CN116082369A - Organic electroluminescent material based on triazolopyridine and organic electroluminescent device - Google Patents

Organic electroluminescent material based on triazolopyridine and organic electroluminescent device Download PDF

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CN116082369A
CN116082369A CN202310143379.0A CN202310143379A CN116082369A CN 116082369 A CN116082369 A CN 116082369A CN 202310143379 A CN202310143379 A CN 202310143379A CN 116082369 A CN116082369 A CN 116082369A
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穆广园
庄少卿
任春婷
徐鹏
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Wuhan Sunshine Optoelectronics Tech Co ltd
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Abstract

The invention relates to the field of photoelectric material application technology, and discloses an organic electroluminescent material based on triazolopyridine and an organic electroluminescent device. The organic electroluminescent material provides an electron transport material and a luminescent main material with excellent comprehensive performance through fine regulation and control of a specific functional group on a triazolopyridine group, effectively solves the technical problems of mismatching of electron transport material and hole transport rate and poor stability in the prior art, and the technical problems of efficiency roll-off and light color impurity of a green main material device, further improves the comprehensive performance of the device in the aspects of driving voltage, efficiency, light color, thermal stability, service life and the like, and accelerates the industrialized development process of the photoelectric material.

Description

Organic electroluminescent material based on triazolopyridine and organic electroluminescent device
The invention relates to a triazolopyridine-based organic electroluminescent material and an organic electroluminescent device, which are divisionally applied for the application of which the application date is 2019, 8, 22 and 2019107795498.
Technical Field
The invention belongs to the technical field of photoelectric material application, and particularly relates to an organic electroluminescent material based on triazolopyridine and an organic electroluminescent device.
Background
An organic light-emitting diode (OLED) has the advantages of self-luminescence, low driving voltage, high contrast, wide viewing angle, wide applicable temperature range and the like, and becomes one of the most developed novel display technologies at present. Through the continuous efforts of researchers and enterprises, researchers have developed many high-performance light-emitting materials and auxiliary electrode materials successively, but commonly used hole-transporting materials such as N, N '-dinaphthyl-N, N' -diphenyl-benzidine (NPB), N, N '-di (3-methylphenyl) -N, N' -diphenyl-1, 1-diphenyl-4, 4-diamine (TPD) have a hole-transporting rate of up to 10 -2 cm 2 V -1 S -1 Of the order of magnitude, but more widely used, aluminum 8-hydroxyquinoline (Alq 3 ) The electron transport rate of (2) is two orders of magnitude different from that of (2), and the electron transport rate of most electron transport materials is only 10 at present -4 ～10 -6 cm 2 V -1 S -1 . That is, the device requirements for balanced implantation are not met. In an organic electroluminescent device, the mobility of carriers of holes of most materials is often hundreds of times that of electrons, and due to mismatching of migration speeds, two carriers have a high probability of not being compounded in a light-emitting layer, so that the photoelectric performance of the device is reduced, such as light-emitting brightness, light-emitting efficiency, color purity and the like, and meanwhile, leakage current is increased, heat is generated, and the service life of the device is reduced. Therefore, matching the migration velocity of the two carriers, i.e., improving the mobility of electrons and effectively confining holes in the light emitting layer, is a key to improving device performance. Nitrogen-containing heterocyclic compounds such as triazine ring and benzimidazole are developed successively The method is applied to the organic light-emitting diode for electron transport materials to improve the electron transport capacity of the device, thereby improving the photoelectric performance of the device. However, the triazine compounds, benzimidazole compounds and benzothiazole compounds, which have been reported, mostly have their conjugated structures changed by chemical modification of substituents, and the HOMO and LUMO energy levels of the compounds are adjusted to prepare electron-transporting hole-blocking materials having suitable energy levels, but the electron-transporting and hole-blocking capacities of many materials are irregular, resulting in great differences in the performance of devices. Therefore, the development of higher rate electron transport materials is of great importance to improve overall device performance.
In addition, in OLED devices, the design and combination of the light-emitting layers plays a key role in the device performance, which directly determines the light-emitting efficiency and lifetime of the device. The excited state lifetime of aryltriazine phosphors is relatively long and severe efficiency roll-off is often observed. Benzimidazole is a very good electron transport group and has many applications in host materials and electron transport materials, however, its stability is still not matched with the practical application requirements of devices. Therefore, the development of a novel material system with high luminous efficiency, low starting voltage, good film forming property, long service life and good stability is an important direction of research in the field.
Disclosure of Invention
The invention aims to provide an organic electroluminescent material and a device based on triazolopyridine, which solve the problem that the photoelectric performance of the device is reduced due to the mismatching of electron/hole migration speed of an electron transport layer of an OLED device at present and the problem that the efficiency of a phosphorescent device is seriously rolled off under high current density, so that the OLED device has excellent comprehensive performance in the aspects of efficiency, thermal stability, light color, service life and the like.
The first aspect of the invention provides an electronic organic electroluminescent material based on triazolopyridine, wherein the compound of the organic electroluminescent material is formed by bonding a triazolopyridine group and a condensed ring structure, and the structural general formula of the compound is shown in formula II:
Figure BDA0004088300470000021
wherein the R is 6 -R 9 Independently selected from hydrogen, cyano, fluoro, deuterium, nitro, C 1 -C 6 Alkyl of C 1 -C 6 Alkoxy, C 1 -C 6 Unsubstituted or substituted by cyano, fluoro, deuterium, nitro, C 1 -C 6 Alkyl, C of (2) 1 -C 6 Alkoxy, C 1 -C 6 Alkylthio-substituted phenyl of (a);
Ar 4 、Ar 5 each of the heterocyclic rings is independently an empty or heterocyclic ring, and the heterocyclic rings and adjacent rings share a carbon-carbon chemical bond to form a condensed structure;
x is each independently C, N or C (R 29 ) And at least one X is N, L 2 Or L 0 X attached thereto is C, ar 4 Or Ar 5 Two X sharing carbon-carbon chemical bond are C;
wherein L is 0 、L 2 Independently of each other, is a single bond, unsubstituted or substituted by cyano, fluoro, nitro, C 1 -C 6 Alkyl-substituted phenylene, unsubstituted or substituted by cyano, fluoro, nitro, C 1 -C 6 Alkyl-substituted biphenylenes of (2) or unsubstituted or substituted by cyano, fluoro, nitro, C 1 -C 6 Alkyl-substituted naphthylene of (a);
R 29 selected from hydrogen, cyano, fluoro, deuterium, nitro, C 1 -C 6 Alkyl of C 1 -C 6 Alkoxy, C 1 -C 6 Unsubstituted or substituted by cyano, fluoro, deuterium, nitro, C 1 -C 6 Alkyl, C of (2) 1 -C 6 Alkoxy, C 1 -C 6 Alkylthio-substituted C of (C) 6 -C 30 Unsubstituted or substituted by cyano, fluoro, deuterium, nitro, C 1 -C 6 Alkyl, C of (2) 1 -C 6 Alkoxy, C 1 -C 6 Alkylthio-substituted C of (C) 6 -C 30 Unsubstituted or substituted by cyano, fluoro,Deuterium, nitro, C 1 -C 6 Alkyl, C of (2) 1 -C 6 Alkoxy, C 1 -C 6 Alkylthio-substituted C of (C) 6 -C 30 An arylamine group of (a);
R 0 independently selected from: hydrogen, fluorine, deuterium, nitro, cyano, hydroxy, C 1 -C 6 Alkyl of C 1 -C 6 Alkoxy, C 1 -C 6 Alkylthio of C 1 -C 6 Unsubstituted or substituted by deuterium, fluorine, cyano, nitro, C 1 -C 6 C substituted by alkyl 6 -C 30 Unsubstituted or substituted by deuterium, fluorine, cyano, nitro, C 1 -C 6 C substituted by alkyl 3 -C 30 Unsubstituted or substituted by deuterium, fluorine, cyano, nitro, C 1 -C 6 C substituted by alkyl 6 -C 30 Unsubstituted or substituted by deuterium, fluorine, cyano, nitro, C 1 -C 6 C substituted by alkyl 6 -C 30 Or, alternatively, unsubstituted or substituted by deuterium, fluorine, cyano, nitro, C 1 -C 6 C substituted by alkyl 6 -C 30 Is an arylboron group.
Further, the formula II may be further represented by compounds represented by the following (B1), (B2), (B3), (B4), (B5), (B6):
Figure BDA0004088300470000031
wherein R is 31 、R 32 Each independently selected from: hydrogen, cyano, fluoro, deuterium, nitro, C 1 -C 6 Alkyl of C 1 -C 6 Alkoxy, C 1 -C 6 Unsubstituted or substituted by cyano, fluoro, deuterium, nitro, C 1 -C 6 Alkyl, C of (2) 1 -C 6 Alkoxy, C 1 -C 6 Alkylthio-substituted phenyl groups of (a).
