a functional layer, wherein the functional layer is located between the cathode and the anode, and the functional layer contains the compound containing triazine and carbazole indole structure of the invention.

[0042] Furthermore, the functional layer includes a light-emitting layer, and the light-emitting layer contains the compound containing triazine and carbazole indole structure described in the present invention.

[0043] Furthermore, the light-emitting layer comprises a main material and a doping material, and the main material comprises the compound containing triazine and carbazole indole structure described in the present invention.

[0044] Furthermore, the light-emitting layer comprises a first host material, a second host material and a doping material, and the first host material comprises the compound containing triazine and carbazole indole structure described in the present invention.

[0045] Furthermore, the second host material is selected from the compound represented by general formula (3) or general formula (4):

[0046]

[0047] In the general formula (3) and the general formula (4), the ring A, ring B, ring C, and ring D are independently substituted or unsubstituted C6-C30 aryl groups, or substituted or unsubstituted C2-C30 heteroaryl groups;

[0048] The L a , L b Each independently represents a single bond, a substituted or unsubstituted C6-C30 arylene group, or a substituted or unsubstituted C2-C30 heteroarylene group;

[0049] Ar1 and Ar2 are independently substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted C2-C30 heteroaryl;

[0050] The substituents for replacing the above substitutable groups are selected from one or more of deuterium atoms, tritium atoms, halogen atoms, cyano groups, C1-C10 alkyl groups, C3-C10 cycloalkyl groups, C6-C30 aryl groups, and C2-C30 heteroaryl groups;

[0051] The heteroatom in the heteroaryl group may be selected from one or more of O, S, N and Si.

[0052] Furthermore, the second host material is selected from the compound represented by Formula-P1 or Formula-P2:

[0053]

[0054] In Formula-P1 and Formula-P2:

[0055] Ra and Rb are independently selected from any structure in the following Group-II:

[0056]

[0057] Any part or all of the hydrogen atoms in the structures of Formula-P1 and Formula-P2 may be substituted with deuterium.

[0058] Further, the general formula-P1 or general formula-P2 is specifically represented by any one of the following structures:

[0059]

[0060]

[0061] Compared with the prior art, the beneficial technical effects of the present invention are:

[0062] The present invention starts from the triazine and carbazole indole structure, introduces a naphthofuran group on the benzene ring (N-Ph) adjacent to the triazine, introduces a benzene ring substitution on the benzene ring connected to the triazine, and protects the triazine from the perspective of steric hindrance; when the compound containing the triazine and carbazole indole structure of the present invention is applied to an organic electroluminescent device, the life stability of the organic electroluminescent device can be enhanced, and at the same time, the voltage of the organic electroluminescent device can be reduced and the efficiency can be improved.

[0063] The compound provided by the present invention introduces deuterium atoms and is applied to the light-emitting layer to help further improve the device life.

[0064] When the compound containing triazine and carbazole indole structure described in the present invention is used in an organic electroluminescent device, the efficiency of the organic electroluminescent device can be further improved by matching with a suitable P-type material. BRIEF DESCRIPTION OF THE DRAWINGS

[0065] Figure 1 is a schematic structural diagram of the organic electroluminescent device described in this embodiment;

[0066] In the figure, 1, transparent substrate layer; 2, anode layer; 3, hole injection layer; 4, hole transport layer; 5, electron blocking layer; 6, light-emitting layer; 7, hole blocking layer; 8, electron transport layer; 9, electron injection layer; 10, cathode layer; 11, CPL layer. DETAILED DESCRIPTION

[0067] The principles and features of the present invention are described below in conjunction with the accompanying drawings and embodiments. The examples given are only used to explain the present invention and are not used to limit the scope of the present invention.

[0068] In the drawings, the sizes of layers and regions may be exaggerated for clarity. It will also be understood that when a layer or element is referred to as being "on" another layer or substrate, the layer or element may be directly on the other layer or substrate, or intervening layers may also be present. In addition, it will be understood that when a layer is referred to as being "between" two layers, the layer may be the only layer between the two layers, or one or more intervening layers may also be present.

