An organic electroluminescent material and organic electroluminescent device based on triazolopyridine

Abstract

The present invention relates to the field of applied optoelectronic materials and discloses a triazolopyridine-based organic electroluminescent material and device. This organic electroluminescent material, through the fine-tuning of triazolopyridine groups with specific functional groups, provides an electron transport material and luminescent host material with excellent overall performance. This effectively addresses the technical issues of mismatched electron and hole transport rates and poor stability in existing technologies, as well as efficiency roll-off and impure light color in green light host devices. This improves the device's overall performance in terms of driving voltage, efficiency, light color, thermal stability, and lifespan, accelerating the industrialization of optoelectronic materials.

Description

[0001] This invention is a divisional application with an application date of August 22, 2019, application number 2019107795498, and the name of the invention being "An organic electroluminescent material and organic electroluminescent device based on triazolopyridine". Technical Field

[0002] The present invention belongs to the field of applied science and technology of optoelectronic materials, and in particular relates to an organic electroluminescent material and an organic electroluminescent device based on triazolopyridine. Background Art

[0003] Organic light-emitting diodes (OLEDs) have become one of the most promising new display technologies due to their advantages such as self-luminescence, low driving voltage, high contrast, wide viewing angle, and wide applicable temperature range. Through the unremitting efforts of scientific researchers and enterprises, researchers have developed many high-performance luminescent materials and auxiliary electrode materials. However, commonly used hole transport materials such as N,N'-dinaphthyl-N,N'-diphenyl-benzidine (NPB) and N,N'-di(3-methylphenyl)-N,N'-diphenyl-1,1-diphenyl-4,4-diamine (TPD) have a hole transport rate of up to 10 -2 cm 2 V -1 S -1 The more widely used 8-hydroxyquinoline aluminum (Alq 3 ) is still two orders of magnitude behind. Currently, the electron transfer rate of most electron transport materials is only 10 -4 ~10 -6 cm 2 V -1 S -1In other words, the device's requirement for balanced injection is not met. In organic electroluminescent devices, the carrier mobility of holes in most materials is typically hundreds of times that of electrons. This mismatch in migration speeds means that the two carriers are highly likely to not recombine in the light-emitting layer, resulting in reduced device optoelectronic performance, such as brightness, luminous efficiency, and color purity. This also increases leakage current, causing device heating and shortening device life. Therefore, matching the migration speeds of the two carriers—in other words, increasing electron mobility and effectively confining holes in the light-emitting layer—is key to improving device performance. Nitrogen-containing heterocyclic compounds, such as triazine rings and benzimidazoles, have been developed as electron transport materials for use in organic light-emitting diodes to enhance the device's electron transport capacity and thus improve its optoelectronic performance. However, reported triazine, benzimidazole, and even benzothiazole compounds have largely been prepared by chemically modifying substituents to alter their conjugated structures and adjust the HOMO and LUMO energy levels to create electron-transporting hole-blocking materials with appropriate energy levels. This results in varying electron transport and hole-blocking capabilities in many materials, leading to significant differences in device performance. Therefore, developing higher-speed electron transport materials is of great significance to improving the performance of the entire device.

[0004] In addition, in OLED devices, the design and combination of the light-emitting layer plays a key role in the performance of the device, which directly determines the luminous efficiency and lifespan of the device. The excited state lifetime of aromatic triazine-based light-emitting materials is relatively long, and severe efficiency roll-off is often observed. Benzimidazole, as a good electron transport group, is widely used in host materials and electron transport materials. However, its stability still does not match the actual application requirements of the device. Therefore, the development of new material systems with high luminous efficiency, low starting voltage, good film forming properties, long life and good stability is an important research direction in this field. Summary of the Invention

[0005] The purpose of the present invention is to provide an organic electroluminescent material and device based on triazolopyridine, which can solve the problem that the photoelectric performance of the current OLED device is degraded due to the mismatch of electron / hole migration speed in the electron transport layer, and the problem that the device efficiency roll-off of phosphorescent devices at high current density is serious, thereby making the OLED device have excellent comprehensive performance in terms of efficiency, thermal stability, light color, life, etc.

[0006] The first aspect of the present invention provides an electronic organic electroluminescent material based on triazolopyridine. The compound of the organic electroluminescent material is formed by bonding a triazolopyridine group to a fused ring structure, and its general structural formula is shown in Formula II:

[0007]

[0008] wherein R6-R9 are independently selected from the group consisting of hydrogen, cyano, fluorine, deuterium, nitro, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, and phenyl which is unsubstituted or substituted with cyano, fluorine, deuterium, nitro, C1-C6 alkyl, C1-C6 alkoxy, or C1-C6 alkylthio;

[0009] Ar4 and Ar5 are each independently empty or a heterobenzene ring, and the heterobenzene ring shares a carbon-carbon chemical bond with the adjacent ring to form a fused structure;

[0010] X is independently C, N or C(R 29 ), and at least one X is N, the X to which L2 or L0 is connected is C, and the two Xs sharing a carbon-carbon chemical bond with Ar4 or Ar5 are C;

[0011] Wherein, L0 and L2 are each independently: a single bond, an unsubstituted or substituted phenylene group by cyano, fluorine, nitro, or C1-C6 alkyl, an unsubstituted or substituted biphenylene group by cyano, fluorine, nitro, or C1-C6 alkyl, or an unsubstituted or substituted naphthylene group by cyano, fluorine, nitro, or C1-C6 alkyl;

[0012] R 29 Selected from: hydrogen, cyano, fluorine, deuterium, nitro, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, unsubstituted or substituted C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio 30 Aryl, unsubstituted or substituted by cyano, fluorine, deuterium, nitro, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio 30 heteroaryl, unsubstituted or substituted by cyano, fluorine, deuterium, nitro, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio 30 aromatic amine groups;

[0013] R0 is independently selected from: hydrogen, fluorine, deuterium, nitro, cyano, hydroxyl, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, C1-C6 silyl, C1-C6 alkyl, unsubstituted or substituted by deuterium, fluorine, cyano, nitro, C1-C6 alkyl 30 Aryl, unsubstituted or substituted by deuterium, fluorine, cyano, nitro, C1-C6 alkyl 30 Heteroaryl, unsubstituted or substituted by deuterium, fluorine, cyano, nitro, C1-C6 alkyl 30 Aromatic amino groups, unsubstituted or substituted by deuterium, fluorine, cyano, nitro, C1-C6 alkyl 30an aromatic silicon group, or a C6-C6 alkyl group that is unsubstituted or substituted with deuterium, fluorine, cyano, nitro, or C1-C6 alkyl 30 of aromatic boron.

[0014] Furthermore, Formula II can be further represented by the following compounds (B1), (B2), (B3), (B4), (B5), and (B6):

[0015]

[0016] Among them, R 31 、R 32 Each is independently selected from the group consisting of hydrogen, cyano, fluorine, deuterium, nitro, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, and phenyl which is unsubstituted or substituted by cyano, fluorine, deuterium, nitro, C1-C6 alkyl, C1-C6 alkoxy, or C1-C6 alkylthio.

[0017] Furthermore, the R0 is selected from the following groups:

[0018]

[0019]

[0020] Preferably, the organic electroluminescent material represented by formula II is selected from the compounds represented by any one of the following structural formulas:

[0021]

[0022]

[0023]

[0024]

[0025] The organic electroluminescent material represented by Formula II of the present invention uses diaza-fused aromatic ring groups with planar, rigid, electron-deficient chemical structures such as phenanthroline, azaanthracene, and quinazoline as high-carrier transmission channels, and electron-deficient triazolopyridine groups bonded to electron-donating groups such as anthracene, fluorene, dibenzopentacyclic ring, carbazole, and aromatic amine on the periphery to form a series of novel luminescent host materials with more balanced hole and electron carriers, thereby solving the problem of severe device efficiency roll-off in phosphorescent devices at high current density. Compared with the compounds in the prior art in which non-nitrogen fused aromatic groups are used as bridging groups, the organic electroluminescent material provided by the present invention has a higher electron migration rate due to the diaza fused aromatic group as an electron-deficient high-carrier transport channel, which cooperates with the electron-deficient triazolopyridine group, thereby maintaining the transmission balance of holes and electrons in the material and avoiding the device efficiency drop caused by triplet exciton annihilation to a certain extent; compared with the compounds not containing triazolopyridine groups, the diaza fused aromatic ring as a bridging group has a better rigid planar structure that reduces the triplet energy level of the material, making it an excellent green light host material. The triazolopyridine group at the end of the organic electroluminescent material has a special N The N bond exhibits a blue-shift characteristic of light color, so that the organic electroluminescent material provided by the present invention can emit more saturated and pure green light when applied to green phosphorescent devices. Compared with the compounds formed by modifying the six-membered ring of triazolopyridine, the organic electroluminescent material provided by the present invention is bonded to the electron-donating site of a large conjugated aromatic group such as anthracene, fluorene, carbazole, and aromatic amine through a rigid coplanar bridging group on the five-membered heterocyclic ring with the strongest electron deficiency of the triazolopyridine group, which is beneficial to the spatial separation of the HOMO orbital and the LUMO orbital, avoiding internal charge transfer of the molecule. At the same time, it exhibits a smaller molecular distance and a compact arrangement, so that the compound of the present invention has higher thermal stability and non-crystalline properties. Therefore, compared with traditional DPEPO and compounds disclosed in the prior art, due to the subtle molecular configuration and group selection, the compound of the present invention has a more balanced hole-electron transfer rate, solving the problem of device efficiency roll-off caused by carrier imbalance and triplet exciton annihilation. In addition, due to the subtle regulation of the group structure and structure of the compound's blue shift in light color, the compound of the present invention has higher thermal stability and non-crystalline properties, becoming a deep green light emitting material with significant improvements in comprehensive performance such as luminous efficiency, thermal stability, light color and lifespan.

[0026] In addition, since the five-membered heterocyclic ring with the strongest electron deficiency of the triazolopyridine group is bonded to the electron-donating site of a large conjugated aromatic group such as anthracene, fluorene, carbazole, and aromatic amine through a rigid coplanar bridging group, the organic electroluminescent material represented by Formula II of the present invention exhibits a smaller molecular distance and a tight arrangement, thereby having a higher refractive index, making it an ideal optical cover layer for preparing a top-emitting device.

[0027] The third aspect of the present invention provides an organic electroluminescent device comprising a cathode, an electron transport layer, a light-emitting layer, a hole transport layer and an anode, or comprising an optical cover layer, a cathode, an electron transport layer, a light-emitting layer, a hole transport layer and an anode, wherein the light-emitting layer and / or the optical cover layer comprises the organic electroluminescent material represented by the above formula II.

