CN107056748B - Compound with triazine and ketone as cores and application thereof in organic electroluminescent device - Google Patents

Compound with triazine and ketone as cores and application thereof in organic electroluminescent device Download PDF

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CN107056748B
CN107056748B CN201610261237.4A CN201610261237A CN107056748B CN 107056748 B CN107056748 B CN 107056748B CN 201610261237 A CN201610261237 A CN 201610261237A CN 107056748 B CN107056748 B CN 107056748B
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triazine
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phenyl
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CN107056748A (en
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李崇
徐凯
张兆超
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Jiangsu Sunera Technology Co Ltd
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Valiant Co Ltd
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Abstract

The invention discloses a compound taking triazine and ketone as core groups and application thereof in an organic electroluminescent device. When the compound is used as a luminescent layer material of an organic electroluminescent device, the current efficiency, the power efficiency and the external quantum efficiency of the device are greatly improved; meanwhile, the service life of the device is obviously prolonged.

Description

Compound with triazine and ketone as cores and application thereof in organic electroluminescent device
Technical Field
The invention relates to the technical field of semiconductors, in particular to a compound taking triazine and ketone as core groups and application of the compound as a light-emitting layer material in an organic light-emitting diode.
Background
The Organic Light Emission Diodes (OLED) device technology can be used for manufacturing novel display products and novel lighting products, is expected to replace the existing liquid crystal display and fluorescent lamp lighting, and has wide application prospect.
The OLED light-emitting device is of a sandwich structure and comprises electrode material film layers and organic functional materials clamped between different electrode film layers, and the various different functional materials are mutually overlapped together according to the application to form the OLED light-emitting device. When voltage is applied to two end electrodes of the OLED light-emitting device as a current device, positive and negative charges in the organic layer functional material film layer are acted through an electric field, and the positive and negative charges are further compounded in the light-emitting layer, namely OLED electroluminescence is generated.
The use of Organic Light Emitting Diodes (OLEDs) for large area flat panel displays and lighting has attracted considerable attention in the industry and academia. However, the conventional organic fluorescent material can emit light only by using 25% singlet excitons formed by electric excitation, and the internal quantum efficiency of the device is low (up to 25%). External quantum efficiencies are generally below 5%, and are far from the efficiencies of phosphorescent devices. Although the phosphorescent material enhances intersystem crossing due to strong spin-orbit coupling of heavy atom centers, singlet excitons and triplet excitons formed by electric excitation can be effectively used for emitting light, so that the internal quantum efficiency of the device reaches 100%. However, the application of phosphorescent materials in OLEDs is limited by the problems of high price, poor material stability, serious device efficiency roll-off and the like. A Thermally Activated Delayed Fluorescence (TADF) material is a third generation organic light emitting material that has been developed following organic fluorescent materials and organic phosphorescent materials. Such materials typically have a small singlet-triplet energy level difference (Δ E)ST) The triplet exciton may passThe intersystem crossing is converted into singlet exciton luminescence. This can make full use of singlet excitons and triplet excitons formed under electrical excitation, and the internal quantum efficiency of the device can reach 100%. Meanwhile, the material has controllable structure, stable property, low price and no need of precious metal, and has wide application prospect in the field of OLEDs.
Although the TADF material can theoretically achieve 100% exciton utilization, in practice there is the problem that (1) the T1 and S1 states of the design molecule have strong CT characteristics, very small energy gaps of S1-T1 states, although high T can be achieved by the TADF process1→S1State exciton conversion but at the same time results in a low S1 state radiative transition rate, and therefore it is difficult to achieve both (or both) high exciton utilization and high fluorescence radiation efficiency; (2) even though doped devices have been employed to mitigate the T exciton concentration quenching effect, most devices of TADF materials suffer from severe roll-off in efficiency at high current densities.
In terms of the actual demand of the current OLED display illumination industry, the development of the current OLED material is far from enough, and lags behind the requirements of panel manufacturing enterprises, and the development of organic functional materials with higher performance is very important as a material enterprise.
Disclosure of Invention
In view of the above problems in the prior art, the present applicant provides a compound with triazine and ketone as core groups and its application in organic electroluminescent devices. The compound takes triazine and ketone as core groups based on a TADF mechanism, and is applied to an organic electroluminescent device as a luminescent layer material.
