CN110964007B - Compound with quinolinone derivative as core and application of compound in organic electroluminescent device - Google Patents
Compound with quinolinone derivative as core and application of compound in organic electroluminescent device Download PDFInfo
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Abstract
The invention discloses a compound taking a quinolinone derivative as a core and application thereof in an organic electroluminescent device. The attached heterocyclic group is an electron donor which facilitates the transport of holes in the light-emitting layer. The nitrogen atom in the benzo-aza-naphthalenone containing heteroatom is saturated atom, which 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 exciton recombination efficiency, reduce the starting voltage and improve the device performance. When the compound is used as a luminescent layer material of an organic electroluminescent device, the current efficiency of the device is greatly improved, and 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 compound taking a quinolinone derivative as a core and application thereof in an organic electroluminescent device.
Background
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.
Disclosure of Invention
In view of the above problems in the prior art, the applicant provides a compound with a quinolinone derivative as a core and an application thereof in an organic electroluminescent device. The compound takes the heteroatom-containing benzoazanaphthalenone as a core, can increase orbital overlap, has higher triplet energy level, and can limit triplet excitons of the compound in a light-emitting layer, thereby improving the light-emitting efficiency.
The technical scheme for solving the technical problems is as follows: a compound taking a quinolinone derivative as a core has a structure shown as a general formula (1):
in the general formula (1), a represents a structure
X represents oxygen atom, sulfur atom, selenium atom, -C (R)1)(R2)-、-N(R3) -or-Si (R)4)(R5)-；
R1～R5Are each independently represented by C1-10Alkyl, substituted or unsubstituted C6-30One of an aryl group, a substituted or unsubstituted 5-30 membered heteroaryl group containing one or more heteroatoms;
wherein R represents a substituted or unsubstituted 5-30 membered heteroaryl group containing one or more heteroatoms, a substituted or unsubstituted C6-30An aryl group;
b and c each independently represent 0 or 1, and b + c is 1;
Rbis represented by a general formula (2) or a general formula (3)The structure shown is as follows:
the general formula (2) and the general formula (3) are connected with a benzene ring in the general formula (1) through a single bond;
wherein R is6、R7Each independently represents a structure represented by a general formula (4) or a general formula (5); ar represents substituted or unsubstituted C6-30Arylene, 5-30 membered heteroarylene substituted or unsubstituted with one or more heteroatoms;
X1、X2、X3respectively, identically or differently, an oxygen atom, a sulfur atom, a selenium atom, -C (R)8)(R9) -or-N (R)10)-；R8～R10Are each independently represented by C1-10Alkyl, substituted or unsubstituted C6-30One of an aryl group, a substituted or unsubstituted 5-30 membered heteroaryl group containing one or more heteroatoms;
(ii) formula (4) or formula (5) is connected by fusing two adjacent positions of the mark with two adjacent positions of the mark in formula (2) or formula (3);
the substituent of the substitutable group is selected from halogen, cyano, C1-10Alkyl radical, C6-30One or more of aryl and 5-30 membered heteroaryl;
the heteroatom is one or more selected from oxygen atom, sulfur atom or nitrogen atom.
As a further improvement of the invention, R is1～R5Each independently represents methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted furyl;
the R represents substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted furyl;
the R is8～R10Each independently represents methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, substituted or unsubstituted phenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted furyl;
the substituent of the substitutable group is one or more selected from fluorine atom, cyano group, methyl group, ethyl group, propyl group, isopropyl group, tertiary butyl group, amyl group, phenyl group, naphthyl group, biphenyl group, naphthyridinyl group or pyridyl group.
As a further improvement of the present invention, the compound structure is represented by any one of general formulae (II-1) to (II-32):
as a further improvement of the present invention, the general formula (2) is represented by:
As a further improvement of the present invention, the general formula (3) is represented by:
As a further improvement of the invention, the specific structural formula of the general formula (1) is as follows:
A method for preparing a compound taking a quinolinone derivative as a core comprises the following synthetic steps:
wherein a, R and RbAs defined in the above general formula (1);
weighing the raw material A and the intermediate B, and dissolving the raw material A and the intermediate B by using a mixed solvent of toluene and ethanol in a volume ratio of 2: 1; adding Na under inert atmosphere2CO3Aqueous solution, Pd (PPh)3)4(ii) a Reacting the mixed solution of the reactants for 10-24 hours at the reaction temperature of 95-110 ℃, cooling and filtering the reaction solution, carrying out rotary evaporation on the filtrate, and passing through a silica gel column to obtain a target product; said raw materialsThe molar ratio of the A to the intermediate B is 1: 1.0-2.0; na (Na)2CO3The mol ratio of the raw material A to the raw material A is 1.0-3.0: 1; pd (PPh)3)4The molar ratio of the raw material A to the raw material A is 0.006-0.02: 1.