[0028] Furthermore, the light-emitting layer is composed of a light-emitting host and a light-emitting guest, and the light-emitting host comprises the organic electroluminescent material represented by the above formula II. DETAILED DESCRIPTION

[0029] It should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention, and are not intended to limit the present invention.

[0030] Synthesis of intermediate 2-bromo-[1,2,4]triazolo[1,5-a]pyridine:

[0031]

[0032] S1. In a 100 mL reaction flask, pyridin-2-amine (1.88 g, 20 mmol), ethyl isothiocyanate (2.89 g, 22 mmol), and 50 mL of epoxy bicyclic solvent were added. The reaction was stirred at room temperature for 10-14 h, and the reaction solution was concentrated. Then, 75 mL of a 1:1 methanol / ethanol mixed solvent, N,N-diethylethylamine (4.05 g, 40 mmol), and hydroxylamine hydrochloride (4.17 g, 60 mmol) were added to the reaction solution. The reaction was carried out at 60°C for 2 h. After cooling to room temperature, the mixture was crystallized and filtered. The filter cake was the crude product of [1,2,4]triazolo[1,5-a]pyridin-2-amine.

[0033] S2. In a 250 mL reaction flask, add the above-mentioned [1,2,4]triazole[1,5-a]pyridine-2-amine, copper bromide (6.7 g, 30 mmol), and 100 mL of acetonitrile. Cool to 0°C under a nitrogen atmosphere, add isobutyl nitrite (3.09 g, 30 mmol), stir for 1 hour, then return to room temperature and continue stirring for 0.5 hour. After TLC monitoring shows that there is almost no raw material remaining, add 1 mol / L aqueous hydrochloric acid solution to adjust the pH to 1, extract with dichloromethane, dry with magnesium sulfate, filter, concentrate the filtrate, and separate by column chromatography to obtain 3.08 g of intermediate 2-bromo-[1,2,4]triazole[1,5-a]pyridine with a yield of 78%.

[0034] Mass spectrometer MALDI-TOF-MS (m / z) = 198.0176, theoretical molecular weight: 198.0230.

[0035] Synthesis of intermediate 2-(4-bromophenyl)-[1,2,4]triazolo[1,5-a]pyridine:

[0036]

[0037] To a 100 mL reaction flask, 2-bromo-[1,2,4]triazolo[1,5-a]pyridine (1.98 g, 10 mmol), (4-bromophenyl)boric acid (2.40 g, 12 mmol), potassium carbonate (2.76 g, 20 mmol), 30 mL of toluene, 15 mL of water and 15 mL of ethanol were added. Under a nitrogen atmosphere, tetrakis(triphenylphosphine)palladium (0.04 g, 0.03 mmol) was added, and the temperature was raised to 85 ° C. The reaction was carried out for 10-24 h. After liquid phase monitoring, almost no raw materials remained, heating was stopped, and the mixture was cooled to room temperature, washed with water, filtered, and the filtrate was concentrated. The filtrate was slurried twice with ethanol together with the filter cake to obtain 2.40 g of the intermediate 2-(4-bromophenyl)-[1,2,4]triazolo[1,5-a]pyridine with a yield of 88%. Mass spectrometer MALDI-TOF-MS (m / z) = 274.1204, theoretical molecular weight: 274.1210;

[0038] The intermediate 2-(3-bromophenyl)-[1,2,4]triazolo[1,5-a]pyridine was prepared by essentially the same method as the intermediate 2-(4-bromophenyl)-[1,2,4]triazolo[1,5-a]pyridine, except that (4-bromophenyl)boronic acid (2.40 g, 12 mmol) was replaced with (3-bromophenyl)boronic acid (2.40 g, 12 mmol).

[0039] According to the synthesis of the synthetic intermediate 2-(4-bromophenyl)-[1,2,4]triazolo[1,5-a]pyridine, the following can be obtained by using the same method (same reaction molar ratio and reaction conditions):

[0040]

[0041] Synthesis Example 1: Synthesis of Compound (1-2)

[0042]

[0043] S1. In a 100 mL reaction flask, 1,4-dibromonaphthalene (2.86 g, 10 mmol) and 50 mL of dry tetrahydrofuran solution were added, and the temperature was lowered to -78°C. Under a nitrogen atmosphere, 8 mL of 2.5 M n-butyllithium in tetrahydrofuran solution was added dropwise, and the reaction was maintained at -78°C for 1-2 h. Triisopropyl borate (22 mmol, 5.08 mL) was then added dropwise. After the addition was complete, the temperature was raised to room temperature. After 8 h, dilute hydrochloric acid was added dropwise to quench the reaction. The tetrahydrofuran was removed by distillation under reduced pressure, and the mixture was dissolved in dichloromethane, washed with water, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated and slurried with ethanol 1-2 times to obtain 1.88 g of naphthalene-1,4-diylboronic acid (yield 87%).

[0044] S2. To a 100 mL reaction flask, add the above-mentioned naphthalene-1,4-diylboronic acid (1.08 g, 5 mmol), 2-(4-bromophenyl)-[1,2,4]triazolo[1,5-a]pyridine (3.29 g, 12 mmol), potassium carbonate (1.38 g, 10 mmol), 30 mL of toluene, 15 mL of water and 15 mL of ethanol. Under a nitrogen atmosphere, add tetrakis(triphenylphosphine)palladium (0.02 g, 0.015 mmol). Heat to 85°C and react for 10-24 h. Liquid phase monitoring shows that there is almost no residual raw material. Stop heating, cool to room temperature, wash with water, filter, concentrate the filtrate, and separate it together with the filter cake by column chromatography using a 1:10 eluent of dichloromethane: petroleum ether, then concentrate and dry to obtain 1.95 g of the target compound (1-2) with a yield of 76%.

[0045] Mass spectrometer MALDI-TOF-MS (m / z) = 514.5932, theoretical molecular weight: 514.5920; elemental analysis: theoretical value: C 34 H 22 N6 (%): C79.36; H4.31; N16.33; measured value: C79.35; H4.30; N16.35.

[0046] Synthesis Example 2: Synthesis of Compound (1-6)

[0047] In Synthesis Example 1, 1,4-dibromonaphthalene (2.86 g, 10 mmol) was replaced with 2,6-dibromonaphthalene (2.86 g, 10 mmol), and 2-(4-bromophenyl)-[1,2,4]triazolo[1,5-a]pyridine (3.29 g, 12 mmol) was replaced with 2-(3-bromophenyl)-[1,2,4]triazolo[1,5-a]pyridine (3.29 g, 12 mmol). The remaining synthesis process was essentially the same as in Synthesis Example 1 (same reaction molar ratio and reaction conditions) to obtain 2.00 g of the target compound (1-6) in a yield of 78%. Mass spectrometry: MALDI-TOF-MS (m / z) = 514.5911, theoretical molecular weight: 514.5920; elemental analysis: theoretical value: C 34 H 22 N6 (%): C79.36; H4.31; N16.33; measured value: C79.35; H4.33; N16.32.

[0048] Synthesis Example 3: Synthesis of Compound (1-9)

[0049]

[0050] S1. In a 100 mL reaction flask, 1,4-dibromonaphthalene (5.72 g, 20 mmol) and 50 mL of dry tetrahydrofuran solution were added, and the temperature was lowered to -78°C. Under a nitrogen atmosphere, 16 mL of 2.5 M n-butyllithium in tetrahydrofuran solution was added dropwise, and the reaction was maintained at -78°C for 1-2 h. Triisopropyl borate (44 mmol, 10.16 mL) was then added dropwise. After the addition was complete, the temperature was raised to room temperature. After 8 h, dilute hydrochloric acid was added dropwise to quench the reaction. The tetrahydrofuran was removed by distillation under reduced pressure, and the mixture was dissolved in dichloromethane, washed with water, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated and slurried with ethanol 1-2 times to obtain 3.80 g of naphthalene-1,4-diyldiboronic acid with a yield of 88%;

[0051] S2. To a 100 mL reaction flask, the above-mentioned naphthalene-1,4-diyldiboronic acid (3.24 g, 15 mmol), 2-(3-bromophenyl)benzoxazole (2.74 g, 10 mmol), potassium carbonate (2.76 g, 20 mmol), 30 mL of toluene, 15 mL of water and 15 mL of ethanol were added. Under a nitrogen atmosphere, tetrakis(triphenylphosphine)palladium (0.04 g, 0.03 mmol) was added, and the temperature was raised to 85 ° C. The reaction was 10-24 h. After liquid phase monitoring, there was essentially no residual raw material. Heating was stopped, the mixture was cooled to room temperature, washed with water, filtered, and the filtrate was concentrated and slurried with ethyl acetate together with the filter cake for 2-3 times to obtain 2.66 g (4-(3-(benzoxazole-2-yl)phenyl)naphthalene-1-yl)boric acid in a yield of 73%;

[0052] S3. To a 100 mL reaction flask, add the above-mentioned (4-(3-(benzoxazol-2-yl)phenyl)naphthalen-1-yl)boric acid (1.83 g, 5 mmol), 2-(3-bromophenyl)-[1,2,4]triazolo[1,5-a]pyridine (1.37 g, 5 mmol), potassium carbonate (1.38 g, 10 mmol), 30 mL of toluene, 15 mL of water and 15 mL of ethanol. Under a nitrogen atmosphere, add tetrakis(triphenylphosphine)palladium (0.02 g, 0.015 mmol). Heat to 85°C and react for 10-24 h. Liquid phase monitoring shows that there is almost no residual raw material. Stop heating, cool to room temperature, wash with water, filter, concentrate the filtrate, and separate it together with the filter cake by column chromatography using a 1:10 eluent of dichloromethane:petroleum ether. Concentrate and dry to obtain 2.11 g of the target compound (1-9) with a yield of 82%.

[0053] Mass spectrometer MALDI-TOF-MS (m / z) = 514.5892, theoretical molecular weight: 514.5880; elemental analysis: theoretical value: C 35 H 22 N4 (%): C81.69; H4.31; N10.89; measured value: C81.67; H4.30; N10.91.

