CN109721619B - Compound with benzimidazolone as core and application of compound in OLED device - Google Patents
Compound with benzimidazolone as core and application of compound in OLED device Download PDFInfo
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Abstract
The invention discloses a benzimidazolone compound and application thereof in an organic electroluminescent device. When the compound is used as a main material of a light-emitting layer of an OLED light-emitting 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
Technical Field
The invention relates to the technical field of semiconductors, in particular to a benzimidazole ketone compound and application thereof as a main material of a light-emitting layer 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 generally have a small singlet-triplet energy level difference (Δ EST), and triplet excitons can be converted into singlet excitons for emission by intersystem crossing. 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.
In recent years, a Thermally Activated Delayed Fluorescence (TADF) host material has a balanced flow of holes and electron carriers, so that the recombination efficiency of the electrons and the holes is improved, and the light-emitting efficiency of a device is further enhanced, and the roll-off of the efficiency is reduced. Meanwhile, the donor and the acceptor of the host material have strong intramolecular charge transfer, so that the triplet state energy level of the material is lowered, and the application of the material in industrial production is limited. At present, the research focus of the bipolar host material adopts saturated atoms to cut off pi conjugation between donor receptors on the basis of containing the donor receptors, and further improves the triplet state energy level of the donor receptors.
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 of benzimidazolone type and its application in organic electroluminescent devices. The compound takes benzimidazolone as a core and is used as a main material of a light-emitting layer to be applied to an organic light-emitting diode. The technical scheme of the invention is as follows:
a compound taking benzimidazolone as a core has a structure shown as a general formula (1) or a general formula (2):
in the general formulas (1) and (2), Ar represents one of a single bond, phenylene or biphenylene;
in the general formula (1) and the general formula (2), R1、R2Independently represent a hydrogen atom, phenyl, naphthyl, biphenyl, terphenyl, dibenzofuran, 9-dimethylfluorene, 9-diphenylfluorene or N-phenylcarbazole; r1、R2The same or different; r1、R2Not being hydrogen atoms at the same time;
R1、R2respectively connected with the carbazole ring in the general formula (1) or the general formula (2) through a C-C single bond or a C-N single bond; r1、R2Can also pass through C in a parallel ring formL1-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 structure shown in the general formula (1) or (2).
The R is1、R2Represented by the structure represented by the general formula (3):
in the general formula (3), Ar1、Ar2Each independently represents one of phenyl, naphthyl, biphenyl, terphenyl, dibenzofuran, 9-dimethyl fluorene or N-phenyl carbazole.
The above-mentioned
Expressed as:
4. The compound of claim 1, wherein the specific structural formula of the compound includes and is not limited to:
A method of preparing the compound, the reaction equation occurring during the preparation being:
the R is represented as:
the specific reaction steps are as follows: weighing bromo-compound of benzimidazolone and RH, and dissolving with toluene; then adding Pd2(dba)3Tri-tert-butylphosphine, sodium tert-butoxide; reacting the mixed solution of the reactants at the reaction temperature of 95-100 ℃ for 10-24 hours under the inert atmosphere, cooling, filtering the reaction solution, performing rotary evaporation on the filtrate, and passing through a silica gel column to obtain a target product;
the molar ratio of the brominated compound to RH is 1: 1.0-1.5; pd2(dba)3The molar ratio of the tert-butyl phosphorus to the brominated compound is 0.006-0.02: 1, and the molar ratio of the sodium tert-butoxide to the brominated compound is 2.0-3.0: 1.
An organic electroluminescent device containing the compound comprises at least one functional layer containing the compound taking benzimidazolone as a core.
An organic electroluminescent device containing the compound comprises a light-emitting layer, wherein the light-emitting layer contains the compound taking benzimidazolone as a core.
A lighting or display element made of the organic electroluminescent device.
The beneficial technical effects of the invention are as follows:
the compound of the invention takes benzimidazolone as a parent nucleus and is connected with an aromatic heterocyclic group, so that the compound has strong rigidity and destroys the molecular symmetry, thereby destroying the crystallinity of molecules and avoiding the aggregation between molecules. The compound contains benzimidazolone as an electron acceptor (A) in a molecule, and is favorable for the transmission of electrons in a light-emitting layer. The attached heterocyclic group is an electron donor (donor, D) which facilitates the transport of holes in the light-emitting layer. The trivalent nitrogen atom in the benzimidazolone is a saturated atom, so that the benzimidazolone not only has strong rigidity, but also is beneficial to improving the triplet energy level of the parent nucleus compound, and the combination of the electron donor and the electron acceptor can improve the mobility of electrons and holes, reduce the starting voltage, improve the recombination efficiency of excitons and improve the performance of devices.
