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CN109748899B - Compound containing ketone and application thereof in organic electroluminescent device - Google Patents

Compound containing ketone and application thereof in organic electroluminescent device Download PDF

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CN109748899B
CN109748899B CN201711071819.7A CN201711071819A CN109748899B CN 109748899 B CN109748899 B CN 109748899B CN 201711071819 A CN201711071819 A CN 201711071819A CN 109748899 B CN109748899 B CN 109748899B
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ketone
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CN109748899A (en
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陈海峰
李崇
张兆超
张小庆
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Jiangsu Sunera Technology Co Ltd
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
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Abstract

The invention discloses a ketone-containing compound and application thereof in an organic electroluminescent device, wherein the compound consists of ketone and spiroanthracene fluorene groups, has deep HOMO energy level and high electron mobility, and is suitable for being used as a hole blocking material or an electron transport material; the structure containing the hole group can balance electrons and holes of the material, so that the material can be used as a main body material of a partial electron type light-emitting layer; in addition, the compound has the characteristics of strong group rigidity, difficult intermolecular crystallization and aggregation and good film forming property. After the organic electroluminescent functional layer material is applied to an OLED 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 containing ketone and application thereof in organic electroluminescent device
Technical Field
The invention relates to the technical field of semiconductors, in particular to a ketone-containing compound and application thereof in an organic electroluminescent device.
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.
At present, the OLED display technology has been applied in the fields of smart phones, tablet computers, and the like, and will further expand to large-size application fields such as televisions, but compared with actual product application requirements, the light emitting efficiency, the service life, and other performances of the OLED device need to be further improved. The research on the improvement of the performance of the OLED light emitting device includes: the driving voltage of the device is reduced, the luminous efficiency of the device is improved, the service life of the device is prolonged, and the like. In order to realize the continuous improvement of the performance of the OLED device, not only the innovation of the structure and the manufacturing process of the OLED device but also the continuous research and innovation of the OLED photoelectric functional material are needed to create the functional material of the OLED with higher performance. The photoelectric functional materials of the OLED applied to the OLED device can be divided into two broad categories from the application, i.e., charge injection transport materials and light emitting materials, and further, the charge injection transport materials can be further divided into electron injection transport materials, electron blocking materials, hole injection transport materials and hole blocking materials, and the light emitting materials can be further divided into main light emitting materials and doping materials. In order to fabricate a high-performance OLED light-emitting device, various organic functional materials are required to have good photoelectric properties, for example, as a charge transport material, good carrier mobility, high glass transition temperature, etc. are required, and as a host material of a light-emitting layer, a material having good bipolar property, appropriate HOMO/LUMO energy level, etc. is required.
The OLED photoelectric functional material film layer for forming the OLED device at least comprises more than two layers of structures, and the OLED device structure applied in industry comprises a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and other various film layers, namely the photoelectric functional material applied to the OLED device at least comprises a hole injection material, a hole transport material, a light emitting material, an electron transport material and the like, and the material type and the matching form have the characteristics of richness and diversity. In addition, for the collocation of OLED devices with different structures, the used photoelectric functional materials have stronger selectivity, and the performance of the same materials in the devices with different structures can also be completely different. Therefore, aiming at the industrial application requirements of the current OLED device, different functional film layers of the OLED device and the photoelectric characteristic requirements of the device, a more suitable OLED functional material or material combination with high performance needs to be selected to realize the comprehensive characteristics of high efficiency, long service life and low voltage of the device. In terms of the actual requirements of the current OLED display illumination industry, the development of the current OLED materials is far from enough, and lags behind the requirements of panel manufacturing enterprises, and it is very important to develop higher-performance organic functional materials as material enterprises.
Disclosure of Invention
In view of the above problems in the prior art, the present applicant provides a ketone-containing compound and its application in an organic electroluminescent device. The compound contains a ketone structure, has higher glass transition temperature and molecular thermal stability, proper HOMO and LUMO energy levels and high electron mobility, and can effectively improve the luminous efficiency of the device and prolong the service life of the OLED device after being applied to the manufacture of the OLED device.
The technical scheme of the invention is as follows: a ketone-containing compound having a structure represented by general formula (1):
Figure BDA0001457116250000021
in the general formula (1), ar 2 Is represented by substituted or unsubstituted C 1-10 Alkyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 5-30 One of heteroaryl;
in the general formula (1), ar 1 、Ar 3 Each independently represents a single bond, substituted or unsubstituted C 6-30 Arylene, substituted or unsubstituted C 5-30 One of heteroarylenes; ar (Ar) 1 May also be represented by substituted or unsubstituted C 1-10 Alkyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 5-30 In the heteroaryl radicalOne of (a) or (b);
in the general formula (1), X represents a carbon atom, an oxygen atom or a sulfur atom;
when X is a carbon atom, k =1,m, n independently represent 0 or 1, and m and n are different;
when X is an oxygen atom or a sulfur atom, k =0,m =0,n =1.
In the general formula (1), X 1 、X 2 Each independently represents a single bond, an oxygen atom, C 1-10 One of linear chain or branched alkyl substituted alkylidene, aryl substituted alkylidene, alkyl substituted imino or aryl substituted imino; x 1 、X 2 At least one is a single bond.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, the structure of the compound is shown as a general formula (2), a general formula (3), a general formula (4) or a general formula (5):
Figure BDA0001457116250000031
further, said Ar 1 、Ar 3 Each independently represents one of a single bond, phenylene, biphenylene or naphthylene; ar (Ar) 1 May also represent one of methyl, phenyl, biphenyl or naphthyl;
Ar 2 expressed as one of methyl, phenyl, biphenyl or naphthyl.