[0054] Synthesis Example 4: Synthesis of Compound (1-21)

[0055] In Synthesis Example 1, 1,4-dibromonaphthalene (2.86 g, 10 mmol) was replaced with 9,10-dibromoanthracene (3.36 g, 10 mmol), and 2-(4-bromophenyl)-[1,2,4]triazolo[1,5-a]pyridine (3.29 g, 12 mmol) was replaced with 2-(3-bromophenyl)-[1,2,4]triazolo[1,5-a]pyridine (3.29 g, 12 mmol). The remaining synthesis process was essentially the same as in Synthesis Example 1 (same reaction molar ratio and reaction conditions) to obtain 2.17 g of the target compound (1-21) in a yield of 77%. Mass spectrometry: MALDI-TOF-MS (m / z) = 564.6509, theoretical molecular weight: 564.6520; elemental analysis: theoretical value: C 38 H 24 N6 (%): C80.83; H4.28; N14.88; measured value: C80.82; H4.30; N14.88.

[0056] Synthesis Example 5: Synthesis of Compound (1-22)

[0057] In Synthesis Example 1, 1,4-dibromonaphthalene (2.86 g, 10 mmol) was replaced with 2,6-dibromoanthracene (3.36 g, 10 mmol), and 2-(4-bromophenyl)-[1,2,4]triazolo[1,5-a]pyridine (3.29 g, 12 mmol) was replaced with 2-bromo-[1,2,4]triazolo[1,5-a]pyridine (2.38 g, 12 mmol). The remainder of the synthesis was carried out in essentially the same manner as in Synthesis Example 1 (same reaction molar ratios and reaction conditions) to obtain 1.53 g of the target compound (1-22) in a yield of 74%. Mass spectrometry: MALDI-TOF-MS (m / z) = 412.4557, theoretical molecular weight: 412.4560; elemental analysis: theoretical value: C 26 H 16 N6 (%): C75.71; H3.91; N20.38; measured value: C75.71; H3.89; N20.40.

[0058] Synthesis Example 6: Synthesis of Compound (1-26)

[0059] Substituting 1,4-dibromonaphthalene (2.86 g, 10 mmol) for 1,5-dibromoanthracene (3.36 g, 10 mmol) in Synthesis Example 1, the remaining synthesis procedures were essentially the same as in Synthesis Example 1 (same reaction molar ratios and reaction conditions) to obtain 2.11 g of the target compound (1-26) in a 75% yield. Mass spectrometry (MALDI-TOF-MS) yield (m / z) = 564.6509, theoretical molecular weight: 564.6520; elemental analysis: theoretical value: C 38 H 24 N6 (%): C80.83; H4.28; N14.88; measured value: C80.85; H4.29; N14.86.

[0060] Synthesis Example 7: Synthesis of Compound (1-33)

[0061] Substituting 1,4-dibromonaphthalene (5.72 g, 20 mmol) for 2,6-dibromoanthracene (6.72 g, 20 mmol) in Synthesis Example 3, the remaining synthesis procedures were essentially the same as in Synthesis Example 3 (same reaction molar ratios and reaction conditions) to obtain 2.37 g of the target compound (1-33) in an 84% yield. Mass spectrometry: MALDI-TOF-MS (m / z) = 564.6476, theoretical molecular weight: 564.6480; elemental analysis: theoretical value: C 39 H 24 N4(%): C82.96; H4.28; N9.92; measured value: C82.98; H4.29; N9.90.

[0062] Synthesis Example 8: Synthesis of Compound (1-46)

[0063] In Synthesis Example 1, 1,4-dibromonaphthalene (2.86 g, 10 mmol) was replaced with 1,6-dibromopyrene (3.60 g, 10 mmol), and 2-(4-bromophenyl)-[1,2,4]triazolo[1,5-a]pyridine (3.29 g, 12 mmol) was replaced with 2-bromo-[1,2,4]triazolo[1,5-a]pyridine (2.38 g, 12 mmol). The remainder of the synthesis was carried out in essentially the same manner as in Synthesis Example 1 (same reaction molar ratios and reaction conditions) to obtain 1.59 g of the target compound (1-46) in a 73% yield. Mass spectrometry: MALDI-TOF-MS (m / z) = 436.4768, theoretical molecular weight: 436.4780; elemental analysis: theoretical value: C 28 H 16 N6 (%): C77.05; H3.70; N19.25; measured value: C77.04; H3.72; N19.24.

[0064] Synthesis Example 9: Synthesis of Compound (1-48)

[0065] Substituting 1,4-dibromonaphthalene (2.86 g, 10 mmol) for 1,6-dibromopyrene (3.60 g, 10 mmol) in Synthesis Example 1, the remaining synthesis procedures were essentially the same as in Synthesis Example 1 (same reaction molar ratios and reaction conditions) to obtain 2.20 g of the target compound (1-48) in a 75% yield. Mass spectrometry: MALDI-TOF-MS (m / z) = 588.6750, theoretical molecular weight: 588.6740; elemental analysis: theoretical value: C 40 H 24 N6 (%): C81.61; H4.11; N14.28; measured value: C81.58; H4.12; N14.30.

[0066] Synthesis Example 10: Synthesis of Compound (1-55)

[0067] Substituting 1,4-dibromonaphthalene (5.72 g, 20 mmol) for 1,8-dibromopyrene (7.20 g, 20 mmol) in Synthesis Example 3, the remaining synthesis procedures were essentially the same as in Synthesis Example 3 (same reaction molar ratios and reaction conditions) to obtain 2.35 g of the target compound (1-55) in an 80% yield. Mass spectrometry: MALDI-TOF-MS (m / z) = 588.6708, theoretical molecular weight: 588.6700; elemental analysis: theoretical value: C 41 H 24N4 (%): C83.65; H4.11; N9.52; measured value: C83.65; H4.08; N9.53.

[0068] Synthesis Example 11: Synthesis of Compound (1-56)

[0069] The 1,4-dibromonaphthalene (5.72 g, 20 mmol) in Synthesis Example 3 was replaced by 1,6-dibromopyrene (7.20 g, 20 mmol), 2-(3-bromophenyl)benzoxazole (2.74 g, 10 mmol) was replaced by 2-bromobenzothiazole (2.14 g, 10 mmol), and 2-(3-bromophenyl)-[1,2,4]triazolo[1,5-a]pyridine (1.37 g, 5 mmol) was replaced by 2-bromo-[1,2,4]triazolo[1,5-a]pyridine (0.99 g, 5 mmol). The rest of the synthesis process was carried out in substantially the same manner as in Synthesis Example 3 (same reaction molar ratio and reaction conditions) to obtain 1.76 g of the target compound (1-56) in a yield of 78%. Mass spectrometer MALDI-TOF-MS (m / z) = 452.5360, theoretical molecular weight: 452.5350; elemental analysis: theoretical value: C 29 H 16 N4 (%): C76.97; H3.56; N12.38; measured value: C76.96; H3.56; N12.40.

[0070] Synthesis Example 12: Synthesis of Compound (1-71)

[0071] In Synthesis Example 3, 2-(3-bromophenyl)benzoxazole (2.74 g, 10 mmol) was replaced with 2-chloro-4,6-di(naphthalen-2-yl)-1,3,5-triazine (3.68 g, 10 mmol), and 2-(3-bromophenyl)-[1,2,4]triazolo[1,5-a]pyridine (1.37 g, 5 mmol) was replaced with 2-bromo-[1,2,4]triazolo[1,5-a]pyridine (0.99 g, 5 mmol). The remainder of the synthesis was carried out in essentially the same manner as in Synthesis Example 3 (with the same reaction molar ratios and reaction conditions) to obtain 2.36 g of the target compound (1-71) in an 82% yield. Mass spectrometry (MALDI-TOF-MS) yielded (m / z) = 576.6638, theoretical molecular weight: 576.6630; elemental analysis: theoretical value: C 39 H 24 N6 (%): C81.23; H4.20; N14.57; measured value: C81.24; H4.20; N14.56.

[0072] Synthesis Example 13: Synthesis of Compound (1-79)

[0073] In Synthesis Example 3, 2-(3-bromophenyl)benzoxazole (2.74 g, 10 mmol) was replaced with 4-(4-chlorophenyl)-2,6-diphenylpyrimidine (3.43 g, 10 mmol), and 2-(3-bromophenyl)-[1,2,4]triazolo[1,5-a]pyridine (1.37 g, 5 mmol) was replaced with 2-bromo-[1,2,4]triazolo[1,5-a]pyridine (0.99 g, 5 mmol). The remainder of the synthesis was carried out in essentially the same manner as in Synthesis Example 3 (with the same reaction molar ratios and reaction conditions) to obtain 2.23 g of the target compound (1-79) in an 81% yield. Mass spectrometry: MALDI-TOF-MS (m / z) = 551.6517, theoretical molecular weight: 551.6530; elemental analysis: theoretical value: C 38 H 25 N5 (%): C82.74; H4.57; N12.70; measured value: C82.73; H4.59; N12.68.

[0074] Synthesis Example 14: Synthesis of Compound (1-96)

[0075] The 1,4-dibromonaphthalene (5.72 g, 20 mmol) in Synthesis Example 3 was replaced with 2,6-dibromonaphthalene (5.72 g, 20 mmol), 2-(3-bromophenyl)benzoxazole (2.74 g, 10 mmol) was replaced with 2-([1,1'-biphenyl]-4-yl)-4-(3-chlorophenyl)-6-phenyl-1,3,5-triazine (4.20 g, 10 mmol), and 2-(3-bromophenyl)-[1,2,4]triazolo[1,5-a]pyridine (1.37 g, 5 mmol) was replaced with 2-bromo-[1,2,4]triazolo[1,5-a]pyridine (0.99 g, 5 mmol). The rest of the synthesis process was carried out in substantially the same manner as in Synthesis Example 3 (same reaction molar ratio and reaction conditions) to obtain 2.60 g of the target compound (1-96) in a yield of 83%. Mass spectrometer MALDI-TOF-MS (m / z) = 628.7378, theoretical molecular weight: 628.7390; elemental analysis: theoretical value: C 43 H 28 N6 (%): C82.14; H4.49; N13.37; measured value: C82.15; H4.46; N13.39.

[0076] Synthesis Example 15: Synthesis of Compound (1-102)

[0077] The 1,4-dibromonaphthalene (5.72 g, 20 mmol) in Synthesis Example 3 was replaced by 9,10-dibromoanthracene (6.72 g, 20 mmol), 2-(3-bromophenyl)benzoxazole (2.74 g, 10 mmol) was replaced by 2-chloro-4,6-diphenylpyridine (2.66 g, 10 mmol), and 2-(3-bromophenyl)-[1,2,4]triazolo[1,5-a]pyridine (1.37 g, 5 mmol) was replaced by 2-bromo-[1,2,4]triazolo[1,5-a]pyridine (0.99 g, 5 mmol). The rest of the synthesis process was carried out in substantially the same manner as in Synthesis Example 3 (same reaction molar ratio and reaction conditions) to obtain 2.12 g of the target compound (1-102) in a yield of 81%. Mass spectrometer MALDI-TOF-MS (m / z) = 524.6258, theoretical molecular weight: 524.6270; elemental analysis: theoretical value: C 37 H 24 N4 (%): C84.71; H4.61; N10.68; measured value: C84.72; H4.60; N10.68.

