CN108250129B - Compound with diaryl anthrone as core and application thereof in organic electroluminescent device - Google Patents

Compound with diaryl anthrone as core and application thereof in organic electroluminescent device Download PDF

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CN108250129B
CN108250129B CN201611248702.7A CN201611248702A CN108250129B CN 108250129 B CN108250129 B CN 108250129B CN 201611248702 A CN201611248702 A CN 201611248702A CN 108250129 B CN108250129 B CN 108250129B
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light
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CN108250129A (en
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缪康健
徐凯
张兆超
李崇
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Valiant Co Ltd
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Abstract

The invention discloses a compound taking diaryl anthrone as a core and application thereof in an organic electroluminescent device. When the compound is used as a luminescent layer material of an OLED luminescent device, the efficiency of the device is greatly improved; meanwhile, the service life of the device is obviously improved, and the structure of the compound is shown as the general formula (1):

Description

Compound with diaryl anthrone as core and application thereof in organic electroluminescent device
Technical Field
The invention relates to the technical field of semiconductors, in particular to a compound taking diaryl anthrone as a core 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 like a sandwich structure and comprises electrode material film layers and organic functional materials clamped between different electrode film layers, and various different functional materials are mutually overlapped together according to purposes to form the OLED light-emitting device. When voltage is applied to electrodes at two ends of the OLED light-emitting device and positive and negative charges in the organic layer functional material film layer are acted through an electric field, the positive and negative charges are further compounded in the light-emitting layer, and OLED electroluminescence is generated.
Currently, the OLED display technology is already applied in the fields of smart phones, tablet computers, and the like, and is further expanded to the large-size application field of televisions, and the like, but compared with the actual product application requirements, the performance of the OLED device, such as light emitting efficiency, service life, and the like, needs to be further improved.
Current research into improving the performance of OLED light emitting devices 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 photoelectric functional material of the OLED are required 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 categories from the aspect of application, namely charge injection transmission materials and luminescent materials. Further, the charge injection transport material may be classified into an electron injection transport material, an electron blocking material, a hole injection transport material, and a hole blocking material, and the light emitting material may be classified into a host light emitting material and a doping material.
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, as a host material of a light-emitting layer, good bipolar, appropriate HOMO/LUMO energy level, etc. are required.
The OLED photoelectric functional material film layer for forming the OLED device at least comprises more than two layers of structures, the OLED device structure applied in industry comprises a hole injection layer, a hole transmission layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transmission 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 transmission material, a light emitting material, an electron transmission 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 material has stronger selectivity, and the performance of the same material in the devices with different structures can be completely different.
Therefore, aiming at the industrial application requirements of the current OLED device and the requirements of different functional film layers and photoelectric characteristics of the OLED device, a more suitable OLED functional material or material combination with higher 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 demand of the current OLED display lighting industry, the development of the current OLED material is far from enough, and lags behind the requirements of panel manufacturing enterprises, and it is very important to develop a higher-performance organic functional material as a material enterprise.
Disclosure of Invention
In view of the above problems in the prior art, the applicant provides a compound with diaryl anthrone as a core and an application thereof in an organic electroluminescent device. The compound takes diaryl anthrone as a core, and is applied to an organic light-emitting diode as a light-emitting layer material.
The technical scheme for solving the technical problems is as follows: a compound with diaryl anthrone as a core has a structure shown in a general formula (1):
Figure DEST_PATH_GDA0001236545910000021
in the general formula (1), m and n are 0 or 1, and m and n are not 0 at the same time;
r represents a structure of the general formula (2):
Figure DEST_PATH_GDA0001236545910000022
R2represented by a hydrogen atom, a structure represented by the general formula (3) or the general formula (4);
Figure DEST_PATH_GDA0001236545910000023
wherein a is selected from
Figure DEST_PATH_GDA0001236545910000024
X1、X2、X3、X4Each independently represents an oxygen atom, a sulfur atom, C1-10Straight chain alkyl substituted alkylene or C1-10One of a branched alkyl-substituted alkylene group, an aryl-substituted alkylene group, an alkyl-substituted tertiary amine group, or an aryl-substituted tertiary amine group; general formula (3) and general formula (4) through CL1-CL2Key, CL2-CL3Key, CL3-CL4Bond or CL4-CL5Is connected with the general formula (2);
R1represented by a structure represented by a general formula (5), a general formula (6), a general formula (7) or a general formula (8);
Figure DEST_PATH_GDA0001236545910000031
wherein, X5Is an oxygen atom, a sulfur atom, C1-10Straight chain alkyl substituted alkylene or C1-10Branched alkyl substituted alkylene, aryl substitutedOne of alkylene, alkyl-substituted tertiary amine or aryl-substituted tertiary amine of (a);
R3、R4each independently represents phenyl, naphthyl, biphenyl, terphenyl, dibenzofuranyl, dibenzothiophenyl or 9, 9-dimethylfluorenyl.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, the R is represented as:
Figure DEST_PATH_GDA0001236545910000032
Figure DEST_PATH_GDA0001236545910000041
Figure DEST_PATH_GDA0001236545910000051
Figure DEST_PATH_GDA0001236545910000052
any one of them.