Further, in the general formula (1)
Figure BDA0001457116250000032
Expressed as:
Figure BDA0001457116250000033
to (3) is provided.
Further, the specific structural formula of the compound is as follows:
Figure BDA0001457116250000034
Figure BDA0001457116250000041
Figure BDA0001457116250000051
Figure BDA0001457116250000061
Figure BDA0001457116250000071
Figure BDA0001457116250000081
Figure BDA0001457116250000091
Figure BDA0001457116250000101
Figure BDA0001457116250000111
Figure BDA0001457116250000121
Figure BDA0001457116250000122
any one of the above.
The invention also provides a preparation method of the compound, and the reaction equation generated in the preparation process is as follows:
(1) When X is an oxygen atom or a sulfur atom, k =0, m =0, n =1:
when Ar is 3 When not representing a single bond:
Figure BDA0001457116250000123
the specific reaction process of the above reaction equation is:
dissolving raw material A and intermediate M in mixed solution of toluene and ethanol, removing oxygen, and adding Pd (PPh) 3 ) 4 And K 2 CO 3 Reacting for 10-24 hours at 95-110 ℃ under inert atmosphere; after the raw materials are completely reacted, cooling and filtering, removing the solvent from the filtrate by rotary evaporation, and passing the crude product through a silica gel column to obtain a target compound;
wherein the dosage of the toluene and the ethanol is 30-50 mL of toluene and 5-10 mL of ethanol used per gram of the raw material A, the molar ratio of the intermediate M to the raw material A is (1-1.5) 1, pd (PPh) 3 ) 4 The molar ratio of the raw material A to the raw material A is (0.006-0.02): 1,K 2 CO 3 The mol ratio of the raw material A to the raw material A is (1.5-2) to 1;
when Ar is 3 When represents a single bond:
Figure BDA0001457116250000124
the specific reaction process of the above reaction equation is:
weighing a raw material A in a nitrogen atmosphere, dissolving the raw material A in tetrahydrofuran, adding a raw material B and tetrakis (triphenylphosphine) palladium, stirring the mixture, adding a potassium carbonate aqueous solution, and heating and refluxing the mixed solution of the reactants at a reaction temperature of 70-90 ℃ for 5-20 hours; after the reaction is finished, cooling and adding water, extracting the mixture by using dichloromethane, drying the extract by using anhydrous sodium sulfate, filtering and concentrating under reduced pressure, and purifying the obtained residue by using a silica gel column to obtain the target compound;
wherein the molar ratio of the raw material A to the raw material B is 1 (1.0-1.5), the molar ratio of the tetrakis (triphenylphosphine) palladium to the raw material A is (0.001-0.02): 1, the molar ratio of the potassium carbonate to the raw material A is (1.0-2.0): 1, the dosage ratio of the THF to the raw material A is 1g: (10-30) ml.
(2) When X is a carbon atom, k =1,m =0, n =1:
when Ar is 3 When not representing a single bond:
Figure BDA0001457116250000131
the specific reaction process of the above reaction equation is:
dissolving raw material A and intermediate N in mixed solution of toluene and ethanol, removing oxygen, and adding Pd (PPh) 3 ) 4 And K 2 CO 3 Reacting for 10-24 hours at 95-110 ℃ under inert atmosphere; after the raw materials are completely reacted, cooling and filtering, removing the solvent from the filtrate by rotary evaporation, and passing the crude product through a silica gel column to obtain a target compound;
wherein the dosage of the toluene and the ethanol is 30-50 mL of toluene and 5-10 mL of ethanol used in each gram of the raw material A, the mol ratio of the intermediate N to the raw material A is (1-1.5) to 1, pd (PPh) 3 ) 4 The mol ratio of the raw material A to the raw material A is (0.006-0.02): 1,K 2 CO 3 The mol ratio of the raw material A to the raw material A is (1.5-2) to 1;
when Ar is 3 When represents a single bond:
Figure BDA0001457116250000132
the specific reaction process of the above reaction equation is:
weighing a raw material A and dissolving the raw material A in tetrahydrofuran under the nitrogen atmosphere, adding a raw material C and tetrakis (triphenylphosphine) palladium, stirring the mixture, adding a potassium carbonate aqueous solution, and heating and refluxing the mixed solution of the reactants at the reaction temperature of 70-90 ℃ for 5-20 hours; after the reaction is finished, cooling and adding water, extracting the mixture by using dichloromethane, drying the extract by using anhydrous sodium sulfate, filtering and concentrating under reduced pressure, and purifying the obtained residue by using a silica gel column to obtain the target compound;
wherein the molar ratio of the raw material A to the raw material C is 1 (1.0-1.5), the molar ratio of the tetrakis (triphenylphosphine) palladium to the raw material A is (0.001-0.02): 1, the molar ratio of the potassium carbonate to the raw material A is (1.0-2.0): 1, the dosage ratio of THF to the raw material A is 1g: (10-30) ml;
(3) When X is a carbon atom, k =1,m =1,n =0:
Figure BDA0001457116250000141
the specific reaction process is as follows:
weighing raw material A and dissolving in tetrahydrofuran under nitrogen atmosphere, adding raw material D and tetrakis (triphenylphosphine) palladium, stirring the mixture, adding potassium carbonate aqueous solution, and heating and refluxing the mixed solution of the reactants at the reaction temperature of 70-90 ℃ for 5-20 hours; after the reaction is finished, water is added for cooling, the mixture is extracted by dichloromethane, the extract liquid is dried by anhydrous sodium sulfate, filtered and concentrated under reduced pressure, and the obtained residue is purified by a silica gel column to obtain the target compound;
the molar ratio of the raw material A to the raw material D is 1.0-1.5, the molar ratio of tetrakis (triphenylphosphine) palladium to the raw material A is 0.001-0.02: 10 to 30ml.