[0078] Synthesis Example 16: Synthesis of Compound (1-121)

[0079] The 1,4-dibromonaphthalene (5.72 g, 20 mmol) in Synthesis Example 3 was replaced by 2,6-dibromoanthracene (6.72 g, 20 mmol), 2-(3-bromophenyl)benzoxazole (2.74 g, 10 mmol) was replaced by 2-chloro-4,6-diphenyl-1,3,5-triazine (2.68 g, 10 mmol), and 2-(3-bromophenyl)-[1,2,4]triazolo[1,5-a]pyridine (1.37 g, 5 mmol) was replaced by 2-bromo-[1,2,4]triazolo[1,5-a]pyridine (0.99 g, 5 mmol). The rest of the synthesis process was carried out in substantially the same manner as in Synthesis Example 3 (same reaction molar ratio and reaction conditions) to obtain 2.16 g of the target compound (1-121) in a yield of 82%. Mass spectrometer MALDI-TOF-MS (m / z) = 526.6040, theoretical molecular weight: 526.6030; elemental analysis: theoretical value: C 35 H 22 N6 (%): C79.83; H4.21; N15.96; measured value: C79.82; H4.23; N15.95.

[0080] Synthesis Example 17: Synthesis of Compound (1-135)

[0081] The 1,4-dibromonaphthalene (5.72 g, 20 mmol) in Synthesis Example 3 was replaced with 9,10-dibromoanthracene (6.72 g, 20 mmol), 2-(3-bromophenyl)benzoxazole (2.74 g, 10 mmol) was replaced with 2-(3-chlorophenyl)-4,6-diphenyl-1,3,5-triazine (3.44 g, 10 mmol), and 2-(3-bromophenyl)-[1,2,4]triazolo[1,5-a]pyridine (1.37 g, 5 mmol) was replaced with 2-bromo-[1,2,4]triazolo[1,5-a]pyridine (0.99 g, 5 mmol). The rest of the synthesis process was carried out in substantially the same manner as in Synthesis Example 3 (same reaction molar ratio and reaction conditions) to obtain 2.41 g of the target compound (1-135) in a yield of 80%. Mass spectrometer MALDI-TOF-MS (m / z) = 602.7002, theoretical molecular weight: 602.7010; elemental analysis: theoretical value: C 41 H 26 N6 (%): C81.71; H4.35; N13.94; measured value: C81.70; H4.33; N13.97.

[0082] Synthesis Example 18: Synthesis of Compound (1-150)

[0083] The 1,4-dibromonaphthalene (5.72 g, 20 mmol) in Synthesis Example 3 was replaced by 9,10-dibromoanthracene (6.72 g, 20 mmol), 2-(3-bromophenyl)benzoxazole (2.74 g, 10 mmol) was replaced by 2-(4-chlorophenyl)-4,6-diphenyl-1,3,5-triazine (3.44 g, 10 mmol), and 2-(3-bromophenyl)-[1,2,4]triazolo[1,5-a]pyridine (1.37 g, 5 mmol) was replaced by 2-(4-bromophenyl)-[1,2,4]triazolo[1,5-a]pyridine (1.37 g, 5 mmol). The rest of the synthesis process was carried out in substantially the same manner as in Synthesis Example 3 (same reaction molar ratio and reaction conditions) to obtain 2.82 g of the target compound (1-150) in a yield of 83%. Mass spectrometer MALDI-TOF-MS (m / z) = 678.7995, theoretical molecular weight: 678.7990; elemental analysis: theoretical value: C 47 H 30 N6 (%): C83.16; H4.45; N12.38; measured value: C83.14; H4.46; N12.40.

[0084] Synthesis Example 19: Synthesis of Compound (1-155)

[0085] In Synthesis Example 3, 1,4-dibromonaphthalene (5.72 g, 20 mmol) was replaced with 2,6-dibromoanthracene (6.72 g, 20 mmol), and 2-(3-bromophenyl)benzoxazole (2.74 g, 10 mmol) was replaced with 2-(3-chlorophenyl)-4,6-diphenyl-1,3,5-triazine (3.44 g, 10 mmol). The remaining synthesis process was essentially the same as in Synthesis Example 3 (same reaction molar ratios and reaction conditions) to obtain 2.88 g of the target compound (1-155) in an 85% yield. Mass spectrometry (MALDI-TOF-MS) (m / z) = 678.7980, theoretical molecular weight: 678.7990; elemental analysis: theoretical value: C 47 H 30 N6 (%): C83.16; H4.45; N12.38; measured value: C83.18; H4.45; N12.37.

[0086] Synthesis Example 20: Synthesis of Compound (1-168)

[0087] In Synthesis Example 3, 1,4-dibromonaphthalene (5.72 g, 20 mmol) was replaced with 2,7-dibromophenanthrene (6.72 g, 20 mmol), and 2-(3-bromophenyl)benzoxazole (2.74 g, 10 mmol) was replaced with 2-(3-chlorophenyl)-4,6-diphenyl-1,3,5-triazine (3.44 g, 10 mmol). The remainder of the synthesis was carried out in essentially the same manner as in Synthesis Example 3 (with the same reaction molar ratios and reaction conditions). 2.78 g of the target compound (1-168) was obtained in an 82% yield. MALDI-TOF-MS (m / z) = 678.7984, theoretical molecular weight: 678.7990; elemental analysis: theoretical value: C 47 H 30 N6 (%): C83.16; H4.45; N12.38; measured value: C83.17; H4.47; N12.36.

[0088] Synthesis Example 21: Synthesis of Compound (1-173)

[0089] In Synthesis Example 3, 1,4-dibromonaphthalene (5.72 g, 20 mmol) was replaced with 1,6-dibromopyrene (7.20 g, 20 mmol), 2-(3-bromophenyl)benzoxazole (2.74 g, 10 mmol) was replaced with 2-chloro-4,6-diphenyl-1,3,5-triazine (2.68 g, 10 mmol), and 2-(3-bromophenyl)-[1,2,4]triazolo[1,5-a]pyridine (1.37 g, 5 mmol) was replaced with 2-bromo-[1,2,4]triazolo[1,5-a]pyridine (0.99 g, 5 mmol). The rest of the synthesis process was carried out in substantially the same manner as in Synthesis Example 3 (same reaction molar ratio and reaction conditions) to obtain 2.20 g of the target compound (1-173) in a yield of 80%. Mass spectrometer MALDI-TOF-MS (m / z) = 550.6244, theoretical molecular weight: 550.6250; elemental analysis: theoretical value: C 37 H 22 N6 (%): C80.71; H4.03; N15.26; measured value: C80.70; H4.05; N15.25.

[0090] Synthesis Example 22: Synthesis of Compound (1-186)

[0091] In Synthesis Example 3, 1,4-dibromonaphthalene (5.72 g, 20 mmol) was replaced with 1,6-dibromopyrene (7.20 g, 20 mmol), and 2-(3-bromophenyl)benzoxazole (2.74 g, 10 mmol) was replaced with 2-(3-chlorophenyl)-4,6-diphenyl-1,3,5-triazine (3.44 g, 10 mmol). The remaining synthesis process was essentially the same as in Synthesis Example 3 (same reaction molar ratios and reaction conditions) to obtain 2.88 g of the target compound (1-186) in an 82% yield. Mass spectrometry: MALDI-TOF-MS (m / z) = 702.8219, theoretical molecular weight: 702.8210; elemental analysis: theoretical value: C 49 H 30 N6 (%): C83.74; H4.30; N11.96; measured value: C83.74; H4.30; N11.96.

[0092] Synthesis Example 23: Synthesis of Compound (1-189)

[0093] Substituting 2-(3-bromophenyl)benzoxazole (2.74 g, 10 mmol) for 2-(3-bromophenyl)-4-phenylquinazoline (3.61 g, 10 mmol) in Synthesis Example 3, the remaining synthesis procedures were essentially the same as in Synthesis Example 3 (same reaction molar ratios and reaction conditions) to obtain 2.40 g of the target compound (1-189) in an 80% yield. Mass spectrometry (MALDI-TOF-MS) yield (m / z) = 601.7134, theoretical molecular weight: 601.7130; elemental analysis: theoretical value: C 42 H 27 N5 (%): C83.84; H4.52; N11.64; Measured value: C83.84; H4.52; N11.64.

[0094] Synthesis Example 24: Synthesis of Compound (1-193)

[0095] In Synthesis Example 3, 1,4-dibromonaphthalene (5.72 g, 20 mmol) was replaced with 2,6-dibromonaphthalene (5.72 g, 20 mmol), and 2-(3-bromophenyl)benzoxazole (2.74 g, 10 mmol) was replaced with 2-(3-bromophenyl)quinazoline (2.85 g, 10 mmol). The remainder of the synthesis was carried out in essentially the same manner as in Synthesis Example 3 (same reaction molar ratios and reaction conditions) to obtain 2.21 g of the target compound (1-193) in an 84% yield. Mass spectrometry: MALDI-TOF-MS (m / z) = 525.6137, theoretical molecular weight: 525.6150; elemental analysis: theoretical value: C 36 H 23 N5 (%): C82.26; H4.41; N13.32; measured value: C82.26; H4.40; N13.34.

[0096] Synthesis Example 25: Synthesis of Compound (1-196)

[0097] The 1,4-dibromonaphthalene (5.72 g, 20 mmol) in Synthesis Example 3 was replaced with 9,10-dibromoanthracene (6.72 g, 20 mmol), and the 2-(3-bromophenyl)benzoxazole (2.74 g, 10 mmol) was replaced with 2-(4-bromophenyl)quinazoline (2.85 g, 10 mmol). The remainder of the synthesis was carried out in essentially the same manner as in Synthesis Example 3 (same reaction molar ratios and reaction conditions) to obtain 2.36 g of the target compound (1-196) in an 82% yield. Mass spectrometry (MALDI-TOF-MS) yield (m / z) = 575.6741, theoretical molecular weight: 575.6750; elemental analysis: theoretical value: C 40 H 25N5 (%): C83.46; H4.38; N12.17; measured value: C83.45; H4.40; N12.15.