Further, the R 0 Selected from the following groups:
Figure BDA0004088300470000032
Figure BDA0004088300470000041
preferably, the organic electroluminescent material represented by formula II is selected from any one of the compounds represented by the following structural formulas:
Figure BDA0004088300470000042
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Figure BDA0004088300470000051
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Figure BDA0004088300470000061
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Figure BDA0004088300470000071
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Figure BDA0004088300470000081
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Figure BDA0004088300470000091
the organic electroluminescent material represented by the formula II is a series of novel luminescent main materials with more balanced hole and electron carriers, which are formed by taking phenanthroline, azaanthracene, quinazoline and other diaza condensed aromatic ring groups with plane, rigidity and electron-deficient chemical structures as high carrier transmission channels, and linking the electron-deficient triazole pyridine groups and the electron-deficient anthracene, fluorene, dibenzo five-membered ring, carbazole, aromatic amine and other groups at the periphery of the diaza condensed aromatic ring groups, so as to solve the problem of serious device efficiency roll-off of a phosphorescent device under high current density. Compared with a compound formed by taking a non-aza condensed ring aromatic group as a bridging group in the prior art, the organic electroluminescent material provided by the invention has higher electron migration rate due to the fact that the diaza condensed ring group is taken as a high carrier transmission channel with electron deficiency and is cooperated with a triazolopyridine group with electron deficiency, so that the transmission balance of holes and electrons in the material is maintained, and the device efficiency drop caused by triplet exciton annihilation is avoided to a certain extent; compared with a compound which does not contain a triazolopyridine group, the better rigid planar structure of the diaza aromatic ring serving as a bridging group reduces the triplet energy level of the material, so that the material becomes an excellent green light main material, and the triazolopyridine group at the tail end of the organic electroluminescent material shows the light color blue shift characteristic due to a special N-N bond, so that the organic electroluminescent material provided by the invention can emit more saturated and pure green light when applied to a green light phosphorescence device; compared with a compound formed by modification on a six-membered ring of triazolopyridine, the organic electroluminescent material provided by the invention is bonded with electron supply sites of large conjugated aromatic groups such as anthracene, fluorene, carbazole and arylamine by a rigid coplanar bridging group on a five-membered heterocycle with the strongest electron deficiency property of the triazolopyridine group, thereby being beneficial to the separation of HOMO orbitals and LUMO orbitals in space, avoiding the transfer of internal charges of molecules, simultaneously showing smaller molecular spacing and being compact in arrangement, so that the compound provided by the invention has higher thermal stability and non-crystallization property. Therefore, compared with the traditional DPEPO and the compound disclosed by the prior art, the compound disclosed by the invention has more balanced hole electron transmission rate due to fine molecular configuration and group selection, solves the problem of device efficiency reduction and rolling caused by unbalanced carrier and annihilation of triplet excitons, and has higher thermal stability and non-crystallization performance due to fine regulation and control of the group structure and structure of light color blue shift of the compound, thereby becoming a dark green light luminescent material with remarkable progress in comprehensive properties such as luminous efficiency, thermal stability, light color, service life and the like.
In addition, the five-membered heterocycle with the strongest electron-deficient property of the triazolopyridine group is bonded with the electron supply sites of large conjugated aromatic groups such as anthracene, fluorene, carbazole and arylamine through a rigid coplanar bridging group, so that the organic electroluminescent material represented by the formula II in the invention has smaller molecular spacing, compact arrangement and higher refractive index, and becomes an ideal optical cover layer for preparing a top-emission device.
In a third aspect, the present invention provides an organic electroluminescent device, which comprises a cathode, an electron transport layer, a light emitting layer, a hole transport layer and an anode, or comprises an optical coating 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 coating layer comprises the organic electroluminescent material represented by formula II.
Further, 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 formula II.
Detailed Description
It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
Synthesis of intermediate 2-bromo- [1,2,4] triazolo [1,5-a ] pyridine:
Figure BDA0004088300470000101
S1, adding pyridine-2-amine (1.88 g,20 mmol), ethyl isothiocyanamide (2.89 g,22 mmol) and 50mL of epoxy bicyclic solvent into a 100mL reaction bottle, stirring at room temperature for reaction for 10-14h, concentrating the reaction liquid, then adding 75mL of methanol/ethanol mixed solvent with volume ratio of 1:1, N, N-diethyl ethylamine (4.05 g,40 mmol) and hydroxylamine hydrochloride (4.17 g,60 mmol) into the reaction liquid, reacting at 60 ℃ for 2h, cooling to room temperature, cooling for crystallization, and filtering to obtain a filter cake which is a crude product of [1,2,4] triazole [1,5-a ] pyridine-2-amine;
s2, adding the [1,2,4] triazole [1,5-a ] pyridine-2-amine, copper bromide (6.7 g,30 mmol) and 100mL acetonitrile into a 250mL reaction bottle, cooling to 0 ℃ under nitrogen atmosphere, adding isobutyl nitrite (3.09 g,30 mmol), stirring for 1h, returning to room temperature, continuously stirring for 0.5h, adding 1mol/L hydrochloric acid aqueous solution to prepare the PH 1 after TLC monitoring the raw materials to be basically free, extracting dichloromethane, drying magnesium sulfate, filtering, concentrating the filtrate, and separating by column chromatography to obtain 3.08g of intermediate 2-bromo- [1,2,4] triazole [1,5-a ] pyridine, wherein the yield is 78%.
Mass spectrometer MALDI-TOF-MS (m/z) = 198.0176, theoretical molecular weight: 198.0230.
synthesis of intermediate 2- (4-bromophenyl) - [1,2,4] triazole [1,5-a ] pyridine:
Figure BDA0004088300470000111
To a 100mL reaction flask, 2-bromo- [1,2,4] triazol [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), 30mL toluene, 15mL water and 15mL ethanol were added, tetra (triphenylphosphine) palladium (0.04 g,0.03 mmol) was added under nitrogen atmosphere, the temperature was raised to 85℃for 10-24 hours, the liquid phase monitoring material was substantially not left, heating was stopped, cooling to room temperature, washing with water, filtering, concentrating the filtrate, and beating twice with ethanol together with the filter cake to obtain 2.40g of intermediate 2- (4-bromophenyl) - [1,2,4] triazol [1,5-a ] pyridine in 88% yield. Mass spectrometer MALDI-TOF-MS (m/z) = 274.1204, theoretical molecular weight: 274.1210;
intermediate 2- (3-bromophenyl) - [1,2,4] triazolo [1,5-a ] pyridine was prepared in substantially the same manner except that (4-bromophenyl) boronic acid (2.40 g,12 mmol) was replaced with (3-bromophenyl) boronic acid (2.40 g,12 mmol).
According to the synthesis of the synthetic intermediate 2- (4-bromophenyl) - [1,2,4] triazole [1,5-a ] pyridine, the preparation method can be obtained by basically the same method (same reaction molar ratio and reaction condition):
Figure BDA0004088300470000112
synthesis example 1: synthetic compound (1-2)
Figure BDA0004088300470000113
S1, adding 1, 4-dibromonaphthalene (2.86 g,10 mmol) into a 100mL reaction bottle, cooling to-78 ℃ with 50mL of dry tetrahydrofuran solution, dropwise adding 8mL of 2.5M n-butyllithium tetrahydrofuran solution under nitrogen atmosphere, keeping the temperature at-78 ℃ for reacting for 1-2h, dropwise adding triisopropyl borate (22 mmol,5.08 mL), cooling to room temperature after the dropwise adding, dropwise adding diluted hydrochloric acid for quenching reaction after 8h, distilling under reduced pressure to remove tetrahydrofuran, adding dichloromethane for dissolving, washing, drying with anhydrous magnesium sulfate, filtering, concentrating filtrate, pulping with ethanol for 1-2 times to obtain 1.88g of naphthalene-1, 4-diyl boric acid, and obtaining the yield of 87%;
S2, adding naphthalene-1, 4-diylboric acid (1.08 g,5 mmol) and 2- (4-bromophenyl) - [1,2,4] triazole [1,5-a ] pyridine (3.29 g,12 mmol), potassium carbonate (1.38 g,10 mmol), 30mL toluene, 15mL water and 15mL ethanol into a 100mL reaction bottle, adding tetra (triphenylphosphine) palladium (0.02 g,0.015 mmol) under nitrogen atmosphere, heating to 85 ℃ for reaction for 10-24h, monitoring the raw materials in liquid phase to be basically no residue, stopping heating, cooling to room temperature, washing with water, filtering, concentrating filtrate, and using dichloromethane together with filter cake: performing column chromatography separation on the leaching solution with petroleum ether of 1:10, concentrating again, and drying to obtain 1.95g of target compound (1-2), with a yield of 76%;
mass spectrometer MALDI-TOF-MS (m/z) = 514.5932, theoretical molecular weight: 514.5920; elemental analysis: theoretical value: c (C) 34 H 22 N 6 (%): c79.36; h4.31; n16.33; actual measurement value: c79.35; h4.30; n16.35.
Synthesis example 2: synthetic compound (1-6)
1, 4-dibromonaphthalene (2.86 g,10 mmol) in Synthesis example 1 was replaced with 2, 6-dibromonaphthalene (2.86 g,10 mmol), 2- (4-bromophenyl) - [1,2,4]]Triazole [1,5-a ]]Pyridine (3.29 g,12 mmol) is replaced by 2- (3-bromophenyl) - [1,2,4]]Triazole [1,5-a ]]Pyridine (3.29 g,12 mmol), other synthetic procedures were carried out in substantially the same manner (same molar ratio of reaction) as in Synthesis example 1 With the reaction conditions), 2.00g of the objective compound (1-6) was obtained in 78% yield. Mass spectrometer MALDI-TOF-MS (m/z) = 514.5911, theoretical molecular weight: 514.5920; elemental analysis: theoretical value: c (C) 34 H 22 N 6 (%): c79.36; h4.31; n16.33; actual measurement value: c79.35; h4.33; n16.32.