An organic electroluminescent device comprises at least one functional layer containing the compound taking the quinolinone derivative as the core.
As a further improvement of the invention, the organic electroluminescent device comprises a light-emitting layer, and the light-emitting layer contains the compound taking the quinolinone derivative as the core.
A lighting or display element comprising the organic electroluminescent device.
The beneficial technical effects of the invention are as follows:
the compound disclosed by the invention contains a combination of an electron donor (Donor, D) and an electron acceptor (acceptor, A) in a molecule, so that orbital overlap can be increased, the luminous efficiency is improved, meanwhile, an aromatic heterocyclic group is connected to obtain a charge transfer state material with HOMO and LUMO space separation, the small energy level difference of an S1 state and a T1 state is realized, and thus reverse intersystem crossing is easy to realize under a thermal stimulation condition.
The compound of the invention takes the quinolinone derivative as a mother nucleus and is connected with the aromatic heterocyclic group, has strong rigidity, and destroys the molecular symmetry, thereby destroying the crystallinity of molecules and avoiding the aggregation among molecules. The compound contains quinolinone derivative 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 nitrogen atom in the benzo-aza-naphthalenone containing heteroatom is saturated atom, which 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 exciton recombination efficiency, reduce the starting voltage and improve the device performance.
The quininone derivative as the parent nucleus has a high triplet energy level, so that triplet excitons of the compound are limited in the light-emitting layer, and the light-emitting efficiency is improved.
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.
Drawings
FIG. 1 is a schematic structural diagram of an OLED device using the materials listed in the present invention;
in the figure: 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 an electron blocking layer, 6 is a light emitting layer, 7 is a hole blocking/electron transport layer, 8 is an electron injection layer, and 9 is a cathode reflection electrode layer.
Fig. 2 is a graph of current efficiency measured at different temperatures for OLED devices prepared in examples of the present invention.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples.
Preparation of intermediate B:
preparation of intermediate I-1:
(1) a500 mL three-necked flask was charged with 0.05mol of the starting material C-1 and 0.06mol of the starting material D-1 under nitrogen protection, dissolved in a mixed solvent (180mL of toluene and 90mL of ethanol), and then charged with 0.15mol of Na2CO3The aqueous solution (2M) was stirred under nitrogen for 1 hour, then 0.0005mol Pd (PPh) was added3)4Heating and refluxing for 15 hours at 100 ℃, sampling the sample, and completely reacting. Naturally cooling, filtering, rotatably evaporating filtrate, and passing through a silica gel column to obtain an intermediate L-1 with the HPLC purity of 93.4 percent and the yield of 64.2 percent.
Elemental analysis Structure (molecular formula C)23H17BrS2): theoretical value C, 63.16; h, 3.92; br, 18.27; s, 14.66; test values are: c, 63.15; h, 3.92; br, 18.27; s, 14.67. ESI-MS (M/z) (M +): theoretical value of 436.00, found value of 436.12。
(2) Weighing 0.01mol of intermediate L-1 and 0.012mol of cesium carbonate under the protection of nitrogen, dissolving with DMSO, heating to 140-150 ℃, and reacting for 8-12 hours; sampling the spot plate, showing no intermediate L-1 remained and complete reaction; cooling the reaction system to room temperature, adding a saturated sodium chloride solution, extracting with ethyl acetate, separating liquid, drying an organic phase with anhydrous sodium sulfate, carrying out reduced pressure rotary evaporation, and passing the obtained crude product through a neutral silica gel column to obtain an intermediate I-1, wherein the HPLC purity is 98.1% and the yield is 88.3%;
elemental analysis Structure (molecular formula C)23H15BrS): theoretical value C, 68.49; h, 3.75; br, 19.81; s, 7.95; test values are: c, 68.48; h, 3.75; br, 19.81; and S, 7.96. ESI-MS (M/z) (M +): theoretical value is 402.01, found 402.08.
The synthesis of the intermediate I-1 comprises two steps: synthesizing an intermediate L-1 from the raw material C-1 and the raw material D-1; intermediate L-1 is subjected to cyclization reaction to form intermediate I-1. Other intermediates I were prepared in a similar manner to intermediate I-1, and the specific structures and starting materials for intermediate I used in the present invention are shown in Table 1.
TABLE 1
Feedstock C and feedstock D were purchased commercially.
Preparation of intermediate II-1:
(1) a three-necked flask was charged with E-1(0.1mol), F-1(0.1mol), potassium carbonate (0.2mol), tetrahydrofuran (300ml), water (100ml) and palladium triphenylphosphine (1g), and refluxed at room temperature for 10 hours under nitrogen protection, and the reaction was completed by sampling the sample. Naturally cooling, extracting with dichloromethane, drying the organic phase, concentrating, and purifying by column chromatography to obtain intermediate M-1-1; HPLC purity 97.5%, yield 68.4%.