[0098] Synthesis Example 26: Synthesis of Compound (1-202)

[0099] In Synthesis Example 3, 1,4-dibromonaphthalene (5.72 g, 20 mmol) was replaced with 1,5-dibromoanthracene (6.72 g, 20 mmol), and 2-(3-bromophenyl)benzoxazole (2.74 g, 10 mmol) was replaced with 2-(3-bromophenyl)-4-phenylquinazoline (3.61 g, 10 mmol). The remainder of the synthesis was carried out in essentially the same manner as in Synthesis Example 3 (same reaction molar ratios and reaction conditions) to obtain 2.64 g of the target compound (1-202) in an 81% yield. Mass spectrometry (MALDI-TOF-MS) yield (m / z) = 651.7744, theoretical molecular weight: 651.7730; elemental analysis: theoretical value: C 46 H 29 N5 (%): C84.77; H4.48; N10.75; measured value: C84.78; H4.48; N10.74.

[0100] Synthesis Example 27: Synthesis of Compound (1-205)

[0101] In Synthesis Example 3, 1,4-dibromonaphthalene (5.72 g, 20 mmol) was replaced with 2,7-dibromophenanthrene (6.72 g, 20 mmol), and 2-(3-bromophenyl)benzoxazole (2.74 g, 10 mmol) was replaced with 2-(3-bromophenyl)-4-phenylquinazoline (3.61 g, 10 mmol). The remainder of the synthesis was carried out in essentially the same manner as in Synthesis Example 3 (same reaction molar ratios and reaction conditions) to obtain 2.67 g of the target compound (1-205) in an 82% yield. Mass spectrometry (MALDI-TOF-MS) yield (m / z) = 651.7721, theoretical molecular weight: 651.7730; elemental analysis: theoretical value: C 46 H 29 N5 (%): C84.77; H4.48; N10.75; measured value: C84.75; H4.48; N10.77.

[0102] Synthesis Example 28: Synthesis of Compound (1-206)

[0103] In Synthesis Example 1, 1,4-dibromonaphthalene (2.86 g, 10 mmol) was replaced with 2,7-dibromophenanthrene (3.36 g, 10 mmol), and 2-(4-bromophenyl)-[1,2,4]triazolo[1,5-a]pyridine (3.29 g, 12 mmol) was replaced with 2-bromo-[1,2,4]triazolo[1,5-a]pyridine (2.38 g, 12 mmol). The remainder of the synthesis was carried out in essentially the same manner as in Synthesis Example 1 (same reaction molar ratios and reaction conditions) to obtain 1.53 g of the target compound (1-206) in a 74% yield. Mass spectrometry: MALDI-TOF-MS (m / z) = 412.4565, theoretical molecular weight: 412.4560; elemental analysis: theoretical value: C 26 H 16 N6 (%): C 75.71; H 3.91; N 20.38; measured value: C 75.72; H 3.90; N 20.38.

[0104] Synthesis Example 29: Synthesis of Compound (1-208)

[0105] In Synthesis Example 1, 1,4-dibromonaphthalene (2.86 g, 10 mmol) was replaced with 2,7-dibromophenanthrene (3.36 g, 10 mmol), and 2-(4-bromophenyl)-[1,2,4]triazolo[1,5-a]pyridine (3.29 g, 12 mmol) was replaced with 2-(3-bromophenyl)-[1,2,4]triazolo[1,5-a]pyridine (3.29 g, 12 mmol). The remainder of the synthesis was carried out in essentially the same manner as in Synthesis Example 1 (same reaction molar ratios and reaction conditions) to obtain 2.14 g of the target compound (1-208) in a 76% yield. Mass spectrometry: MALDI-TOF-MS (m / z) = 564.6511, theoretical molecular weight: 564.6520; elemental analysis: theoretical value: C 38 H 24 N6 (%): C80.83; H4.28; N14.88; measured value: C80.82; H4.28; N14.90.

[0106] Synthesis Example 30: Synthesis of Compound (1-216)

[0107] In Synthesis Example 3, 2-(3-bromophenyl)benzoxazole (2.74 g, 10 mmol) was replaced with 9-(4-bromophenyl)-9H-2,7-azacarbazole (3.24 g, 10 mmol), and 2-(3-bromophenyl)-[1,2,4]triazolo[1,5-a]pyridine (1.37 g, 5 mmol) was replaced with 2-bromo-[1,2,4]triazolo[1,5-a]pyridine (0.99 g, 5 mmol). The remainder of the synthesis was carried out in essentially the same manner as in Synthesis Example 3 (same reaction molar ratios and reaction conditions) to obtain 1.95 g of the target compound (1-216) in an 80% yield. Mass spectrometry (MALDI-TOF-MS) revealed (m / z) = 488.5547, theoretical molecular weight: 488.5540; elemental analysis: theoretical value: C 32 H 20 N6 (%): C78.67; H4.13; N17.20; measured value: C78.65; H4.14; N17.21.

[0108] According to the above-mentioned Synthesis Examples 1 to 30, compounds (1-1) to (1-216) other than the above-mentioned compounds can be prepared using substantially the same method (same reaction molar ratio and reaction conditions).

[0109] Synthesis Example 38: Synthesis of Compound (2-3)

[0110] In Synthesis Example 3, 1,4-dibromonaphthalene (5.72 g, 20 mmol) was replaced with 3,8-dibromo-1,10-phenanthroline (6.76 g, 20 mmol), 2-(3-bromophenyl)benzoxazole (2.74 g, 10 mmol) was replaced with 4-bromobenzonitrile (1.82 g, 10 mmol), and 2-(3-bromophenyl)-[1,2,4]triazolo[1,5-a]pyridine (1.37 g, 5 mmol) was replaced with 2-bromo-[1,2,4]triazolo[1,5-a]pyridine (0.99 g, 5 mmol). The rest of the synthesis process was carried out in substantially the same manner as in Synthesis Example 3 (same reaction molar ratio and reaction conditions) to obtain 1.55 g of the target compound (2-3) in a yield of 78%. Mass spectrometer MALDI-TOF-MS (m / z) = 398.4287, theoretical molecular weight: 398.4290; elemental analysis: theoretical value: C 25 H 14 N6 (%): C75.36; H3.54; N21.09; measured value: C75.34; H3.55; N21.11.

[0111] Synthesis Example 39: Synthesis of Compound (2-9)

[0112] In Synthesis Example 3, 1,4-dibromonaphthalene (5.72 g, 20 mmol) was replaced with 3,8-dibromo-1,10-phenanthroline (6.76 g, 20 mmol), 2-(3-bromophenyl)benzoxazole (2.74 g, 10 mmol) was replaced with 9-bromo-10-phenylanthracene (3.33 g, 10 mmol), and 2-(3-bromophenyl)-[1,2,4]triazolo[1,5-a]pyridine (1.37 g, 5 mmol) was replaced with 2-bromo-[1,2,4]triazolo[1,5-a]pyridine (0.99 g, 5 mmol). The rest of the synthesis process was carried out in substantially the same manner as in Synthesis Example 3 (same reaction molar ratio and reaction conditions) to obtain 2.11 g of the target compound (2-9) with a yield of 77%. Mass spectrometer MALDI-TOF-MS (m / z) = 549.6359, theoretical molecular weight: 549.6370; elemental analysis: theoretical value: C 38 H 23 N5 (%): C83.04; H4.22; N12.74; measured value: C83.05; H4.20; N12.75.

[0113] Synthesis Example 40: Synthesis of Compound (2-15)

[0114] In Synthesis Example 3, 1,4-dibromonaphthalene (5.72 g, 20 mmol) was replaced with 3,8-dibromo-1,10-phenanthroline (6.76 g, 20 mmol), 2-(3-bromophenyl)benzoxazole (2.74 g, 10 mmol) was replaced with 3-bromo-9,9-diphenyl-9H-fluorene (3.97 g, 10 mmol), and 2-(3-bromophenyl)-[1,2,4]triazolo[1,5-a]pyridine (1.37 g, 5 mmol) was replaced with 2-bromo-[1,2,4]triazolo[1,5-a]pyridine (0.99 g, 5 mmol). The rest of the synthesis process was carried out in substantially the same manner as in Synthesis Example 3 (same reaction molar ratio and reaction conditions) to obtain 2.30 g of the target compound (2-15) in a yield of 75%. Mass spectrometer MALDI-TOF-MS (m / z) = 613.7251, theoretical molecular weight: 613.7240; elemental analysis: theoretical value: C 43 H 27 N5 (%): C84.15; H4.43; N11.41; measured value: C84.15; H4.42; N11.43.

[0115] Synthesis Example 41: Synthesis of Compound (2-17)

[0116]

[0117] S1. In a 250 mL reaction flask, 3,8-dibromo-1,10-phenanthroline (10.14 g, 30 mmol), 3-phenyl-9H-carbazole (4.87 g, 20 mmol), tri-tert-butylphosphine tetrafluoroborate (0.35 g, 1.2 mmol), potassium carbonate (8.29 g, 60 mmol), and 100 mL of xylene were added. Under a nitrogen atmosphere, palladium acetate (0.14 g, 0.6 mmol) was added, and the temperature was raised to 145°C for 10-24 h. After liquid phase monitoring, almost no raw materials remained, heating was stopped, and the mixture was cooled to room temperature, washed with water, filtered, and the filtrate was concentrated and slurried with ethyl acetate 2-3 times together with the filter cake to obtain 7.90 g of 3-bromo-8-(3-phenyl-9H-carbazole-9-yl)-1,10-phenanthroline with a yield of 79%;

[0118] S2. In a 100 mL reaction flask, add the above-mentioned 3-bromo-8-(3-phenyl-9H-carbazole-9-yl)-1,10-phenanthroline (5.00 g, 10 mmol) and 50 mL of dry tetrahydrofuran solution, cool to -78°C, add 4 mL of 2.5 M n-butyllithium tetrahydrofuran solution dropwise under a nitrogen atmosphere, keep at -78°C for reaction 1-2 h, then add triisopropyl borate (11 mmol, 2.54 mL) dropwise, warm to room temperature after the addition is complete, add dilute hydrochloric acid dropwise after 8 h to quench the reaction, remove tetrahydrofuran by distillation under reduced pressure, add dichloromethane to dissolve, wash with water, dry over anhydrous magnesium sulfate, filter, concentrate the filtrate, and beat with ethanol 1-2 times to obtain 4.19 g (8-(3-phenyl-9H-carbazole-9-yl)-1,10-phenanthroline-3-yl) boronic acid, with a yield of 90%.