[0069] As the substrate of the organic electroluminescent device of the present invention, any substrate commonly used in organic electroluminescent devices can be used. Examples are transparent substrates such as glass or transparent plastic substrates; opaque substrates such as silicon substrates; flexible PI film substrates. Different substrates have different mechanical strengths, thermal stability, transparency, surface smoothness, and waterproofness. Depending on the properties of the substrate, its use direction is different. In the present invention, a transparent PI film substrate is preferably used. The thickness of the substrate is not particularly limited.

[0070] Anode is formed on substrate, and anode can be transmission electrode, semi-transmission electrode or reflection electrode. When anode is transmission electrode, it can be formed using transparent metal oxide, such as indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO) or indium tin zinc oxide (ITZO) etc. When anode is semi-transmission electrode or reflection electrode, it can include Ag, Mg, Al, Pt, Pd, Au, Ni, Nd, Ir, Cr or metal mixture. Anode can have single layer structure or include two or more layers of multilayer structure. In addition, the thickness of anode layer depends on the material used, is usually 50-500nm, preferably 70-300nm, and more preferably 100-200nm.

[0071] The organic functional material layer disposed between the anode and the cathode may include, from bottom to top, a hole transport region, a light emitting layer and an electron transport region.

[0072] Examples of the hole transport region constituting the organic electroluminescent device include a hole injection layer, a hole transport layer, and an electron blocking layer.

[0073] As the material for the hole injection layer, the hole transport layer, and the electron blocking layer, any material can be selected from known related materials used for organic electroluminescent devices.

[0074] The hole injection layer contains a main organic material that can conduct holes, and also contains a P-type dopant material with a deep HOMO energy level (the corresponding LUMO energy level will also be very deep). Based on empirical summary, in order to achieve smooth injection of holes from the anode to the organic film layer, the HOMO energy level of the main organic material used in the hole injection layer that conducts holes must have certain characteristics with the P-doped material, so that the charge transfer state between the main material and the dopant material can be realized, the ohmic contact between the buffer layer and the anode can be achieved, and efficient injection from the electrode to the hole injection conduction can be achieved.

[0075] In view of the above empirical summary, for the host organic materials that conduct holes at different HOMO energy levels, different P-doped materials need to be selected to match them in order to achieve ohmic contact at the interface and improve the hole injection effect.

[0076] Therefore, in one embodiment of the present invention, in order to better inject holes, the hole injection layer further comprises a P-type doping material with charge conductivity selected from the following: WO2011073149A, EP1968131A1, EP2276085A1, EP2213662A1, EP1722602A1, EP2045848A1, DE102007031220A1, US201 The compounds disclosed in any one of WO2012095143A1, WO0181555A1, US20100102709A1, WO2009003455A1, WO2010094378A1, WO2011120709A1, US20100096600A1, DE102012209523A1, CN101728485A and WO2012095143A1, but are not limited thereto.

[0077] In the hole injection layer of the present invention, the ratio of the host organic material conducting holes to the P-type doping material is 99:1-95:5, preferably 99:1-97:3, based on mass.

[0078] The thickness of the hole injection layer of the present invention may be 5-100 nm, preferably 5-50 nm, and more preferably 5-20 nm, but the thickness is not limited to this range.

[0079] In a preferred embodiment, the hole-conducting host organic material and the hole transport layer comprise the same aromatic amine organic compound.

[0080] As the hole transport layer material of the present invention, it can be selected from the following compounds disclosed in the prior art:

[0081]

[0082]

[0083] The thickness of the hole transport layer of the present invention may be 5-200 nm, preferably 10-150 nm, but the thickness is not limited to this range.

[0084] In one embodiment of the present invention, the electron blocking layer material of the present invention may be selected from the following compounds disclosed in the prior art:

[0085]

[0086] The thickness of the electron blocking layer of the present invention may be 1-40 nm, preferably 10-40 nm, but the thickness is not limited to this range.