The invention also provides a method for preparing the compound, wherein the reaction equation is as follows:
Figure DEST_PATH_GDA0001236545910000061
wherein m, n and R are as defined in claim 1;
the preparation method comprises the following steps:
1) dissolving bromo-10, 10-diphenyl anthrone and an amino compound with toluene, wherein the amount of the toluene is 30-50ml of toluene used per gram of the bromo-10, 10-diphenyl anthrone, and the molar ratio of the bromo-10, 10-diphenyl anthrone to the amino compound is 1 (1.2-3.0);
2) adding Pd into the reaction system in the step 1)2(dba)3And sodium tert-butoxide; the Pd2(dba)3The molar ratio of the sodium tert-butoxide to the bromo-10, 10-diphenyl anthrone is (0.006-0.02): 1, and the molar ratio of the sodium tert-butoxide to the bromo-10, 10-diphenyl anthrone is (2.0-5.0): 1.
3) Under the protection of inert gas, reacting the mixed solution at 95-110 ℃ for 10-24 h, naturally cooling to room temperature, filtering the reaction solution, carrying out reduced pressure rotary evaporation on the filtrate until no solvent exists, and passing through a neutral silica gel column to obtain a target product, wherein the reduced pressure rotary evaporation conditions are-0.09 MPa and 85 ℃.
The invention also provides a compound used for preparing an organic electroluminescent device.
The invention also provides an organic electroluminescent device which comprises a light-emitting layer, wherein the light-emitting layer comprises the compound.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, the organic electroluminescent device further comprises a transparent substrate layer, an ITO anode layer, a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer/electron transport layer, an electron injection layer and a cathode reflection electrode layer, wherein the transparent substrate layer, the ITO anode layer, the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the hole blocking layer/electron transport layer, the electron injection layer and the cathode reflection electrode layer are sequentially stacked from bottom to top.
The beneficial technical effects of the invention are as follows:
the diaryl anthrone is used as a mother nucleus and is connected with an aromatic heterocyclic group, so that the diaryl anthrone has strong rigidity, and the molecular symmetry is damaged, thereby the crystallinity of molecules is damaged, and the aggregation effect among molecules is avoided. The compound structure contains a five-membered ring heterocycle as an electron acceptor (A), which is favorable for the transmission of electrons in the 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 parent nucleus diaryl anthrone 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 to be applied to the manufacture of OLED luminescent devices, and can obtain good device performance as a luminescent layer main body material, so that the efficiency of the device is greatly improved; meanwhile, the service life of the device is obviously prolonged. The compound material has good application effect in OLED luminescent devices and good industrialization prospect.
Drawings
FIG. 1 is a schematic 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 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. 2a is a HOMO visualization effect diagram of Compound 14;
FIG. 2b is a graph of the LUMO visualization effect of Compound 14;
FIG. 3a is a HOMO visualization effect graph of compound 18;
FIG. 3b is a graph of the LUMO visualization effect of Compound 18;
FIG. 4a is a HOMO visualization effect graph of Compound 43;
FIG. 4b is a graph of the LUMO visualization effect of Compound 43;
FIG. 5a is a HOMO visualization effect diagram of compound CBP;
FIG. 5b is a graph of the LUMO visualization effect of compound CBP.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples.