Elemental analysis Structure (molecular formula C)19H16BrNO2): theoretical value C, 61.64; h, 4.36; br, 21.58; n, 3.78; o, 8.64; test values are: c, 61.65; h, 4.36; br, 21.57; n, 3.77; o, 8.65. ESI-MS (M/z) (M +): theoretical value is 369.04, found 369.10.
(2) Adding the intermediate M-1-1(0.03mol), triphenylphosphine (0.24mol) and o-dichlorobenzene (200ml) into a three-neck flask, heating and refluxing for 5 hours at 180 ℃ under the protection of nitrogen, cooling, removing the solvent by rotary evaporation, and recrystallizing the crude product with tetrahydrofuran and ethanol to obtain an intermediate M-2-1; HPLC purity 96.4%, yield 89.0%.
Elemental analysis Structure (molecular formula C)19H16BrN): theoretical value C, 67.47; h, 4.77; br, 23.62; n, 4.14; test values are: c, 67.46; h, 4.77; br, 23.63; n, 4.14. ESI-MS (M/z) (M +): theoretical value is 337.05, found 336.98.
(3) In a 250mL three-mouth bottle, under the protection of nitrogen, 0.02mol of intermediate M-2-1, iodobenzene, 0.05mol of sodium tert-butoxide and 0.2mmol of Pd are added2(dba)3Stirring and mixing 0.2mmol of tri-tert-butylphosphine with 150mL of toluene, heating to 110-120 ℃, carrying out reflux reaction for 12-24 hours, and sampling a sample point plate to show that no intermediate M-2-1 remains 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 II-1; HPLC purity 95.6%, yield 86.8%.
Elemental analysis Structure (molecular formula C)25H20BrN): theoretical value C, 72.47; h, 4.87; br, 19.28; n, 3.38; test values are: c, 72.47; h, 4.86; br, 19.28; and N, 3.39. ESI-MS (M/z) (M +): theoretical value is 413.08, found 413.12.
The synthesis of the intermediate II-1 comprises three steps: synthesizing an intermediate M-1-1 from the raw material E-1 and the raw material F-1; the intermediate M-1-1 undergoes cyclization reaction to form an intermediate M-2-1; intermediate M-2-1 and iodobenzene are used for synthesizing intermediate II-1. The preparation method of other intermediate II is similar to that of intermediate II-1, and the specific structure and preparation raw materials of the intermediate II used in the invention are shown in Table 2.
TABLE 2
Feedstock E and feedstock F were purchased commercially.
Preparation of intermediate III-1:
(1) a three-necked flask was charged with G-1(0.1mol) as a starting material, H-1(0.1mol) as a starting material, potassium carbonate (0.2mol), tetrahydrofuran (300ml), water (100ml) and palladium tetratriphenylphosphine (1G), and the mixture was refluxed at 100 ℃ for 10 hours under nitrogen protection, sampled and spotted on a plate, and the reaction was completed. Naturally cooling, extracting with dichloromethane, drying the organic phase, concentrating, and purifying by column chromatography to obtain intermediate N-1-1; HPLC purity 98.3%, yield 87.1%.
Elemental analysis Structure (molecular formula C)10H7NO2S): theoretical value C, 58.52; h, 3.44; n, 6.82; o, 15.59; s, 15.62; test values are: c, 58.52; h, 3.43; n, 6.82; o, 15.59; s, 15.63. ESI-MS (M/z) (M +): theoretical value is 205.02, found 205.13.
(2) Adding intermediate N-1-1(0.03mol), triphenylphosphine (0.24mol) and o-dichlorobenzene (200ml) into a three-neck flask, heating and refluxing for 5 hours at 180 ℃ under the protection of nitrogen, cooling, removing the solvent by rotary evaporation, and recrystallizing the crude product with tetrahydrofuran and ethanol to obtain intermediate N-2-1; HPLC purity 93.4%, yield 88.6%.
Elemental analysis Structure (molecular formula C)10H7NS): theoretical value C, 69.33; h, 4.07; n, 8.09; s, 18.51; test value: c, 69.32; h, 4.07; n, 8.10; s, 18.51. ESI-MS (M/z) (M +): the theoretical value was 173.03, found 173.05.
(3) In a 250mL three-neck flask, under the protection of nitrogen, 0.02mol of intermediate N-2-1, raw material Q, 0.05mol of sodium tert-butoxide and 0.2mmol of Pd are added2(dba)3Stirring and mixing 0.2mmol of tri-tert-butylphosphine with 150mL of toluene, heating to 110-120 ℃, carrying out reflux reaction for 12-24 hours, and sampling a sample point plate to show that no intermediate N-2-1 remains 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 III-1; HPLC purity 97.2%, yield 87.4%.