[0087] After forming the hole injection layer, the hole transport layer and the electron blocking layer, a corresponding light emitting layer is formed on the electron blocking layer.

[0088] The light-emitting layer may include a host material and a guest material. The host material may include the compound described above in the present invention.

[0089] The guest material of the light-emitting region of the organic electroluminescent device of the present invention may be selected from the following compounds disclosed in the prior art:

[0090]

[0091] In the light-emitting layer of the present invention, the ratio of the host material to the doping material used is 99:1-70:30, preferably 99:1-85:15 and more preferably 97:3-87:13, based on mass.

[0092] The thickness of the light-emitting layer can be adjusted to optimize the light-emitting efficiency and the driving voltage. The preferred thickness range is 5 nm to 50 nm, more preferably 10-50 nm, but the thickness is not limited to this range.

[0093] In the present invention, the electron transport region may include, from bottom to top, a hole blocking layer, an electron transport layer, and an electron injection layer disposed on the light emitting layer, but is not limited thereto.

[0094] The hole blocking layer is a layer that blocks holes injected from the anode from passing through the light-emitting layer and entering the cathode, thereby extending the life of the device and improving the performance of the device. The hole blocking layer of the present invention can be arranged on the light-emitting layer. As the hole blocking layer material of the organic electroluminescent device of the present invention, compounds with hole blocking function known in the prior art can be used, for example:

[0095]

[0096] The thickness of the hole blocking layer of the present invention may be 2-200 nm, preferably 5-150 nm, and more preferably 5-100 nm, but the thickness is not limited to this range.

[0097] The electron transport layer may be disposed on the light-emitting layer or (if present) the hole blocking layer. The electron transport layer material is a material that easily receives electrons from the cathode and transfers the received electrons to the light-emitting layer. Preferably, the material has a high electron mobility. As the electron transport layer of the organic electroluminescent device of the present invention, the electron transport layer materials for organic electroluminescent devices known in the prior art can be used, for example:

[0098]

[0099] The thickness of the electron transport layer of the present invention may be 10-80 nm, preferably 20-60 nm, and more preferably 25-45 nm, but the thickness is not limited to this range.

[0100] The electron injection layer may be disposed on the electron transport layer. The electron injection layer material is generally preferably a material having a low work function so that electrons are easily injected into the organic functional material layer. As the electron injection layer material of the organic electroluminescent device of the present invention, the electron injection layer material for organic electroluminescent devices known in the prior art can be used, for example, lithium; lithium salts such as 8-hydroxyquinoline lithium, lithium fluoride, lithium carbonate or lithium azide; or cesium salts such as cesium fluoride, cesium carbonate or cesium azide.

[0101] The thickness of the electron injection layer of the present invention may be 0.1-5 nm, preferably 0.5-3 nm, and more preferably 0.8-1.5 nm, but the thickness is not limited to this range.

[0102] The cathode may be disposed above the electron transport region. The cathode may be a transmissive electrode, a semi-transmissive electrode or a reflective electrode. When the cathode is a transmissive electrode, the cathode may include, for example, Li, Yb, Ca, LiF / Ca, LiF / Al, Al, Mg, BaF, Ba, Ag or a compound or mixture thereof; when the cathode is a semi-transmissive electrode or a reflective electrode, the cathode may include Ag, Mg, Yb, Al, Pt, Pd, Au, Ni, Nd, Ir, Cr, Li, Ca, LiF / Ca, LiF / Al, Mo, Ti or a compound or mixture thereof, but is not limited thereto. The thickness of the cathode depends on the material used, and is typically 10-50 nm, preferably 15-20 nm.

[0103] In order to improve the light extraction efficiency of the organic electroluminescent device, a light extraction layer (i.e., CPL layer, also called covering layer) may be added on the cathode of the device. Any material known in the art may be used as the CPL layer material, for example:

[0104]

[0105] The thickness of the CPL cover layer is typically 5-300 nm, preferably 20-100 nm and more preferably 40-80 nm.