[0119] S3. To a 100 mL reaction flask, add the above-mentioned (8-(3-phenyl-9H-carbazol-9-yl)-1,10-phenanthroline-3-yl)boric acid (2.33 g, 5 mmol), 2-bromo-[1,2,4]triazolo[1,5-a]pyridine (0.99 g, 5 mmol), potassium carbonate (1.38 g, 10 mmol), 30 mL of toluene, 15 mL of water, and 15 mL of ethanol. Under a nitrogen atmosphere, add tetrakis(triphenylphosphine)palladium (0.02 g, 0.015 mmol). The temperature was raised to 85°C and the reaction was carried out for 10-24 hours. After liquid chromatography, almost no raw material remained. Heating was stopped, the mixture was cooled to room temperature, washed with water, filtered, and the filtrate was concentrated. The filtrate and the filter cake were separated by column chromatography using a 1:10 eluent of dichloromethane:petroleum ether. The mixture was concentrated and dried to obtain 2.07 g of the target compound (2-17) in a yield of 77%.

[0120] Mass spectrometer MALDI-TOF-MS (m / z) = 538.6122, theoretical molecular weight: 538.6140; elemental analysis: theoretical value: C 36 H 22N6 (%): C80.28; H4.12; N15.60; measured value: C80.27; H4.13; N15.60.

[0121] Synthesis Example 42: Synthesis of Compound (2-21)

[0122] In Synthesis Example 3, 1,4-dibromonaphthalene (5.72 g, 20 mmol) was replaced with 3,8-dibromo-1,10-phenanthroline (6.76 g, 20 mmol), 2-(3-bromophenyl)benzoxazole (2.74 g, 10 mmol) was replaced with 2-bromo-9-phenyl-9H-carbazole (3.22 g, 10 mmol), and 2-(3-bromophenyl)-[1,2,4]triazolo[1,5-a]pyridine (1.37 g, 5 mmol) was replaced with 2-bromo-[1,2,4]triazolo[1,5-a]pyridine (0.99 g, 5 mmol). The rest of the synthesis process was carried out in substantially the same manner as in Synthesis Example 3 (same reaction molar ratio and reaction conditions) to obtain 2.10 g of the target compound (2-21) in a yield of 78%. Mass spectrometer MALDI-TOF-MS (m / z) = 538.6147, theoretical molecular weight: 538.6140; elemental analysis: theoretical value: C 36 H 22 N6 (%): C80.28; H4.12; N15.60; measured value: C80.28; H4.11; N15.61.

[0123] Synthesis Example 43: Synthesis of Compound (2-27)

[0124] In Synthesis Example 3, 1,4-dibromonaphthalene (5.72 g, 20 mmol) was replaced with 3,8-dibromo-1,10-phenanthroline (6.76 g, 20 mmol), 2-(3-bromophenyl)benzoxazole (2.74 g, 10 mmol) was replaced with 2-(3-bromophenyl)-1-phenyl-1H-benzimidazole (3.49 g, 10 mmol), and 2-(3-bromophenyl)-[1,2,4]triazolo[1,5-a]pyridine (1.37 g, 5 mmol) was replaced with 2-bromo-[1,2,4]triazolo[1,5-a]pyridine (0.99 g, 5 mmol). The rest of the synthesis process was carried out in substantially the same manner as in Synthesis Example 3 (same reaction molar ratio and reaction conditions) to obtain 2.15 g of the target compound (2-27) in a yield of 76%. Mass spectrometer MALDI-TOF-MS (m / z) = 565.6392, theoretical molecular weight: 565.6400; elemental analysis: theoretical value: C 37 H 23 N7 (%): C78.57; H4.10; N17.33; measured value: C78.55; H4.12; N17.33.

[0125] Synthesis Example 44: Synthesis of Compound (2-35)

[0126] In Synthesis Example 3, 1,4-dibromonaphthalene (5.72 g, 20 mmol) was replaced with 3,8-dibromo-1,10-phenanthroline (6.76 g, 20 mmol), 2-(3-bromophenyl)benzoxazole (2.74 g, 10 mmol) was replaced with 4-bromo-N,N-diphenylaniline (3.24 g, 10 mmol), and 2-(3-bromophenyl)-[1,2,4]triazolo[1,5-a]pyridine (1.37 g, 5 mmol) was replaced with 2-bromo-[1,2,4]triazolo[1,5-a]pyridine (0.99 g, 5 mmol). The rest of the synthesis process was carried out in substantially the same manner as in Synthesis Example 3 (same reaction molar ratio and reaction conditions) to obtain 2.11 g of the target compound (2-35) in a yield of 78%. Mass spectrometer MALDI-TOF-MS (m / z) = 540.6304, theoretical molecular weight: 540.6300; elemental analysis: theoretical value: C 36 H 24 N6 (%): C 79.98; H 4.47; N 15.55; Measured value: C 79.98; H 4.45; N 15.57.

[0127] Synthesis Example 45: Synthesis of Compound (2-41)

[0128] In Synthesis Example 3, 1,4-dibromonaphthalene (5.72 g, 20 mmol) was replaced with 3,8-dibromo-1,10-phenanthroline (6.76 g, 20 mmol), and 2-(3-bromophenyl)benzoxazole (2.74 g, 10 mmol) was replaced with 2-bromo-9,10-diphenylanthracene (4.09 g, 10 mmol). The remainder of the synthesis was carried out in essentially the same manner as in Synthesis Example 3 (same reaction molar ratios and reaction conditions) to obtain 2.81 g of the target compound (2-41) in an 80% yield. Mass spectrometry (MALDI-TOF-MS) yielded (m / z) = 701.8320, theoretical molecular weight: 701.8330; elemental analysis: theoretical value: C 50 H 31 N5 (%): C85.57; H4.45; N9.98; measured value: C85.56; H4.47; N9.97.

[0129] Synthesis Example 46: Synthesis of Compound (2-45)

[0130] In Synthesis Example 3, 1,4-dibromonaphthalene (5.72 g, 20 mmol) was replaced with 3,8-dibromo-1,10-phenanthroline (6.76 g, 20 mmol), and 2-(3-bromophenyl)benzoxazole (2.74 g, 10 mmol) was replaced with 9-(3-bromophenyl)-9H-carbazole (3.22 g, 10 mmol). The remainder of the synthesis was carried out in essentially the same manner as in Synthesis Example 3 (same reaction molar ratios and reaction conditions) to obtain 2.43 g of the target compound (2-45) in a 79% yield. Mass spectrometry (MALDI-TOF-MS) yield (m / z) = 614.7109, theoretical molecular weight: 614.7120; elemental analysis: theoretical value: C 42 H 26 N6 (%): C82.06; H4.26; N13.67; measured value: C82.06; H4.25; N13.69.

[0131] Synthesis Example 47: Synthesis of Compound (2-49)

[0132] In Synthesis Example 3, 1,4-dibromonaphthalene (5.72 g, 20 mmol) was replaced with 3,8-dibromo-1,10-phenanthroline (6.76 g, 20 mmol), 2-(3-bromophenyl)benzoxazole (2.74 g, 10 mmol) was replaced with 2-(4-bromophenyl)benzothiazole (2.90 g, 10 mmol), and 2-(3-bromophenyl)-[1,2,4]triazolo[1,5-a]pyridine (1.37 g, 5 mmol) was replaced with 2-(4-bromophenyl)-[1,2,4]triazolo[1,5-a]pyridine (1.37 g, 5 mmol). The rest of the synthesis process was carried out in substantially the same manner as in Synthesis Example 3 (same reaction molar ratio and reaction conditions) to obtain 2.24 g of the target compound (2-49) in a yield of 77%. Mass spectrometer MALDI-TOF-MS (m / z) = 582.6862, theoretical molecular weight: 582.6850; elemental analysis: theoretical value: C 37 H 22 N6 (%): C 76.27; H 3.81; N 14.42; measured value: C 76.25; H 3.80; N 14.43.

[0133] Synthesis Example 48: Synthesis of Compound (2-56)

[0134] In Synthesis Example 3, 1,4-dibromonaphthalene (5.72 g, 20 mmol) was replaced by 9,10-dichloro-1,5-diazaanthracene (4.98 g, 20 mmol), 2-(3-bromophenyl)benzoxazole (2.74 g, 10 mmol) was replaced by 5'-bromo-1,1':3',1"-terphenyl (3.09 g, 10 mmol), 2-(3-bromophenyl)-[1,2,4]triazolo[1,5-a]pyridine (1.37 g, 5 mmol) was replaced with 2-bromo-[1,2,4]triazolo[1,5-a]pyridine (0.99 g, 5 mmol). The rest of the synthesis process was essentially the same as in Synthesis Example 3 (same reaction molar ratios and reaction conditions) to obtain 1.97 g of the target compound (2-56) in a 75% yield. Mass spectrometry MALDI-TOF-MS (m / z) = 525.6134, theoretical molecular weight: 525.6150; elemental analysis: theoretical value: C 36 H 23 N5 (%): C82.26; H4.41; N13.32; measured value: C82.25; H4.40; N13.35.

[0135] Synthesis Example 49: Synthesis of Compound (2-66)

[0136] In Synthesis Example 3, 1,4-dibromonaphthalene (5.72 g, 20 mmol) was replaced with 9,10-dichloro-2,6-diazaanthracene (4.98 g, 20 mmol), 2-(3-bromophenyl)benzoxazole (2.74 g, 10 mmol) was replaced with 2-bromo-9,9-dimethyl-9H-fluorene (2.73 g, 10 mmol), and 2-(3-bromophenyl)-[1,2,4]triazolo[1,5-a]pyridine (1.37 g, 5 mmol) was replaced with 2-bromo-[1,2,4]triazolo[1,5-a]pyridine (0.99 g, 5 mmol). The rest of the synthesis process was carried out in substantially the same manner as in Synthesis Example 3 (same reaction molar ratio and reaction conditions) to obtain 1.86 g of the target compound (2-66) in a yield of 76%. Mass spectrometer MALDI-TOF-MS (m / z) = 489.5830, theoretical molecular weight: 489.5820; elemental analysis: theoretical value: C 33 H 23 N5 (%): C80.96; H4.74; N14.31; measured value: C80.98; H4.74; N14.28.

[0137] Synthesis Example 50: Synthesis of Compound (2-79)

[0138] In Synthesis Example 41, 3,8-dibromo-1,10-phenanthroline (10.14 g, 30 mmol) was replaced with 9,10-dichloro-1,5-diazaanthracene (4.98 g, 20 mmol), and 3-phenyl-9H-carbazole (4.87 g, 20 mmol) was replaced with 3,6-diphenyl-9H-carbazole (3.19 g, 10 mmol). The remainder of the synthesis was carried out in essentially the same manner as in Synthesis Example 42 (with the same reaction molar ratios and reaction conditions). 2.27 g of the target compound (2-79) was obtained in a 74% yield. MALDI-TOF-MS (m / z) = 614.7132, theoretical molecular weight: 614.7120; elemental analysis: theoretical value: C 42 H 26 N6 (%): C82.06; H4.26; N13.67; measured value: C82.06; H4.25; N13.69.