Elemental analysis Structure (molecular formula C)16H10BrNS): theoretical value C, 58.55; h, 3.07; br, 24.34; n, 4.27; s, 9.77; test values are: c, 58.55; h, 3.07; br, 24.35; n, 4.26; s, 9.77. ESI-MS (M/z) (M +): theoretical value is 326.97, found 327.10.
The synthesis of the intermediate III-1 comprises three steps: synthesizing an intermediate N-1-1 from the raw material G-1 and the raw material H-1; the intermediate N-1-1 is subjected to cyclization reaction to form an intermediate N-2-1; intermediate N-2-1 and m-dibromobenzene are synthesized into intermediate III-1. The preparation method of other intermediate III is similar to that of intermediate III-1, and the specific structure and preparation raw materials of intermediate III used in the invention are shown in Table 3.
TABLE 3
Example 1: synthesis of Compound 2:
in a 250mL three-necked flask, nitrogen gas was introduced, and 0.01mol of the starting material A-1, 0 was added.015mol of intermediate I-1, dissolved in a mixed solvent of toluene and ethanol (wherein the mixed solvent is 90mL of toluene and 45mL of ethanol), and then 0.03mol of Na is added2CO3Aqueous solution (2M), stirred for 1h under nitrogen and then 0.0001mol Pd (PPh) was added3)4Heating and refluxing for 15h at 100 ℃, sampling a sample point plate, and completely reacting. Naturally cooling, filtering, rotatably evaporating filtrate, and passing residue through a silica gel column to obtain the target product with the purity of 98.1 percent and the yield of 84.9 percent. Elemental analysis Structure (molecular formula C)52H36N2OS): theoretical value C, 84.75; h, 4.92; n, 3.80; o, 2.17; s, 4.35; test values are: c, 84.75; h, 4.91; n, 3.82; o, 2.17; s, 4.34. ESI-MS (M/z) (M +): theoretical value is 736.25, found 736.19.
Example 2: synthesis of compound 12:
compound 12 is prepared as in example 1, except that starting material A-2 is used in place of starting material A-1 and intermediate II-1 is used in place of intermediate I-1. Elemental analysis Structure (molecular formula C)51H36N4O): theoretical value C, 84.97; h, 5.03; n, 7.77; o, 2.22; test values are: c, 84.96; h, 5.03; n, 7.77; o, 2.23. HPLC-MS: the molecular weight of the material is 720.29, and the measured molecular weight is 720.35.
Example 3: synthesis of compound 33:
compound 33 was prepared as in example 1, except that starting material A-3 was used in place of starting material A-1 and intermediate III-1 was used in place of intermediate I-1. Elemental analysis Structure (molecular formula C)43H27N3OS): theoretical value C, 81.49; h, 4.29; n, 6.63; o, 2.52; s, 5.06; test values are: c, 81.48; h, 4.29; n, 6.63; o, 2.53; and S, 5.06. HPLC-MS: the molecular weight of the material is 633.19, and the measured molecular weight is 633.22.
Example 4: synthesis of compound 44:
compound 44 was prepared as in example 1, except that starting material A-4 was used in place of starting material A-1 and intermediate III-2 was used in place of intermediate I-1. Elemental analysis Structure (molecular formula C)41H24N2O2Se): theoretical value C, 75.11; h, 3.69; n, 4.27; o, 4.88; se, 12.04; test values are: c, 75.12; h, 3.69; n, 4.27; o, 4.87; se, 12.04. HPLC-MS: the molecular weight of the material is 656.10, and the measured molecular weight is 656.16.
Example 5: synthesis of compound 46:
compound 46 was prepared as in example 1, except that starting material A-5 was used in place of starting material A-1 and intermediate III-3 was used in place of intermediate I-1. Elemental analysis Structure (molecular formula C)46H34N2O2): theoretical value C, 85.42; h, 5.30; n, 4.33; o, 4.95; test values are: c, 85.42; h, 5.30; n, 4.32; and O, 4.96. HPLC-MS: the molecular weight of the material is 646.26, and the measured molecular weight is 646.29.
Example 6: synthesis of compound 52:
compound 52 was prepared as in example 1, except that starting material A-6 was used in place of starting material A-1 and intermediate I-2 was used in place of intermediate I-1. Elemental analysis Structure (molecular formula C)40H22N2O2SSe): theoretical value C, 71.32; h, 3.29; n, 4.16; o, 4.75; s, 4.76; se, 11.72; test values are: c, 71.32; h, 3.29; n, 4.15; o, 4.75; s, 4.76; se, 11.73. HPLC-MS: the molecular weight of the material is 674.06, and the measured molecular weight is 674.23.
Example 7: synthesis of compound 67:
compound 67 was prepared as in example 1, except that starting material A-7 was used in place of starting material A-1 and intermediate I-3 was used in place of intermediate I-1. Elemental analysis Structure (molecular formula C)41H23NOS3): theoretical value C, 76.73; h, 3.61; n, 2.18; o, 2.49; s, 14.99; test values are: c, 76.74; h, 3.61; n, 2.18; o, 2.49; s, 14.98. HPLC-MS: the molecular weight of the material is 641.09, and the measured molecular weight is 640.95.