The technical scheme of the invention is as follows:
a compound taking triazine and ketone as core groups has a structure shown in a general formula (1):
Figure BDA0000973390110000021
in the general formula (1), Ar1、Ar2Are independent of each otherRepresents phenyl, C1-10Straight or branched chain alkyl substituted phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl or benzophenanthryl;
in the general formula (1), D represents-Ar-R or-R; wherein Ar represents phenyl, C1-10Straight or branched chain alkyl substituted phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl or benzophenanthryl;
r is represented by general formula (2), general formula (3), general formula (4) or general formula (5):
Figure BDA0000973390110000022
Figure BDA0000973390110000031
wherein R is1、R2Independently select hydrogen or a structure shown in a general formula (6):
Figure BDA0000973390110000032
a is
Figure BDA0000973390110000033
X2、X3Respectively is oxygen atom, sulfur atom, selenium atom, C1-10One of a linear or branched alkyl substituted alkylene, aryl substituted alkylene, alkyl or aryl substituted amine group; a through CL1-CL2Key, CL2-CL3Key, CL3-CL4Key, CL4-CL5Key, CL‘1-CL’2Key, CL‘2-CL’3Key, CL‘3-CL’4Bond or CL‘4-CL’5The bond is connected with the general formula (2) or the general formula (4);
R3、R4independently selected hydrogen or a structure represented by the general formula (7):
Figure BDA0000973390110000034
b is
Figure BDA0000973390110000035
X2、X3Respectively is oxygen atom, sulfur atom, selenium atom, C1-10One of a linear or branched alkyl substituted alkylene, aryl substituted alkylene, alkyl or aryl substituted amine group; b by CL1-CL2Key, CL2-CL3Key, CL3-CL4Key, CL‘1-CL’2Key, CL‘2-CL’3Bond or CL‘3-CL’4The bond is connected with the general formula (3) or the general formula (5);
R5represents phenyl, C1-10Straight or branched chain alkyl substituted phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl or benzophenanthryl; x1Is oxygen atom, sulfur atom, selenium atom, C1-10One of a linear or branched alkyl substituted alkylene, aryl substituted alkylene, alkyl or aryl substituted amine group;
in the general formula (1), L is represented by the general formula (8), (9) or (10):
Figure BDA0000973390110000036
wherein, X4Represents a carbonyl group, C1-10One of a linear or branched alkyl-substituted alkylene group, an aryl-substituted alkylene group, an oxygen atom, an alkyl group or an aryl-substituted amine group;
wherein, X5Is represented by C1-10One of linear or branched alkyl substituted alkylidene, aryl substituted alkylidene, alkyl or aryl substituted alkylidene group;
said X5-represents the attachment of D to X5To any atom to which it belongs.
In the compounds when a represents
Figure BDA0000973390110000042
And with CL4-CL5Bond or CL‘4-CL’5When connected to a bond, X1And X2Overlap in position of (2), taking only X1Or X2；X3Represented by oxygen atom, sulfur atom, selenium atom, C1-10One of a linear or branched alkyl substituted alkylene, an aryl substituted alkylene, an alkyl or an aryl substituted amine.
The general structural formula of the compound is as follows:
Figure BDA0000973390110000041
Figure BDA0000973390110000051
any one of the above.
In the compound, R is:
Figure BDA0000973390110000052
Figure BDA0000973390110000061
Figure BDA0000973390110000071
Figure BDA0000973390110000072
any one of the above.
The specific structural formula of the compound taking triazine and ketone as core groups is as follows:
Figure BDA0000973390110000073
Figure BDA0000973390110000081
Figure BDA0000973390110000091
Figure BDA0000973390110000101
Figure BDA0000973390110000111
a light-emitting device comprising the compound, wherein the compound is used as a host material of a light-emitting layer and is used for manufacturing an organic electroluminescent device.
A light-emitting device containing the compound is used as a doping material of a light-emitting layer and used for manufacturing an organic electroluminescent device.
The beneficial technical effects of the invention are as follows:
the compound takes triazine and ketone groups as mother cores, one side of the ketone group is connected with an aromatic heterocyclic group, the molecular symmetry is destroyed, so that the crystallinity of molecules is destroyed, the aggregation effect among the molecules is avoided, most of the molecules are rigid groups, the compound has good film-forming property and fluorescence quantum efficiency, and can be used as a luminescent layer doping material; the compound has a molecular structure of D-A-A structure, and comprises an electron donor (Donor, D, an aromatic heterocyclic group) and two electron acceptors (acceptors, A, triazine and ketone groups), the combination can increase orbital overlap and improve luminous efficiency, and meanwhile, the structure can obtain a charge transfer state material with HOMO and LUMO space separation, so that small S is realized1State and T1The energy level difference of the states, thereby realizing reverse intersystem crossing under the condition of thermal stimulation, and being suitable for being used as a main body material of a luminescent layer material.
The compound can be used as a luminescent layer material for manufacturing an OLED luminescent device, and can be used as a luminescent layer main body material or a doping material to obtain good device performance, and the current efficiency, the power efficiency and the external quantum efficiency of the device are greatly improved; meanwhile, the service life of the device is obviously prolonged.
The compound material has good application effect in OLED luminescent devices and good industrialization prospect.
Drawings
FIG. 1 is a schematic diagram of a device structure employing the compounds of the present invention;
wherein, 1 is a transparent substrate layer, 2 is an ITO anode layer, 3 is a hole injection layer, 4 is a hole transport layer, 5 is a luminescent layer, 6 is an electron transport layer, 7 is an electron injection layer, and 8 is a cathode reflection electrode layer.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples.