[0106] The organic electroluminescent device of the present invention may further include an encapsulation structure. The encapsulation structure may be a protective structure that prevents foreign substances such as moisture and oxygen from entering the organic layer of the organic electroluminescent device. The encapsulation structure may be, for example, a can, such as a glass can or a metal can; or a thin film covering the entire surface of the organic layer.

[0107] The method for preparing the organic electroluminescent device of the present invention comprises laminating an anode, a hole injection layer, a hole transport layer, an electron blocking layer, an organic film layer, an electron transport layer, an electron injection layer and a cathode successively on a substrate, and optionally a covering layer. In this regard, vacuum deposition, vacuum evaporation, spin coating, casting, LB method, inkjet printing, laser printing or LITI methods can be used, but are not limited thereto. In the present invention, it is preferred to use a vacuum evaporation method to form the various layers. Those skilled in the art can conventionally select various process conditions in the vacuum evaporation method according to actual needs.

[0108] The raw materials and intermediates involved in the synthesis examples of the present invention can be purchased from the market or prepared by conventional preparation methods in the art.

[0109] Synthesis Example:

[0110] The raw materials and intermediates involved in the synthesis examples of the present invention can be purchased from the market or prepared by conventional preparation methods in the art.

[0111] Example 1

[0112]

[0113] Synthesis of raw material-3:

[0114] Add raw material-1 (15.38 g, 60.0 mmol), raw material-2 (15.74 g, 60.0 mmol), cesium carbonate (58.65 g, 180.0 mmol), and DMF (350 mL) into the bottle in sequence, replace nitrogen, stir at 120°C overnight, cool down after the reaction, add ethyl acetate to dilute the reaction solution, filter, wash the organic phase with saturated brine, dry over anhydrous sodium sulfate, and distill under reduced pressure to remove part of the solvent, then stir and add petroleum ether to precipitate solids, filter and dry to obtain raw material-3, LC-MS: measured value: 499.14 ([M+H]+), theoretical value: 498.17.

[0115] Synthesis of compound 1:

[0116] Add raw material-3 (7.48 g, 15.0 mmol) and DMF (150 mL) into the bottle, protect with nitrogen, cool with ice water, add sodium hydride (0.54 g, 22.5 mmol, 60%) into the bottle, react for half an hour, add raw material-4 (5.16 g, 15.0 mmol), then stir at room temperature overnight, add ethyl acetate to dilute the reaction solution, wash the reaction solution with saturated brine, filter, and separate and purify the crude product by silica gel column chromatography to obtain compound 1.

[0117] LC-MS: Measured value: 806.45 ([M+H]+), theoretical value: 805.28. Elemental analysis structure: C 57 H 35 N5O, tested value: C, 85.01; H, 4.42; N, 8.73, theoretical value: C, 84.95; H, 4.38; N, 8.69.

[0118] Example 2

[0119]

[0120] The synthesis of compound 2 was based on the synthesis of compound 1, except that raw material-2a was used instead of raw material-3;

[0121] LC-MS: Measured value: 806.34 ([M+H]+), Calculated value: 805.28. Elemental analysis structure C 57 H 35 N5O, tested value: C, 84.92; H, 4.44; N, 8.63; theoretical value: C, 84.95; H, 4.38; N, 8.69.

[0122] Example 3

[0123]

[0124] The synthesis of starting material-3b referred to the synthesis of starting material-3, except that starting material-3a was used to replace starting material-2; LC-MS: found: 499.25 ([M+H]+), theoretical: 498.17.

[0125] The synthesis of compound 37 was carried out by referring to the synthesis of compound 1, except that raw material-3b was used to replace raw material-3;

[0126] LC-MS: Measured value: 806.27 ([M+H]+), Calculated value: 805.28. Elemental analysis structure C 57 H 35 N5O, tested value: C, 84.97; H, 4.36; N, 8.59; theoretical value: C, 84.95; H, 4.38; N, 8.69.