The present invention also provides an organic electroluminescent device comprising at least one functional layer containing the above ketone-containing compound.
On the basis of the technical scheme, the invention can be improved as follows.
Further, the organic electroluminescent device includes a light-emitting layer containing the above ketone-containing compound.
Further, the organic electroluminescent device comprises a hole blocking layer/electron transporting layer containing the above ketone-containing compound.
The invention also provides a lighting or display element comprising an organic electroluminescent device as described above.
The beneficial technical effects of the invention are as follows:
the compound takes ketone and spiroanthracene fluorene groups as a framework, the ketone and spiroanthracene fluorene groups are connected through a single bond or an aromatic group, the ketone and spiroanthracene fluorene groups are electronic groups, and have deep HOMO energy level and high electron mobility, and the HOMO energy level can be freely adjusted through modification of other aromatic groups, so that the compound can be used as an electronic type luminescent material and also can be used as a hole blocking or electron transport layer material. The structure containing the hole group can balance electrons and holes of the material, so that the material can be used as a main body material of a polarized electron type light-emitting layer.
In addition, the ketone and spiroanthracene fluorene groups are electron withdrawing groups, the formed molecules have no symmetry, the aggregation among the molecules is avoided, and the compound group has the characteristics of strong rigidity, difficult crystallization and aggregation among the molecules, good film forming property and high glass transition temperature and thermal stability.
After the compound is used as an organic electroluminescent functional layer material to be applied to an OLED 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, and the OLED luminescent device has a good application effect and a good industrialization prospect.
Drawings
FIG. 1 is a schematic structural diagram of an OLED device using the materials listed in 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 transmission or electron blocking layer, 5 is a luminescent layer, 6 is an electron transmission or hole blocking layer, 7 is an electron injection layer, and 8 is a cathode reflection electrode layer.
Fig. 2 is a graph of current efficiency versus temperature.
Detailed Description
Example 1: synthesis of intermediate M:
Figure BDA0001457116250000151
(1) Dissolving raw material B and raw material E in a mixed solution of toluene and ethanol, removing oxygen, and adding Pd (PPh) 3 ) 4 And K 2 CO 3 Reacting for 10-24 hours at 95-110 ℃ under inert atmosphere; after the raw materials are completely reacted, cooling and filtering, removing the solvent from the filtrate by rotary evaporation, and passing the crude product through a silica gel column to obtain a target compound;
wherein the dosage of the toluene and the ethanol is 30-50 mL of toluene and 5-10 mL of ethanol used per gram of the raw material E, the molar ratio of the raw material B to the raw material E is (1-1.5): 1,Pd (PPh) 3 ) 4 The molar ratio of the raw material E to the raw material E is (0.006-0.02): 1,K 2 CO 3 The molar ratio of the raw material E to the raw material E is (1.5-2): 1.
(2) Weighing an intermediate S, dissolving the intermediate S in tetrahydrofuran under the protection of nitrogen, cooling to-78 ℃, adding 1.6mol/L tetrahydrofuran solution of n-butyllithium into a reaction system, reacting at-78 ℃ for 3h, adding triisopropyl borate, reacting for 2h, raising the temperature of the reaction system to 0 ℃, adding 2mol/L hydrochloric acid solution, stirring for 3h, completely reacting, adding diethyl ether for extraction, adding anhydrous magnesium sulfate into an extract liquid, drying, performing rotary evaporation, and recrystallizing by using an ethanol solvent to obtain an intermediate M;
wherein the molar ratio of the intermediate S to the n-butyllithium is 1 (1-1.5); the molar ratio of the intermediate S to the triisopropyl borate is 1 (1-1.5).
Synthesis example of intermediate M-1:
Figure BDA0001457116250000161
(1) 0.01mol of the raw material E-2 and 0.012mol of the raw material B-1 were dissolved in 150mL (V) of toluene and ethanol Toluene ：V Ethanol =5: 1) Adding 0.0002mol of Pd (PPh) into the mixed solution after deoxygenation 3 ) 4 And 0.02molK 2 CO 3 Reacting at 110 ℃ for 24 hours under an inert atmosphere, cooling and filtering after the raw materials react completely, removing the solvent from the filtrate by rotary evaporation, and passing the crude product through a silica gel column to obtain an intermediate target product S-2; elemental analysis Structure (molecular formula C) 19 H 11 BrO 2 ): theoretical value C,64.98; h,3.16; br,22.75; test values are: c,64.98; h,3.16; br,22.74; ESI-MS (M/z) (M +): theoretical value is 349.99, found 350.55.
(2) Weighing 0.01mol of intermediate S-2 under the protection of nitrogen, dissolving in tetrahydrofuran, cooling to-78 ℃, adding 8ml of 1.6mol/L n-butyllithium tetrahydrofuran solution into a reaction system, reacting at-78 ℃ for 3h, adding 0.013mol of triisopropyl borate, reacting for 2h, raising the temperature of the reaction system to 0 ℃, adding 10ml of 2mol/L hydrochloric acid solution, stirring for 3h, reacting completely, adding diethyl ether for extraction, adding anhydrous magnesium sulfate into an extract, drying, rotary evaporating, and recrystallizing with an ethanol solvent to obtain an intermediate M-2; elemental analysis Structure (molecular formula C) 19 H 13 BO 4 ): theoretical value C,72.19; h,4.15; b,3.42; test values are: c,72.19; h,4.15; b,3.43.ESI-MS (M/z) (M) + ): theoretical value is 316.09, found 316.49.