EXAMPLE 1 Synthesis of Compound 1
Figure BDA0000973390110000121
Specific synthetic routes for this compound are now provided:
Figure BDA0000973390110000122
in a 500ml four-necked flask, 0.01mol of 4, 6-diphenyl- [1,3,5] was charged under an atmosphere of nitrogen gas]Triazine-2-carbonyl chloride, 0.03mol of 9, 9-dimethyl-10-phenyl-9, 10-dihydroacridine 2-boronic acid, dissolved in a mixed solvent (180ml of toluene, 90ml of ethanol) and then 0.03mol of Na was added2CO3Aqueous solution (2M) and then 0.0001mol Pd (PPh) was added3)4Heating and refluxing for 10-24 h, sampling the sample, and completing the reaction. Naturally cooling, filtering, rotary evaporating the filtrate, passing through a silica gel column to obtain the target product with the HPLC purity of 99.2 percent and the yield58.00％。
Elemental analysis Structure (molecular formula C)37H28N4O): theoretical value C, 81.59; h, 5.18; n, 10.29; o, 2.94; test values are: c, 81.66; h, 5.12; n, 10.25; o, 2.97.
HPLC-MS: the molecular weight of the material is 544.23, and the measured molecular weight is 544.64.
EXAMPLE 2 Synthesis of Compound 5
Figure BDA0000973390110000131
Specific synthetic routes for this compound are now provided:
Figure BDA0000973390110000132
in a 500ml four-necked flask, 0.01mol of 2-chloro-4, 6-bis (3, 5-dimethylphenyl) - [1,3,5] was charged under an atmosphere of nitrogen gas]Triazine, 0.03mol2, 6-anthraquinone diboronic acid, 0.01mol10- (4-bromophenyl) -9, 9-dimethyl-9, 10-dihydro-acridine, dissolved in a mixed solvent (180ml toluene, 90ml ethanol), and then 0.03mol Na was added2CO3Aqueous solution (2M) and then 0.0001mol Pd (PPh) was added3)4Heating and refluxing for 10-24 h, sampling the sample, and completing the reaction. Naturally cooling, filtering, rotatably evaporating filtrate, and passing through a silica gel column to obtain a target product with the HPLC purity of 99.0 percent and the yield of 35.00 percent.
Elemental analysis Structure (molecular formula C)54H42N4O2): theoretical value C, 83.26; h, 5.43; n, 7.19; o, 4.11; test values are: c, 83.35; h, 5.36; n, 7.22; and O, 4.07.
HPLC-MS: the molecular weight of the material is 778.33, and the measured molecular weight is 779.14.
EXAMPLE 3 Synthesis of Compound 6
Figure BDA0000973390110000133
Specific synthetic routes for this compound are now provided:
Figure BDA0000973390110000134
500ml four-necked flask, under an atmosphere of nitrogen gas, was charged with 0.01mol of 2-chloro-4-naphthalen-2-yl-6-phenyl- [1,3, 5%]Triazine, 0.03mol of 2, 7-xanthone diboronic acid, 0.01mol of 2-bromo-9, 9, 10-triphenyl-9, 10-dihydroacridine, dissolved in a mixed solvent (180ml of toluene, 90ml of ethanol), and then 0.03mol of Na was added2CO3Aqueous solution (2M) and then 0.0001mol Pd (PPh) was added3)4Heating and refluxing for 10-24 h, sampling the sample, and completing the reaction. Naturally cooling, filtering, rotatably evaporating filtrate, and passing through a silica gel column to obtain a target product with the HPLC purity of 98.96 percent and the yield of 46.00 percent.
Elemental analysis Structure (molecular formula C)63H40N4O2): theoretical value C, 85.50; h, 4.56; n, 6.33; o, 3.62; test values are: c, 85.56; h, 4.52; n, 6.31; and O, 3.61.
HPLC-MS: the molecular weight of the material is 884.32, and the measured molecular weight is 884.60.
EXAMPLE 4 Synthesis of Compound 7
Figure BDA0000973390110000141
Specific synthetic routes for this compound are now provided:
Figure BDA0000973390110000142
500ml four-necked flask, under an atmosphere of nitrogen, was charged with 0.01mol of 2-chloro-4-phenanthren-9-yl-6-phenyl- [1,3, 5%]Triazine, 0.03mol of 10, 10-dimethyl-anthrone 2, 7-diboronic acid, 0.01mol of 10- (4-bromophenyl) -9, 9-diphenyl-9, 10-dihydroacridine, dissolved in a mixed solvent (180ml of toluene, 90ml of ethanol), and then 0.03mol of Na was added2CO3Aqueous solution (2M) and then 0.0001mol Pd (PPh) was added3)4Heating reflux 10-2After 4 hours, the reaction was completed by sampling the spot plate. Naturally cooling, filtering, rotatably evaporating filtrate, and passing through a silica gel column to obtain a target product with the HPLC purity of 98.69 percent and the yield of 38.00 percent.
Elemental analysis Structure (molecular formula C)70H48N4O): theoretical value C, 87.47; h, 5.03; n, 5.83; o, 1.66; test values are: c, 87.55; h, 5.09; n, 5.75; o, 1.61.
HPLC-MS: the molecular weight of the material is 960.38, and the measured molecular weight is 960.88.
EXAMPLE 5 Synthesis of Compound 8
Figure BDA0000973390110000151
Specific synthetic routes for this compound are now provided:
Figure BDA0000973390110000152
compound 8 was prepared as in example 4, except that the starting 2-chloro-4, 6-diphenyl- [1,3,5] triazine was used in place of 2-chloro-4-phenanthren-9-yl-6-phenyl- [1,3,5] triazine, 10, 10-diphenyl-anthrone 2, 7-diboronic acid was used in place of 10, 10-dimethyl-anthrone 2, 7-diboronic acid, and 2-bromo-5, 10-diphenyl-5, 10-dihydro-phenazine was used in place of 10- (4-bromophenyl) -9, 9-diphenyl-9, 10-dihydroacridine.