Synthesis example 3: synthetic compound (1-9)
Figure BDA0004088300470000121
S1, adding 1, 4-dibromonaphthalene (5.72 g,20 mmol) into a 100mL reaction bottle, cooling to-78 ℃ with 50mL of dry tetrahydrofuran solution, dropwise adding 16mL of 2.5M n-butyllithium tetrahydrofuran solution under nitrogen atmosphere, keeping the temperature at-78 ℃ for reacting for 1-2h, dropwise adding triisopropyl borate (44 mmol,10.16 mL), cooling to room temperature after the dropwise adding, dropwise adding diluted hydrochloric acid for quenching reaction after 8h, distilling under reduced pressure to remove tetrahydrofuran, adding dichloromethane for dissolving, washing, drying with anhydrous magnesium sulfate, filtering, concentrating filtrate, pulping with ethanol for 1-2 times to obtain 3.80g of naphthalene-1, 4-diyl diboronic acid, and obtaining the yield of 88%;
s2, adding the naphthalene-1, 4-diyl diboronic acid (3.24 g,15 mmol), 2- (3-bromophenyl) benzoxazole (2.74 g,10 mmol), potassium carbonate (2.76 g,20 mmol), 30mL of toluene, 15mL of water and 15mL of ethanol into a 100mL reaction bottle, adding tetrakis (triphenylphosphine) palladium (0.04 g,0.03 mmol) under nitrogen atmosphere, heating to 85 ℃ for reaction for 10-24h, stopping heating the liquid phase monitoring raw materials, cooling to room temperature, washing with water, filtering, concentrating the filtrate, pulping with ethyl acetate for 2-3 times together with a filter cake to obtain 2.66g (4- (3- (benzoxazol-2-yl) phenyl) naphthalene-1-yl) boric acid, and obtaining 73% yield;
S3, adding the (4- (3- (benzoxazol-2-yl) phenyl) naphthalene-1-yl) boric acid (1.83 g,5 mmol), 2- (3-bromophenyl) - [1,2,4] triazole [1,5-a ] pyridine (1.37 g,5 mmol), potassium carbonate (1.38 g,10 mmol), 30mL toluene, 15mL water and 15mL ethanol into a 100mL reaction bottle, adding tetra (triphenylphosphine) palladium (0.02 g,0.015 mmol) under nitrogen atmosphere, heating to 85 ℃ for reaction for 10-24h, and performing liquid phase monitoring on the raw materials without residual, stopping heating, cooling to room temperature, washing with water, filtering, concentrating filtrate, and using dichloromethane with filter cake: performing column chromatography separation on the leaching solution with petroleum ether of 1:10, concentrating again, and drying to obtain 2.11g of target compound (1-9) with the yield of 82%;
mass spectrometer MALDI-TOF-MS (m/z) = 514.5892, theoretical molecular weight: 514.5880; elemental analysis: theoretical value: c (C) 35 H 22 N 4 (%): c81.69; h4.31; n10.89; actual measurement value: c81.67; h4.30; n10.91.
Synthesis example 4: synthetic compound (1-21)
1, 4-dibromonaphthalene (2.86 g,10 mmol) in Synthesis example 1 was replaced with 9, 10-dibromoanthracene (3.36 g,10 mmol), 2- (4-bromophenyl) - [1,2,4]]Triazole [1,5-a ]]Pyridine (3.29 g,12 mmol) is replaced by 2- (3-bromophenyl) - [1,2,4]]Triazole [1,5-a ]]Pyridine (3.29 g,12 mmol) and other synthetic procedures were carried out in substantially the same manner (same reaction molar ratio and reaction conditions) as in synthetic example 1 to obtain 2.17g of the objective compound (1-21) in 77% yield. Mass spectrometer MALDI-TOF-MS (m/z) = 564.6509, theoretical molecular weight: 564.6520; elemental analysis: theoretical value: c (C) 38 H 24 N 6 (%): c80.83; h4.28; n14.88; actual measurement value: c80.82; h4.30; n14.88.
Synthesis example 5: synthetic compound (1-22)
1, 4-dibromonaphthalene (2.86 g,10 mmol) in Synthesis example 1 was replaced with 2, 6-dibromoanthracene (3.36 g,10 mmol), 2- (4-bromophenyl) - [1,2, 4)]Triazole [1,5-a ]]Pyridine (3.29 g,12 mmol) is replaced by 2-bromo- [1,2,4 ]]Triazole [1,5-a ]]Pyridine (2.38 g,12 mmol) and other synthetic procedures were carried out in substantially the same manner (same reaction molar ratio and reaction conditions) as in synthetic example 1 to obtain 1.53g of the objective compound (1-22) in 74% yield. Mass spectrometer MALDI-TOF-MS (m/z) = 412.4557, theoretical molecular weight: 412.4560; elemental analysis: theoretical value: c (C) 26 H 16 N 6 (%): c75.71; h3.91; n20.38; actual measurement value: c75.71; h3.89; n20.40.
Synthesis example 6: synthetic compound (1-26)
1, 4-Dibromonaphthalene (2.86 g,10 mmol) in Synthesis example 1 was replaced with 1, 5-dibromoanthracene (3.36 g,10 mmol), and other syntheses were performedThe procedure was as in Synthesis example 1 in substantially the same manner (same reaction molar ratio and reaction conditions), to obtain 2.11g of the title compound (1-26) in a yield of 75%. Mass spectrometer MALDI-TOF-MS (m/z) = 564.6509, theoretical molecular weight: 564.6520; elemental analysis: theoretical value: c (C) 38 H 24 N 6 (%): c80.83; h4.28; n14.88; actual measurement value: c80.85; h4.29; n14.86.
Synthesis example 7: synthetic Compound (1-33)
1, 4-dibromonaphthalene (5.72 g,20 mmol) in Synthesis example 3 was replaced with 2, 6-dibromoanthracene (6.72 g,20 mmol), and the other synthesis procedures were the same as in Synthesis example 3 (same reaction molar ratio and reaction conditions), whereby 2.37g of the objective compound (1-33) was obtained in 84% yield. Mass spectrometer MALDI-TOF-MS (m/z) = 564.6476, theoretical molecular weight: 564.6480; elemental analysis: theoretical value: c (C) 39 H 24 N 4 (%): c82.96; h4.28; n9.92; actual measurement value: c82.98; h4.29; n9.90.
Synthesis example 8: synthetic Compound (1-46)
1, 4-dibromonaphthalene (2.86 g,10 mmol) in Synthesis example 1 was replaced with 1, 6-dibromopyrene (3.60 g,10 mmol), 2- (4-bromophenyl) - [1,2,4 ]]Triazole [1,5-a ]]Pyridine (3.29 g,12 mmol) is replaced by 2-bromo- [1,2,4 ]]Triazole [1,5-a ]]Pyridine (2.38 g,12 mmol) and other synthetic procedures were carried out in substantially the same manner (same reaction molar ratio and reaction conditions) as in synthetic example 1 to obtain 1.59g of the objective compound (1-46) in 73% yield. Mass spectrometer MALDI-TOF-MS (m/z) = 436.4768, theoretical molecular weight: 436.4780; elemental analysis: theoretical value: c (C) 28 H 16 N 6 (%): c77.05; h3.70; n19.25; actual measurement value: c77.04; h3.72; n19.24.
Synthesis example 9: synthetic compound (1-48)
1, 4-dibromonaphthalene (2.86 g,10 mmol) in Synthesis example 1 was replaced with 1, 6-dibromopyrene (3.60 g,10 mmol), and the other synthesis procedures were the same as in Synthesis example 1 (same reaction molar ratio and reaction conditions), whereby 2.20g of the objective compound (1-48) was obtained in 75% yield. Mass spectrometer MALDI-TOF-MS (m/z) = 588.6750, theoretical molecular weight: 588.6740. Elemental analysis: theoretical value: c (C) 40 H 24 N 6 (%): c81.61; h4.11; n14.28; actual measurement value: c81.58; h4.12; n14.30.
Synthesis example 10: synthetic Compound (1-55)
1, 4-dibromonaphthalene (5.72 g,20 mmol) in Synthesis example 3 was replaced with 1, 8-dibromopyrene (7.20 g,20 mmol), and the other synthesis procedures were carried out in substantially the same manner (same reaction molar ratio and reaction conditions) as in Synthesis example 3 to obtain 2.35g of the objective compound (1-55) in 80% yield. Mass spectrometer MALDI-TOF-MS (m/z) = 588.6708, theoretical molecular weight: 588.6700; elemental analysis: theoretical value: c (C) 41 H 24 N 4 (%): c83.65; h4.11; n9.52; actual measurement value: c83.65; h4.08; n9.53.
Synthesis example 11: synthetic Compound (1-56)
1, 4-Dibromonaphthalene (5.72 g,20 mmol) in Synthesis example 3 was replaced with 1, 6-dibromopyrene (7.20 g,20 mmol), 2- (3-bromophenyl) benzoxazole (2.74 g,10 mmol) was replaced with 2-bromobenzothiazole (2.14 g,10 mmol), 2- (3-bromophenyl) - [1,2,4]Triazole [1,5-a ]]Pyridine (1.37 g,5 mmol) replaced with 2-bromo- [1,2,4]Triazole [1,5-a ]]Pyridine (0.99 g,5 mmol) and other synthetic procedures were followed in substantially the same manner (same reaction molar ratio and reaction conditions) as in synthetic example 3 to give 1.76g of the title compound (1-56) in 78% yield. Mass spectrometer MALDI-TOF-MS (m/z) = 452.5360, theoretical molecular weight: 452.5350; elemental analysis: theoretical value: c (C) 29 H 16 N 4 (%): c76.97; h3.56; n12.38; actual measurement value: c76.96; h3.56; n12.40.
Synthesis example 12: synthetic Compound (1-71)
2- (3-bromophenyl) benzoxazole (2.74 g,10 mmol) in Synthesis example 3 was replaced with 2-chloro-4, 6-bis (naphthalen-2-yl) -1,3, 5-triazine (3.68 g,10 mmol), 2- (3-bromophenyl) - [1,2,4 ]]Triazole [1,5-a ]]Pyridine (1.37 g,5 mmol) replaced with 2-bromo- [1,2,4]Triazole [1,5-a ]]Pyridine (0.99 g,5 mmol) and other synthetic procedures were followed in substantially the same manner (same reaction molar ratio and reaction conditions) as in synthetic example 3 to give 2.36g of the title compound (1-71) in 82% yield. Mass spectrometer MALDI-TOF-MS (m/z) = 576.6638, reason Theoretical molecular weight: 576.6630; elemental analysis: theoretical value: c (C) 39 H 24 N 6 (%): c81.23; h4.20; n14.57; actual measurement value: c81.24; h4.20; n14.56.