[0127] Example 4

[0128]

[0129] Synthesis of raw material 4a: Add raw material-5 (6.84g, 30.0mmol), raw material-6g (5.25, 30.0mmol), 1,4-dioxane / water (50mL / 10mL), potassium carbonate (13.82g, 100.0mmol) and Pd(PPh3)4 (1.16g, 1.0mmol) to a bottle in sequence, protect with nitrogen, stir at 80℃ for 12h, cool to room temperature, evaporate the solvent, dilute with ethyl acetate, wash with saturated brine, dry with anhydrous Na2SO4, filter, concentrate the filtrate under reduced pressure and separate by column chromatography to obtain raw material-4a. LC-MS: measured value: 279.11, theoretical value: 278.06.

[0130]

[0131] The synthesis of starting material-4b referred to the synthesis of starting material-3, except that starting material-2 was replaced by starting material-4a; LC-MS: found: 515.22 ([M+H]+), theoretical value: 514.15.

[0132] The synthesis of compound-63 was carried out by referring to the synthesis of compound-1, except that raw material-4b was used instead of raw material-3;

[0133] LC-MS: Measured value: 822.38 ([M+H]+), Calculated value: 821.26. Elemental analysis structure C 57 H 35 N5S, tested value: C, 83.36; H, 4.33; N, 8.50; S, 3.95; theoretical value: C, 83.29; H, 4.29; N, 8.52; S, 3.90.

[0134] Example 5

[0135]

[0136] The synthesis of starting material-5c refers to the synthesis of starting material-4a, except that starting material 5a is used instead of starting material 5, and starting material 5b is used instead of starting material 6. LC-MS: Measured value: 270.15 ([M+H]+), theoretical value: 269.12.

[0137] The synthesis of starting material 5d was based on the synthesis of starting material 4b, except that starting material 5c was used instead of starting material 4a. LC-MS: Measured value: 506.36 ([M+H]+), Calculated value: 505.22.

[0138] The synthesis of compound 101 was based on the synthesis of compound 1, except that raw material-5d was used instead of raw material-3;

[0139] LC-MS: Measured value: 813.36 ([M+H]+), Calculated value: 812.33. Elemental analysis structure C 57 H 28 D7N5O, tested value: C, 84.27; H, 5.11; N, 8.65; theoretical value: C, 84.21; H, 5.21; N, 8.61.

[0140] Example 6

[0141]

[0142] The synthesis of raw material-6c referred to the synthesis of raw material-3, except that raw material-1 was replaced by raw material-6a, and raw material-2 was replaced by raw material-6b; LC-MS: measured value: 687.14 ([M+H]+), theoretical value: 686.11.

[0143] Synthesis of raw material-6d:

[0144] Raw material-6c (85.0 g, 0.124 mol), THF (800 mL), ethanol (600 mL), water (600 mL) and ammonium chloride (66.12 g, 1.236 mol) were added to the bottle in sequence, and then zinc powder (40.4 g, 0.618 mol) was added, and the mixture was stirred at 80°C for 24 hours under nitrogen flow protection. After the reaction was completed, the reaction body was cooled to room temperature, filtered through diatomaceous earth, the filtrate was separated, the organic phase was washed with saturated brine, dried over anhydrous sodium sulfate, filtered, concentrated and purified by column chromatography to obtain raw material-6d; LC-MS: measured value: 657.12 ([M+H]+), theoretical value: 656.13.

[0145] Synthesis of raw material-6e:

[0146] Add raw material-6d (62.08 g, 94.4 mmol) dissolved in 1,4-dioxane / water = 1000 mL / 200 mL, phenylboronic acid (17.27 g, 141.6 mmol), sodium carbonate (30.02 g, 283.2 mmol) and Pd(dppf)Cl2 dichloromethane complex (7.62 g, 9.4 mmol) to the bottle in sequence, and then heat to 90°C and stir for 3 h under nitrogen protection. After the reaction is completed, cool to room temperature, remove the solvent, dilute the crude product with dichloromethane (800 mL), wash with water, wash the organic phase with saturated brine, dry with anhydrous Na2SO4, filter, concentrate and purify by column chromatography to obtain raw material-6e. LC-MS: Measured value: 655.20 ([M+H]+), theoretical value: 654.25.