The parent nucleus benzimidazolone has higher triplet state energy level, so that triplet state excitons of the compound are limited in the luminescent layer, the luminescent efficiency is improved, and the compound is suitable for being used as a luminescent layer main body material.
The compound can be used as a luminescent layer material for manufacturing an OLED luminescent device, can obtain good device performance as a luminescent layer main body material, and greatly improves the current efficiency, the power efficiency and the external quantum efficiency of the device; 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 view of the structure of an organic electroluminescent device obtained by using the preparation of the compound 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.
Fig. 2 is a graph of current efficiency versus temperature.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples.
Example 1:
a. intermediate of the general formula (1)
The synthetic route of (A) is as follows:
R1is represented by a hydrogen atom, R2When not representing a hydrogen atom:
weighing raw material I, dissolving in acetic acid, and cooling to 0 ℃ by using an ice salt bath; weighing liquid bromine, dissolving the liquid bromine in glacial acetic acid, slowly dropwise adding the liquid bromine into an acetic acid solution containing a nitro compound raw material I, stirring at room temperature, reacting for 6-12 hours, after the reaction is finished, dropwise adding a sodium hydroxide aqueous solution to neutralize the reaction solution, extracting with dichloromethane, filtering an organic phase, carrying out reduced pressure rotary evaporation on the filtrate until no fraction is obtained, and passing through a silica gel column to obtain an intermediate S1; in the reaction, the molar ratio of the raw material I to the liquid bromine is 1: 1-3;
weighing the raw material II and the intermediate S1, dissolving the raw material II and the intermediate S1 in toluene, adding a mixed solution of potassium carbonate, palladium tetratriphenylphosphine, ethanol and water in an inert atmosphere, stirring and heating to 110-120 ℃, reacting for 10-24 hours, cooling to room temperature after the reaction is finished, filtering, layering the filtrate, carrying out reduced pressure rotary evaporation on an organic phase until no fraction is produced, and passing through a silica gel column to obtain an intermediate S2; in the reaction, the molar ratio of the intermediate S1 to the raw material II is 1: 1-2; the molar ratio of the intermediate S1 to the potassium carbonate is 1: 1-3; the molar ratio of the intermediate S1 to the palladium tetratriphenylphosphine is 1: 0.01-0.05;
dissolving the intermediate S2 in o-dichlorobenzene in an inert atmosphere, adding triphenylphosphine, stirring and reacting at 170-190 ℃ for 12-16 hours, cooling to room temperature after the reaction is finished, filtering, carrying out reduced pressure rotary evaporation on the filtrate until no fraction is obtained, and passing through a silica gel column to obtain an intermediate M1; in the reaction, the molar ratio of the intermediate S2 to triphenylphosphine is 1: 1-2;
taking intermediate M1-1 as an example:
adding 0.04mol of nitrobenzene and 100ml of acetic acid into a 250ml three-necked bottle, stirring for dissolving, and cooling to 0 ℃ by using an ice salt bath; weighing 0.05mol of Br2Dissolving in 50ml acetic acid, slowly dripping a bromine acetic acid solution into the reaction system, heating to room temperature after dripping, and stirring for reaction for 12 hours; sampling a point plate, wherein no nitrobenzene is left and the reaction is complete; adding NaOH aqueous solution to neutralize the reaction solution, extracting with dichloromethane, layering, filtering the organic phase, decompressing and rotary steaming the filtrate until no distillation occursSeparating, passing through a neutral silica gel column to obtain an intermediate S1-1 with HPLC purity of 99.4% and yield of 78.9%;
elemental analysis Structure C6H4BrNO2: theoretical value C, 35.68; h, 2.00; br, 39.56; n, 6.93; test values are: c, 35.68; h, 2.00; br, 39.56; n, 6.92; ESI-MS (M/z) (M +): theoretical value is 200.94, found 201.51.
Adding 0.05mol of intermediate S1-1, 0.06mol of raw material II-1 and 100ml of toluene into a 250ml three-neck flask under the protection of nitrogen, stirring and mixing, and then adding 0.0025mol of Pd (PPh)3)40.075mol of potassium carbonate, 50ml of mixed solution of water and ethanol in a ratio of 1:1, stirring and heating to 120 ℃, carrying out reflux reaction for 24 hours, and sampling a sample point plate to show that no intermediate S1-1 remains and the reaction is complete; naturally cooling to room temperature, filtering, layering the filtrate, carrying out reduced pressure rotary evaporation on the organic phase until no fraction is obtained, and passing through a neutral silica gel column to obtain an intermediate S2-1 with the HPLC purity of 99.6% and the yield of 69.2%;
elemental analysis Structure C18H11NO3: theoretical value C, 74.73; h, 3.83; n, 4.84; test values are: c, 74.73; h, 3.83; n, 4.83; ESI-MS (M/z) (M +): theoretical value is 289.07, found 289.59.