Synthesis example 13: synthetic Compound (1-79)
2- (3-bromophenyl) benzoxazole (2.74 g,10 mmol) in Synthesis example 3 was replaced with 4- (4-chlorophenyl) -2, 6-diphenylpyrimidine (3.43 g,10 mmol), 2- (3-bromophenyl) - [1,2,4 ]]Triazole [1,5-a ]]Pyridine (1.37 g,5 mmol) replaced with 2-bromo- [1,2,4]Triazole [1,5-a ]]Pyridine (0.99 g,5 mmol) and other synthetic procedures were followed in substantially the same manner (same reaction molar ratio and reaction conditions) as in synthetic example 3 to give 2.23g of the title compound (1-79) in 81% yield. Mass spectrometer MALDI-TOF-MS (m/z) = 551.6517, theoretical molecular weight: 551.6530; elemental analysis: theoretical value: c (C) 38 H 25 N 5 (%): c82.74; h4.57; n12.70; actual measurement value: c82.73; h4.59; n12.68.
Synthesis example 14: synthetic compound (1-96)
1, 4-Dibromonaphthalene (5.72 g,20 mmol) in Synthesis example 3 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- ([ 1,1' -biphenyl)]-4-yl) -4- (3-chlorophenyl) -6-phenyl-1, 3, 5-triazine (4.20 g,10 mmol), 2- (3-bromophenyl) - [1,2,4 ]Triazole [1,5-a ]]Pyridine (1.37 g,5 mmol) replaced with 2-bromo- [1,2,4]Triazole [1,5-a ]]Pyridine (0.99 g,5 mmol) and other synthetic procedures were carried out in substantially the same manner (same reaction molar ratio and reaction conditions) as in synthetic example 3 to obtain 2.60g of the objective compound (1-96) in 83% yield. Mass spectrometer MALDI-TOF-MS (m/z) = 628.7378, theoretical molecular weight: 628.7390; elemental analysis: theoretical value: c (C) 43 H 28 N 6 (%): c82.14; h4.49; n13.37; actual measurement value: c82.15; h4.46; n13.39.
Synthesis example 15: synthetic Compound (1-102)
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-chloro-4, 6-diphenylpyridine (2.66 g,10 mmol), 2- (3-bromophenyl) - [1,2,4]Triazole [1,5-a ]]Pyridine (1.37 g)5 mmol) of 2-bromo- [1,2,4]Triazole [1,5-a ]]Pyridine (0.99 g,5 mmol) and other synthetic procedures were carried out in substantially the same manner (same reaction molar ratio and reaction conditions) as in synthetic example 3 to obtain 2.12g of the objective 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 (C) 37 H 24 N 4 (%): c84.71; h4.61; n10.68; actual measurement value: c84.72; h4.60; n10.68.
Synthesis example 16: synthetic compound (1-121)
1, 4-Dibromonaphthalene (5.72 g,20 mmol) in Synthesis example 3 was replaced with 2, 6-dibromoanthracene (6.72 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), 2- (3-bromophenyl) - [1,2, 4)]Triazole [1,5-a ]]Pyridine (1.37 g,5 mmol) replaced with 2-bromo- [1,2,4]Triazole [1,5-a ]]Pyridine (0.99 g,5 mmol) and other synthetic procedures were followed in substantially the same manner (same reaction molar ratio and reaction conditions) as in synthetic example 3 to give 2.16g of the title compound (1-121) in 82% yield. Mass spectrometer MALDI-TOF-MS (m/z) = 526.6040, theoretical molecular weight: 526.6030; elemental analysis: theoretical value: c (C) 35 H 22 N 6 (%): c79.83; h4.21; n15.96; actual measurement value: c79.82; h4.23; n15.95.
Synthesis example 17: synthetic compound (1-135)
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), 2- (3-bromophenyl) - [1,2,4]Triazole [1,5-a ]]Pyridine (1.37 g,5 mmol) replaced with 2-bromo- [1,2,4]Triazole [1,5-a ]]Pyridine (0.99 g,5 mmol) and other synthetic procedures were carried out in substantially the same manner (same reaction molar ratio and reaction conditions) as in synthetic example 3 to obtain 2.41g of the title compound (1-135) in 80% yield. Mass spectrometer MALDI-TOF-MS (m/z) = 602.7002, theoretical molecular weight: 602.7010; elemental analysis: theoretical value: c (C) 41 H 26 N 6 (%): c81.71; h4.35; n13.94; actual measurement value: c81.70; h4.33; n13.97.
Synthesis example 18: synthetic compound (1-150)
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- (4-chlorophenyl) -4, 6-diphenyl-1, 3, 5-triazine (3.44 g,10 mmol), 2- (3-bromophenyl) - [1,2,4]Triazole [1,5-a ]]Pyridine (1.37 g,5 mmol) is replaced by 2- (4-bromophenyl) - [1,2,4 ]]Triazole [1,5-a ]]Pyridine (1.37 g,5 mmol) and other synthetic procedures were followed in substantially the same manner (same molar ratio and reaction conditions) as in synthetic example 3 to give 2.82g of the title compound (1-150) in 83% yield. Mass spectrometer MALDI-TOF-MS (m/z) = 678.7995, theoretical molecular weight: 678.7990; elemental analysis: theoretical value: c (C) 47 H 30 N 6 (%): c83.16; h4.45; n12.38; actual measurement value: c83.14; h4.46; n12.40.
Synthesis example 19: synthetic compound (1-155)
1, 4-dibromonaphthalene (5.72 g,20 mmol) in Synthesis example 3 was replaced with 2, 6-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 the other synthesis procedures were carried out in substantially the same manner (same reaction molar ratio and reaction conditions) as in Synthesis example 3 to obtain 2.88g of the objective compound (1-155) in 85% yield. Mass spectrometer MALDI-TOF-MS (m/z) = 678.7980, theoretical molecular weight: 678.7990; elemental analysis: theoretical value: c (C) 47 H 30 N 6 (%): c83.16; h4.45; n12.38; actual measurement value: c83.18; h4.45; n12.37.
Synthesis example 20: synthetic Compound (1-168)
1, 4-dibromonaphthalene (5.72 g,20 mmol) in Synthesis example 3 was replaced with 2, 7-dibromophenanthrene (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 the other synthesis procedures were carried out in substantially the same manner (same reaction molar ratio and reaction conditions) as in Synthesis example 3 to obtain 2.78g of the objective compound (1-168) in 82% yield. Mass spectrometer MALDI-TOF-MS (m/z) = 678.7984, theoretical molecular weight: 678.7990; elemental analysis: theoretical value: c (C) 47 H 30 N 6 (%): c83.16; h4.45; n12.38; actual measurement value: c83.17; h4.47; n12.36.
Synthesis example 21: synthetic Compound (1-173)
1, 4-Dibromonaphthalene (5.72 g,20 mmol) in Synthesis example 3 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), 2- (3-bromophenyl) - [1,2, 4)]Triazole [1,5-a ]]Pyridine (1.37 g,5 mmol) replaced with 2-bromo- [1,2,4]Triazole [1,5-a ]]Pyridine (0.99 g,5 mmol) and other synthetic procedures were carried out in substantially the same manner (same reaction molar ratio and reaction conditions) as in synthetic example 3 to obtain 2.20g of the objective compound (1-173) in 80% yield. Mass spectrometer MALDI-TOF-MS (m/z) = 550.6244, theoretical molecular weight: 550.6250; elemental analysis: theoretical value: c (C) 37 H 22 N 6 (%): c80.71; h4.03; n15.26; actual measurement value: c80.70; h4.05; n15.25.
Synthesis example 22: synthetic compound (1-186)
1, 4-dibromonaphthalene (5.72 g,20 mmol) in Synthesis example 3 was replaced with 1, 6-dibromopyrene (7.20 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 the other synthesis procedures were carried out in substantially the same manner (same reaction molar ratio and reaction conditions) as in Synthesis example 3 to obtain 2.88g of the objective compound (1-186) in 82% yield. Mass spectrometer MALDI-TOF-MS (m/z) = 702.8219, theoretical molecular weight: 702.8210; elemental analysis: theoretical value: c (C) 49 H 30 N 6 (%): c83.74; h4.30; n11.96; actual measurement value: c83.74; h4.30; n11.96.
Synthesis example 23: synthetic compound (1-189)
2- (3-bromophenyl) benzoxazole (2.74 g,10 mmol) in Synthesis example 3 was replaced with 2- (3-bromophenyl) -4-phenylquinazoline (3.61 g,10 mmol), and the other synthesis was carried out in substantially the same manner (same reaction molar ratio and reaction conditions) as in Synthesis example 3 to obtain 2.40g of the objective compound (1-189) in 80% yield. Mass spectrometer MALDI-TOF-MS (m/z) = 601.7134, theoretical molecular weight: 601.71 30; elemental analysis: theoretical value: c (C) 42 H 27 N 5 (%): c83.84; h4.52; n11.64; actual measurement value: c83.84; h4.52; n11.64.
Synthesis example 24: synthetic compound (1-193)
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- (3-bromophenyl) quinazoline (2.85 g,10 mmol), and the other synthesis procedures were carried out in substantially the same manner (same reaction molar ratio and reaction conditions) as in Synthesis example 3 to obtain 2.21g of the objective compound (1-193) in 84% yield. Mass spectrometer MALDI-TOF-MS (m/z) = 525.6137, theoretical molecular weight: 525.6150; elemental analysis: theoretical value: c (C) 36 H 23 N 5 (%): c82.26; h4.41; n13.32; actual measurement value: c82.26; h4.40; n13.34.
Synthesis example 25: synthetic Compound (1-196)
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- (4-bromophenyl) quinazoline (2.85 g,10 mmol), and the other synthesis procedures were carried out in substantially the same manner (same reaction molar ratio and reaction conditions) as in Synthesis example 3 to obtain 2.36g of the objective compound (1-196) in 82% yield. Mass spectrometer MALDI-TOF-MS (m/z) = 575.6741, theoretical molecular weight: 575.6750; elemental analysis: theoretical value: c (C) 40 H 25 N 5 (%): c83.46; h4.38; n12.17; actual measurement value: c83.45; h4.40; n12.15.