Example 8: synthesis of compound 82:
compound 82 was prepared as in example 1, except that starting material A-8 was used in place of starting material A-1 and intermediate II-2 was used in place of intermediate I-1. Elemental analysis Structure (molecular formula C)53H32N2O2Se): theoretical value C, 78.80; h, 3.99; n, 3.47; o, 3.96; se, 9.77; test values are: c, 78.80; h, 3.99; n, 3.46; o, 3.97; se, 9.77. HPLC-MS: the molecular weight of the material is 808.16, and the measured molecular weight is 808.07.
Example 9: synthesis of compound 96:
compound 96 is prepared as in example 1, except that starting material A-9 is used in place of starting material A-1 and intermediate II-3 is used in place of intermediate I-1. Elemental analysis Structure (molecular formula C)62H40N2O2): theoretical value C, 88.13; h, 4.77; n, 3.32; o, 3.79; test values are: c, 88.12; h, 4.77; n, 3.33; o, 3.79. HPLC-MS: the molecular weight of the material is 844.31, and the measured molecular weight is 844.23.
Example 10: synthesis of compound 108:
the synthetic route is as follows:
compound 108 is prepared as in example 1, except that starting material A-10 is used in place of starting material A-1 and intermediate III-4 is used in place of intermediate I-1. Elemental analysis Structure (molecular formula C)48H30N4O2): theoretical value C, 82.98; h, 4.35; n, 8.06; o, 4.61; test values are: c, 82.98; h, 4.35; n, 8.06; and O, 4.61. HPLC-MS: the molecular weight of the material is 694.24, and the measured molecular weight is 694.26.
Example 11: synthesis of compound 130:
compound 130 is prepared as in example 1, except that starting material A-11 is used in place of starting material A-1 and intermediate III-5 is used in place of intermediate I-1. Elemental analysis Structure (molecular formula C)47H29N3OSSe): theoretical value C, 74.01; h, 3.83; n, 5.51; o, 2.10; s, 4.20; se, 10.35; test values are: c, 74.02; h, 3.83; n, 5.52; o, 2.10; s, 4.20; se, 10.33. HPLC-MS: the molecular weight of the material is 763.12, and the measured molecular weight is 763.04.
Example 12: synthesis of compound 132:
compound 132 was prepared as in example 1, except that starting material A-12 was used in place of starting material A-1 and intermediate III-6 was used in place of intermediate I-1. Elemental analysis Structure (molecular formula C)47H31N3O3): theoretical value C, 82.32; h, 4.56; n, 6.13; o, 7.00; test values are: c, 82.31; h, 4.56; n, 6.13; and O, 7.01.HPLC-MS: the molecular weight of the material is 685.24, and the measured molecular weight is 685.36.
Example 13: synthesis of compound 155:
compound 155 can be prepared as in example 1, except that starting material A-13 is used instead of starting material A-1 and intermediate II-4 is used instead of intermediate I-1. Elemental analysis Structure (molecular formula C)56H39N3O): theoretical value C, 87.36; h, 5.11; n, 5.46; o, 2.08; test values are: c, 87.37; h, 5.11; n, 5.45; and O, 2.08. HPLC-MS: the molecular weight of the material is 769.31, and the measured molecular weight is 769.28.
Example 14: synthesis of compound 168:
compound 168 can be prepared as in example 1, except that starting material A-14 is used instead of starting material A-1 and intermediate I-4 is used instead of intermediate I-1. Elemental analysis Structure (molecular formula C)47H27NO2SSe): theoretical value C, 75.39; h, 3.63; n, 1.87; o, 4.27; s, 4.28; se, 10.55; test values are: c, 75.38; h, 3.63; n, 1.87; o, 4.28; s, 4.28; se, 10.55. HPLC-MS: the molecular weight of the material is 749.09, and the measured molecular weight is 749.15.
Example 15: synthesis of compound 183:
compound 183 was prepared as in example 1, except that starting material A-15 was used in place of starting material A-1 and intermediate II-5 was used in place of intermediate I-1. Elemental analysis Structure (molecular formula C)42H25N3O3): theoretical value C, 81.41; h, 4.07; n, 6.78; o, 7.75; test values are: c, 81.42; h, 4.08; n, 6.78; and O,7.73. HPLC-MS: the molecular weight of the material is 619.19, and the measured molecular weight is 619.23.