EXAMPLE 6 Synthesis of Compound 9
Figure BDA0000973390110000153
Specific synthetic routes for this compound are now provided:
Figure BDA0000973390110000154
compound 9 was prepared as in example 4, except that the starting material 2-biphenyl-3-yl-4-chloro-6-phenyl- [1,3,5] triazine was substituted for 2-chloro-4-phenanthren-9-yl-6-phenyl- [1,3,5] triazine, 10-phenyl-10H-acridone-2, 7-diboronic acid was substituted for 10, 10-dimethyl-anthrone 2, 7-diboronic acid, and 5- (4-bromophenyl) -10-phenyl-5, 10-dihydro-phenazine was substituted for 10- (4-bromophenyl) -9, 9-diphenyl-9, 10-dihydroacridine.
EXAMPLE 7 Synthesis of Compound 11
Figure BDA0000973390110000161
Specific synthetic routes for this compound are now provided:
Figure BDA0000973390110000162
compound 11 was prepared as in example 2, except that the starting material, 3-bromo-10-phenyl-10H-phenoxazine, was substituted for 10- (4-bromophenyl) -9, 9-dimethyl-9, 10-dihydro-acridine.
EXAMPLE 8 Synthesis of Compound 12
Figure BDA0000973390110000163
Specific synthetic routes for this compound are now provided:
Figure BDA0000973390110000164
compound 12 is prepared as in example 2, except that the starting material 2-chloro-4, 6-diphenyl- [1,3,5] triazine is substituted for 2-chloro-4, 6-bis (3, 5-dimethylphenyl) - [1,3,5] triazine, and 10-biphenyl-3-yl-3-bromo-10H-phenoxazine is substituted for 10- (4-bromophenyl) -9, 9-dimethyl-9, 10-dihydro-acridine.
EXAMPLE 9 Synthesis of Compound 14
Figure BDA0000973390110000165
Specific synthetic routes for this compound are now provided:
Figure BDA0000973390110000171
compound 14 was prepared as in example 5, except that the starting material, 11- (4-bromophenyl) -6, 6-dimethyl-6, 11-dihydro-13-oxa-11-aza-indole [1,2-b ] anthracene, was substituted for 2-bromo-5, 10-diphenyl-5, 10-dihydro-phenazine.
EXAMPLE 10 Synthesis of Compound 16
Figure BDA0000973390110000172
Specific synthetic routes for this compound are now provided:
Figure BDA0000973390110000173
in a 500ml four-necked flask, 0.01mol of 4-naphthalen-2-yl-6-phenyl- [1,3,5] was added under an atmosphere of nitrogen gas]Triazine-2-carbonyl chloride, 0.03mol of 6, 6-dimethyl-6, 11-dihydro-13-oxa-11-aza-indole [1,2-b ]]Anthracene, 0.03mol of sodium tert-butoxide, 1X 10-4mol Pd2(dba)3，1×10-4Heating and refluxing tri-tert-butylphosphine and 150ml toluene for 24 hr, sampling the sample, and reacting completely; naturally cooling, filtering, rotatably evaporating filtrate, and passing through a silica gel column to obtain the target product with the purity of 97.5 percent and the yield of 72.90 percent.
Elemental analysis Structure (molecular formula C)41H28N4O2): theoretical value C, 80.90; h, 4.64; n, 9.20; o,5.26 test value: c, 80.95; h, 4.60; n,9.23O, 5.22.
HPLC-MS: the molecular weight of the material is 608.22, and the measured molecular weight is 608.72.
EXAMPLE 11 Synthesis of Compound 19
Figure BDA0000973390110000181
Specific synthetic routes for this compound are now provided:
Figure BDA0000973390110000182
the preparation process of the intermediate A is as follows:
in a 500ml four-necked flask, under a nitrogen-purged atmosphere, 0.01mol of 2, 7-dibromo-10, 10-dimethyl-10H-anthrone, 0.01mol of 6, 6-dimethyl-13, 13-diphenyl-11, 13-dihydro-6H-11-aza-indole [1,2-b ] were added]Anthracene, 0.03mol of sodium tert-butoxide, 1X 10-4mol Pd2(dba)3，1×10-4Heating and refluxing tri-tert-butylphosphine and 150ml toluene for 24 hr, sampling the sample, and reacting completely; naturally cooling, filtering, rotatably evaporating filtrate, and passing through a silica gel column to obtain the target product with the purity of 95.5 percent and the yield of 68.90 percent.
HPLC-MS: the molecular weight of the material is 747.21, and the measured molecular weight is 747.26.
The preparation process of the target compound is as follows:
in a 500ml four-necked flask, 0.01mol of intermediate A and 0.03mol of 2-chloro-4, 6-diphenyl- [1,3,5] were charged under an atmosphere of nitrogen gas]Triazine, 150ml DMF,0.0001mol Pd (OAc)2And 0.03mol of potassium carbonate, reacting at 130-140 ℃ for 10-24 hours, naturally cooling, filtering, rotatably evaporating filtrate, and passing through a silica gel column to obtain a target product with the purity of 99.1% and the yield of 28.50%.