Adding 0.04mol of intermediate S2-1, 0.05mol of triphenylphosphine and 100ml of o-dichlorobenzene into a 250ml three-necked bottle under the protection of nitrogen, stirring and mixing, heating to 180 ℃, reacting for 12 hours, sampling a point plate, and displaying that no intermediate S2-1 is left, and the reaction is complete; naturally cooling to room temperature, filtering, carrying out reduced pressure rotary evaporation on the filtrate until no fraction is obtained, and passing through a neutral silica gel column to obtain an intermediate M1-1, wherein the HPLC purity is 99.7%, and the yield is 71.5%; elemental analysis Structure C18H11NO: theoretical value C, 84.03; h, 4.31; n, 5.44; test values are: c, 84.03; h, 4.31; n, 5.45; ESI-MS (M/z) (M +): theoretical value is 257.08, found 257.04.
R1、R2When none represents a hydrogen atom:
weighing raw material III, dissolving in acetic acid, and cooling to 0 ℃ by using an ice salt bath; weighing liquid bromine, dissolving the liquid bromine in glacial acetic acid, slowly dropwise adding the liquid bromine into an acetic acid solution containing a nitro compound raw material III, stirring at room temperature, reacting for 6-12 hours, after the reaction is finished, dropwise adding a sodium hydroxide aqueous solution to neutralize the reaction solution, extracting with dichloromethane, filtering an organic phase, carrying out reduced pressure rotary evaporation on the filtrate until no fraction is obtained, and passing through a silica gel column to obtain an intermediate S3; in the reaction, the molar ratio of the raw material III to the liquid bromine is 1: 1-3;
weighing the raw material II and the intermediate S3, dissolving the raw material II and the intermediate S3 in toluene, adding a mixed solution of potassium carbonate, palladium tetratriphenylphosphine, ethanol and water in an inert atmosphere, stirring and heating to 110-120 ℃, reacting for 10-24 hours, cooling to room temperature after the reaction is finished, filtering, layering the filtrate, carrying out reduced pressure rotary evaporation on an organic phase until no fraction is produced, and passing through a silica gel column to obtain an intermediate S4; in the reaction, the molar ratio of the intermediate S3 to the raw material II is 1: 1-2; the molar ratio of the intermediate S3 to the potassium carbonate is 1: 1-3; the molar ratio of the intermediate S3 to the palladium tetratriphenylphosphine is 1: 0.01-0.05;
dissolving the intermediate S4 in o-dichlorobenzene in an inert atmosphere, adding triphenylphosphine, stirring and reacting at 170-190 ℃ for 12-16 hours, cooling to room temperature after the reaction is finished, filtering, carrying out reduced pressure rotary evaporation on the filtrate until no fraction is obtained, and passing through a silica gel column to obtain an intermediate M2; in the reaction, the molar ratio of the intermediate S4 to triphenylphosphine is 1: 1-2;
taking intermediate M2-1 as an example:
in a 250ml three-necked flask, 0.04mol of 3-nitrodibenzo [ b, d ] was added]Furan and 100ml acetic acid, stirring and dissolving, and cooling to 0 ℃ by using an ice salt bath; weighing 0.05mol of Br2Dissolving in 50ml acetic acid, slowly dripping a bromine acetic acid solution into the reaction system, heating to room temperature after dripping, and stirring for reaction for 12 hours; sample point plate showing no 3-nitrodibenzo [ b, d ]]The furan is remained and the reaction is complete; adding NaOH aqueous solution to neutralize the reaction solution, extracting with dichloromethane, layering, filtering the organic phase, and filteringCarrying out rotary evaporation on the liquid under reduced pressure until no fraction is obtained, and passing through a neutral silica gel column to obtain an intermediate S3-1, wherein the HPLC purity is 99.3 percent, and the yield is 68.9 percent; elemental analysis Structure C12H6BrNO3: theoretical value C, 49.35; h, 2.07; br, 27.36; n, 4.80; test values are: c, 49.33; h, 2.08; br, 27.37; n, 4.81; ESI-MS (M/z) (M +): theoretical value is 290.95, found 291.90.