Example 16: synthesis of compound 205:
(1) a500 mL three-necked flask was charged with 0.05mol of starting material J and 0.06mol of starting material K under nitrogen protection, dissolved in a mixed solvent (180mL of toluene and 90mL of ethanol), and then charged with 0.15mol of Na2CO3The aqueous solution (2M) was stirred under nitrogen for 1 hour, then 0.0005mol Pd (PPh) was added3)4Heating and refluxing for 15 hours at 100 ℃, sampling the sample, and completely reacting. Naturally cooling, filtering, rotatably evaporating filtrate, and passing through a silica gel column to obtain an intermediate T1 with HPLC purity of 94.8% and yield of 76.4%. Elemental analysis Structure (molecular formula C)20H13BrO2Se): theoretical value C, 54.08; h, 2.95; br, 17.99; o, 7.20; se, 17.78; test values are: c, 54.08; h, 2.96; br, 17.99; o, 7.20; se, 17.77. ESI-MS (M/z) (M)+): theoretical value is 443.93, found 443.82.
(2) Adding 0.03mol of intermediate T1 and 0.036mol of p-toluenesulfonic acid into a 250mL three-neck flask under the protection of nitrogen, dissolving the mixture in 100mL of toluene, heating to 100 ℃, and reacting for 15 hours; a sample point panel indicated no intermediate T1 remained and the reaction was complete; after the reaction is finished, adding a saturated sodium carbonate solution into the reaction system for quenching, extracting with ethyl acetate, separating, drying an organic phase with anhydrous sodium sulfate, decompressing and carrying out rotary evaporation until no fraction is produced, and passing the obtained crude product through a neutral silica gel column to obtain an intermediate T2 with the HPLC purity of 98.7% and the yield of 88.2%.
Elemental analysis Structure (molecular formula C)20H11BrOSe): theoretical value C, 56.37; h, 2.60; br, 18.75; o, 3.75; se, 18.53; test values are: c, 56.37; h, 2.60; br, 18.74; o, 3.75; se, 18.54. ESI-MS (M/z) (M)+): theoretical value is 425.92, found 425.87.
(3) Compound 205 can be prepared as in example 1, except that starting material A-16 is substituted for starting material A-1 and intermediate T2 is substituted for intermediateI-1. Elemental analysis Structure (molecular formula C)45H31NO2SSe): theoretical value C, 74.17; h, 4.29; n, 1.92; o, 4.39; s, 4.40; se, 10.83; test values are: c, 74.17; h, 4.30; n, 1.91; o, 4.40; s, 4.40; se, 10.82. HPLC-MS: the molecular weight of the material is 729.12, and the measured molecular weight is 729.18.
Example 17: synthesis of compound 213:
compound 213 is prepared as in example 1, except that starting material A-17 is used in place of starting material A-1 and intermediate I-5 is used in place of intermediate I-1. Elemental analysis Structure (molecular formula C)41H23NOSSe2): theoretical value C, 66.94; h, 3.15; n, 1.90; o, 2.17; s, 4.36; se, 21.47; test values are: c, 66.95; h, 3.15; n, 1.90; o, 2.17; s, 4.36; se, 21.46. HPLC-MS: the molecular weight of the material is 736.98, and the measured molecular weight is 737.05.
Example 18: synthesis of compound 221:
(1) a500 mL three-necked flask was charged with 0.05mol of starting material O and 0.06mol of starting material P under nitrogen protection, dissolved in a mixed solvent (180mL of toluene and 90mL of ethanol), and then charged with 0.15mol of Na2CO3The aqueous solution (2M) was stirred under nitrogen for 1 hour, then 0.0005mol Pd (PPh) was added3)4And heating and refluxing for 15 hours, sampling a sample point plate, and completely reacting. Naturally cooling, filtering, rotatably evaporating the filtrate, and passing through a silica gel column to obtain an intermediate Q1 with the HPLC purity of 95.4 percent and the yield of 75.2 percent. Elemental analysis Structure (molecular formula C)19H17BrO2): theoretical value C, 63.88; h, 4.80; br, 22.37; o, 8.96; measuringTest values are as follows: c, 63.88; h, 4.79; br, 22.37; o, 8.97. ESI-MS (M/z) (M)+): theoretical value is 356.04, found 356.19.
(2) Adding 0.03mol of intermediate Q1 and 0.036mol of p-toluenesulfonic acid into a 250mL three-neck flask under the protection of nitrogen, dissolving the mixture in 100mL of toluene, heating to 100 ℃, and reacting for 15 hours; a sample point panel indicated no intermediate Q1 remained and the reaction was complete; after the reaction is finished, adding a saturated sodium carbonate solution into the reaction system for quenching, extracting with ethyl acetate, separating, drying an organic phase with anhydrous sodium sulfate, decompressing and carrying out rotary evaporation until no fraction is produced, and passing the obtained crude product through a neutral silica gel column to obtain an intermediate Q2 with the HPLC purity of 96.1% and the yield of 86.8%.