Elemental analysis Structure (molecular formula C)65H48N4O): theoretical value C, 86.64; h, 5.37; n, 6.22; o,1.78 test value: c, 86.71; h, 5.35; n, 6.21; o, 1.73.
HPLC-MS: the molecular weight of the material is 900.38, and the measured molecular weight is 900.86.
EXAMPLE 12 Synthesis of Compound 25
Figure BDA0000973390110000191
Specific synthetic routes for this compound are now provided:
Figure BDA0000973390110000192
compound 25 is prepared as in example 4, except that the starting material 2-biphenyl-4-yl-4-chloro-6-phenyl- [1,3,5] triazine is substituted for 2-chloro-4-phenanthren-9-yl-6-phenyl- [1,3,5] triazine and the starting material 6-biphenyl-4-yl-1-bromo-11, 11-dimethyl-6, 11-dihydro-13-oxa-6-aza-indole [1,2-b ] anthracene is substituted for 10- (4-bromophenyl) -9, 9-diphenyl-9, 10-dihydroacridine.
EXAMPLE 13 Synthesis of Compound 28
Figure BDA0000973390110000193
Specific synthetic routes for this compound are now provided:
Figure BDA0000973390110000194
compound 28 is prepared as in example 1, except that the starting material, 11-p-phenylboronic acid-11H-6, 13-dioxa-11-aza-indole [1,2-b ] anthracene, is substituted for 9, 9-dimethyl-10-phenyl-9, 10-dihydroacridine 2-boronic acid.
EXAMPLE 14 Synthesis of Compound 31
Figure BDA0000973390110000201
Specific synthetic routes for this compound are now provided:
Figure BDA0000973390110000202
compound 31 is prepared as in example 4, except that the starting material 2-chloro-4- (3, 5-dimethylphenyl) -6-phenyl- [1,3,5] triazine is substituted for 2-chloro-4-phenanthren-9-yl-6-phenyl- [1,3,5] triazine, 3-bromo-6, 11, 13-triphenyl-11, 13-dihydro-6H-6, 11, 13-triaza-indole [1,2-b ] anthracene for 10- (4-bromophenyl) -9, 9-diphenyl-9, 10-dihydroacridine.
EXAMPLE 15 Synthesis of Compound 33
Figure BDA0000973390110000203
The preparation process of the intermediate A is as follows:
a500 ml four-necked flask was charged with 0.01mol of 2-bromo-10- (4-bromophenyl) -10H-acridin-9-one, 0.01mol of 5H-8, 13-dioxa-5-aza-indole [1,2-a ] under an atmosphere of nitrogen gas]Anthracene, 0.03mol of sodium tert-butoxide, 1X 10- 4mol Pd2(dba)3，1×10-4Heating and refluxing tri-tert-butylphosphine and 150ml toluene for 24 hr, sampling the sample, and reacting completely; naturally cooling, filtering, rotatably evaporating filtrate, and passing through a silica gel column to obtain the target product with the purity of 97.5 percent and the yield of 48.23 percent.
HPLC-MS: the molecular weight of the material is 620.07, and the measured molecular weight is 620.59.
The preparation process of the target compound is as follows:
a500 ml four-necked flask was charged with 0.01mol of intermediate A and 0.03mol of 2-biphenyl 4-yl-4-chloro-6-phenyl- [1,3,5] in an atmosphere of nitrogen gas]Triazine, 150ml DMF,0.0001mol Pd (OAc)2And 0.03mol of potassium carbonate, reacting at 130-140 ℃ for 10-24 hours, naturally cooling, filtering, rotatably evaporating filtrate, and passing through a silica gel column to obtain a target product with the purity of 99.8% and the yield of 31.50%.
Elemental analysis Structure (molecular formula C)58H35N5O3: theoretical value C, 81.96; h, 4.15; n, 8.24; o,5.65 test value: c, 82.05; h, 4.12; n, 8.22; and O, 5.61.
HPLC-MS: the molecular weight of the material is 849.27, and the measured molecular weight is 849.62.
EXAMPLE 16 Synthesis of Compound 39
Figure BDA0000973390110000211
Compound 39 is prepared as in example 15, except that the starting material 6- (3' -bromobiphenyl-4-yl) -13, 13-dimethyl-6, 13-dihydro-11-oxa-6-aza-indole [1,2-b ] anthracene, 2-chloro-4, 6-diphenyl- [1,3,5] triazine is substituted for 5- (4-bromophenyl) -5H-8, 13-dioxa-5-aza-indole [1,2-a ] anthracene and for 2-biphenyl 4-yl-4-chloro-6-phenyl- [1,3,5] triazine.