Synthesis of intermediate of general formula (2):
Figure DEST_PATH_GDA0001236545910000071
wherein R is11Is composed of
Figure DEST_PATH_GDA0001236545910000072
One of (1), R12Is composed of
Figure DEST_PATH_GDA0001236545910000073
Ar11And Ar12Respectively phenyl, naphthyl or biphenyl; x11 and X12 are each an oxygen atom, a sulfur atom,
Figure DEST_PATH_GDA0001236545910000083
Figure DEST_PATH_GDA0001236545910000082
One of (1), R13Is methyl or phenyl;
weighing the raw material I-1 and the raw material II-2, stirring and dissolving the raw materials with toluene, adding a mixed solution of potassium carbonate, tetratriphenylphosphine palladium, ethanol and water in an inert atmosphere, stirring and heating to 120 ℃ for reaction at the temperature of 110-24 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 obtained, and passing through a silica gel column to obtain an intermediate S1; in the reaction, the molar ratio of the raw material I-1 to the raw material II-1 is 1: 1-2; the molar ratio of the raw material I-1 to the potassium carbonate is 1: 1-3; the molar ratio of the raw material I-1 to the tetratriphenylphosphine palladium is 1: 0.01-0.05;
dissolving the intermediate S1 in o-dichlorobenzene in an inert atmosphere, adding triphenylphosphine, heating to 170-190 ℃, stirring for reacting 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 produced, and passing through a neutral silica gel column to obtain an intermediate S2; in the reaction, the molar ratio of the intermediate S1 to triphenylphosphine is 1: 1-2;
weighing the intermediate S2, 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 an intermediate S2, 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 S2 to the liquid bromine is 1: 1-3;
if the halogenated position of the intermediate S3 is C-N coupling, the reaction steps are as follows:
under the protection of nitrogen, sequentially adding the intermediate S3, the raw material III-1, sodium tert-butoxide and Pd2(dba)3And tri-tert-butylphosphine, stirring and mixing with toluene, heating to 110-120 ℃, performing reflux reaction for 12-24 hours, and sampling a sample point plate to show that no intermediate S3 remains 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 S4-1; in the reaction, the molar ratio of the intermediate S3 to the raw material III-1 is 1: 1-2; the molar ratio of the intermediate S3 to the sodium tert-butoxide is 1: 1-3; the molar ratio of the intermediate S3 to the tri-tert-butylphosphine is 1: 1-3; intermediate S3 and Pd2(dba)3Is 1: 0.01-0.05;
if the halogenated position of the intermediate S3 is C-C coupling, the reaction steps are as follows:
under the protection of nitrogen, sequentially adding the intermediate S3 and the raw material III-2, dissolving with toluene, adding potassium carbonate, tetratriphenylphosphine palladium, ethanol and an aqueous solution, stirring, heating to 110-120 ℃, and reacting for 10-24 hours; after the reaction is finished, cooling to room temperature, filtering, layering the filtrate, carrying out reduced pressure rotary distillation on the organic phase until no fraction is obtained, and passing through a neutral silica gel column to obtain an intermediate S4-2; in the above reaction, the molar ratio of intermediate S3 to starting material iii-2 was 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 tetratriphenyl phosphonium palladium is 1: 0.01-0.05.
Taking the synthesis example of intermediate M2:
Figure DEST_PATH_GDA0001236545910000091
adding 0.5mol of 2-boric acid dibenzofuran, 0.6mol of 2-bromonitrobenzene and 500mL of toluene into a 1000mL three-necked flask under the protection of nitrogen, stirring for dissolving, and adding 0.025mol of Pd (PPh)3)41mol of potassium carbonate, 50mL of ethanol and 50mL of water, stirring and heating to 120 ℃, refluxing and reacting for 24 hours, and sampling a sample point plate to show that no raw material is left and the reaction is complete; naturally cooling to room temperature, filtering, layering the filtrate, taking the organic phase, carrying out reduced pressure rotary evaporation until no fraction is obtained,passing through a neutral silica gel column to obtain a compound M2-1;
adding 0.2mol of compound M2-1 and 500mL of toluene in a 500mL three-neck flask under the protection of nitrogen, stirring for dissolving, adding 0.25mol of tri-tert-butylphosphine, stirring and heating to 120 ℃, refluxing for reaction for 24 hours, and sampling a sample point plate to show that no raw material remains and the reaction is complete; naturally cooling to room temperature, filtering, layering filtrate, taking an organic phase, carrying out reduced pressure rotary evaporation until no fraction is obtained, and passing through a neutral silica gel column to obtain a compound M2-2;