Synthesis example 26: synthetic compound (1-202)
1, 4-dibromonaphthalene (5.72 g,20 mmol) in Synthesis example 3 was replaced with 1, 5-dibromoanthracene (6.72 g,20 mmol), 2- (3-bromophenyl) benzoxazole (2.74 g,10 mmol) was replaced with 2- (3-bromophenyl) -4-phenylquinazoline (3.61 g,10 mmol), and the other synthesis procedures were carried out in substantially the same manner (same reaction molar ratio and reaction conditions) as in Synthesis example 3 to obtain 2.64g of the objective compound (1-202) in 81% yield. Mass spectrometer MALDI-TOF-MS (m/z) = 651.7744, theoretical molecular weight: 651.7730; elemental analysis: theoretical value: c (C) 46 H 29 N 5 (%): c84.77; h4.48; n10.75; actual measurement value: c84.78; h4.48; n10.74.
Synthesis example 27: synthetic compound (1-205)
1, 4-dibromonaphthalene (5.72 g,20 mmol) in Synthesis example 3 was replaced with 2, 7-dibromophenanthrene (6.72 g,20 mmol), 2- (3-bromophenyl) benzoxazole (2.74 g,10 mmol) was replaced with 2- (3-bromophenyl) -4-phenylquinazoline (3.61 g,10 mmol), and the other synthesis procedures were carried out in substantially the same manner (same reaction molar ratio and reaction conditions) as in Synthesis example 3 to obtain 2.67g of the objective compound (1-205) in 82% yield. Mass spectrometer MALDI-TOF-MS (m/z) = 651.7721, theoretical molecular weight: 651.7730; elemental analysis: theoretical value: c (C) 46 H 29 N 5 (%): c84.77; h4.48; n10.75; actual measurement value: c84.75; h4.48; n10.77.
Synthesis example 28: synthetic compound (1-206)
1, 4-dibromonaphthalene (2.86 g,10 mmol) in Synthesis example 1 was replaced with 2, 7-dibromophenanthrene (3.36 g,10 mmol), 2- (4-bromophenyl) - [1,2,4 ]]Triazole [1,5-a ]]Pyridine (3.29 g,12 mmol) is replaced by 2-bromo- [1,2,4 ]]Triazole [1,5-a ]]Pyridine (2.38 g,12 mmol) and other synthetic procedures were followed in substantially the same manner (same reaction molar ratio and reaction conditions) as in synthetic example 1 to give 1.53g of the title compound (1-206) in 74% yield. Mass spectrometer MALDI-TOF-MS (m/z) = 412.4565, theoretical molecular weight: 412.4560; elemental analysis: theoretical value: c (C) 26 H 16 N 6 (%): c75.71; h3.91; n20.38; actual measurement value: c75.72; h3.90; n20.38.
Synthesis example 29: synthetic Compound (1-208)
1, 4-dibromonaphthalene (2.86 g,10 mmol) in Synthesis example 1 was replaced with 2, 7-dibromophenanthrene (3.36 g,10 mmol), 2- (4-bromophenyl) - [1,2,4 ]]Triazole [1,5-a ]]Pyridine (3.29 g,12 mmol) is replaced by 2- (3-bromophenyl) - [1,2,4 ]]Triazole [1,5-a ]]Pyridine (3.29 g,12 mmol) and other synthetic procedures were followed in substantially the same manner (same reaction molar ratio and reaction conditions) as in synthetic example 1 to give 2.14g of the title compound (1-208) in a yield of 76%. Mass spectrometer MALDI-TOF-MS (m/z) = 564.6511, theoretical molecular weight: 564.6520; element separation And (3) analysis: theoretical value: c (C) 38 H 24 N 6 (%): c80.83; h4.28; n14.88; actual measurement value: c80.82; h4.28; n14.90.
Synthesis example 30: synthetic Compound (1-216)
2- (3-bromophenyl) benzoxazole (2.74 g,10 mmol) in Synthesis example 3 was replaced with 9- (4-bromophenyl) -9H-2, 7-azacarbazole (3.24 g,10 mmol), 2- (3-bromophenyl) - [1,2,4]Triazole [1,5-a ]]Pyridine (1.37 g,5 mmol) replaced with 2-bromo- [1,2,4]Triazole [1,5-a ]]Pyridine (0.99 g,5 mmol) and other synthetic procedures were carried out in substantially the same manner (same reaction molar ratio and reaction conditions) as in synthetic example 3 to obtain 1.95g of the objective compound (1-216) in 80% yield. Mass spectrometer MALDI-TOF-MS (m/z) = 488.5547, theoretical molecular weight: 488.5540; elemental analysis: theoretical value: c (C) 32 H 20 N 6 (%): c78.67; h4.13; n17.20; actual measurement value: c78.65; h4.14; n17.21.
Compounds (1-1) to (1-216) other than the above-mentioned compounds can be prepared in substantially the same manner (same reaction molar ratio and reaction conditions) as in synthesis examples 1 to 30 described above.
Synthesis example 38: synthetic compound (2-3)
1, 4-Dibromonaphthalene (5.72 g,20 mmol) in Synthesis example 3 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), 2- (3-bromophenyl) - [1,2, 4) ]Triazole [1,5-a ]]Pyridine (1.37 g,5 mmol) replaced with 2-bromo- [1,2,4]Triazole [1,5-a ]]Pyridine (0.99 g,5 mmol) and other synthetic procedures were carried out in substantially the same manner (same reaction molar ratio and reaction conditions) as in synthetic example 3 to obtain 1.55g of the objective compound (2-3) in 78% yield. Mass spectrometer MALDI-TOF-MS (m/z) = 398.4287, theoretical molecular weight: 398.4290; elemental analysis: theoretical value: c (C) 25 H 14 N 6 (%): c75.36; h3.54; n21.09; actual measurement value: c75.34; h3.55; n21.11.
Synthesis example 39: synthetic compound (2-9)
1, 4-dibromonaphthalene (5.72 g,20 mmol) in Synthesis example 3 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), 2- (3-bromophenyl) - [1,2,4 ]]Triazole [1,5-a ]]Pyridine (1.37 g,5 mmol) replaced with 2-bromo- [1,2,4]Triazole [1,5-a ]]Pyridine (0.99 g,5 mmol) and other synthetic procedures were carried out in substantially the same manner (same reaction molar ratio and reaction conditions) as in synthetic example 3 to obtain 2.11g of the objective compound (2-9) in 77% yield. Mass spectrometer MALDI-TOF-MS (m/z) = 549.6359, theoretical molecular weight: 549.6370; elemental analysis: theoretical value: c (C) 38 H 23 N 5 (%): c83.04; h4.22; n12.74; actual measurement value: c83.05; h4.20; n12.75.
Synthesis example 40: synthetic compound (2-15)
1, 4-Dibromonaphthalene (5.72 g,20 mmol) in Synthesis example 3 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), 2- (3-bromophenyl) - [1,2,4 ]]Triazole [1,5-a ]]Pyridine (1.37 g,5 mmol) replaced with 2-bromo- [1,2,4]Triazole [1,5-a ]]Pyridine (0.99 g,5 mmol) and other synthetic procedures were carried out in substantially the same manner (same reaction molar ratio and reaction conditions) as in synthetic example 3 to obtain 2.30g of the objective compound (2-15) in 75% yield. Mass spectrometer MALDI-TOF-MS (m/z) = 613.7251, theoretical molecular weight: 613.7240; elemental analysis: theoretical value: c (C) 43 H 27 N 5 (%): c84.15; h4.43; n11.41; actual measurement value: c84.15; h4.42; n11.43.
Synthesis example 41: synthetic compound (2-17)
Figure BDA0004088300470000201
S1, adding 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 100mL of dimethylbenzene into a 250mL reaction bottle, adding palladium acetate (0.14 g,0.6 mmol) under a nitrogen atmosphere, heating to 145 ℃ for reaction for 10-24H, stopping heating the liquid phase monitoring raw materials, cooling to room temperature, washing with water, filtering, concentrating the filtrate, pulping 2-3 times with ethyl acetate together with a filter cake to obtain 7.90g of 3-bromo-8- (3-phenyl-9H-carbazole-9-yl) -1, 10-phenanthroline, and obtaining the yield 79%;
S2, adding the 3-bromo-8- (3-phenyl-9H-carbazole-9-yl) -1, 10-phenanthroline (5.00 g,10 mmol) into a 100mL reaction bottle, cooling to-78 ℃, dropwise adding 4mL of 2.5M n-butyllithium tetrahydrofuran solution under nitrogen atmosphere, keeping the temperature at-78 ℃ for reaction for 1-2H, dropwise adding triisopropyl borate (11 mmol,2.54 mL), dropwise adding diluted hydrochloric acid for quenching reaction after the dropwise adding is finished, decompressing and distilling to remove tetrahydrofuran, adding dichloromethane for dissolving, washing, drying with anhydrous magnesium sulfate, filtering, concentrating filtrate, pulping with ethanol for 1-2 times to obtain 4.19g (8- (3-phenyl-9H-carbazole-9-yl) -1, 10-phenanthroline-3-yl) boric acid, and obtaining 90% of yield.
S3, adding the (8- (3-phenyl-9H-carbazole-9-yl) -1, 10-phenanthroline-3-yl) boric acid (2.33 g,5 mmol), 2-bromo- [1,2,4] triazole [1,5-a ] pyridine (0.99 g,5 mmol), potassium carbonate (1.38 g,10 mmol), 30mL toluene, 15mL water and 15mL ethanol into a 100mL reaction bottle, adding tetrakis (triphenylphosphine) palladium (0.02 g,0.015 mmol) under nitrogen atmosphere, heating to 85 ℃ for reaction for 10-24H, monitoring the raw materials in a liquid phase to be basically free of residue, stopping heating, cooling to room temperature, washing with water, filtering, concentrating filtrate, and using methylene chloride together with filter cake: performing column chromatography separation on the leaching solution with petroleum ether of 1:10, concentrating again, and drying to obtain 2.07g of target compound (2-17) with the yield of 77%;
Mass spectrometer MALDI-TOF-MS (m/z) = 538.6122, theoretical molecular weight: 538.6140; elemental analysis: theoretical value: c (C) 36 H 22 N 6 (%): c80.28; h4.12; n15.60; actual measurement value: c80.27; h4.13; n15.60.