Elemental analysis Structure (molecular formula C)19H15BrO): theoretical value C, 67.27; h, 4.46; br, 23.55; o, 4.72; test values are: c, 67.27; h, 4.46; br, 23.54; and O, 4.73. ESI-MS (M/z) (M)+): theoretical value is 338.03, found 337.94.
(3) Compound 221 can be prepared as described in example 1, except that starting material A-18 is used instead of starting material A-1 and intermediate Q2 is used instead of intermediate I-1. Elemental analysis Structure (molecular formula C)40H35NO2): theoretical value C, 85.53; h, 6.28; n, 2.49; o, 5.70; test values are: c, 85.52; h, 6.28; n, 2.49; and O, 5.71. HPLC-MS: the molecular weight of the material is 561.27, and the measured molecular weight is 561.35.
Example 19: synthesis of compound 224:
compound 224 was prepared as in example 1, except that starting material A-19 was used in place of starting material A-1 and intermediate I-6 was used in place of intermediate I-1. Elemental analysis Structure (molecular formula C)41H31NO2S): theoretical value C, 81.83; h, 5.19; n, 2.33; o, 5.32; s, 5.33; test values are: c, 81.83; h, 5.20; n, 2.33; o, 5.32; and S, 5.32. HPLC-MS: the molecular weight of the material is 601.21, and the measured molecular weight is 601.14.
Example 20: synthesis of compound 238:
compound 238 was prepared as in example 1, except that starting material A-20 was used in place of starting material A-1 and intermediate II-6 was used in place of intermediate I-1. Elemental analysis Structure (molecular formula C)56H34N2O3S): theoretical value C, 82.53; h, 4.21; n, 3.44; o, 5.89; s, 3.93; test values are: c, 82.53; h, 4.22; n, 3.44; o, 5.89; and S, 3.92. HPLC-MS: the molecular weight of the material is 814.23, and the measured molecular weight is 814.35.
The compound is used in a light-emitting device, has high glass transition temperature (Tg) and triplet state energy level (T1), and suitable HOMO and LUMO energy levels, and can be used as a host material of a light-emitting layer. The compounds prepared in the above examples of the present invention were tested for thermal properties, T1 energy level, and HOMO energy level, respectively, and the results are shown in table 4.
TABLE 4
Note: the triplet energy level T1 was measured by Hitachi F4600 fluorescence spectrometer under the conditions of 2X 10- 5A toluene solution of mol/L; the glass transition temperature Tg is determined by differential scanning calorimetry (DSC, DSC204F1 DSC, Germany Chi corporation), the heating rate is 10 ℃/min; the highest occupied molecular orbital HOMO energy level was tested by the ionization energy test system (IPS-3), which is an atmospheric environment.
The data in the table show that the compound has high glass transition temperature, can improve the phase stability of the material film, and further improves the service life of the device; the compound contains an electron donor and an electron acceptor, so that electrons and holes of an OLED device using 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 OLED device are improved. Meanwhile, the material has a proper HOMO energy level, so that the problem of carrier injection can be solved, and the voltage of a device can be reduced; therefore, after the organic material is applied to a light emitting layer of an OLED device, the light emitting efficiency of the device can be effectively improved, and the service life of the device can be effectively prolonged.
Preparing a device:
the effect of the synthesized compound of the present invention as a material for a light emitting layer in a device is explained in detail by device examples 1 to 20 and device comparative example 1 below. Device examples 2-20 and device comparative example 1 compared with device example 1, the manufacturing process of the device was completely the same, and the same substrate material and electrode material were used, and the film thickness of the electrode material was also kept the same, except that the material of the light emitting layer in the device was changed. The device stack structure is shown in table 5, and the performance test results of each device are shown in tables 6 and 7.
Device example 1
As shown in fig. 1, an electroluminescent device is specifically manufactured by the following steps:
a) cleaning the ITO anode layer 2 on the transparent substrate layer 1, respectively ultrasonically cleaning the ITO anode layer 2 with deionized water, acetone and ethanol for 15 minutes, and then treating the ITO anode layer 2 in a plasma cleaner for 2 minutes; b) evaporating a hole injection layer material HAT-CN on the ITO anode layer 2 in a vacuum evaporation mode, wherein the thickness of the hole injection layer material HAT-CN is 10nm, and the hole injection layer material HAT-CN is used as a hole injection layer 3; c) evaporating a hole transport layer material compound HT-1 on the hole injection layer 3 in a vacuum evaporation mode, wherein the thickness of the hole transport layer material compound HT-1 is 60nm, and the hole transport layer material compound is a hole transport layer 4; d) evaporating a compound EB-1 on the hole transport layer 4 in a vacuum evaporation mode, wherein the thickness of the compound EB-1 is 10nm, and the layer is an electron blocking layer 5; e) evaporating a light-emitting layer 6 on the electron blocking layer 5 in a vacuum evaporation mode, wherein the main material is the compound 2, the doping material is BD, and the mass ratio of the compound 2 to the BD is 95:5, and the thickness of the compound 2 to the BD is 35 nm; f) evaporating hole blocking/electron transporting materials ET-1 and Liq on the light emitting layer 6 in a vacuum evaporation mode, wherein the mass ratio of the hole blocking/electron transporting materials ET-1 to Liq is 1:1, the thickness of the hole blocking/electron transporting materials ET-1 to Liq is 35nm, and the layer is used as a hole blocking/electron transporting layer 7; g) vacuum evaporating an electron injection layer LiF with the thickness of 1nm on the hole blocking/electron transport layer 7, wherein the layer is an electron injection layer 8; h) on the electron injection layer 8, cathode Al (100nm) was vacuum-evaporated, and this layer was a cathode reflective electrode layer 9.