adding 0.1mol of compound M2-2 and 100mL of acetic acid into a 250mL three-neck flask under the protection of nitrogen, stirring and dissolving at room temperature, and slowly dropwise adding 0.12mol of Br at 0 DEG C250mL of the acetic acid solution was stirred at room temperature for 12 hours. Adding NaOH aqueous solution (2mol/L) to neutralize to neutrality, separating out solid, filtering to obtain filter cake, drying under vacuum, passing through neutral silica gel column to obtain compound M2-3;
adding 0.03mol of compound M2-3, 0.036mol of diphenylamine and 150mL of toluene into a 250mL three-necked bottle under the protection of nitrogen, stirring and mixing, and then adding 0.09mol of sodium tert-butoxide and 0.015mol of Pd2(dba)30.015mol of tri-tert-butylphosphine is heated to 120 ℃, and reflux reaction is carried out for 24 hours; naturally cooling to room temperature, filtering, performing reduced pressure rotary evaporation on the filtrate (0.09 MPa, 85 ℃), and passing through a neutral silica gel column to obtain an intermediate M2;
the structures of the intermediates and the specific structures of the raw materials for synthesizing the intermediates are shown in table 1;
TABLE 1
Figure DEST_PATH_GDA0001236545910000092
Figure DEST_PATH_GDA0001236545910000101
Figure DEST_PATH_GDA0001236545910000111
Example 1: synthesis of Compound 5:
Figure DEST_PATH_GDA0001236545910000112
adding metal magnesium (0.21mol) into a 1L three-necked bottle with a constant pressure dropping funnel, dissolving para-bromoiodobenzene (0.20mol) in 300mL tetrahydrofuran, placing the solution into the constant pressure dropping funnel, heating the three-necked bottle under the protection of nitrogen until the temperature in the bottle reaches 65 ℃, adding 50mL tetrahydrofuran solution of para-bromoiodobenzene through the constant pressure dropping funnel, slowly dropping the rest part after the reaction is initiated, finishing dropping for 1h, reacting for 2h at the reflux temperature, and transferring the solution into the constant pressure funnel after the temperature is reduced to the room temperature for standby;
dissolving anthraquinone (0.20mol) in 200mL tetrahydrofuran, adding into a 2L three-necked bottle, slowly dropwise adding the solution for later use, reacting at a reflux temperature for 3h, cooling to 25 ℃ after the reaction is finished, slowly pouring the reaction solution into 200g of dilute hydrochloric acid with the mass concentration of 10%, stirring for 15min, separating, collecting an organic phase, removing the solvent under reduced pressure to obtain a viscous liquid, and directly using the viscous liquid in the next reaction without refining;
adding 250g of benzene into the obtained viscous liquid, adding 100mL of boron trifluoride diethyl etherate (1mol/L) under stirring, reacting for 4 hours at the temperature of 60-65 ℃, quenching, removing the solvent under reduced pressure, and performing column chromatography to obtain a raw material A, wherein the HPLC purity is 99.5%, and the yield is 45%;
0.01mol of intermediate M1 and 0.015mol of raw material A are weighed and dissolved in 150mL of anhydrous toluene, 0.02mol of sodium tert-butoxide and 10 mol of sodium tert-butoxide are added after deoxygenation-4mol Pd2(dba)3Heating and refluxing for 12 hours, sampling a sample, and completely reacting the raw materials; naturally cooling to room temperature (20-25 ℃), filtering, collecting filtrate, performing reduced pressure rotary evaporation (-0.09MPa, 85 ℃), and performing column chromatography to obtain a target product, wherein the HPLC purity is 99.4%, and the yield is 74.6%.
Elemental analysis Structure (molecular formula C)57H40N2O): theoretical value C, 89.03; h, 5.24; n, 3.64; test values are: c, 89.05; h, 5.25; n, 3.64;
MS m/z：769.98[M+H]+the theoretical value is as follows: 769.95.
example 2: synthesis of compound 12:
the synthetic route is as follows:
Figure DEST_PATH_GDA0001236545910000121
prepared according to the synthetic method for compound 5 in example 1, except that intermediate M2 is used instead of intermediate M1;
elemental analysis Structure (molecular formula C)56H36N2O2): theoretical value C, 87.48; h, 4.72; n, 3.64; test values are: c, 87.50; h, 4.72; n, 3.63;
MS m/z：769.94[M+H]+the theoretical value is as follows: 769.91.
example 3: synthesis of compound 14:
the synthetic route is as follows:
Figure DEST_PATH_GDA0001236545910000131
prepared according to the synthetic method for compound 5 in example 1, except that intermediate M3 is used instead of intermediate M1;
elemental analysis Structure (molecular formula C)59H40N2O2): theoretical value C, 87.60; h, 4.98; n, 3.46; test values are: c, 87.63; h, 4.97; n, 3.46;
MS m/z：809.99[M+H]+the theoretical value is as follows: 809.97.
example 4: synthesis of compound 18:
the synthetic route is as follows:
Figure DEST_PATH_GDA0001236545910000132
prepared according to the synthetic method for compound 5 in example 1, except that intermediate M4 is used instead of intermediate M1;
elemental analysis Structure (molecular formula C)59H39NO2): theoretical value C, 89.25; h, 4.95; n, 1.76; test values are: c, 89.54; h, 4.95; n, 1.77;
MS m/z：794.98[M+H]+the theoretical value is as follows: 794.95.