EXAMPLE 17 Synthesis of Compound 42
Figure BDA0000973390110000212
Specific synthetic routes for this compound are now provided:
Figure BDA0000973390110000213
compound 42 is prepared as in example 3, except that the starting material 2-biphenyl-3-yl-4-chloro-6-phenyl- [1,3,5] triazine is substituted for 2-chloro-4-naphthalen-2-yl-6-phenyl- [1,3,5] triazine, 14- (4-bromophenyl) -7,7,12, 12-tetramethyl-7, 14-dihydro-12H-5-oxa-14-aza-pentacene for 2-bromo-9, 9, 10-triphenyl-9, 10-dihydroacridine.
EXAMPLE 18 Synthesis of Compound 45
Figure BDA0000973390110000221
Specific synthetic routes for this compound are now provided:
Figure BDA0000973390110000222
compound 45 was prepared as in example 6, except that the starting material, 5- (4-bromophenyl) -14, 14-dimethyl-7-phenyl-7, 14-dihydro-5H-12-oxa-5, 7-diaza-pentacene, was substituted for 5- (4-bromophenyl) -10-phenyl-5, 10-dihydro-phenazine.
EXAMPLE 19 Synthesis of Compound 49
Figure BDA0000973390110000223
Compound 49 was prepared as in example 11, except that starting material B was substituted for 6, 6-dimethyl-13, 13-diphenyl-11, 13-dihydro-6H-11-aza-indole [1,2-B ] anthracene.
EXAMPLE 20 Synthesis of Compound 54
Figure BDA0000973390110000224
Figure BDA0000973390110000231
Compound 54 can be prepared as in example 11, except that the starting material 2, 7-dibromo-10-phenyl-10H-acridone is substituted for 2, 7-dibromo-10, 10-dimethyl-10H-anthrone, and the starting material C is substituted for 6, 6-dimethyl-13, 13-diphenyl-11, 13-dihydro-6H-11-aza-indole [1,2-b ] anthracene
EXAMPLE 21 Synthesis of Compound 55
Figure BDA0000973390110000232
Compound 55 was prepared as in example 10, except that starting material D was substituted for 6, 6-dimethyl-6, 11-dihydro-13-oxa-11-aza-indole [1,2-b ] anthracene.
The compound of the present invention can be used as a light emitting layer material, and the results of thermal properties, light emission spectra, fluorescence quantum efficiency and cyclic voltammetry stability measurements of the compound 14 of the present invention, the compound 42 of the present invention and the existing material CBP are shown in table 1.
TABLE 1
Figure BDA0000973390110000233
Note: the thermal weight loss temperature Td is a temperature at which 1% of the weight is lost in a nitrogen atmosphere in Japan islandThe measurement is carried out on a TGA-50H thermogravimetric analyzer of Jin corporation, and the nitrogen flow is 20 mL/min; lambda [ alpha ]PLThe fluorescence emission wavelength of the sample solution is measured by using a Japanese topotecan SR-3 spectroradiometer; phi f is the fluorescence quantum efficiency of the solid powder (measured by using a solid fluorescence quantum efficiency testing system consisting of a Maya2000Pro fiber optic spectrometer of American marine optics, a C-701 integrating sphere of American blue-phenanthrene company and a LLS-LED light source of marine optics, in a method of Adv. Mater.1997, 9, 230-; the cyclic voltammetry stability is characterized by observing the redox characteristics of the material by cyclic voltammetry; and (3) testing conditions are as follows: the test sample was dissolved in a mixed solvent of dichloromethane and acetonitrile at a volume ratio of 2:1 at a concentration of 1mg/mL, and the electrolyte was 0.1M of an organic solution of tetrabutylammonium tetrafluoroborate or hexafluorophosphate. The reference electrode is an Ag/Ag + electrode, the counter electrode is a titanium plate, the working electrode is an ITO electrode, and the cycle time is 20 times.
Thermal annealing conditions: to be provided with
Figure BDA0000973390110000242
The compound is evaporated on the quartz glass at the evaporation rate, the quartz glass is packaged and then is added into an oven at 100 ℃ for drying for 72 hours, the quartz glass is taken out and cooled to the room temperature, and the crystal form of the quartz glass is observed by AFM.
The data in the table show that the compound has good oxidation-reduction stability and high thermal stability, and is suitable for being used as a host material of a light-emitting layer; meanwhile, the compound has a proper light-emitting spectrum and a high phi f, so that the efficiency and the service life of an OLED device using the compound as a doping material are improved.
The effect of the compound synthesized by the present invention as a host material for a light emitting layer in a device is explained in detail by examples 22 to 35 and comparative example 1. Examples 23-35 compared with example 22, the device was fabricated by the same process, and the same substrate material and electrode material were used, and the thickness of the electrode material was kept the same, except that the material of the light-emitting layer was changed. In comparison with comparative example 1, the light-emitting layer materials of the devices of comparative example 1 were the conventional materials, and the light-emitting layer materials of the devices of examples 22 to 35 were the compounds of the present invention. The structural composition of the resulting devices of each example is shown in table 2. The results of the performance test of each device are shown in table 3.
Example 22
ITO anode layer 2/hole injection layer 3 (molybdenum trioxide, MoO)3Thickness 10 nm)/hole transport layer 4(TAPC, thickness 80 nm)/light-emitting layer 5 (compound 1 and GD-19 as 100: 5 in a weight ratio of 30 nm/electron transport layer 6(TPBI, thickness 40 nm)/electron injection layer 7(LiF, thickness 1nm)/Al
Figure BDA0000973390110000241
The preparation process comprises the following steps:
the ITO anode layer 2 (having a film thickness of 150nm) was washed by alkali washing, pure water washing, drying, and then ultraviolet-ozone washing to remove organic residues on the surface of the transparent ITO.