The intermediate M is prepared by a synthesis method of the intermediate M-1, and the specific structure is shown in Table 1.
TABLE 1
Figure BDA0001457116250000162
Figure BDA0001457116250000171
Figure BDA0001457116250000181
Example 2: synthesis of Compound 3:
Figure BDA0001457116250000182
in a 250mL three-necked flask, 0.01mol of starting material A-1 and 0.012mol of intermediate M-1 were dissolved in 150mL (V) of toluene and ethanol Toluene ：V Ethanol =5: 1) Adding 0.0002mol of Pd (PPh) into the mixed solution after deoxygenation 3 ) 4 And 0.02mol of K 2 CO 3 Reacting at 110 ℃ for 24 hours under an inert atmosphere, cooling and filtering after the raw materials react completely, removing the solvent from the filtrate by rotary evaporation, and passing the crude product through a silica gel column to obtain a target product; elemental analysis Structure (molecular formula C) 47 H 32 O 2 ): theoretical value C,89.78; h,5.13; test values: c,89.77; h,5.13; ESI-MS (M/z) (M +): theoretical value is 628.24, found 628.55.
Example 3: synthesis of compound 10:
Figure BDA0001457116250000191
in a 250mL three-necked flask, 0.01mol of starting material A-2 and 0.012mol of intermediate M-2 were dissolved in 150mL (V) of toluene and ethanol Toluene ：V Ethanol =5: 1) Adding 0.0002mol of Pd (PPh) into the mixed solution after deoxygenation 3 ) 4 And 0.02mol of K 2 CO 3 Reacting at 110 ℃ for 24 hours under an inert atmosphere, cooling and filtering after the raw materials react completely, removing the solvent from the filtrate by rotary evaporation, and passing the crude product through a silica gel column to obtain a target product; elemental analysis Structure (molecular formula C) 44 H 26 O 3 ): theoretical value C,87.69; h,4.35; test values are: c,87.68; h,4.35; ESI-MS (M/z) (M +): theoretical value is 602.19, found 602.77.
Example 4: synthesis of compound 19:
Figure BDA0001457116250000192
compound 19 was prepared as in example 2, except that starting material A-1 was replaced with starting material A-2 and intermediate M-3 was used in the replacementAn intermediate M-1. Elemental analysis Structure (molecular formula C) 44 H 26 O 3 ): theoretical value C,87.69; h,4.35; test values are: c,87.70; h,4.35.ESI-MS (M/z) (M) + ): theoretical value is 602.19, found 602.61.
Example 5: synthesis of compound 20:
Figure BDA0001457116250000193
compound 20 was prepared as in example 2, except that starting material A-1 was replaced with starting material A-3 and intermediate M-1 was replaced with intermediate M-3. Elemental analysis Structure (molecular formula C) 44 H 26 O 3 ): theoretical value C,87.69; h,4.35; test values: c,87.69; h,4.35.ESI-MS (M/z) (M) + ): theoretical value is 602.19, found 602.74.
Example 6: synthesis of compound 28:
Figure BDA0001457116250000194
weighing 0.01mol of raw material A-2 in a 250mL three-neck flask in a nitrogen atmosphere, dissolving in 100mL tetrahydrofuran, adding 0.012mol of raw material B-1 and 0.0002mol of tetrakis (triphenylphosphine) palladium, stirring the mixture, adding 0.02mol of potassium carbonate aqueous solution, and heating and refluxing the mixed solution of the reactants at a reaction temperature of 90 ℃ for 20 hours; after the reaction is finished, cooling and adding water, extracting the mixture by using dichloromethane, drying the extract by using anhydrous sodium sulfate, filtering and concentrating under reduced pressure, and purifying the obtained residue by using a silica gel column to obtain the target compound; elemental analysis Structure (molecular formula C) 38 H 22 O 3 ): theoretical value C,86.67; h,4.21; test values are: c,86.66; h,4.21.ESI-MS (M/z) (M) + ): theoretical value is 526.16, found 526.74.
Example 7: synthesis of compound 39:
Figure BDA0001457116250000201
compound 39 is prepared as in example 2, except that intermediate M-4 is substituted for intermediate M-1. Elemental analysis Structure (molecular formula C) 47 H 32 O 2 ): theoretical value C,89.78; h,5.13; test values are: c,89.79; h,5.13.ESI-MS (M/z) (M) + ): theoretical value is 628.24, found 628.53.
Example 8: synthesis of compound 50:
Figure BDA0001457116250000202
compound 50 was prepared as in example 2, except that starting material A-1 was replaced with starting material A-4 and intermediate M-1 was replaced with intermediate M-5. Elemental analysis Structure (molecular formula C) 44 H 26 O 3 ): theoretical value C,87.69; h,4.35; test values are: c,87.68; h,4.35.ESI-MS (M/z) (M) + ): theoretical value is 602.19, found 602.49.
Example 9: synthesis of compound 61:
Figure BDA0001457116250000203
compound 61 can be prepared as in example 2, except that starting material A-1 is replaced with starting material A-5 and intermediate M-1 is replaced with intermediate M-6. Elemental analysis Structure (molecular formula C) 44 H 26 O 3 ): theoretical value C,87.69; h,4.35; test values: c,87.69; h,4.34.ESI-MS (M/z) (M) + ): theoretical value is 602.19, found 602.82.