example 5: synthesis of compound 28:
the synthetic route is as follows:
Figure DEST_PATH_GDA0001236545910000133
prepared according to the synthetic method for compound 5 in example 1, except that intermediate M5 is used instead of intermediate M1;
elemental analysis Structure (molecular formula C)62H46N2O): theoretical value C, 89.18; h, 5.55; n, 3.35; test values are: c, 89.20; h, 5.54; n, 3.35;
MS m/z：836.12[M+H]+the theoretical value is as follows: 836.05.
example 6: synthesis of compound 36:
the synthetic route is as follows:
Figure DEST_PATH_GDA0001236545910000141
prepared according to the synthetic method for compound 5 in example 1, except that intermediate M6 is used instead of intermediate M1;
elemental analysis Structure (molecular formula C)62H46N2O): theoretical value C, 89.18; h, 5.55; n, 3.35; test values are: c, 89.19; h, 5.54; n, 3.36;
MS m/z：836.06[M+H]+the theoretical value is as follows: 836.05.
example 7: synthesis of compound 43:
the synthetic route is as follows:
Figure DEST_PATH_GDA0001236545910000142
prepared according to the synthetic method for compound 5 in example 1, except that intermediate M7 is used instead of intermediate M1;
elemental analysis Structure (molecular formula C)56H34N2O3): theoretical value C, 85.91; h, 4.38; n, 3.58; test values are: c, 85.94; h, 4.38; n, 3.57;
MS m/z：783.92[M+H]+the theoretical value is as follows: 783.89.
example 8: synthesis of compound 56:
the synthetic route is as follows:
Figure DEST_PATH_GDA0001236545910000143
prepared according to the synthetic method for compound 5 in example 1, except that intermediate M8 is used instead of intermediate M1;
elemental analysis Structure (molecular formula C)56H34N2O3): theoretical value C, 85.91; h, 4.38; n, 3.58; test values are: c, 85.93; h, 4.37; n, 3.58;
MS m/z：783.94[M+H]+the theoretical value is as follows: 783.89.
example 9: synthesis of compound 66:
the synthetic route is as follows:
Figure DEST_PATH_GDA0001236545910000151
prepared according to the synthetic method for compound 5 in example 1, except that intermediate M9 is used instead of intermediate M1;
elemental analysis Structure (molecular formula C)62H46N2O): theoretical value C, 89.18; h, 5.55; n, 3.35; test values are: c, 89.21; h, 5.54; n, 3.35;
MS m/z：836.12[M+H]+the theoretical value is as follows: 836.05.
example 10: synthesis of compound 75:
the synthetic route is as follows:
Figure DEST_PATH_GDA0001236545910000152
prepared according to the synthetic method for compound 5 in example 1, except that intermediate M10 is used instead of intermediate M1;
elemental analysis Structure (molecular formula C)56H36N2O2): theoretical value C, 87.48; h, 4.72; n, 3.64; test values are: c, 87.50; h, 4.72; n, 3.63;
MS m/z：769.94[M+H]+the theoretical value is as follows: 769.91.
example 11: synthesis of compound 87:
the synthetic route is as follows:
Figure DEST_PATH_GDA0001236545910000161
prepared according to the synthetic method for compound 5 in example 1, except that intermediate M11 is used instead of intermediate M1;
elemental analysis Structure (molecular formula C)62H46N2O): theoretical value C, 89.18; h, 5.55; n, 3.35; test values are: c, 89.21; h, 5.54; n, 3.35;
MS m/z：836.15[M+H]+the theoretical value is as follows: 836.05.
example 12: synthesis of compound 96:
the synthetic route is as follows:
Figure DEST_PATH_GDA0001236545910000162
prepared according to the synthetic method for compound 5 in example 1, except that intermediate M12 is used instead of intermediate M1;
elemental analysis Structure (molecular formula C)56H34N2O3): theoretical value C, 85.91; h, 4.38; n, 3.58; test values are: c, 85.95; h, 4.39; n, 3.56;
MS m/z：783.92[M+H]+the theoretical value is as follows: 783.89.
example 13: synthesis of compound 96:
the synthetic route is as follows:
Figure DEST_PATH_GDA0001236545910000163
prepared according to the synthetic method for compound 5 in example 1, except that intermediate M13 is used instead of intermediate M1;
elemental analysis Structure (molecular formula C)62H46N2O): theoretical value C, 89.18; h, 5.55; n, 3.35; test values are: c, 89.21; h, 5.54; n, 3.35;
MS m/z：836.11[M+H]+the theoretical value is as follows: 836.05.
the compound of the present invention can be used as a light-emitting layer material, and the compound of the present invention, and the conventional material CBP were measured for the state of thermal evaporation and the T1 level, respectively, and the results of the measurements are shown in table 2.