[0147] Synthesis of raw material-6f:

[0148] Under nitrogen protection, add the raw material-6e (39.09 g, 59.7 mmol) to a mixed solution of acetonitrile (800 mL), concentrated hydrochloric acid (200 mL) and water (200 mL) in the bottle at 0°C, add a solution of sodium nitrite (4.94 g, 71.6 mol) in water (50 mL) dropwise, stir and react at 0°C for 1 hour, then add a solution of potassium iodide (99.1 g, 0.597 mol; water 250 mL), and continue to react at 0°C for 1 hour. After the reaction is completed, the reaction solution is extracted with dichloromethane, the organic phase is washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and the filtrate is concentrated under reduced pressure and purified by column chromatography to obtain the raw material-6f. LC-MS: Measured value: 766.13 ([M+H]+), theoretical value: 765.14.

[0149] Synthesis of compound 108:

[0150] Raw material-6f (26.86 g, 35.1 mmol), 1,4-dioxane / water (500 mL / 100 mL), raw material-6g (7.38 g, 34.8 mmol), potassium carbonate (14.55 g, 105.3 mmol) and Pd(dppf)Cl2 dichloromethane complex (2.84 g, 3.5 mmol) were added to the reaction system in sequence, and then heated to 60°C and stirred for 3 hours. After the reaction, the temperature was lowered to room temperature. The solvent was evaporated, the crude product was diluted with dichloromethane, washed with water, the organic phase was washed with saturated brine, dried over anhydrous Na2SO4, filtered, and the filtrate was concentrated under reduced pressure and purified by column chromatography to obtain crude compound 108.

[0151] LC-MS: Measured value: 806.30 ([M+H]+), Calculated value: 805.28. Elemental analysis structure C 57 H 35 N5O, tested value: C, 84.92; H, 4.41; N, 8.66; theoretical value: C, 84.95; H, 4.38; N, 8.69.

[0152] Example 7

[0153]

[0154] The synthesis of starting material-7a refers to the synthesis of starting material-6e: the difference is that starting material-6g is used instead of phenylboronic acid. LC-MS: Measured value: 745.33 ([M+H]+), theoretical value: 744.26.

[0155] The synthesis of starting material-7b was similar to that of starting material-6f except that starting material-7a was used instead of starting material-6d. LC-MS: Measured value: 856.16 ([M+H]+), theoretical value: 855.15.

[0156] The synthesis of compound 116 was based on the synthesis of compound 108, except that phenylboronic acid was used instead of raw material -6g. LC-MS: Measured value: 806.37 ([M+H]+), theoretical value: 805.28. Elemental analysis structure C 57 H 35 N5O, tested value: C, 85.06; H, 4.40; N, 8.75; theoretical value: C, 84.95; H, 4.38; N, 8.69.

[0157] Example 8

[0158]

[0159] The synthesis of starting material-8b referred to the synthesis of starting material-4b, except that starting material-8a was used to replace starting material-1; LC-MS: found: 525.20 ([M+H]+), theoretical: 524.21.

[0160] The synthesis of compound 167 was based on the synthesis of compound 63, except that raw material 8b was used instead of raw material 4b, and raw material 8c was used instead of raw material 4; LC-MS: measured value: 846.45 ([M+H]+), theoretical value: 845.41. Elemental analysis structure C 57 H 11 D 24 N5S, tested value: C, 80.95; H, 7.22; N, 8.22; S, 3.85; theoretical value: C, 80.91; H, 7.02; N, 8.28; S, 3.79.