Synthesis example 42: synthetic compound (2-21)
1, 4-Dibromonaphthalene (5.72 g,20 mmol) in Synthesis example 3 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), 2- (3-bromophenyl) - [1,2,4 ]]Triazole [1,5-a ]]Pyridine (1.37 g,5 mmol) replaced with 2-bromo- [1,2,4]Triazole [1,5-a ]]Pyridine (0.99 g,5 mmol), other synthetic procedures were followed as in synthetic example 3Substantially the same method (same reaction molar ratio and reaction conditions) gave 2.10g of the objective compound (2-21) in 78% yield. Mass spectrometer MALDI-TOF-MS (m/z) = 538.6147, theoretical molecular weight: 538.6140; elemental analysis: theoretical value: c (C) 36 H 22 N 6 (%): c80.28; h4.12; n15.60; actual measurement value: c80.28; h4.11; n15.61.
Synthesis example 43: synthetic Compound (2-27)
1, 4-Dibromonaphthalene (5.72 g,20 mmol) in Synthesis example 3 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), 2- (3-bromophenyl) - [1,2,4 ]Triazole [1,5-a ]]Pyridine (1.37 g,5 mmol) replaced with 2-bromo- [1,2,4]Triazole [1,5-a ]]Pyridine (0.99 g,5 mmol) and other synthetic procedures were followed in substantially the same manner (same reaction molar ratio and reaction conditions) as in synthetic example 3 to give 2.15g of the objective 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 (C) 37 H 23 N 7 (%): c78.57; h4.10; n17.33; actual measurement value: c78.55; h4.12; n17.33.
Synthesis example 44: synthetic compound (2-35)
1, 4-Dibromonaphthalene (5.72 g,20 mmol) in Synthesis example 3 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), 2- (3-bromophenyl) - [1,2, 4)]Triazole [1,5-a ]]Pyridine (1.37 g,5 mmol) replaced with 2-bromo- [1,2,4]Triazole [1,5-a ]]Pyridine (0.99 g,5 mmol) and other synthetic procedures were carried out in substantially the same manner (same reaction molar ratio and reaction conditions) as in synthetic example 3 to obtain 2.11g of the objective compound (2-35) in 78% yield. Mass spectrometer MALDI-TOF-MS (m/z) = 540.6304, theoretical molecular weight: 540.6300; elemental analysis: theoretical value: c (C) 36 H 24 N 6 (%): c79.98; h4.47; n15.55; actual measurement value: c79.98; h4.45; n15.57.
Synthesis example 45: synthetic compound (2-41)
Will be described in synthetic example 31, 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, 10-diphenylanthracene (4.09 g,10 mmol), and the other synthesis procedures were carried out in substantially the same manner (same reaction molar ratio and reaction conditions) as in synthesis example 3 to obtain 2.81g of the objective compound (2-41) in 80% yield. Mass spectrometer MALDI-TOF-MS (m/z) = 701.8320, theoretical molecular weight: 701.8330; elemental analysis: theoretical value: c (C) 50 H 31 N 5 (%): c85.57; h4.45; n9.98; actual measurement value: c85.56; h4.47; n9.97.
Synthesis example 46: synthetic compound (2-45)
1, 4-dibromonaphthalene (5.72 g,20 mmol) in Synthesis example 3 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- (3-bromophenyl) -9H-carbazole (3.22 g,10 mmol), and the other synthesis procedures were carried out in substantially the same manner (same reaction molar ratio and reaction conditions) as in Synthesis example 3 to obtain 2.43g of the objective compound (2-45) in 79% yield. Mass spectrometer MALDI-TOF-MS (m/z) = 614.7109, theoretical molecular weight: 614.7120; elemental analysis: theoretical value: c (C) 42 H 26 N 6 (%): c82.06; h4.26; n13.67; actual measurement value: c82.06; h4.25; n13.69.
Synthesis example 47: synthetic compound (2-49)
1, 4-Dibromonaphthalene (5.72 g,20 mmol) in Synthesis example 3 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), 2- (3-bromophenyl) - [1,2, 4)]Triazole [1,5-a ]]Pyridine (1.37 g,5 mmol) is replaced by 2- (4-bromophenyl) - [1,2,4 ]]Triazole [1,5-a ]]Pyridine (1.37 g,5 mmol) and other synthetic procedures were followed in substantially the same manner (same reaction molar ratio and reaction conditions) as in synthetic example 3 to give 2.24g of the title compound (2-49) in 77% yield. Mass spectrometer MALDI-TOF-MS (m/z) = 582.6862, theoretical molecular weight: 582.6850; elemental analysis: theoretical value: c (C) 37 H 22 N 6 (%): c76.27; h3.81; n14.42; actual measurement value: c76.25; h3.80; n14.43.
Synthesis example 48: synthetic Compound (2-56)
1, 4-Dibromonaphthalene (5.72 g,20 mmol) in Synthesis example 3 was replaced with 9, 10-dichloro-1, 5-diazaanthracene (4.98 g,20 mmol), 2- (3-bromophenyl) benzoxazole (2.74 g,10 mmol) was replaced with 5' -bromo-1, 1':3',1 "-terphenyl (3.09 g,10 mmol), 2- (3-bromophenyl) - [1,2,4 ] ]Triazole [1,5-a ]]Pyridine (1.37 g,5 mmol) replaced with 2-bromo- [1,2,4]Triazole [1,5-a ]]Pyridine (0.99 g,5 mmol) and other synthetic procedures were carried out in substantially the same manner (same reaction molar ratio and reaction conditions) as in synthetic example 3 to obtain 1.97g of the objective compound (2-56) in 75% yield. Mass spectrometer MALDI-TOF-MS (m/z) = 525.6134, theoretical molecular weight: 525.6150; elemental analysis: theoretical value: c (C) 36 H 23 N 5 (%): c82.26; h4.41; n13.32; actual measurement value: c82.25; h4.40; n13.35.
Synthesis example 49: synthetic compound (2-66)
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), 2- (3-bromophenyl) benzoxazole (2.74 g,10 mmol) was replaced with 2-bromo-9, 9-dimethyl-9H-fluorene (2.73 g,10 mmol), 2- (3-bromophenyl) - [1,2,4 ]]Triazole [1,5-a ]]Pyridine (1.37 g,5 mmol) replaced with 2-bromo- [1,2,4]Triazole [1,5-a ]]Pyridine (0.99 g,5 mmol) and other synthetic procedures were followed in substantially the same manner (same reaction molar ratio and reaction conditions) as in synthetic example 3 to give 1.86g of the title 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 (C) 33 H 23 N 5 (%): c80.96; h4.74; n14.31; actual measurement value: c80.98; h4.74; n14.28.
Synthesis example 50: synthetic Compound (2-79)
The 3, 8-dibromo-1, 10-phenanthroline (10.14 g,30 mmol) in Synthesis example 41 was replaced with 9, 10-dichloro-1, 5-diazaanthracene (4.98 g,20 mmol), 3-phenyl-9H-carbazole (4.87 g,20 mmol) was replaced with 3, 6-diphenyl-9H-carbazole (3.19 g,10 mmol), and the other synthesis procedures were carried out in substantially the same manner (same reaction molar ratio and reaction conditions) as in Synthesis example 42 to obtain 2.27g of the title compound (2-79) in 74% yield. Mass spectrometer MALDI-TOF-MS (m/z) =614.7132 theoretical molecular weight: 614.7120; elemental analysis: theoretical value: c (C) 42 H 26 N 6 (%): c82.06; h4.26; n13.67; actual measurement value: c82.06; h4.25; n13.69.
Synthesis example 51: synthetic compound (2-85)
3, 8-dibromo-1, 10-phenanthroline (10.14 g,30 mmol) in Synthesis example 41 was replaced with 9, 10-dichloro-2, 6-diazaanthracene (4.98 g,20 mmol), 3-phenyl-9H-carbazole (4.87 g,20 mmol) was replaced with diphenylamine (1.69 g,10 mmol), and the other synthesis procedures were carried out in substantially the same manner (same reaction molar ratio and reaction conditions) as in Synthesis example 42 to obtain 1.74g of the title compound (2-85) in 75% yield. Mass spectrometer MALDI-TOF-MS (m/z) = 464.5328, theoretical molecular weight: 464.5320; elemental analysis: theoretical value: c (C) 30 H 20 N 6 (%): c77.57; h4.34; n18.09; actual measurement value: c77.56; h4.33; n18.11.
Synthesis example 52: synthetic compound (2-90)
1, 4-dibromonaphthalene (2.86 g,10 mmol) in Synthesis example 1 was replaced with 9, 10-dichloro-1, 5-diazaanthracene (4.98 g,10 mmol), 2- (4-bromophenyl) - [1,2,4 ]]Triazole [1,5-a ]]Pyridine (3.29 g,12 mmol) is replaced by 2-bromo- [1,2,4 ]]Triazole [1,5-a ]]Pyridine (2.38 g,12 mmol) and other synthetic procedures were carried out in substantially the same manner (same reaction molar ratio and reaction conditions) as in synthetic example 1 to obtain 1.45g of the objective compound (2-90) in a yield of 70%. Mass spectrometer MALDI-TOF-MS (m/z) = 414.4327, theoretical molecular weight: 414.4320; elemental analysis: theoretical value: c (C) 24 H 14 N 8 (%): c69.56; h3.41; n27.04; actual measurement value: c69.55; h3.40; n27.05.