Example 10: synthesis of compound 69:
Figure BDA0001457116250000211
in a 250mL three-necked flask, 0.01mol of the raw material A-6 was weighed out and dissolved in 100mL of tetrahydrofuran under a nitrogen atmosphere, and 0.01mol of the solution was added2mol of raw material B-2 and 0.0002mol of tetrakis (triphenylphosphine) palladium are added, the mixture is stirred, 0.02mol of potassium carbonate aqueous solution is added, and the mixed solution of the reactants is heated and refluxed for 20 hours at the reaction temperature of 90 ℃; after the reaction is finished, cooling and adding water, extracting the mixture by using dichloromethane, drying the extract by using anhydrous sodium sulfate, filtering and concentrating under reduced pressure, and purifying the obtained residue by using a silica gel column to obtain the target compound; elemental analysis Structure (molecular formula C) 41 H 28 O 2 ): theoretical value C,89.10; h,5.11; test values are: c,89.10; h,5.12.ESI-MS (M/z) (M) + ): theoretical value is 552.21, found 552.54.
Example 11: synthesis of compound 73:
Figure BDA0001457116250000212
compound 73 was prepared as in example 2, except that starting material A-1 was replaced with starting material A-2 and intermediate M-1 was replaced with intermediate M-7. Elemental analysis Structure (molecular formula C) 50 H 30 O 3 ): theoretical value C,88.47; h,4.46; test values are: c,88.47; h,4.47.ESI-MS (M/z) (M) + ): theoretical value is 678.22, found 678.74.
Example 12: synthesis of compound 83:
Figure BDA0001457116250000213
compound 83 is prepared as in example 2, except that starting material A-1 is replaced with starting material A-3 and intermediate M-1 is replaced with intermediate M-8. Elemental analysis Structure (molecular formula C) 50 H 30 O 3 ): theoretical value C,88.47; h,4.46; test values are: c,88.46; h,4.46.ESI-MS (M/z) (M) + ): theoretical value is 678.22, found 678.81.
Example 13: synthesis of compound 96:
Figure BDA0001457116250000214
compound 96 is prepared as in example 2, except that starting material A-6 is substituted for starting material A-1 and intermediate M-9 is substituted for intermediate M-1. Elemental analysis Structure (molecular formula C) 53 H 36 O 2 ): theoretical value C,90.31; h,5.15; test values are: c,90.31; h,5.14.ESI-MS (M/z) (M) + ): theoretical value is 704.27, found 704.91.
Example 14: synthesis of compound 115:
Figure BDA0001457116250000221
compound 115 was prepared as in example 2, except that starting material A-1 was replaced with starting material A-5 and intermediate M-1 was replaced with intermediate M-10. Elemental analysis Structure (molecular formula C) 50 H 30 O 3 ): theoretical value C,88.47; h,4.46; test values: c,88.47; h,4.47.ESI-MS (M/z) (M) + ): theoretical value is 678.22, found 678.88.
Example 15: synthesis of compound 128:
Figure BDA0001457116250000222
compound 128 was prepared as in example 2, except that starting material A-1 was replaced with starting material A-3 and intermediate M-1 was replaced with intermediate M-11. Elemental analysis Structure (molecular formula C) 50 H 30 O 3 ): theoretical value C,88.47; h,4.46; test values are: c,88.46; h,4.46.ESI-MS (M/z) (M) + ): theoretical value is 678.22, found 678.76.
Example 16: synthesis of compound 144:
Figure BDA0001457116250000223
compound 144 was prepared as in example 2, exceptThe method is characterized in that a raw material A-4 is used for replacing a raw material A-1, and an intermediate M-12 is used for replacing an intermediate M-1. Elemental analysis Structure (molecular formula C) 53 H 36 O 2 ): theoretical value C,90.31; h,5.15; test values are: c,90.30; h,5.15.ESI-MS (M/z) (M) + ): theoretical value is 704.27, found 704.74.
Example 17: synthesis of compound 155:
Figure BDA0001457116250000224
compound 155 can be prepared as in example 2, except that starting material A-1 is replaced with starting material A-3 and intermediate M-1 is replaced with intermediate M-13. Elemental analysis Structure (molecular formula C) 50 H 30 O 3 ): theoretical value C,88.47; h,4.46; test values are: c,88.46; h,4.46.ESI-MS (M/z) (M) + ): theoretical value is 678.22, found 678.84.
Example 18: synthesis of compound 163:
Figure BDA0001457116250000231
compound 163 was prepared as in example 2, except that starting material A-1 was replaced with starting material A-2 and intermediate M-1 was replaced with intermediate M-14. Elemental analysis Structure (molecular formula C) 50 H 30 O 3 ): theoretical value C,88.47; h,4.46; test values are: c,88.46; h,4.46.ESI-MS (M/z) (M) + ): theoretical value is 678.22, found 678.46.
Example 19: synthesis of compound 177:
Figure BDA0001457116250000232
compound 177 is prepared as in example 2, except that starting material A-6 is substituted for starting material A-1 and intermediate M-15 is substituted for intermediate M-1. Elemental analysis Structure (molecular formula C) 53 H 36 O 2 ): theoretical valueC,90.31; h,5.15; test values are: c,90.31; h,5.15.ESI-MS (M/z) (M) + ): theoretical value is 704.27, found 704.89.