[0161] Device Example 1

[0162] like Figure 1As shown, the transparent substrate layer 1 is a transparent PI film, and the anode layer 2 (ITO (15nm) / Ag (150nm) / ITO (15nm)) is washed, that is, the cleaning agent washing (SemiClean M-L20), pure water washing, drying, and then ultraviolet-ozone washing are performed in sequence to remove organic residues on the surface of the anode layer 2. On the anode layer 2 after the above washing, HT-1 and P-1 are evaporated on the anode layer 2 using a vacuum evaporation device as a hole injection layer 3, with a film thickness of 10nm, and a mass ratio of HT-1 to P-1 of 97:3. Then HT-1 is evaporated as a hole transport layer 4 with a thickness of 130nm. Subsequently, EB-1 is evaporated as an electron blocking layer 5 with a thickness of 35nm. After the evaporation of the electron blocking layer 5 material is completed, the light-emitting layer 6 of the OLED light-emitting device is prepared, and its structure includes the compound 1 and GH-19 used in the OLED light-emitting layer 6 as the main materials, GD-1 as the doping material, the doping ratio of the doping material is 6% (mass ratio), and the thickness of the light-emitting layer is 40nm. After the above-mentioned light-emitting layer 6, HB-1 is vacuum-evaporated to a thickness of 5nm, and this layer is the hole blocking layer 7. After the above-mentioned hole blocking layer 7, ET-1 and Liq are vacuum-evaporated to a mass ratio of 1:1, and the film thickness is 35nm. This layer is the electron transport layer 8. On the electron transport layer 8, a LiF layer with a film thickness of 1nm is prepared by a vacuum evaporation device. This layer is the electron injection layer 9. On the electron injection layer 9, a Mg:Ag electrode layer with a film thickness of 15nm is prepared by a vacuum evaporation device. The mass ratio of Mg and Ag is 1:9. This layer is used as the cathode layer 10. On the cathode layer 10, CP-1 was vacuum evaporated to form the CPL layer 11 with a thickness of 70 nm to obtain an organic electroluminescent device.

[0163] The molecular structure formula of the relevant materials is shown below:

[0164]

[0165]

[0166] After the OLED light-emitting device is completed as described above, the anode and cathode are connected with a known driving circuit, and the voltage, current efficiency and life of the device are measured. Device Examples 2-9 and Comparative Examples 1-6 prepared by the same method are shown in Table 2; the difference is that different N-type host materials are used to replace compound 1, and different P-type hosts are used to replace GH-19. The test results of the voltage, current efficiency and life of the obtained device are shown in Table 3.

[0167] Table 2

[0168]

[0169]

[0170]

[0171] Table 3

[0172]

[0173] Note: Voltage and current efficiency are calculated at a current density of 10 mA / cm 2 The test was conducted under the following conditions: IVL (current-voltage-luminance) test system (Suzhou Fushida Scientific Instrument Co., Ltd.); the life test system was EAS-62C OLED device life tester from Japan System Technology Co., Ltd.; LT95 refers to the life test under 20mA / cm 2 The time it takes for the device brightness to decay to 95% under the condition of .

[0174] It can be seen from the device data results in Table 3 that compared with Comparative Examples 1 to 6, when Examples 1 to 8 are applied to devices, the life performance of the compounds of the present invention is significantly improved, and the efficiency and voltage are significantly improved.

[0175] From the device life of compound 2 and compound 101, it can be found that deuteration can significantly improve the life of the device. Compound 63 exhibits a lower voltage in the device. Deuteration studies have shown that the stability of the life of compound 167 has been significantly improved by comparing device example 4 and device example 8. Comparing device example 6 and device example 9, after replacing the P-type material, its efficiency has been further significantly improved.

[0176] In summary, the above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A compound containing triazine and carbazole indole structure, characterized in that: The structure of the compound containing triazine and carbazole indole structure is shown in general formula (1) or general formula (2): In the general formula (1) and the general formula (2), X represents S or O; A2 and A3 independently represent substituted or unsubstituted phenyl groups, hydrogen atoms; A4 and A5 independently represent substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, cyano, or hydrogen atom, wherein A4 and A5 represent that the number of hydrogen atoms is 0 or 1; The hydrogen atoms in the triazine and carbazole indole structure-containing compound may be partially or completely deuterated; The substituent for substituting the above substitutable group may be selected from a F atom and a cyano group.