Adding 0.05mol of intermediate S3-1, 0.06mol of raw material II-1 and 100ml of toluene into a 250ml three-neck flask under the protection of nitrogen, stirring and mixing, and then adding 0.0025mol of Pd (PPh)3)40.075mol of potassium carbonate, 50ml of mixed solution of water and ethanol in a ratio of 1:1, stirring and heating to 120 ℃, carrying out reflux reaction for 24 hours, and sampling a sample point plate to show that no intermediate S3-1 remains and the reaction is complete; naturally cooling to room temperature, filtering, layering the filtrate, carrying out reduced pressure rotary evaporation on the organic phase until no fraction is obtained, and passing through a neutral silica gel column to obtain an intermediate S4-1, wherein the HPLC purity is 99.0% and the yield is 78.2%; elemental analysis Structure C24H13NO4: theoretical value C, 75.98; h, 3.45; n, 3.69; test values are: c, 75.96; h, 3.45; n, 3.68; ESI-MS (M/z) (M +): theoretical value is 379.08, found 379.80.
Adding 0.04mol of intermediate S4-1, 0.05mol of triphenylphosphine and 100ml of o-dichlorobenzene into a 250ml three-necked bottle under the protection of nitrogen, stirring and mixing, heating to 180 ℃, reacting for 12 hours, sampling a point plate, and displaying that no intermediate S4-1 is left, and the reaction is complete; naturally cooling to room temperature, filtering, carrying out reduced pressure rotary distillation on the filtrate until no fraction is obtained, and passing through a neutral silica gel column to obtain an intermediate M2-1, wherein the HPLC purity is 99.2% and the yield is 75.5%; elemental analysis Structure C24H13NO2: theoretical value C, 82.98; h, 3.77; n, 4.03; test values are: c, 82.97; h, 3.77; n, 4.02; ESI-MS (M/z) (M +): theoretical value is 347.09, found 347.51.
Intermediate M1 was prepared from the synthetic scheme for intermediate M1-1; intermediate M2 was prepared from the synthetic scheme for intermediate M2-1; the specific structure employed in the preparation process is shown in table 1:
TABLE 1
b. Synthesis of intermediate N
Wherein L is1And L2Independently of one another, selected from bromine atoms or
And L is1And L2Not simultaneously present.
Dissolving the raw material A, the raw material B, HBTU and DIPEA in DMF in the atmosphere of nitrogen, stirring at room temperature for reaction for 5 hours, and sampling a sample point plate to show that the reaction is complete; adding ethyl acetate into the reaction mixed solution for dilution, and washing with water and brine in sequence; the organic layer was separated using a separatory funnel, MgSO4Drying and filtering, carrying out reduced pressure rotary evaporation on the filtrate, and passing through a neutral silica gel column to obtain an intermediate S5; in the reaction, the molar ratio of the raw material A to the raw material B is 1: 1.5-2; the molar ratio of the raw material A to the HBTU is 1: 10-20; the molar ratio of the raw material A to the DIPEA is 1: 10-20;
adding intermediate S5, controlling the temperature of the reaction solution at 0 ℃, and dropwise adding BBr3(1.0M of CH2Cl2Solution), stirring and reacting for 5 hours, taking a sample point plate, and indicating that the reaction is complete; adding saturated ammonium chloride solution into the reaction solution for dilution, naturally heating to room temperature, adding CH2Cl2Diluting, and washing with saline; the organic layer was separated using a separatory funnel, MgSO4Drying and filtering, carrying out reduced pressure rotary evaporation on the filtrate, and passing through a neutral silica gel column to obtain an intermediate S6; in the above reaction, intermediate S5 reacts with BBr3The molar ratio of (A) to (B) is 1: 2-3;
dissolving the intermediate S6 in dry acetone, cooling to 0 ℃, dropwise adding a dry acetone solution dissolved by dichlorocarbon sulfide, naturally heating after dropwise adding, stirring and reacting for 5 hours at room temperature, filtering, and washing the solid with acetone for 2 times to obtain an intermediate N; in the reaction, the molar ratio of the intermediate S6 to the dichlorocarbon sulfide is 1: 100;
taking the intermediate N-1 as an example:
adding 0.01mol of raw material A-1, 0.02mol of raw material B-1, 0.15mol of HBTU, 0.15mol of DIPEA and 80ml of DMF into a 250ml four-neck flask in the atmosphere of introducing nitrogen, stirring at room temperature for reaction for 5 hours, and sampling a point plate to show that the reaction is complete; adding 80ml ethyl acetate into the reaction mixed solution for dilution, and washing by using 100ml water and 100ml saline water in sequence; the organic layer was separated using a separatory funnel, MgSO4Drying and filtering, carrying out reduced pressure rotary evaporation on the filtrate, and passing through a neutral silica gel column to obtain an intermediate S5-1; elemental analysis Structure (molecular formula C)14H13BrN2O2): theoretical value C, 52.36; h, 4.08; br, 24.88; n, 8.72; test values are: c, 52.36; h, 4.08; br, 24.88; n, 8.71. ESI-MS (M/z) (M)+): theoretical value is 320.02, found 320.75.