Example 20: synthesis of compound 196:
Figure BDA0001457116250000233
compound 196 is prepared as in example 2, except starting material A-5 is substituted for starting material A-1 and intermediate M-16 is substituted for intermediate M-1. Elemental analysis Structure (molecular formula C) 50 H 30 O 3 ): theoretical value C,88.47; h,4.46; test values are: c,88.47; h,4.45.ESI-MS (M/z) (M) + ): theoretical value is 678.22, found 678.86.
Example 21: synthesis of compound 218:
Figure BDA0001457116250000234
compound 218 is prepared as in example 2, except that starting material A-1 is replaced with starting material A-3 and intermediate M-1 is replaced with intermediate M-17. Elemental analysis Structure (molecular formula C) 50 H 30 O 3 ): theoretical value C,88.47; h,4.46; test values are: c,88.46; h,4.46.ESI-MS (M/z) (M) + ): theoretical value is 678.22, found 678.59.
Example 22: synthesis of compound 231:
Figure BDA0001457116250000241
compound 231 was prepared as in example 2, except that starting material A-6 was used in place of starting material A-1 and intermediate M-18 was used in place of intermediate M-1. Elemental analysis Structure (molecular formula C) 53 H 36 O 2 ): theoretical value C,90.31; h,5.15; test values are: c,90.30; h,5.15.ESI-MS (M/z) (M) + ): theoretical value is 704.27, found 704.95.
Example 23: synthesis of compound 242:
Figure BDA0001457116250000242
compound 242 was prepared as in example 6, except that starting material B-1 was replaced with starting material C-1 and starting material A-1 was replaced with starting material A-4. Elemental analysis Structure (molecular formula C) 41 H 28 O 2 ): theoretical value C,89.10; h,5.11; test values are: c,89.11; h,5.11.ESI-MS (M/z) (M) + ): theoretical value is 552.21, found 552.74.
Example 24: synthesis of compound 261:
Figure BDA0001457116250000243
compound 261 can be prepared by the same method as in example 6, except that starting material B-1 is replaced with starting material D-1 and starting material A-1 is replaced with starting material A-6. Elemental analysis Structure (molecular formula C) 54 H 38 O): theoretical value C,92.27; h,5.45; test values are: c,92.26; h,5.45.ESI-MS (M/z) (M) + ): theoretical value is 702.29, found 702.66.
The organic compound is used in a light-emitting device, has high Tg (glass transition temperature) temperature and triplet state energy level (T1), and suitable HOMO and LUMO energy levels, can be used as a hole blocking/electron transporting material, and can also be used as a light-emitting layer material. The compound of the present invention and the existing material were tested for thermal properties, T1 level and HOMO level, respectively, and the results are shown in table 2.
TABLE 2
Figure BDA0001457116250000244
Figure BDA0001457116250000251
Note: three-wireThe state energy level T1 is tested by an F4600 fluorescence spectrometer of Hitachi, and the test condition of the material is 2X 10 -5 A toluene solution of (4); the glass transition temperature Tg is measured by differential scanning calorimetry (DSC, DSC204F1 differential scanning calorimeter of Germany Tissian corporation), and the heating rate is 10 ℃/min; the thermogravimetric temperature Td is a temperature at which 1% of the weight loss is observed in a nitrogen atmosphere, and is measured on a TGA-50H thermogravimetric analyzer of Shimadzu corporation, japan, and the nitrogen flow rate is 20mL/min; the highest occupied molecular orbital HOMO energy level was tested by the ionization energy test system (IPS 3) in an atmospheric environment.
As can be seen from the data in the table above, compared with the CBP and TPBi materials applied at present, the organic compound of the invention has high glass transition temperature, can improve the phase stability of the material film, and further improves the service life of the device; the material has high triplet state energy level, and can block energy loss of a light-emitting layer, so that the light-emitting efficiency of the device is improved. Meanwhile, the material and the application material have similar HOMO energy levels. Therefore, after the organic material containing ketone is applied to different functional layers of an OLED device, the luminous efficiency of the device can be effectively improved, and the service life of the device can be effectively prolonged.
The application effect of the synthesized OLED material in the device is described in detail by device examples 1-23 and device comparative example 1. Compared with the device embodiment 1, the device embodiments 2 to 23 and the device comparative example 1 of the present invention have the same manufacturing process, and adopt the same substrate material and electrode material, and the film thickness of the electrode material is also kept consistent, except that the device embodiments 2 to 15 change the material of the light emitting layer in the device; device examples 16-23 were prepared by changing the hole blocking/electron transporting layer materials of the devices, and the results of the performance tests of the devices obtained in each example are shown in table 3.