Synthesis example 53: synthetic compound (2-106)
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), 2- (3-bromophenyl) benzoxazole (2.74 g,10 mmol) was replaced with 10- (3-bromophenyl) -2, 9-diphenylanthracene (4.85 g,10 mmol), and the other synthesis procedures were followed in substantially the same manner (same reaction molar ratio and reaction conditions) as in Synthesis example 3 to give 2.92g of the objective compound (2-106) in 75% yield. MALDI-T of mass spectrometer OF-MS (m/z) = 777.9301, theoretical molecular weight: 777.9310; elemental analysis: theoretical value: c (C) 56 H 35 N 5 (%): c86.46; h4.54; n9.00; actual measurement value: c86.47; h4.53; n9.00.
Synthesis example 54: synthetic compound (2-112)
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), 2- (3-bromophenyl) benzoxazole (2.74 g,10 mmol) was replaced with 9- (4-bromophenyl) -9H-carbazole (3.22 g,10 mmol), 2- (3-bromophenyl) - [1,2, 4)]Triazole [1,5-a ]]Pyridine (1.37 g,5 mmol) is replaced by 2- (4-bromophenyl) - [1,2,4 ]]Triazole [1,5-a ]]Pyridine (1.37 g,5 mmol) and other synthetic procedures were followed in substantially the same manner (same reaction molar ratio and reaction conditions) as in synthetic example 3 to give 2.34g of the title 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 (C) 42 H 26 N 6 (%): c82.06; h4.26; n13.67; actual measurement value: c82.08; h4.25; n13.67.
Synthesis example 55: synthetic Compound (2-115)
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), and the other synthesis procedures were the same as in Synthesis example 1 (same reaction molar ratio and reaction conditions), to obtain 2.04g of the objective compound (2-115) in 72% yield. Mass spectrometer MALDI-TOF-MS (m/z) = 566.6277, theoretical molecular weight: 566.6280; elemental analysis: theoretical value: c (C) 36 H 22 N 8 (%): c76.31; h3.91; n19.78; actual measurement value: c76.30; h3.90; n19.80.
Synthesis example 56: synthetic compound (2-119)
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), and the other synthesis procedures were the same as in Synthesis example 3 (same reaction molar ratio and reaction conditions), to obtain 2.12g of the objective compound (2-119) in 75% yield. Mass spectrometer MALDI-TOF-MS (m/z) = 566.6255, theoretical molecular weight: 566.6240; elemental analysis: theoretical value: c (C) 37 H 22 N 6 (%): c78.43; h3.91; n14.83; actual measurement value: c78.46; h3.90; n14.82.
Synthesis example 57: synthetic compound (2-123)
1.64g of the target compound (2-123) was obtained in 73% yield by substituting 2, 4-dichloroquinazoline (3.98 g,20 mmol) for 1, 4-dibromonaphthalene (5.72 g,20 mmol) and naphthalene-2-ylboronic acid (1.72 g,10 mmol) for 2- (3-bromophenyl) benzoxazole (2.74 g,10 mmol) in synthetic example 3 and by substantially the same procedure (same reaction molar ratio and reaction conditions) in accordance with synthetic example 3. Mass spectrometer MALDI-TOF-MS (m/z) = 449.5163, theoretical molecular weight: 449.5170; elemental analysis: theoretical value: c (C) 30 H 19 N 5 (%): c80.16; h4.26; n15.58; actual measurement value: c80.15; h4.25; n15.60.
Synthesis example 58: synthetic compound (2-137)
1, 4-dibromonaphthalene (5.72 g,20 mmol) in Synthesis example 3 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), 2- (3-bromophenyl) - [1,2, 4)]Triazole [1,5-a ]]Pyridine (1.37 g,5 mmol) is replaced by 2- (4-bromophenyl) - [1,2,4 ]]Triazole [1,5-a ]]Pyridine (1.37 g,5 mmol) and other synthetic procedures were followed in substantially the same manner (same reaction molar ratio and reaction conditions) as in synthetic example 3 to give 2.14g of the title compound (2-137) in 76% yield. Mass spectrometer MALDI-TOF-MS (m/z) = 564.6509, theoretical molecular weight: 564.6520; elemental analysis: theoretical value: c (C) 38 H 24 N 6 (%): c80.83; h4.28; n14.88; actual measurement value: c80.81; h4.29; n14.90.
Synthesis example 59: synthetic compound (2-141)
1, 4-dibromonaphthalene (5.72 g,20 mmol) in Synthesis example 3 was replaced with 2, 4-dichloroquinazoline (3.98 g,20 mmol), 2- (3-bromophenyl) benzoxazole (2.74 g,10 mmol) was replaced with 3-bromo-N, N-diphenylaniline (3.24 g,10 mmol), and the other synthesis procedures were carried out in substantially the same manner (same reaction molar ratio and reaction conditions) as in Synthesis example 3 to obtain 2.04g of the objective compound (2-141) in 72% yield . Mass spectrometer MALDI-TOF-MS (m/z) = 566.6685, theoretical molecular weight: 566.6680; elemental analysis: theoretical value: c (C) 38 H 26 N 6 (%): c80.54; h4.62; n14.83; actual measurement value: c80.57; h4.60; n14.82.
Compounds (2-1) to (2-150) other than the above-mentioned compounds were obtained in substantially the same manner (same reaction molar ratio and reaction conditions) as in the above-mentioned synthetic examples 38 to 59.
Device example 1-1
The glass substrate with the 100nm ITO transparent film is sequentially washed by acetone, isopropanol and deionized water respectively in an ultrasonic mode, vacuum-dried for 2 hours at 105 ℃, then washed by UV ozone for 15 minutes, and the ITO glass substrate is conveyed to a vacuum evaporator.
On the surface on the side where the ITO thin film was formed, molybdenum trioxide (MoO) 3 ) To form a hole injection layer 10nm thick;
next, 4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline ] (TAPC) was vacuum-evaporated on the hole injection layer to form a hole transport layer 70nm thick;
next, 1, 3-bis (9H-carbazol-9-yl) benzene (mCP) was vacuum-evaporated on the hole transport layer to form an electron blocking layer of 15 nm;
next, 4' -bis (9-carbazole) biphenyl (CBP, 95wt% as a light-emitting host material) and tris (2-phenylpyridine) iridium (Ir (ppy)) were co-vacuum-evaporated on the electron blocking layer 3 As a light-emitting guest material, 5 wt%) to form a light-emitting layer having a thickness of 30 nm;
next, the compound 1-2 prepared in the above synthesis example 1 was vacuum evaporated on the above light-emitting layer to form an electron transport layer with a thickness of 15 nm;
next, vacuum evaporating lithium fluoride (LiF) on the electron transport layer to form an electron injection layer with a thickness of 1 nm;
finally, aluminum (Al) was vacuum-deposited on the electron injection layer to form a 100nm cathode.
Device examples 1-2 to device examples 1-38
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 above were used in place of the compound 1-2 prepared in synthesis example 1 above, respectively.
Device comparative examples 1-39 to device comparative examples 1-42
An organic electroluminescent device was produced in the same manner as in device example 1-1, except that 3,3'- [5' - [3- (3-pyridyl) phenyl ] [1,1':3',1 "-terphenyl ] -3,3" -diyl ] bipyridine (TmPyPB) or the following compounds C1, C2, and C3 were used instead of the compound 1-2 produced in synthesis example 1, respectively;
Figure BDA0004088300470000261
the organic electroluminescent devices prepared in the above device examples and device comparative examples were subjected to performance test, and the results are shown in table 1:
TABLE 1
Figure BDA0004088300470000262
Figure BDA0004088300470000271
As can be confirmed from the data in Table 1 above, compared with the compound C1 formed by using the conventional TmPyPB, biphenyl as the bridging group between electron acceptors, the compound C2 not containing the triazolopyridine group mentioned in the present invention, and the compound C3 modified on the six-membered ring of the electron donating site of the triazolopyridine group, the organic electroluminescent material represented by formula I provided by the present invention has high triplet electron withdrawing groups such as triazolopyridine, benzoxazole, benzothiazole, azacarbazole, quinazoline and the like bonded at symmetrical sites on the periphery thereof due to the highly conjugated rigid coplanar groups such as naphthalene, anthracene, phenanthrene, pyrene and the like as high carrier transport channels, has a high electron transporting rate (10 -2 Order of magnitude)The compound has better matching electron migration rate, hole blocking capability and higher thermal stability, effectively overcomes the incompatibility contradiction between the high mobility and the high triplet exciton confinement of the traditional electron transport material, and can effectively limit holes to a luminescent layer when being used as the electron transport material, thereby being an electron transport material with obvious progress in comprehensive performances such as efficiency, electron migration rate, thermal stability, light color, service life and the like.
Device example 2-1
The glass substrate with the 120nm ITO transparent film is sequentially washed by acetone, isopropanol and deionized water respectively in an ultrasonic mode, vacuum-dried for 2 hours at 105 ℃, then washed by UV ozone for 15 minutes, and the ITO glass substrate is conveyed to a vacuum evaporator.
On the surface on the side where the ITO thin film was formed, molybdenum trioxide (MoO) 3 ) To form a hole injection layer 10nm thick;
next, 4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline ] (TAPC) was vacuum-evaporated on the hole injection layer to form a hole transport layer 70nm thick;
next, 1, 3-bis (9H-carbazol-9-yl) benzene (mCP) was vacuum-evaporated on the hole transport layer to form an electron blocking layer of 15 nm;
next, tris (2-phenylpyridine) iridium (Ir (ppy)) is co-vacuum deposited on the electron-blocking layer 3 As a light-emitting guest material, 5 wt%) and 4,4' -bis (9-carbazole) biphenyl (CBP, as a light-emitting host material, 90 wt%) to form a light-emitting layer having a thickness of 30 nm;
next, the compound 2-3 prepared in example 39 was synthesized by vacuum evaporation on the above light-emitting layer to form an electron transport layer with a thickness of 15 nm;
next, vacuum evaporating lithium fluoride (LiF) on the electron transport layer to form an electron injection layer with a thickness of 1 nm;
Finally, aluminum (Al) was vacuum-deposited on the electron injection layer to form a 100nm cathode.