TABLE 2
Compound (I) State of thermal evaporation T1(eV) Function of
Compound (I) Melt type 2.85 Host material
Compound (I) Melt type 2.90 Host material
Compound CBP Sublimation type 2.70 Host material
Note: the thermal evaporation state is measured by a Korean ANS-INC (100 x 100) evaporation device, the vacuum degree is less than 5 x 10 < -7 > Torr, the temperature rise rate is 10 ℃/min at a first temperature rise region (0-200 ℃); the temperature rise rate of the second temperature rise region (200-
Figure DEST_PATH_GDA0001236545910000171
Evaporating at the evaporation rate for 10min, and naturally cooling to room temperature. T1 is the phosphorescence emission spectrum of the test compound and is calculated from the phosphorescence emission peak (test equipment: FLS980 fluorescence spectrometer by Edinburgh Instruments, Optistat DN-V2 cryo-module by Oxford Instruments).
As can be seen from the data in the table above, the compound of the present invention has high thermal evaporation rate stability, and the heat transfer inside the material is better than that of a sublimation type material, such that material deterioration caused by local overheating due to uneven heat transfer is avoided, and long-time evaporation is facilitated. In addition, the compound has a higher T1 energy level, avoids energy from being transmitted back to a main material from a doping material, and is suitable for being used as a luminescent layer material; meanwhile, the compound contains an electron donor (Donor, D) and an electron acceptor (acceptor, A), so that electrons and holes of an OLED device applying the compound reach a balanced state, the recombination rate of the electrons and the holes is ensured, and the efficiency and the service life of the device are improved.
The HOMO and LUMO energy levels of the compound are calculated and visualized by using quantum chemistry de novo calculation software ORCA, and the calculation method adopts a B3LYP hybridization functional, group 6-31g (d). The visualized HOMO and LUMO profiles of compound 14, compound 18, compound 43, and compound CBP are shown in FIGS. 2a-5 b.
From the spatial distribution of HOMO and LUMO in the molecule, it can be seen that the HOMO and LUMO energy levels of the compounds of the present invention are in a spatially separated state and the HOMO and LUMO overlap is small compared to the compound CBP. The compound of the invention has two parts of an electron donor (Donor, D) and an electron acceptor (acceptor, A), so that electrons and holes of an OLED device of the compound of the invention can reach a balanced state more easily, the recombination rate of the electrons and the holes is ensured, and the efficiency and the service life of the device are improved.
The effect of the compound synthesized in the examples of the present invention as a host material for a light emitting layer in a device is described in detail below by examples 14 to 21 and comparative examples 1 to 3. In examples 15 to 21 and comparative examples 1 to 3, the manufacturing process of the device was completely the same as that of example 14, and the same substrate material and electrode material were used, and the film thickness of the electrode material was kept the same, except that the material of the light emitting layer was changed in the device.
Example 14
Transparent substrate layer 1/ITO anode layer 2/hole injection layer 3 (molybdenum trioxide, MoO)3Thickness 10 nm)/hole transport layer 4(TAPC, thickness 80 nm)/light-emitting layer 5 (compound 5 and GD-19 as 100:5, 30nm in thickness)/electron transport layer 6(TPBI, 40nm in thickness)/electron injection layer 7(LiF, 1nm in thickness)/cathode reflective electrode layer 8 (Al). The molecular structural formula of the related material is shown as follows:
Figure DEST_PATH_GDA0001236545910000181
the preparation process comprises the following steps:
the transparent substrate layer 1 is made of transparent material. 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.
After the above-mentioned washing is carried outOn the washed ITO anode layer 2, molybdenum trioxide MoO with a film thickness of 10nm was deposited by a vacuum deposition apparatus3The hole injection layer 3 is used. Subsequently, TAPC was evaporated to a thickness of 80nm as the hole transport layer 4.
After the evaporation of the hole transport material is finished, the light-emitting layer 5 of the OLED light-emitting device is manufactured, and the structure of the light-emitting layer 5 comprises the material compound 5 used by the OLED light-emitting layer 5 as a main material, GD-19 as a doping material, the doping proportion of the doping material is 5% by weight, and the thickness of the light-emitting layer is 30 nm.
After the light-emitting layer 5, the electron transport layer material is continuously vacuum evaporated to be TPBI. The vacuum evaporation film thickness of the material was 40nm, and this layer was an electron transport layer 6.