Device example 1:
as shown in fig. 1, an electroluminescent device is prepared by the steps of: a) Cleaning the ITO anode layer 2 on the transparent substrate layer 1, respectively ultrasonically cleaning the ITO anode layer 2 for 15 minutes by using deionized water, acetone and ethanol, and then treating the ITO anode layer 2 in a plasma cleaner for 2 minutes; b) Evaporating hole injection layer material HAT-CN on ITO anode layer 2 by vacuum evaporation with thickness of 10nm, this layer serves as the hole injection layer 3; c) Evaporating a hole transport material NPB (N-propyl-N-boron) on the hole injection layer 3 in a vacuum evaporation mode, wherein the thickness of the hole transport material NPB is 80nm, and the hole transport layer/electron blocking layer 4 is formed; d) A luminescent layer 5 is evaporated on the hole transport/electron blocking layer 4, the host material is the compound 10 and the compound GH prepared in the embodiment of the invention, and the doping material is Ir (ppy) 3 Compound 10, GH and Ir (ppy) 3 The mass ratio of the three components is 50; e) An electron transport material TPBI is evaporated on the light-emitting layer 5 in a vacuum evaporation mode, the thickness of the TPBI is 40nm, and the organic material of the TPBI layer is used as a hole blocking/electron transport layer 6; f) Vacuum evaporating an electron injection layer LiF with the thickness of 1nm on the hole blocking/electron transport layer 6, wherein the layer is an electron injection layer 7; g) Vacuum evaporating cathode Al (100 nm) on the electron injection layer 7, which is a cathode reflection electrode layer 8; after the electroluminescent device was fabricated according to the above procedure, the driving voltage and current efficiency of the device were measured, and the results are shown in table 3. The molecular structural formula of the related material is shown as follows:
Figure BDA0001457116250000261
device example 2: ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 80nm, material: NPB)/light-emitting layer 5 (thickness: 40nm, material: compound 19, GH and Ir (ppy) prepared in the examples of the present invention 3 The composition of the mixture of 50: 35nm, material: TPBI)/electron injection layer 7 (thickness: 1nm, material: liF)/Al (thickness: 100 nm).
Device example 3: ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 80nm, material: NPB)/light emitting layer 5 (thickness: 40nm, material: compound 28, GH and Ir (ppy) prepared in the example of the present invention 3 50/10 in a weight ratio of 50: 35nm, material: TPBI)/electron injection layer 7 (thickness: 1nm, material: liF)/Al (thickness: 100 nm)。
Device example 4: ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 80nm, material: NPB)/light emitting layer 5 (thickness: 40nm, material: compound 50, GH and Ir (ppy) prepared in the examples of the present invention 3 50/10 in a weight ratio of 50: 35nm, material: TPBI)/electron injection layer 7 (thickness: 1nm, material: liF)/Al (thickness: 100 nm).
Device example 5: ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 80nm, material: NPB)/light emitting layer 5 (thickness: 40nm, material: compound 61, GH and Ir (ppy) prepared in the example of the present invention 3 50/10 in a weight ratio of 50: 35nm, material: TPBI)/electron injection layer 7 (thickness: 1nm, material: liF)/Al (thickness: 100 nm).
Device example 6: ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 80nm, material: NPB)/light emitting layer 5 (thickness: 40nm, material: compound 69, GH and Ir (ppy) prepared in the examples of the present invention 3 The composition of the mixture of 50: 35nm, material: TPBI)/electron injection layer 7 (thickness: 1nm, material: liF)/Al (thickness: 100 nm).
Device example 7: ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 80nm, material: NPB)/light emitting layer 5 (thickness: 40nm, material: compound 73, GH and Ir (ppy) prepared in the examples of the present invention 3 50/10 in a weight ratio of 50: 35nm, material: TPBI)/electron injection layer 7 (thickness: 1nm, material: liF)/Al (thickness: 100 nm).
Device example 8: ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 80nm, material: NPB)/light emitting layer 5 (thickness: 40nm, material: compound 96, GH and I prepared in the examples of the present inventionr(ppy) 3 The composition of the mixture of 50: 35nm, material: TPBI)/electron injection layer 7 (thickness: 1nm, material: liF)/Al (thickness: 100 nm).
Device example 9: ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 80nm, material: NPB)/light emitting layer 5 (thickness: 40nm, material: compound 115, GH and Ir (ppy) prepared in the example of the present invention 3 50/10 in a weight ratio of 50: 35nm, material: TPBI)/electron injection layer 7 (thickness: 1nm, material: liF)/Al (thickness: 100 nm).
Device example 10: ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 80nm, material: NPB)/light emitting layer 5 (thickness: 40nm, material: compound 144, GH and Ir (ppy) prepared in the examples of the present invention 3 50/10 in a weight ratio of 50: 35nm, material: TPBI)/electron injection layer 7 (thickness: 1nm, material: liF)/Al (thickness: 100 nm).
Device example 11: ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 80nm, material: NPB)/light emitting layer 5 (thickness: 40nm, material: compound 163, GH and Ir (ppy) prepared in the example of the present invention 3 The composition of the mixture of 50: 35nm, material: TPBI)/electron injection layer 7 (thickness: 1nm, material: liF)/Al (thickness: 100 nm).
Device example 12: ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 80nm, material: NPB)/light emitting layer 5 (thickness: 40nm, material: compounds 177 prepared according to the examples of the present invention, GH and Ir (ppy) 3 50/10 in a weight ratio of 50: 35nm, material: TPBI)/electron injection layer 7 (thickness: 1nm, material: liF)/Al (thickness: 100 nm).
Device example 13: ITO anode layer 2 (thickness: 15)0 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 80nm, material: NPB)/light-emitting layer 5 (thickness: 40nm, material: compounds 196, GH and Ir (ppy) prepared in the examples of the invention 3 50/10 in a weight ratio of 50: 35nm, material: TPBI)/electron injection layer 7 (thickness: 1nm, material: liF)/Al (thickness: 100 nm).
Device example 14: ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 80nm, material: NPB)/light emitting layer 5 (thickness: 40nm, material: compounds 231, GH and Ir (ppy) prepared in the examples of the present invention 3 50/10 in a weight ratio of 50: 35nm, material: TPBI)/electron injection layer 7 (thickness: 1nm, material: liF)/Al (thickness: 100 nm).
Device example 15: ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 80nm, material: NPB)/light emitting layer 5 (thickness: 40nm, material: compounds 261, GH, and Ir (ppy) prepared according to the example of the present invention 3 50/10 in a weight ratio of 50: 35nm, material: TPBI)/electron injection layer 7 (thickness: 1nm, material: liF)/Al (thickness: 100 nm).