[0139] Synthesis Example 51: Synthesis of Compound (2-85)

[0140] In Synthesis Example 41, 3,8-dibromo-1,10-phenanthroline (10.14 g, 30 mmol) was replaced with 9,10-dichloro-2,6-diazaanthracene (4.98 g, 20 mmol), and 3-phenyl-9H-carbazole (4.87 g, 20 mmol) was replaced with diphenylamine (1.69 g, 10 mmol). The remainder of the synthesis was carried out in essentially the same manner as in Synthesis Example 42 (same reaction molar ratios and reaction conditions) to obtain 1.74 g of the target compound (2-85) in a 75% yield. Mass spectrometry (MALDI-TOF-MS) yield (m / z) = 464.5328, theoretical molecular weight: 464.5320; elemental analysis: theoretical value: C 30 H 20 N6 (%): C77.57; H4.34; N18.09; measured value: C77.56; H4.33; N18.11.

[0141] Synthesis Example 52: Synthesis of Compound (2-90)

[0142] In Synthesis Example 1, 1,4-dibromonaphthalene (2.86 g, 10 mmol) was replaced with 9,10-dichloro-1,5-diazaanthracene (4.98 g, 10 mmol), and 2-(4-bromophenyl)-[1,2,4]triazolo[1,5-a]pyridine (3.29 g, 12 mmol) was replaced with 2-bromo-[1,2,4]triazolo[1,5-a]pyridine (2.38 g, 12 mmol). The remaining synthesis process was essentially the same as in Synthesis Example 1 (same reaction molar ratios and reaction conditions) to obtain 1.45 g of the target compound (2-90) in a 70% yield. Mass spectrometry: MALDI-TOF-MS (m / z) = 414.4327, theoretical molecular weight: 414.4320; elemental analysis: theoretical value: C 24 H 14 N8(%): C69.56; H3.41; N27.04; measured value: C69.55; H3.40; N27.05.

[0143] Synthesis Example 53: Synthesis of Compound (2-106)

[0144] In Synthesis Example 3, 1,4-dibromonaphthalene (5.72 g, 20 mmol) was replaced with 9,10-dichloro-2,6-diazaanthracene (4.98 g, 20 mmol), and 2-(3-bromophenyl)benzoxazole (2.74 g, 10 mmol) was replaced with 10-(3-bromophenyl)-2,9-diphenylanthracene (4.85 g, 10 mmol). The remainder of the synthesis was carried out in essentially the same manner as in Synthesis Example 3 (same reaction molar ratios and reaction conditions) to obtain 2.92 g of the target compound (2-106) in a 75% yield. Mass spectrometry (MALDI-TOF-MS) yield (m / z) = 777.9301, theoretical molecular weight: 777.9310; elemental analysis: theoretical value: C 56 H 35 N5 (%): C86.46; H4.54; N9.00; measured value: C86.47; H4.53; N9.00.

[0145] Synthesis Example 54: Synthesis of Compound (2-112)

[0146] In Synthesis Example 3, 1,4-dibromonaphthalene (5.72 g, 20 mmol) was replaced with 9,10-dichloro-2,6-diazaanthracene (4.98 g, 20 mmol), 2-(3-bromophenyl)benzoxazole (2.74 g, 10 mmol) was replaced with 9-(4-bromophenyl)-9H-carbazole (3.22 g, 10 mmol), and 2-(3-bromophenyl)-[1,2,4]triazolo[1,5-a]pyridine (1.37 g, 5 mmol) was replaced with 2-(4-bromophenyl)-[1,2,4]triazolo[1,5-a]pyridine (1.37 g, 5 mmol). The rest of the synthesis process was carried out in substantially the same manner as in Synthesis Example 3 (same reaction molar ratio and reaction conditions) to obtain 2.34 g of the target compound (2-112) in a yield of 76%. Mass spectrometer MALDI-TOF-MS (m / z) = 614.7134, theoretical molecular weight: 614.7120; elemental analysis: theoretical value: C 42 H 26 N6 (%): C82.06; H4.26; N13.67; measured value: C82.08; H4.25; N13.67.

[0147] Synthesis Example 55: Synthesis of Compound (2-115)

[0148] The 1,4-dibromonaphthalene (2.86 g, 10 mmol) in Synthesis Example 1 was replaced with 9,10-dichloro-1,5-diazaanthracene (2.49 g, 10 mmol). The remaining synthesis process was essentially the same as in Synthesis Example 1 (same reaction molar ratios and reaction conditions) to obtain 2.04 g of the target compound (2-115) in a 72% yield. Mass spectrometry: MALDI-TOF-MS (m / z) = 566.6277, theoretical molecular weight: 566.6280; elemental analysis: theoretical value: C 36 H 22 N8(%): C76.31; H3.91; N19.78; measured value: C76.30; H3.90; N19.80.

[0149] Synthesis Example 56: Synthesis of Compound (2-119)

[0150] The 1,4-dibromonaphthalene (5.72 g, 20 mmol) in Synthesis Example 3 was replaced with 9,10-dichloro-2,6-diazaanthracene (4.98 g, 20 mmol). The remaining synthesis process was essentially the same as in Synthesis Example 3 (same reaction molar ratios and reaction conditions) to obtain 2.12 g of the target compound (2-119) in a 75% yield. Mass spectrometry: MALDI-TOF-MS (m / z) = 566.6255, theoretical molecular weight: 566.6240; elemental analysis: theoretical value: C37 H 22 N6 (%): C 78.43; H 3.91; N 14.83; measured value: C 78.46; H 3.90; N 14.82.

[0151] Synthesis Example 57: Synthesis of Compound (2-123)

[0152] In Synthesis Example 3, 1,4-dibromonaphthalene (5.72 g, 20 mmol) was replaced with 2,4-dichloroquinazoline (3.98 g, 20 mmol), and 2-(3-bromophenyl)benzoxazole (2.74 g, 10 mmol) was replaced with naphthalene-2-ylboronic acid (1.72 g, 10 mmol). The remainder of the synthesis was carried out in essentially the same manner as in Synthesis Example 3 (same reaction molar ratios and reaction conditions) to obtain 1.64 g of the target compound (2-123) in a 73% yield. Mass spectrometry: MALDI-TOF-MS (m / z) = 449.5163, theoretical molecular weight: 449.5170; elemental analysis: theoretical value: C 30 H 19 N5 (%): C80.16; H4.26; N15.58; measured value: C80.15; H4.25; N15.60.

[0153] Synthesis Example 58: Synthesis of Compound (2-137)

[0154] In Synthesis Example 3, 1,4-dibromonaphthalene (5.72 g, 20 mmol) was replaced with 4,8-dichloro-1,5-naphthyridine (3.98 g, 20 mmol), 2-(3-bromophenyl)benzoxazole (2.74 g, 10 mmol) was replaced with 9-(4-bromophenyl)-9H-carbazole (3.22 g, 10 mmol), and 2-(3-bromophenyl)-[1,2,4]triazolo[1,5-a]pyridine (1.37 g, 5 mmol) was replaced with 2-(4-bromophenyl)-[1,2,4]triazolo[1,5-a]pyridine (1.37 g, 5 mmol). The rest of the synthesis process was carried out in substantially the same manner as in Synthesis Example 3 (same reaction molar ratio and reaction conditions) to obtain 2.14 g of the target compound (2-137) in a yield of 76%. Mass spectrometer MALDI-TOF-MS (m / z) = 564.6509, theoretical molecular weight: 564.6520; elemental analysis: theoretical value: C 38 H 24 N6 (%): C80.83; H4.28; N14.88; measured value: C80.81; H4.29; N14.90.

[0155] Synthesis Example 59: Synthesis of Compound (2-141)

[0156] In Synthesis Example 3, 1,4-dibromonaphthalene (5.72 g, 20 mmol) was replaced with 2,4-dichloroquinazoline (3.98 g, 20 mmol), and 2-(3-bromophenyl)benzoxazole (2.74 g, 10 mmol) was replaced with 3-bromo-N,N-diphenylaniline (3.24 g, 10 mmol). The remaining synthesis process was essentially the same as in Synthesis Example 3 (same reaction molar ratios and reaction conditions) to obtain 2.04 g of the target compound (2-141) in a 72% yield. Mass spectrometry: MALDI-TOF-MS (m / z) = 566.6685, theoretical molecular weight: 566.6680; elemental analysis: theoretical value: C 38 H 26 N6 (%): C80.54; H4.62; N14.83; measured value: C80.57; H4.60; N14.82.

[0157] According to the above-mentioned synthesis examples 38 to 59, compounds (2-1) to (2-150) other than the above-mentioned compounds can be prepared by basically the same method (same reaction molar ratio and reaction conditions).

[0158] Device Example 1-1

[0159] The glass substrate with a 100 nm ITO transparent film was ultrasonically cleaned with acetone, isopropyl alcohol and deionized water for 10 min each, vacuum dried at 105°C for 2 h, and then UV ozone washed for 15 min. The ITO glass substrate was then transferred to a vacuum evaporator.

[0160] On the surface where the ITO film is formed, molybdenum trioxide (MoO3) is vacuum evaporated to form a 10nm thick hole injection layer;

[0161] Next, 4,4'-cyclohexylbis[N,N-di(4-methylphenyl)aniline] (TAPC) was vacuum-deposited on the hole injection layer to form a 70 nm thick hole transport layer.

[0162] Next, 1,3-di(9H-carbazol-9-yl)benzene (mCP) was vacuum-evaporated on the hole transport layer to form a 15 nm electron blocking layer.

[0163] Next, 4,4'-bis(9-carbazole)biphenyl (CBP, as a light-emitting host material, 95 wt%) and tris(2-phenylpyridine)iridium (Ir(ppy)3, as a light-emitting guest material, 5 wt%) were co-vapor-deposited on the electron blocking layer to form a 30 nm thick light-emitting layer.

[0164] Next, on the light-emitting layer, compound 1-2 prepared in Synthesis Example 1 was vacuum-deposited to form an electron transport layer with a thickness of 15 nm.

[0165] Next, lithium fluoride (LiF) is vacuum-evaporated on the electron transport layer to form an electron injection layer with a thickness of 1 nm.