On the electron transport layer 6, a lithium fluoride (LiF) layer having a film thickness of 1nm was formed by a vacuum deposition apparatus, and this layer was an electron injection layer 7.
On the electron injection layer 7, an aluminum (Al) layer having a film thickness of 80nm was formed by a vacuum deposition apparatus, and this layer was used as the cathode reflection electrode layer 8.
After the OLED light emitting device was completed as described above, the anode and the cathode were connected by a known driving circuit, and the light emitting efficiency, the light emission spectrum, and the current-voltage characteristics of the device were measured.
Example 15
Transparent substrate layer 1/ITO anode layer 2/hole injection layer 3 (molybdenum trioxide, MoO)3Thickness 10 nm)/hole transport layer 4(TAPC, thickness 80 nm)/light-emitting layer 5 (compound 12 and GD-19 mixed at a weight ratio of 100:5, thickness 30 nm)/electron transport layer 6(TPBI, thickness 40 nm)/electron injection layer 7(LiF, thickness 1 nm)/cathode reflective electrode layer 8 (Al).
Example 16
Transparent substrate layer 1/ITO anode layer 2/hole injection layer 3 (molybdenum trioxide, MoO)3Thickness 10 nm)/hole transport layer 4(TAPC, thickness 80 nm)/light-emitting layer 5 (compound 14 and ir (ppy)3 mixed in a weight ratio of 100:10, thickness 30 nm)/electron transport layer 6(TPBI, thickness 40 nm)/electron injection layer 7(LiF, thickness 1 nm)/cathode reflective electrode layer 8 (Al).
Example 17
Transparent substrate layer 1/ITO anode layer 2/hole injection layer 3 (molybdenum trioxide, MoO)3Thickness 10 nm)/hole transport layer 4(TAPC, thickness 80 nm)/light-emitting layer 5 (compound 18 and ir (ppy)3 mixed in a weight ratio of 100:10, thickness 30 nm)/electron transport layer 6(TPBI, thickness 40 nm)/electron injection layer 7(LiF, thickness 1 nm)/cathode reflective electrode layer 8 (Al).
Example 18
Transparent substrate layer 1/ITO anode layer 2/hole injection layer 3 (molybdenum trioxide, MoO)3Thickness 10 nm)/hole transport layer 4(TAPC, thickness 80 nm)/luminescent layer 5 (compound 28 and GD-PACTZ mixed in a weight ratio of 100:5, thickness 30 nm)/electron transport layer 6(TPBI, thickness 40 nm)/electron injection layer 7(LiF, thickness 1 nm)/cathode reflective electrode layer 8 (Al).
Example 19
Transparent substrate layer 1/ITO anode layer 2/hole injection layer 3 (molybdenum trioxide, MoO)3Thickness 10 nm)/hole transport layer 4(TAPC, thickness 80 nm)/light-emitting layer 5 (compound 36 and GD-PACTZ mixed in a weight ratio of 100:5, thickness 30 nm)/electron transport layer 6(TPBI, thickness 40 nm)/electron injection layer 7(LiF, thickness 1 nm)/cathode reflective electrode layer 8 (Al).
Example 20
Transparent substrate layer 1/ITO anode layer 2/hole injection layer 3 (molybdenum trioxide, MoO)3Thickness 10 nm)/hole transport layer 4(TAPC, thickness 80 nm)/light emitting layer 5 (compound 43, GH-204 and ir (ppy)3, mixed at a weight ratio of 70:30:10, thickness 30 nm)/electron transport layer 6(TPBI, thickness 40 nm)/electron injection layer 7(LiF, thickness 1 nm)/cathode reflective electrode layer 8 (Al).
Example 21
Transparent substrate layer 1/ITO anode layer 2/hole injection layer 3 (molybdenum trioxide, MoO)3Thickness 10 nm)/hole transport layer 4(TAPC, thickness 80 nm)/light-emitting layer 5 (compound 56, GH-204 and GD-PACTZ mixed at a weight ratio of 70:30:5, thickness 30 nm)/electron transport layer 6(TPBI, thickness 40 nm)/electron injection layer 7(LiF, thickness 1 nm)/cathode reflective electrode layer 8 (Al).
Comparative example 1
Transparent substrate layer 1/ITO anode layer 2/hole injection layer 3 (molybdenum trioxide, MoO)3Thickness 10 nm)/hole transportLayer 4(TAPC, thickness 80 nm)/light-emitting layer 5(CBP and GD-19 are mixed in a weight ratio of 100:5, thickness 30 nm)/electron transport layer 6(TPBI, thickness 40 nm)/electron injection layer 7(LiF, thickness 1 nm)/cathode reflective electrode layer 8 (Al).