Device example 16: ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 80nm, material: NPB)/light-emitting layer 5 (thickness: 40nm, material: CBP and Ir (ppy) 3 A mixed composition of 90: 35nm, material: compound 3)/electron injection layer 7 (thickness: 1nm, material: liF)/Al (thickness: 100 nm).
Device example 17: ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 80nm, material: NPB)/light-emitting layer 5 (thickness: 40nm, material: CBP and Ir (ppy) 3 A mixed composition of 90: 35nm, material: examples of the inventionCompound 20)/electron injection layer 7 (thickness: 1nm, material: liF)/Al (thickness: 100 nm).
Device example 18: ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 80nm, material: NPB)/light-emitting layer 5 (thickness: 40nm, material: CBP and Ir (ppy) 3 A mixed composition of 90: 35nm, material: compound 39)/electron injection layer 7 (thickness: 1nm, material: liF)/Al (thickness: 100 nm).
Device example 19: ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 80nm, material: NPB)/light-emitting layer 5 (thickness: 40nm, material: CBP and Ir (ppy) 3 A mixed composition of 90: 35nm, material: compound 83 prepared in the present example)/electron injection layer 7 (thickness: 1nm, material: liF)/Al (thickness: 100 nm).
Device example 20: ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 80nm, material: NPB)/light-emitting layer 5 (thickness: 40nm, material: CBP and Ir (ppy) 3 A mixed composition of 90: 35nm, material: compound 128)/electron injection layer 7 (thickness: 1nm, material: liF)/Al (thickness: 100 nm).
Device example 21: ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 80nm, material: NPB)/light-emitting layer 5 (thickness: 40nm, material: CBP and Ir (ppy) 3 A mixed composition of 90: 35nm, material: compound 155)/electron injection layer 7 (thickness: 1nm, material: liF)/Al (thickness: 100 nm).
Device example 22: ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 80nm, material: NPB)/light-emitting layer 5 (thickness: 40nm, material: NPB)/light-emitting layer: CBP and Ir (ppy) 3 A mixed composition of 90: 35nm, material: compound 218)/electron injection layer 7 (thickness: 1nm, material: liF)/Al (thickness: 100 nm).
Device example 23: ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 80nm, material: NPB)/light-emitting layer 5 (thickness: 40nm, material: CBP and Ir (ppy) 3 A mixed composition of 90: 35nm, material: compound 242)/electron injection layer 7 (thickness: 1nm, material: liF)/Al (thickness: 100 nm).
Device comparative example 1: ITO anode layer 2 (thickness: 150 nm)/hole injection layer 3 (thickness: 10nm, material: HAT-CN)/hole transport layer 4 (thickness: 80nm, material: NPB)/light-emitting layer 5 (thickness: 40nm, material: CBP and Ir (ppy) 3 A mixed composition of 90: 35nm, material: TPBI)/electron injection layer 7 (thickness: 1nm, material: liF)/Al (thickness: 100 nm). The inspection data of the obtained electroluminescent device are shown in Table 3.
TABLE 3
Figure BDA0001457116250000301
From the results in table 3, it can be seen that the organic compound of the present invention can be applied to the fabrication of OLED light emitting devices, and compared with the comparative examples, the efficiency and lifetime of the organic compound are greatly improved compared with those of the known OLED materials, especially the lifetime of the organic compound is greatly prolonged.
Further, the efficiency of the OLED device prepared by the material of the invention is stable when the OLED device works at low temperature, and the results of the efficiency tests of the device examples 4, 12 and 21 and the device comparative example 1 at the temperature range of-10-80 ℃ are shown in the table 4 and the figure 2.
TABLE 4
Figure BDA0001457116250000302
As can be seen from the data in table 4 and fig. 2, device examples 4, 12, and 21 are device structures in which the material of the present invention is combined with a known material, and compared with device comparative example 1, the efficiency is not only high at low temperature, but also steadily increases during the temperature increase.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (7)

1. A ketone-containing compound having a structure represented by general formula (4):
Figure FDA0003890586030000011
ar is 3 Represents one of a single bond, phenylene, biphenylene or naphthylene;
the above-mentioned
Figure FDA0003890586030000012
Expressed as:
Figure FDA0003890586030000013
one kind of (1).
2. The compound of claim 1, wherein the compound has the specific formula:
Figure FDA0003890586030000014
Figure FDA0003890586030000021
Figure FDA0003890586030000031
Figure FDA0003890586030000041
Figure FDA0003890586030000051
Figure FDA0003890586030000061
Figure FDA0003890586030000071
Figure FDA0003890586030000081
Figure FDA0003890586030000091
Figure FDA0003890586030000092
any one of the above.
3. A ketone-containing compound having a specific structural formula:
Figure FDA0003890586030000093
any one of the above.
4. An organic electroluminescent element comprising at least one functional layer containing a ketone-containing compound according to any one of claims 1 to 3.
5. The organic electroluminescent device according to claim 4, comprising a light-emitting layer containing the ketone-containing compound according to any one of claims 1 to 3.
6. The organic electroluminescent device according to claim 4, comprising a hole blocking layer/electron transport layer containing the ketone-containing compound according to any one of claims 1 to 3.
7. A lighting or display element comprising an organic electroluminescent device as claimed in any one of claims 4 to 6.
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CN113004270B (en) * 2019-12-20 2023-08-01 江苏三月科技股份有限公司 Compound with xanthone skeleton as core and application thereof

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