After the electroluminescent device was fabricated according to the above procedure, IVL data and light decay life of the device were measured, and the results are shown in table 6. The molecular structural formula of the related material is shown as follows:
the device examples 2 to 20 and the comparative example 1 were completely the same as those of the device example 1 in terms of the manufacturing process, 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 used for the light-emitting layer was different. See table 5 for specific data.
TABLE 5
The efficiency and lifetime data for each of the examples and comparative examples are shown in table 6.
TABLE 6
As can be seen from the device data results of table 6, the organic light emitting device of the present invention achieves a greater improvement in both efficiency and lifetime over OLED devices of known materials.
In order to compare the efficiency attenuation of different devices under high current density, the efficiency attenuation coefficient phi is defined and expressed, and the efficiency attenuation coefficient phi represents that the driving current is 100mA/cm2The larger the phi value is, the more serious the efficiency roll-off of the device is, and otherwise, the problem of rapid attenuation of the device under high current density is controlled. The device examples 1 to 20 and comparative example 1 were each measured for the attenuation coefficient of efficiency φ, and the results are shown in Table 7:
TABLE 7
From the data in table 7, it can be seen from the comparison of the efficiency roll-off coefficients of the examples and the comparative examples that the organic light emitting device of the present invention can effectively reduce the efficiency roll-off.
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, 5 and 9 and the device comparative example 1 at the temperature of-10-80 ℃, and the obtained results are shown in the table 8 and the figure 2.
TABLE 8
As can be seen from the data in table 8 and fig. 2, device examples 1, 5, and 9 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 during the temperature increase process.
Claims (6)
1. A compound taking a quinolinone derivative as a core is characterized in that the structure of the compound is shown as a general formula (1):
in the general formula (1), a represents a structure
X represents oxygen atom, sulfur atom, selenium atom, -C (R)1)(R2) -or-N (R)3)-；
The R is1～R2Each independently represents one of methyl, phenyl or pyridyl;
the R is3Represented as one of phenyl or furyl;
wherein R represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted furyl group;
b and c each independently represent 0 or 1, and b + c is 1;
Rbrepresented by a structure represented by general formula (2) or general formula (3):
the general formula (2) is represented by:
the general formula (3) is represented by:
the general formula (2) and the general formula (3) are connected with a benzene ring in the general formula (1) through a single bond;
wherein Ar represents substituted or unsubstituted C6An arylene group;
the substituent of the substitutable group is one or more selected from methyl, isopropyl and tert-butyl.
2. The compound according to claim 1, wherein the specific formula of the general formula (1) is:
3. A compound taking quinolinone derivatives as cores is characterized in that the specific structural formula of the compound is as follows:
4. An organic electroluminescent element comprising at least one functional layer containing the quinolinone derivative-centered compound according to claim 1.
5. The organic electroluminescent device according to claim 4, comprising a light-emitting layer, wherein the light-emitting layer contains the quinolinone derivative-centered compound according to claim 1.
6. A lighting or display element, characterized in that it comprises an organic electroluminescent device as claimed in claim 4 or 5.
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| CN112979687B (en) * | 2021-03-01 | 2023-07-18 | 深圳大学 | Thermal activation delay fluorescent material and preparation method and application thereof |
| CN113121560A (en) * | 2021-03-29 | 2021-07-16 | 北京大学深圳研究生院 | Benzothienobenzo five-membered heterocyclic material and preparation method and application thereof |
| CN114736212A (en) * | 2022-04-29 | 2022-07-12 | 临沂大学 | Furo [3,2-b ] indole derivative and synthetic method and application thereof |
| CN114685517B (en) * | 2022-05-05 | 2023-10-24 | 武汉天马微电子有限公司 | Organic compound containing nitrogen heteroaromatic ring and electroluminescent application thereof |
| WO2023247345A1 (en) | 2022-06-20 | 2023-12-28 | Merck Patent Gmbh | Heterocycles for photoelectric devices |
| WO2023247338A1 (en) | 2022-06-20 | 2023-12-28 | Merck Patent Gmbh | Organic heterocycles for photoelectric devices |
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