Comparative example 2
Transparent substrate layer 1/ITO anode layer 2/hole injection layer 3 (molybdenum trioxide, MoO)3Thickness 10 nm)/hole transport layer 4(TAPC, thickness 80 nm)/light emitting layer 5(CBP and ir (ppy)3, mixed at a weight ratio of 100:10, thickness 30 nm)/electron transport layer 6(TPBI, thickness 40 nm)/electron injection layer 7(LiF, thickness 1 nm)/cathode reflective electrode layer 8 (Al).
Comparative example 3
Transparent substrate layer 1/ITO anode layer 2/hole injection layer 3 (molybdenum trioxide, MoO)3Thickness 10 nm)/hole transport layer 4(TAPC, thickness 80 nm)/light-emitting layer 5(CBP and GD-PACTZ mixed in a weight ratio of 100:5, thickness 30 nm)/electron transport layer 6(TPBI, thickness 40 nm)/electron injection layer 7(LiF, thickness 1 nm)/cathode electrode layer 8 (Al).
The test results of the fabricated OLED light emitting device are shown in table 4.
TABLE 3
Figure DEST_PATH_GDA0001236545910000201
Figure DEST_PATH_GDA0001236545910000211
TABLE 4
Figure DEST_PATH_GDA0001236545910000212
In comparative example 1, the current efficiency was 6.5cd/A (@10 mA/cm)2) (ii) a LT95 lifetime decay was 3.8Hr at 5000nit brightness. The current efficiency of comparative example 2 was 24.6cd/A (@10 mA/cm)2) (ii) a LT95 lifetime decay was 4.3Hr at 5000nit brightness. Comparative example 3 has a current efficiency of 25.1cd/A (@10 mA/cm)2) (ii) a LT95 lifetime decay at 5000nit luminanceThe reduced to 7.8 Hr. The life test system is an OLED device life tester which is researched by the owner of the invention together with Shanghai university.
The results in table 4 show that the compound of the present invention can be used as a host material of a light emitting layer for fabricating an OLED light emitting device; compared with the comparative example 1, the OLED material has the advantages that the efficiency, the voltage and the service life are greatly improved compared with the known OLED material, and particularly the driving service life of the device is greatly prolonged.
In order to further embody the advantages of the compound in industrial application, the invention compares the performance change conditions of devices under different doping material ratios, and defines the doping concentration dependence coefficient
Figure DEST_PATH_GDA0001236545910000224
Carrying out representation;
Figure DEST_PATH_GDA0001236545910000221
it indicates a drive current of 10mA/cm2The devices with different doping concentrations have the uniformity degree among the maximum value mu max, the minimum value and the average value of the efficiency,
Figure DEST_PATH_GDA0001236545910000222
the larger the value is, the larger the influence of the doping proportion on the efficiency of the device is, the evaporation rate of the material needs to be strictly controlled during industrial application, and the industrial application window is smaller; on the contrary, the requirement of the device performance on the doping ratio is not good, the industrial production is easy to realize, the production cost is reduced, and the method has a good industrial application prospect.
Referring to the preparation methods of examples 14 to 21, and using the same substrate material and electrode material, the film thickness of the electrode material was also kept consistent, except that the doping ratio was changed; the structure and test results of each device are shown in table 5:
TABLE 5
Figure DEST_PATH_GDA0001236545910000223
Figure DEST_PATH_GDA0001236545910000231
From the data application, the compound has good application effect in an OLED light-emitting device as a light-emitting layer material, and has good industrialization prospect.
Although the present invention has been disclosed by way of examples and preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments. On the contrary, it is intended to cover various modifications and similar arrangements as would be apparent to those skilled in the art. The scope of the following claims is, therefore, to be accorded the broadest interpretation so as to encompass all such modifications and similar arrangements.

Claims (4)

1. A compound with diaryl anthrone as a core is characterized in that the specific structural formula of the compound is as follows:
Figure FDA0003239622090000011
Figure FDA0003239622090000012
any one of them.
2. Use of a compound according to claim 1 for the preparation of an organic electroluminescent device.
3. An organic electroluminescent device comprising a light-emitting layer, characterized in that the light-emitting layer comprises the compound of claim 1.
4. The organic electroluminescent device according to claim 3, further comprising a transparent substrate layer, an ITO anode layer, a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer/electron transport layer, an electron injection layer, and a cathode reflective electrode layer, wherein the transparent substrate layer, the ITO anode layer, the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the hole blocking layer/electron transport layer, the electron injection layer, and the cathode reflective electrode layer are sequentially stacked from bottom to top.
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