Adding 0.06mol of intermediate S5-1 into a 250ml four-mouth bottle, controlling the temperature of the reaction solution at 0 ℃, and dropwise adding 0.18mol of BBr3(1.0M of CH2Cl2Solution), stirring and reacting for 5 hours, taking a sample point plate, and indicating that the reaction is complete; diluting the reaction solution with 20ml saturated ammonium chloride solution, naturally heating to room temperature, adding 50ml CH2Cl2Diluting, washing with 100ml of saline; the organic layer was separated using a separatory funnel, MgSO4Drying and filtering, carrying out reduced pressure rotary evaporation on the filtrate, and passing through a neutral silica gel column to obtain an intermediate S6-1; elemental analysis Structure (molecular formula C)13H11BrN2O2): theoretical value C, 50.84; h, 3.61; br, 26.01; n, 9.12; test values are: c, 50.84; h, 3.61; br, 26.01; and N, 9.13. ESI-MS (M/z) (M)+): theoretical value is 306.00, found 306.81.
250ml of three-necked bottle is added0.05mol of intermediate S6-1, 30ml of dry acetone, cooling to 0 ℃, dropwise adding 30ml of dry acetone solution dissolved by 400ml of dichlorosulfurated carbon (d is 1.5,5mol), naturally heating after dropwise adding, stirring and reacting for 5 hours at room temperature, filtering, and washing the solid with acetone for 2 times to obtain an intermediate N-1; elemental analysis Structure (molecular formula C)14H7BrN2O2): theoretical value C, 53.36; h, 2.24; br, 25.36; n, 8.89; test values are: c, 53.36; h, 2.24; br, 25.36; and N, 8.88. ESI-MS (M/z) (M)+): theoretical value is 313.97, found 314.21.
The intermediate benzimidazolone bromide N prepared by the synthesis method in the reaction general formula is shown in the table 2.
TABLE 2
Example 2: synthesis of Compound 6
A250 ml four-necked flask was charged with 0.01mol of intermediate M1-1, 0.015mol of intermediate N-1, 0.03mol of sodium tert-butoxide, and 1X 10 under a nitrogen atmosphere-4mol Pd2(dba)3，1×10-4Heating and refluxing the tri-tert-butylphosphine and 150ml of toluene for 24 hours, sampling a sample, completely reacting, naturally cooling, filtering, rotatably evaporating filtrate, and passing through a silica gel column to obtain a target product. Elemental analysis Structure (molecular formula C)32H17N3O3): theoretical value C, 78.20; h, 3.49; n, 8.55; test values are: c, 78.20; h, 3.49; n, 8.54. ESI-MS (M/z) (M)+): theoretical value is 491.13, found 491.54.
Example 3: synthesis of Compound 15
Compound 15 was prepared as in example 2, except intermediate M1-2 was used in place of intermediate M1-1. Elemental analysis Structure (molecular formula C)35H23N3O2): theoretical value C, 81.22; h, 4.48; n, 8.12; test values are: c, 81.22; h, 4.48; n, 8.11. ESI-MS (M/z) (M)+): theoretical value is 517.18, found 517.94.
Example 4: synthesis of Compound 24
Compound 24 was prepared as in example 2, except intermediate M1-1 was replaced with intermediate M1-3 and intermediate N-1 was replaced with intermediate N-2. Elemental analysis Structure (molecular formula C)35H23N3O2): theoretical value C, 81.22; h, 4.48; n, 8.12; test values are: c, 81.22; h, 4.48; and N, 8.13. ESI-MS (M/z) (M)+): theoretical value is 517.18, found 517.88.
Example 5: synthesis of Compound 33
Compound 33 was prepared as in example 2, except intermediate M1-4 was used in place of intermediate M1-1. Elemental analysis Structure (molecular formula C)38H22N4O2): theoretical value C, 80.55; h, 3.91; n, 9.89; test values are: c, 80.55; h, 3.91; and N, 9.88. ESI-MS (M/z) (M)+): theoretical value is 566.17, found 566.71.