On the washed ITO anode layer 2, molybdenum trioxide MoO having a film thickness of 10nm was deposited by a vacuum deposition apparatus3The hole injection layer 3 is used. Subsequently, TAPC was evaporated to a thickness of 80nm as the hole transport layer 4.
After the evaporation of the hole transport material is finished, the light-emitting layer 5 of the OLED light-emitting device is manufactured, and the structure of the light-emitting layer 5 comprises the material compound 1 used by the OLED light-emitting layer 5 as a main material, GD-19 as a doping material, the doping proportion of the doping material is 5% by weight, and the thickness of the light-emitting layer is 30 nm.
After the light-emitting layer 5, the electron transport layer material is continuously vacuum evaporated to be TPBI. The vacuum evaporation film thickness of the material was 40nm, and this layer was an electron transport layer 6.
On the electron transport layer 6, a lithium fluoride (LiF) layer having a film thickness of 1nm was formed by a vacuum deposition apparatus, and this layer was an electron injection layer 7.
On the electron injection layer 7, an aluminum (Al) layer having a film thickness of 80nm was formed by a vacuum deposition apparatus, and this layer was used as the cathode reflection electrode layer 8.
After the OLED light emitting device was completed as described above, the anode and the cathode were connected by a known driving circuit, and the light emitting efficiency, the light emission spectrum, and the current-voltage characteristics of the device were measured. The test results of the fabricated OLED light emitting device are shown in table 3.
TABLE 2
Figure BDA0000973390110000251
Figure BDA0000973390110000261
TABLE 3
Device code Current efficiency Color(s) LT95 Life
Example 22 3.6 Green light 4.1
Example 23 2.9 Green light 2.6
Example 24 3.0 Green light 3.0
Example 25 2.8 Green light 2.5
Example 26 4.2 Green light 3.5
Example 27 3.6 Green light 4.2
Example 28 2.7 Green light 4.9
Example 29 3.0 Green light 3.1
Example 30 3.2 Green light 2.8
Example 31 2.9 Green light 4.4
Example 32 3.9 Green light 5.0
Example 33 3.1 Green light 4.3
Example 34 3.8 Green light 2.8
Example 35 3.5 Green light 2.9
Comparative example 1 1.0 Green light 1.0
The device test performance is referred to comparative example 1, and each performance index of the device of comparative example 1 is set to 1.0. The current efficiency of comparative example 1 was 6.5cd/A (@10 mA/cm)2) (ii) a CIE color coordinates (0.32, 0.61); LT95 lifetime decay was 3.8Hr at 5000 brightness. The life test system is an OLED device life tester which is researched by the owner of the invention together with Shanghai university.
The effect of the compound synthesized by the present invention as a doping material for a light emitting layer in a device is illustrated by examples 36 to 42 and comparative example 2. Compared with the embodiment 22, the manufacturing processes of the devices of 36-42 and comparative example 2 of the present invention are completely the same, and the same substrate material and electrode material are adopted, and the film thickness of the electrode material is also kept consistent, except that the material of the light emitting layer in the device is changed, and the doping concentration is changed to 7%. The structural composition of the resulting device of each example is shown in table 4. The results of the performance test of each device are shown in table 5.
TABLE 4
Figure BDA0000973390110000271
TABLE 5
Device code Current efficiency Color(s) LT95 Life
Example 36 3.6 Green light 4.6
Example 37 2.9 Green light 3.2
Example 38 3.6 Green light 3.0
Example 39 3.5 Green light 3.9
Example 40 3.0 Green light 3.5
EXAMPLE 41 3.2 Green light 2.8
Example 42 2.8 Green light 4.1
Comparative example 2 1.0 Green light 1.0
The device test performance is referred to comparative example 2, and each performance index of the device of comparative example 2 is set to 1.0. Comparative example 2 has a current efficiency of 9.5cd/A (@10 mA/cm)2) (ii) a CIE color coordinates (0.27, 0.65); LT95 lifetime decay was 8.2Hr at 5000 brightness. The life test system is an OLED device life tester which is researched by the owner of the invention together with Shanghai university.
The results in table 3 show that the compound of the present invention can be used as a host material of a light emitting layer for fabrication of an OLED light emitting device, and compared with comparative example 1, the efficiency and lifetime of the OLED light emitting device are greatly improved compared with those of the known OLED material, and especially the driving lifetime of the device is greatly prolonged.
The results in table 5 show that the compound of the present invention can be applied to the fabrication of OLED light emitting devices as a doping material of a light emitting layer, and compared with comparative example 2, the efficiency and lifetime of the compound are greatly improved compared with those of known OLED materials, especially the driving lifetime of the device is greatly improved.
From the data application, the compound has good application effect in an OLED light-emitting device as a light-emitting layer material, and has good industrialization prospect.