[0166] Finally, aluminum (Al) was vacuum-deposited on the electron injection layer to form a cathode with a thickness of 100 nm.

[0167] Device Example 1-2 to Device Example 1-38

[0168] An organic electroluminescent device was prepared in the same manner as in Device Example 1-1, except that the compounds synthesized in Synthesis Examples 2-30 and 38 were used to replace Compound 1-2 prepared in Synthesis Example 1.

[0169] Device Comparative Example 1-39 to Device Comparative Example 1-42

[0170] An organic electroluminescent device was prepared by the same method as in Device Example 1-1, except that 3,3'-[5'-[3-(3-pyridyl)phenyl][1,1':3',1"-terphenyl]-3,3"-diyl]dipyridine (TmPyPB) or the following compounds C1, C2, and C3 were used to replace the compound 1-2 prepared in Synthesis Example 1;

[0171]

[0172] The performance of the organic electroluminescent devices prepared in the above device examples and device comparative examples was tested, and the results are shown in Table 1:

[0173] Table 1

[0174]

[0175]

[0176] From the data in Table 1 above, it can be confirmed that compared with the compound C1 formed by using the traditional TmPyPB and biphenyl as the bridging group between the electron acceptors, the compound C2 not containing the triazolopyridine group mentioned in the present invention, and the compound C3 modified on the electron-donating site of the triazolopyridine group, the organic electroluminescent material represented by Formula I provided by the present invention has a hole transport rate (10 -2The present invention has an electron transfer rate that is more closely matched to the electron transfer rate of the present invention (orders of magnitude), has hole blocking ability, and gives the compound higher thermal stability, effectively overcoming the incompatibility between "high mobility and high triplet exciton confinement" in traditional electron transport materials. In addition, the compound of the present invention can effectively confine holes in the light-emitting layer when used as an electron transport material. It is an electron transport material with significant improvements in comprehensive performance such as efficiency, electron transfer rate, thermal stability, light color, and lifespan.

[0177] Device Example 2-1

[0178] The glass substrate with a 120 nm ITO transparent film was ultrasonically cleaned with acetone, isopropyl alcohol and deionized water for 10 min each, vacuum dried at 105°C for 2 h, and then UV ozone washed for 15 min. The ITO glass substrate was then transferred to a vacuum evaporator.

[0179] On the surface where the ITO film is formed, molybdenum trioxide (MoO3) is vacuum evaporated to form a 10nm thick hole injection layer;

[0180] Next, 4,4'-cyclohexylbis[N,N-di(4-methylphenyl)aniline] (TAPC) was vacuum-deposited on the hole injection layer to form a 70 nm thick hole transport layer.

[0181] Next, 1,3-di(9H-carbazol-9-yl)benzene (mCP) was vacuum-evaporated on the hole transport layer to form a 15 nm electron blocking layer.

[0182] Next, tris(2-phenylpyridine)iridium (Ir(ppy)3, as a luminescent guest material, 5 wt%) and 4,4'-bis(9-carbazole)biphenyl (CBP, as a luminescent host material, 90 wt%) were co-vapor-deposited on the electron-blocking layer to form a 30 nm thick light-emitting layer.

[0183] Next, compound 2-3 prepared in Synthesis Example 39 was vacuum-deposited on the light-emitting layer to form an electron transport layer with a thickness of 15 nm.

[0184] Next, lithium fluoride (LiF) is vacuum-evaporated on the electron transport layer to form an electron injection layer with a thickness of 1 nm.

[0185] Finally, aluminum (Al) was vacuum-deposited on the electron injection layer to form a cathode with a thickness of 100 nm.

[0186] Device Example 2-2 to Device Example 2-23

[0187] An organic electroluminescent device was prepared in the same manner as in Device Example 2-1, except that the compounds synthesized in Synthesis Examples 39-60 were used to replace Compound 2-3 prepared in Synthesis Example 38.

[0188] Device Comparative Example 2-24 to Device Comparative Example 2-25

[0189] An organic electroluminescent device was prepared by the same method as in Device Example 2-1, except that Compound C4 and C5 shown below were used instead of Compound 2-3.

[0190]

[0191] The performance of the organic electroluminescent devices prepared in the above device examples and device comparative examples was tested, and the results are shown in Table 2:

[0192] Table 2

[0193]

[0194] The data in Table 2 above confirm that, compared with the conventional CBP, the compound C4 in which the electron-donating site of the triazolopyridine is modified on the six-membered ring and the electron-donating group anthracene is used as a bridging group, and the compound C5 in which the large conjugated electron-donating group is used as a bridging group, the organic electroluminescent material represented by Formula II provided by the present invention uses a planar, rigid, electron-deficient diaza-fused aromatic ring group as a high-carrier transport channel. The electron-deficient triazolopyridine group is bonded to the electron-donating anthracene, fluorene, dibenzo-pentacyclic ring, carbazole, aromatic amine, and other groups on its periphery, forming a series of novel light-emitting host materials with more balanced hole and electron carriers. This solves the problem of severe device efficiency roll-off in phosphorescent devices at high current densities, and fully utilizes the properties of the diaza-fused aromatic ring to reduce the triplet energy level and blue shift of the material, so that the organic electroluminescent material provided by the present invention emits a purer and saturated blue light when applied to green phosphorescent devices, thereby significantly improving the overall performance of driving voltage, efficiency, glass transition temperature, and device life.

[0195] Device Example 3-1

[0196] The glass substrate with a 120 nm ITO transparent film was ultrasonically cleaned with acetone, isopropyl alcohol and deionized water for 10 min each, vacuum dried at 105°C for 2 h, and then UV ozone washed for 15 min. The ITO glass substrate was then transferred to a vacuum evaporator.

[0197] On the surface where the ITO film is formed, molybdenum trioxide (MoO3) is vacuum evaporated to form a 10nm thick hole injection layer;

[0198] Next, 4,4'-cyclohexylbis[N,N-di(4-methylphenyl)aniline] (TAPC) was vacuum-deposited on the hole injection layer to form a 70 nm thick hole transport layer.

[0199] Next, 1,3-di(9H-carbazol-9-yl)benzene (mCP) was vacuum-evaporated on the hole transport layer to form a 15 nm electron blocking layer.

[0200] Next, tris(2-phenylpyridine)iridium (Ir(ppy)3, as a luminescent guest material, 5 wt%) and 4,4'-bis(9-carbazole)biphenyl (CBP, as a luminescent host material, 90 wt%) were co-vapor-deposited on the electron-blocking layer to form a 30 nm thick light-emitting layer.

[0201] Next, the compound 1-2 prepared in Synthesis Example 1 was vacuum-deposited on the light-emitting layer to form a hole-blocking layer with a thickness of 10 nm.

[0202] Next, 3,3'-[5'-[3-(3-pyridyl)phenyl][1,1':3',1"-terphenyl]-3,3"-diyl]dipyridine (TmPyPB) was vacuum-deposited on the hole-blocking layer to form an electron transport layer with a thickness of 15 nm.

[0203] Next, lithium fluoride (LiF) is vacuum-evaporated on the electron transport layer to form an electron injection layer with a thickness of 1 nm.

[0204] Finally, aluminum (Al) was vacuum-deposited on the electron injection layer to form a cathode with a thickness of 100 nm.

[0205] Device Example 3-2 to Device Example 3-7

[0206] An organic electroluminescent device was prepared in the same manner as in Device Example 3-1, except that the compounds synthesized in Synthesis Example 1-38 were used to replace Compound 1-2 prepared in Synthesis Example 1.

[0207] Device Comparative Examples 3-9 to Device Examples 3-10

[0208] An organic electroluminescent device was prepared in the same manner as in Device Example 3-1, except that the following compounds C1 and C3 were used to replace the compound 1-2 prepared in Synthesis Example 1.

[0209]

[0210] The performance of the organic electroluminescent devices prepared in the above device examples and device comparative examples was tested, and the results are shown in Table 3:

[0211]

[0212] The data in Table 3 above confirm that, compared with conventional devices that do not contain hole-blocking layer materials, devices in which compound C1 formed by biphenyl as a bridging group between electron acceptors serves as a hole-blocking layer, and devices in which compound C3 modified on the six-membered ring at the electron-donating site of the triazolopyridine group serves as a hole-blocking layer, the organic electroluminescent material formed by the organic electroluminescent material represented by Formula I provided by the present invention has a deeper LUMO due to the special N-N bond of the triazolopyridine group and the further introduction of electron-withdrawing groups at the strong electron-withdrawing sites of the triazolopyridine group through high carrier channels. This has a hole-blocking ability and can be applied to organic electroluminescent devices as a hole-blocking layer to improve device performance.

[0213] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. An electronic organic electroluminescent material based on triazolopyridine, characterized in that: The compound of the organic electroluminescent material is formed by bonding a triazolopyridine group with a condensed ring structure, and its general structural formula is shown in Formula II: Wherein, said R6-R9 are independently selected from: hydrogen; Formula II is represented by the following compounds (B1), (B2), (B3), and (B4): Among them, R 31 、R 32 each independently selected from: hydrogen; L0, L2 are independently: a single bond, a phenylene group; R0 is independently selected from: hydrogen, unsubstituted or substituted C6-C6 alkyl, C1-C6 alkyl 30 Aryl, unsubstituted C3-C 30 Heteroaryl, unsubstituted C6-C 30 of aromatic amine groups.

2. An electronic organic electroluminescent material based on triazolopyridine, characterized in that: The compound of the organic electroluminescent material is formed by bonding a triazolopyridine group with a condensed ring structure, and its general structural formula is shown in Formula II: Wherein, said R6-R9 are independently selected from: hydrogen; Formula II is represented by the following compounds (B1), (B2), (B3), and (B4): Among them, R 31 、R 32 Each independently selected from: hydrogen; L0, L2 are independently: a single bond, a phenylene group; R0 is selected from the following groups:

3. An electronic organic electroluminescent material based on triazolopyridine, characterized in that: The organic electroluminescent material is selected from the compounds represented by any one of the following structural formulas:

4. An organic electroluminescent device comprising a cathode, an electron transport layer, a light emitting layer, a hole transport layer and an anode, or comprising an optical cover layer, a cathode, an electron transport layer, a light emitting layer, a hole transport layer and an anode, characterized in that: The light-emitting layer and / or the optical cover layer comprises the organic electroluminescent material according to claim 3 .

5. The organic electroluminescent device according to claim 4, characterized in that: The light-emitting layer is composed of a light-emitting host and a light-emitting guest, and the light-emitting host comprises the organic electroluminescent material according to claim 3.

Images