Example 6: synthesis of Compound 44
Compound 44 was prepared as in example 2, except intermediate M1-1 was replaced with intermediate M1-5Intermediate N-2 replaces intermediate N-1. Elemental analysis Structure (molecular formula C)38H22N4O2): theoretical value C, 80.55; h, 3.91; n, 9.89; test values are: c, 80.54; h, 3.91; and N, 9.88. ESI-MS (M/z) (M)+): theoretical value is 566.17, found 566.75.
Example 7: synthesis of Compound 54
Compound 54 was prepared as in example 2, except intermediate M1-6 was used in place of intermediate M-1. Elemental analysis Structure (molecular formula C)34H19N3O2): theoretical value C, 81.42; h, 3.82; n, 8.38; test values are: c, 81.42; h, 3.82; n, 8.37. ESI-MS (M/z) (M)+): theoretical value is 501.15, found 501.66.
Example 8: synthesis of Compound 62
Compound 62 was prepared as in example 2, except intermediate M1-8 was used in place of intermediate M1-1. Elemental analysis Structure (molecular formula C)42H26N4O2): theoretical value C, 81.54; h, 4.24; n, 9.06; test values are: c, 81.54; h, 4.24; and N, 9.05. ESI-MS (M/z) (M)+): theoretical value is 618.21, found 618.84.
Example 9: synthesis of Compound 73
Compound 73 was prepared as in example 2, except intermediate M1-1 was replaced with intermediate M1-9 and intermediate N-1 was replaced with intermediate N-5. Elemental analysis Structure (molecular formula C)42H25N3O2): theoretical value C,83.56(ii) a H, 4.17; n, 6.96; test values are: c, 83.56; h, 4.17; and N, 6.95. ESI-MS (M/z) (M)+): theoretical value is 603.19, found 603.94.
Example 10: synthesis of Compound 82
Compound 82 was prepared as in example 2, except intermediate N-5 was used in place of intermediate N-1. Elemental analysis Structure (molecular formula C)38H21N3O3): theoretical value C, 80.41; h, 3.73; n, 7.40; test values are: c, 80.41; h, 3.73; and N, 7.41. ESI-MS (M/z) (M)+): theoretical value is 567.16, found 567.55.
Example 11: synthesis of Compound 91
Compound 91 was prepared as in example 2, except intermediate M1-1 was replaced with intermediate M1-2 and intermediate N-1 was replaced with intermediate N-5. Elemental analysis Structure (molecular formula C)41H27N3O2): theoretical value C, 82.95; h, 4.58; n, 7.08; test values are: c, 82.94; h, 4.58; and N, 7.07. ESI-MS (M/z) (M)+): theoretical value is 593.21, found 593.61.
Example 12: synthesis of Compound 97
Compound 97 can be prepared as in example 2, except that intermediate M1-1 is replaced with intermediate M1-2 and intermediate N-1 is replaced with intermediate N-6. Elemental analysis Structure (molecular formula C)41H27N3O2): theoretical value C, 82.95; h, 4.58; n, 7.08; test values are: c, 82.95; h, 4.58; and N, 7.09. ESI-MS (M/z) (M)+): theory of the inventionThe value was 593.21, found 593.63.
Example 13: synthesis of Compound 109
Compound 109 was prepared as in example 2, except intermediate M1-1 was replaced with intermediate M1-4 and intermediate N-1 was replaced with intermediate N-5. Elemental analysis Structure (molecular formula C)44H26N4O2): theoretical value C, 82.23; h, 4.08; n, 8.72; test values are: c, 82.24; h, 4.08; and N, 8.72. ESI-MS (M/z) (M)+): theoretical value is 642.21, found 642.99.
Example 14: synthesis of Compound 111
Compound 111 was prepared as in example 2, except intermediate M1-1 was replaced with intermediate M1-7 and intermediate N-1 was replaced with intermediate N-5. Elemental analysis Structure (molecular formula C)44H26N4O2): theoretical value C, 82.23; h, 4.08; n, 8.72; test values are: c, 82.25; h, 4.08; and N, 8.72. ESI-MS (M/z) (M)+): theoretical value is 642.21, found 642.95.
Example 15: synthesis of Compound 114
Compound 114 was prepared as in example 2, except intermediate M1-1 was replaced with intermediate M1-5 and intermediate N-1 was replaced with intermediate N-5. Elemental analysis Structure (molecular formula C)44H26N4O2): theoretical value C, 82.23; h, 4.08; n, 8.72; test values are: c, 82.24; h, 4.07; and N, 8.72. ESI-MS (M/z) (M)+): theoretical value is 642.21, found 642.82.