Although the present invention has been disclosed by way of examples and preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments. On the contrary, it is intended to cover various modifications and similar arrangements as would be apparent to those skilled in the art. The scope of the following claims is, therefore, to be accorded the broadest interpretation so as to encompass all such modifications and similar arrangements.

Claims (3)

1. A compound with triazine and ketone as core groups is characterized in that the structure of the compound is shown as a general formula (1):
Figure FDA0002576580830000011
in the general formula (1), Ar1、Ar2Each independently represents phenyl, C1-10Straight or branched chain alkyl substituted phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl or benzophenanthryl;
in the general formula (1), D represents ArR or R; wherein Ar represents phenyl, C1-10Straight or branched chain alkyl substituted phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl or benzophenanthryl;
r is represented by general formula (2), general formula (3), general formula (4) or general formula (5):
Figure FDA0002576580830000012
wherein R is1、R2Independently select hydrogen or a structure shown in a general formula (6):
Figure FDA0002576580830000013
a is
Figure FDA0002576580830000014
X2、X3Respectively is oxygen atom, sulfur atom, selenium atom, C1-10One of a linear or branched alkyl substituted alkylene, aryl substituted alkylene, alkyl or aryl substituted amine group; a through CL1-CL2Key, CL2-CL3Key, CL3-CL4Key, CL’1-CL’2Key, CL’2-CL’3Bond or CL’3-CL’4The bond is connected with the general formula (2) or the general formula (4);
R3、R4independently selected hydrogen or a structure represented by the general formula (7):
Figure FDA0002576580830000021
b is
Figure FDA0002576580830000022
X2、X3Respectively is oxygen atom, sulfur atom, selenium atom, C1-10One of a linear or branched alkyl substituted alkylene, aryl substituted alkylene, alkyl or aryl substituted amine group; b by CL1-CL2Key, CL2-CL3Key, CL3-CL4Key, CL’1-CL’2Key, CL’2-CL’3Bond or CL’3-CL’4Is connected with the general formula (3) or the general formula (5);
R5represents phenyl, C1-10Straight or branched chain alkyl substituted phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl or benzophenanthryl; x1Is oxygen atom, sulfur atom, selenium atom, C1-10One of a linear or branched alkyl substituted alkylene, aryl substituted alkylene, alkyl or aryl substituted amine group;
in the general formula (1), L is represented by the general formula (8), (9) or (10):
Figure FDA0002576580830000023
wherein, X4Is represented by C1-10One of a linear or branched alkyl-substituted alkylene group, an aryl-substituted alkylene group, an oxygen atom, an alkyl group or an aryl-substituted amine group;
wherein, X5Is represented by C1-10One of linear or branched alkyl substituted alkylidene, aryl substituted alkylidene, alkyl or aryl substituted alkylidene group;
said X5-represents the attachment of D to X5To any atom to which it belongs.
2. The compound of claim 1, characterized by the general structural formula:
Figure FDA0002576580830000031
any one of the above.
3. The compound taking triazine and ketone as core groups is characterized in that the specific structural formula of the compound taking triazine and ketone as core groups is as follows:
Figure FDA0002576580830000041
Figure FDA0002576580830000051
Figure FDA0002576580830000061
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CN107057680A (en) * 2016-04-25 2017-08-18 中节能万润股份有限公司 A kind of compound as core using anthrone and its application on organic electroluminescence device
CN107602574A (en) * 2017-09-29 2018-01-19 江苏三月光电科技有限公司 A kind of compound and its application using cyano group benzene as core
CN109748906A (en) * 2017-11-02 2019-05-14 江苏三月光电科技有限公司 It is a kind of to contain anthrone and nitrogenous heterocyclic compound and its application on OLED
CN110878091B (en) * 2018-09-05 2021-11-30 江苏三月科技股份有限公司 Organic compound based on triazine and anthrone structure and application thereof
CN110963998A (en) * 2018-09-30 2020-04-07 江苏三月光电科技有限公司 Compound containing anthrone and nitrogen heterocycle and application thereof in OLED
CN111848589B (en) * 2019-04-30 2022-04-05 江苏三月科技股份有限公司 Xanthone derivative, preparation method and application thereof, and light-emitting device comprising xanthone derivative
CN112300792B (en) * 2019-07-24 2023-05-12 南京高光半导体材料有限公司 Green main material and organic electroluminescent device using same
CN113121514B (en) * 2019-12-30 2024-03-01 江苏三月科技股份有限公司 Compound with dibenzo five-membered heterocycle as core and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105074950A (en) * 2013-04-08 2015-11-18 默克专利有限公司 Organic electroluminescent device with thermally activated delayed fluorescence material
CN105102581A (en) * 2013-04-08 2015-11-25 默克专利有限公司 Organic electroluminescent device

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6502334B2 (en) * 2013-10-08 2019-04-17 メルク パテント ゲーエムベーハー Materials for electronic devices
KR101663527B1 (en) * 2014-01-22 2016-10-10 주식회사 엠비케이 New organic electroluminescent compounds and organic electroluminescent device comprising the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105074950A (en) * 2013-04-08 2015-11-18 默克专利有限公司 Organic electroluminescent device with thermally activated delayed fluorescence material
CN105102581A (en) * 2013-04-08 2015-11-25 默克专利有限公司 Organic electroluminescent device

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