2. A compound containing triazine and carbazole indole structure according to claim 1, characterized in that: The structure of the compound containing triazine and carbazole indole structure is selected from the following structural formula: In general formula-2a to general formula-2h, A2 and A3 are independently represented by phenyl or hydrogen atom; A4 and A5 independently represent phenyl, biphenyl, cyano, or hydrogen atom, wherein the number of hydrogen atoms represented by A4 and A5 is 0 or 1. The hydrogen atoms in the triazine and carbazole indole structure-containing compound may be partially or completely deuterated.

3. A compound containing triazine and carbazole indole structure according to claim 1, characterized in that: The structure of the compound containing triazine and carbazole indole structure is selected from the following structural formula: Wherein, X represents S or O; A2 and A3 independently represent substituted or unsubstituted phenyl groups, hydrogen atoms; A4 and A5 independently represent substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, cyano, or hydrogen atom, wherein A4 and A5 represent that the number of hydrogen atoms is 0 or 1; The hydrogen atoms in the triazine and carbazole indole structure-containing compound may be partially or completely deuterated; The substituent for substituting the above substitutable group may be selected from a F atom and a cyano group.

4. A compound containing triazine and carbazole indole structure according to claim 1, characterized in that: The structure of the compound containing triazine and carbazole indole structure is selected from the following structural formula: Wherein, X represents S or O; A2 and A3 independently represent substituted or unsubstituted phenyl groups, hydrogen atoms; A4 and A5 independently represent substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, cyano, or hydrogen atom, wherein A4 and A5 represent that the number of hydrogen atoms is 0 or 1; The hydrogen atoms in the triazine and carbazole indole structure-containing compound may be partially or completely deuterated; The substituent for substituting the above substitutable group may be selected from a F atom and a cyano group.

5. The compound containing triazine and carbazole indole structure according to claim 1, characterized in that: The compound containing triazine and carbazole indole structure is selected from any one of the following structures:

6. An organic electroluminescent device comprising a cathode, an anode and a functional layer, wherein the functional layer is located between the cathode and the anode, characterized in that: The functional layer contains the compound containing triazine and carbazolindole structure according to any one of claims 1 to 5. Preferably, the functional layer includes a light-emitting layer, and the light-emitting layer contains the compound containing triazine and carbazole indole structure according to any one of claims 1 to 5. Preferably, the light-emitting layer comprises a host material and a dopant material, and the host material comprises the compound containing triazine and carbazole indole structure according to any one of claims 1 to 5.

7. An organic electroluminescent device according to claim 6, characterized in that: The light-emitting layer comprises a first host material, a second host material and a doping material, wherein the first host material comprises the compound containing triazine and carbazole indole structure according to any one of claims 1 to 5.

8. An organic electroluminescent device according to claim 7, characterized in that: The second host material is selected from the compounds represented by general formula (3) or general formula (4): In the general formula (3) and the general formula (4), the ring A, ring B, ring C, and ring D are independently substituted or unsubstituted C6-C30 aryl groups, or substituted or unsubstituted C2-C30 heteroaryl groups; The L a , L b Each independently represents a single bond, a substituted or unsubstituted C6-C30 arylene group, or a substituted or unsubstituted C2-C30 heteroarylene group; Ar1 and Ar2 are independently substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted C2-C30 heteroaryl; The substituents for replacing the above substitutable groups are selected from one or more of deuterium atoms, tritium atoms, halogen atoms, cyano groups, C1-C10 alkyl groups, C3-C10 cycloalkyl groups, C6-C30 aryl groups, and C2-C30 heteroaryl groups; The heteroatom in the heteroaryl group may be selected from one or more of O, S, N and Si.

9. An organic electroluminescent device according to claim 7, characterized in that: The second host material is selected from the compound represented by Formula-P1 or Formula-P2: In general formula-P1 and general formula-P2: Ra and Rb are independently selected from any structure in the following Group-II: Any part or all of the hydrogen atoms in the structures of Formula-P1 and Formula-P2 may be substituted with deuterium.

10. An organic electroluminescent device according to claim 9, characterized in that: The general formula-P1 or general formula-P2 is specifically represented by any one of the following structures:

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