Example 16: synthesis of Compound 125
Compound 125 was prepared as in example 2, except intermediate N-7 was used in place of intermediate N-1. Elemental analysis Structure (molecular formula C)38H21N3O3): theoretical value C, 80.41; h, 3.73; n, 7.40; test values are: c, 80.41; h, 3.73; and N, 7.42. ESI-MS (M/z) (M)+): theoretical value is 567.16, found 567.61.
Example 17: synthesis of Compound 137
Compound 137 can be prepared as in example 2, except that intermediate M1-1 is replaced with intermediate M1-3 and intermediate N-1 is replaced with intermediate N-7. Elemental analysis Structure (molecular formula C)41H27N3O2): theoretical value C, 82.95; h, 4.58; n, 7.08; test values are: c, 82.94; h, 4.58; and N, 7.09. ESI-MS (M/z) (M)+): theoretical value is 593.21, found 593.68.
Example 18: synthesis of Compound 152
Compound 152 is prepared as in example 2, except intermediate M1-1 is replaced with intermediate M1-4 and intermediate N-1 is replaced with intermediate N-7. Elemental analysis Structure (molecular formula C)44H26N4O2): theoretical value C, 82.23; h, 4.08; n, 8.72; test values are: c, 82.25; h, 4.07; and N, 8.72. ESI-MS (M/z) (M)+): theoretical value is 642.21, found 642.64.
Example 19: synthesis of Compound 163
Compound 163 was prepared as in example 2, except intermediate M1-1 was replaced with intermediate M1-5 and intermediate N-1 was replaced with intermediate N-8. Elemental analysis Structure (molecular formula C)44H26N4O2): theoretical value C, 82.23; h, 4.08; n, 8.72; test values are: c, 82.25; h, 4.07; n, 8.73. ESI-MS (M/z) (M)+): theoretical value is 642.21, found 642.73.
Example 20: synthesis of Compound 174
Compound 174 was prepared as in example 2, except intermediate M1-1 was replaced with intermediate M1-5 and intermediate N-1 was replaced with intermediate N-8. Elemental analysis Structure (molecular formula C)44H23N3O4): theoretical value C, 80.36; h, 3.53; n, 6.39; test values are: c, 80.36; h, 3.53; and N, 6.38. ESI-MS (M/z) (M)+): theoretical value is 657.17, found 657.57.
The compound of the present invention can be used as a light emitting layer material, and the compound 24, the compound 73, the compound 109, and the conventional material CBP are tested for thermal performance, light emission spectrum, and cyclic voltammetry stability, and the test results are shown in table 3.
TABLE 3
Note: the thermogravimetric analysis temperature Td was a temperature at which 1% weight loss was observed in a nitrogen atmosphere and was determined by TGA-50H thermogravimetric analysis of Shimadzu corporation, JapanMeasuring on the instrument, wherein the nitrogen flow is 20 mL/min; Δ Est is the fluorescence emission spectrum and phosphorescence emission spectrum of the test compound, respectively, and calculated from the fluorescence emission peak and phosphorescence emission peak (test equipment: FLS980 fluorescence spectrometer by Edinburgh Instruments, Optistat DN-V2 cryomodule by Oxford Instruments); lambda [ alpha ]PLThe fluorescence emission wavelength of the sample solution is measured by using a Japanese topotecan SR-3 spectroradiometer; 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.
As can be seen from the data in the table above, the compound of the present invention has good oxidation-reduction stability, high thermal stability and appropriate light emission spectrum, such that the efficiency and lifetime of the OLED device using the compound of the present invention as the light emitting layer material are improved. The following device examples 1 to 19 and comparative examples 1 and 2 will explain in detail the effect of the compound synthesized by the present invention as a host material for a light-emitting layer in a device. The structural composition of the resulting device of each example is shown in table 4. The test results of the resulting devices are shown in table 5.