Device examples 2-2 to 2-23
An organic electroluminescent device was prepared in the same manner as in device example 2-1, except that the compounds synthesized in the above synthesis examples 39-60 were used in place of the compounds 2-3 prepared in the above synthesis example 38, respectively.
Device comparative examples 2-24 to device comparative examples 2-25
An organic electroluminescent device was prepared in the same manner as in device example 2-1, except that compounds 2-3 were replaced with compounds C4 and C5 as shown below.
Figure BDA0004088300470000281
The organic electroluminescent devices prepared in the above device examples and device comparative examples were subjected to performance test, and the results are shown in table 2:
TABLE 2
Figure BDA0004088300470000282
From the data in table 2 above, it can be confirmed that, compared with the traditional CBP, the compound C4 modified on the six-membered ring of the electron-donating site of the triazolopyridine and having the electron-donating group anthracene as the bridging group, and the compound C5 having the large conjugated electron-donating group as the bridging group, the organic electroluminescent material represented by formula II provided by the present invention uses the diaza-condensed aromatic ring group having a plane, rigidity and electron deficiency as the high carrier transmission channel, and the groups of the triazolopyridine group and the electron-donating group, such as anthracene, fluorene, dibenzofive-membered ring, carbazole, and arylamine, which are bonded on the periphery thereof, form a series of novel luminescent host materials having more balanced hole and electron carriers, so as to solve the problem of serious device efficiency roll-off of the phosphorescent device under high current density, and make full use of the characteristics of the reduced material triplet energy level and light color blue shift of the diaza-condensed aromatic ring, so that the organic electroluminescent material provided by the present invention emits more saturated blue light when applied to the phosphorescent device, and further has significant improvements in comprehensive performances such as voltage, driving efficiency, glass transition, and life.
Device example 3-1
The glass substrate with the 120nm ITO transparent film is sequentially washed by acetone, isopropanol and deionized water respectively in an ultrasonic mode, vacuum-dried for 2 hours at 105 ℃, then washed by UV ozone for 15 minutes, and the ITO glass substrate is conveyed to a vacuum evaporator.
On the surface on the side where the ITO thin film was formed, molybdenum trioxide (MoO) 3 ) To form a hole injection layer 10nm thick;
next, 4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline ] (TAPC) was vacuum-evaporated on the hole injection layer to form a hole transport layer 70nm thick;
next, 1, 3-bis (9H-carbazol-9-yl) benzene (mCP) was vacuum-evaporated on the hole transport layer to form an electron blocking layer of 15 nm;
next, tris (2-phenylpyridine) iridium (Ir (ppy)) is co-vacuum deposited on the electron-blocking layer 3 As a light-emitting guest material, 5 wt%) and 4,4' -bis (9-carbazole) biphenyl (CBP, as a light-emitting host material, 90 wt%) to form a light-emitting layer having a thickness of 30 nm;
next, the compound 1-2 prepared in the above synthesis example 1 was vacuum evaporated on the above light-emitting layer to form a hole blocking layer with a thickness of 10 nm;
next, 3'- [5' - [3- (3-pyridyl) phenyl ] [1,1':3',1 '-terphenyl ] -3, 3' -diyl ] bipyridine (TmPyPB) was vacuum evaporated on the hole blocking layer to form an electron transport layer having a thickness of 15 nm;
Next, vacuum evaporating lithium fluoride (LiF) on the electron transport layer to form an electron injection layer with a thickness of 1 nm;
finally, aluminum (Al) was vacuum-deposited on the electron injection layer to form a 100nm cathode.
Device examples 3-2 to 3-7
An organic electroluminescent device was prepared in the same manner as in device example 3-1, except that the compounds synthesized in synthesis examples 1 to 38 above were used in place of the compounds 1 to 2 prepared in synthesis example 1 above, respectively.
Device comparative examples 3-9 to device examples 3-10
An organic electroluminescent device was prepared in the same manner as in device example 3-1, except that the following compounds C1, C3 were used in place of the compound 1-2 prepared in synthesis example 1 described above.
Figure BDA0004088300470000301
The organic electroluminescent devices prepared in the above device examples and device comparative examples were subjected to performance test, and the results are shown in table 3:
Figure BDA0004088300470000302
as can be confirmed from the data in Table 3 above, compared with the conventional device which does not contain a hole blocking layer material, the device which takes the compound C1 formed by taking biphenyl as a bridging group between electron acceptors as a hole blocking layer and takes the compound C3 modified on the six-membered ring of the electron supply site of the triazolopyridine group as the hole blocking layer, the organic electroluminescent material formed by the organic electroluminescent material shown in the formula I provided by the invention has the advantage that the special N-N bond of the triazolopyridine group, the compound LUMO is deeper due to the further introduction of the electron withdrawing group on the strong electron withdrawing site of the triazolopyridine group through the high carrier channel, and has hole blocking capability, and can be applied to the organic electroluminescent device as the hole blocking layer of the device to improve the device performance.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (6)

1. An electronic organic electroluminescent material based on triazolopyridine is characterized in that a compound of the organic electroluminescent material is formed by bonding a triazolopyridine group and a condensed ring structure, and the structural general formula of the compound is shown in formula II:
Figure FDA0004088300460000011
wherein the R is 6 -R 9 Independently selected from hydrogen, cyano, fluoro, deuterium, nitro, C 1 -C 6 Alkyl of C 1 -C 6 Alkoxy, C 1 -C 6 Unsubstituted or substituted by cyano, fluoro, deuterium, nitro, C 1 -C 6 Alkyl, C of (2) 1 -C 6 Alkoxy, C 1 -C 6 Alkylthio-substituted phenyl of (a);
Ar 4 、Ar 5 each of the heterocyclic rings is independently an empty or heterocyclic ring, and the heterocyclic rings and adjacent rings share a carbon-carbon chemical bond to form a condensed structure;
x is each independently C, N or C (R 29 ) And at least one X is N, L 2 Or L 0 X attached thereto is C, ar 4 Or Ar 5 Two X sharing carbon-carbon chemical bond are C;
wherein L is 0 、L 2 Independently of each other, is a single bond, unsubstituted or substituted by cyano, fluoro, nitro, C 1 -C 6 Alkyl-substituted phenylene, unsubstituted or substituted by cyano, fluoro, nitro, C 1 -C 6 Alkyl-substituted biphenylenes of (2) or unsubstituted or substituted by cyano, fluoro, nitro, C 1 -C 6 Alkyl-substituted naphthylene of (a);
R 29 selected from hydrogen, cyano, fluoro, deuterium, nitro, C 1 -C 6 Alkyl of C 1 -C 6 Alkoxy, C 1 -C 6 Unsubstituted or substituted by cyano, fluoro, deuterium, nitro, C 1 -C 6 Alkyl, C of (2) 1 -C 6 Alkoxy, C 1 -C 6 Alkylthio-substituted C of (C) 6 -C 30 Unsubstituted or substituted by cyano, fluoro, deuterium, nitro, C 1 -C 6 Alkyl, C of (2) 1 -C 6 Alkoxy, C 1 -C 6 Alkylthio-substituted C of (C) 6 -C 30 Unsubstituted or substituted by cyano, fluoro, deuterium, nitro, C 1 -C 6 Alkyl, C of (2) 1 -C 6 Alkoxy, C 1 -C 6 Alkylthio-substituted C of (C) 6 -C 30 An arylamine group of (a);
R 0 independently selected from: hydrogen, fluorine, deuterium, nitro, cyano, hydroxy, C 1 -C 6 Alkyl of C 1 -C 6 Alkoxy, C 1 -C 6 Alkylthio of C 1 -C 6 Unsubstituted or substituted by deuterium, fluorine, cyano, nitro, C 1 -C 6 C substituted by alkyl 6 -C 30 Unsubstituted or substituted by deuterium, fluorine, cyano, nitro, C 1 -C 6 C substituted by alkyl 3 -C 30 Unsubstituted or substituted by deuterium, fluorine, cyano, nitro, C 1 -C 6 C substituted by alkyl 6 -C 30 Unsubstituted or substituted by deuterium, fluorine, cyano, nitro, C 1 -C 6 C substituted by alkyl 6 -C 30 Or, alternatively, unsubstituted or substituted by deuterium, fluorine, cyano, nitro, C 1 -C 6 C substituted by alkyl 6 -C 30 Is an arylboron group.
2. The triazolopyridine-based electronic electroluminescent material according to claim 1, wherein the formula II is represented by the following compounds represented by (B1), (B2), (B3), (B4), (B5) and (B6):
Figure FDA0004088300460000021
wherein R is 31 、R 32 Each independently selected from: hydrogen, cyano, fluoro, deuterium, nitro, C 1 -C 6 Alkyl of C 1 -C 6 Alkoxy, C 1 -C 6 Unsubstituted or substituted by cyano, fluoro, deuterium, nitro, C 1 -C 6 Alkyl, C of (2) 1 -C 6 Alkoxy, C 1 -C 6 Alkylthio-substituted phenyl groups of (a).
3. The triazolopyridine-based electronic organic electroluminescent material according to claim 1, wherein the R 0 Selected from the following groups:
Figure FDA0004088300460000031
4. the triazolopyridine-based electronic organic electroluminescent material according to claim 3, wherein the organic electroluminescent material represented by formula II is selected from any one of compounds represented by the following structural formulas:
Figure FDA0004088300460000041
/>
Figure FDA0004088300460000051
/>
Figure FDA0004088300460000061
/>
Figure FDA0004088300460000071
/>
Figure FDA0004088300460000081
/>
Figure FDA0004088300460000091
5. 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 coating 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 coating layer comprises the organic electroluminescent material according to claim 4.
6. The organic electroluminescent device according to claim 5, wherein the light-emitting layer is composed of a light-emitting host and a light-emitting guest, the light-emitting host comprising the organic electroluminescent material according to claim 4.
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