Device example 1
Transparent substrate layer 1/ITO anode layer 2/hole injection layer 3(HAT-CN, thickness 10 nm)/hole transport layer 4(HT-8, thickness 80 nm)/light-emitting layer 5 (compound 6 and GD-7 mixed according to a weight ratio of 90: 10, thickness 30 nm)/electron transport layer 6(ET-201, thickness 35 nm)/electron injection layer 7(Liq, thickness 1 nm)/cathode reflective electrode layer 8 (Al). The structural formula of the material is as follows:
the preparation process comprises the following steps:
the transparent substrate layer 1 is a transparent substrate such as a transparent PI film, glass, or the like. 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 ITO anode layer 2 after the above washing, HAT-CN having a film thickness of 10nm was deposited by a vacuum deposition apparatus to be used as the hole injection layer 3. Subsequently, HT-8 was evaporated to a thickness of 80nm as the hole transport layer 4. After the evaporation of the hole transport material is finished, a light-emitting layer 5 of the OLED light-emitting device is manufactured, and the structure of the light-emitting layer 5 comprises a material compound 6 used by the OLED light-emitting layer 5 as a main material and GD-7 as a doping material, wherein the doping proportion of the doping material is 10% 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 ET-201. The vacuum-deposited thickness of this material was 35nm, and this layer was electron transport layer 6. On the electron transport layer 6, a Liq 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 cathode were connected by a known driving circuit, and the current efficiency of the device and the lifetime of the device were measured.
TABLE 4
TABLE 5
From the results of table 5, it can be seen that the compound of the present invention can be applied to the fabrication of OLED light emitting devices, and compared with comparative examples 1 and 2, the compound has a great improvement in both efficiency and lifetime, and particularly, the driving lifetime of the device is greatly improved.
From the test data provided by the embodiment, the compound has good application effect and good industrialization prospect in an OLED light-emitting device as a light-emitting layer material. Further, the efficiency of the OLED device prepared by the material is stable when the OLED device works at low temperature, the efficiency test is carried out on the device examples 1, 9 and 18 and the device comparative example 1 at the temperature of-10-80 ℃, and the obtained results are shown in the table 6 and the figure 2.
TABLE 6
As can be seen from the data in table 6 and fig. 2, device examples 1, 9 and 18 are device structures in which the material of the present invention and the known material are combined, and compared with device comparative example 1, the efficiency is high at low temperature, and the efficiency is smoothly increased in the temperature increasing process.
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 (4)
1. A compound with benzimidazolone as a core is characterized in that the specific structural formula of the compound is as follows:
2. An organic electroluminescent device comprising the compound of claim 1, comprising a light-emitting layer, wherein the light-emitting layer comprises the benzimidazolone-based compound;
the structure of the organic electroluminescent device comprises: transparent substrate layer (1)/ITO anode layer (2)/hole injection layer (3)/hole transport layer (4)/light-emitting layer (5)/electron transport layer (6)/electron injection layer (7)/cathode reflective electrode layer (8);
the material of the hole injection layer (3) is HAT-CN with the thickness of 10 nm;
the hole transport layer (4) is made of HT-8 and has the thickness of 80 nm;
the material of the luminescent layer (5) is the compound taking benzimidazolone as the core and GD-7 is prepared according to the ratio of 90: 10, and the thickness is 30 nm;
the material of the electron transport layer (6) is ET-201, and the thickness is 35 nm;
the material of the electron injection layer (7) is Liq, and the thickness is 1 nm;
the cathode reflecting electrode layer (8) is made of Al;
the structural formula of the material is as follows:
HAT-CN HT-8 ET-201
Liq Ir(PPy)3 GD-7。
3. the organic electroluminescent device according to claim 2, wherein the specific preparation process is as follows:
the transparent substrate layer (1) is a transparent substrate, and the transparent substrate is a transparent PI film or glass;
washing the ITO anode layer (2) with the film thickness of 150nm, namely sequentially carrying out alkali washing, pure water washing and drying, and then carrying out ultraviolet-ozone washing to remove organic residues on the surface of the transparent ITO;
HAT-CN with a thickness of 10nm is evaporated on the ITO anode layer (2) after the washing by a vacuum evaporation device to be used as a hole injection layer (3);
then evaporating HT-8 with the thickness of 80nm as a hole transport layer (4);
after the evaporation of the hole transport material is finished, a light-emitting layer (5) of the OLED light-emitting device is manufactured, and the structure of the OLED light-emitting device comprises that a compound taking benzimidazolone as a core is used as a main material of the OLED light-emitting layer (5), GD-7 is used as a doping material, the doping proportion of the doping material is 10% by weight, and the thickness of the light-emitting layer is 30 nm;
continuing to vacuum-evaporate an electron transport layer material ET-201 after the light-emitting layer (5), wherein the vacuum-evaporated film thickness of the material is 35nm, and the layer is an electron transport layer (6);
a step of forming a Liq layer having a thickness of 1nm, which is an electron injection layer (7), on the electron transport layer (6) by a vacuum deposition apparatus;
on the electron injection layer (7), an aluminum layer having a thickness of 80nm was formed by a vacuum deposition apparatus, and this layer was used as a cathode reflective electrode layer (8).
4. A lighting or display element made of the organic electroluminescent device of claim 2.
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