CN117088918A - Phosphorescent iridium complex, light-emitting layer, organic electroluminescent device and electronic equipment - Google Patents

Phosphorescent iridium complex, light-emitting layer, organic electroluminescent device and electronic equipment Download PDF

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CN117088918A
CN117088918A CN202311223194.7A CN202311223194A CN117088918A CN 117088918 A CN117088918 A CN 117088918A CN 202311223194 A CN202311223194 A CN 202311223194A CN 117088918 A CN117088918 A CN 117088918A
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晏志平
毕海
王悦
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Jihua Hengye Foshan Electronic Materials Co ltd
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Abstract

The iridium complex has high photoluminescence quantum yield and short excited state life. The device prepared by the iridium complex has excellent performance, high external quantum efficiency, low starting voltage and low efficiency roll-off, and has potential application value in the field of OLED illumination and display.

Description

Phosphorescent iridium complex, light-emitting layer, organic electroluminescent device and electronic equipment
Technical Field
The application belongs to the field of organic electroluminescence, and relates to a phosphorescent iridium complex, a luminescent layer, an organic electroluminescent device and electronic equipment.
Background
Since this century, the rapid development of information technology has greatly pushed the revolution of society, changing people's lifestyle. The capturing, processing and displaying of information has been closely related to human acquisition of knowledge and improvement of quality of life. Studies have shown that 70% of the pathways for obtaining knowledge are from vision, and thus vision-related display technologies hold a significant position. In 2000, the display technology of the Organic Light Emitting Diode (OLED) has been known as the third generation display technology, and the Organic Light Emitting Diode (OLED) has the advantages of self-luminescence, high brightness, high efficiency, high resolution, wide viewing angle, ultra-thin display, capability of preparing flexible devices, and the like, so that the organic light emitting diode has become a focus of attention.
With the development of photoelectric materials and device preparation technologies, OLEDs have taken up a great market in the field of small-size displays such as mobile phones, and have also made great progress in large-size displays such as televisions. The materials of each layer in the OLED device can be divided into an electrode material, a light emitting material, a carrier injection material and a carrier transport material according to their functions, and the use of materials with different functions will greatly determine the device performance (light emitting efficiency, efficiency roll-off, lifetime, etc.) of the OLED. The luminescent material is the core of the OLED, and compared with the traditional fluorescent luminescent material, phosphorescent complexes (such as ruthenium, rhodium, iridium, platinum and the like) with heavy metal centers can obtain excitons of a singlet state and a triplet state simultaneously due to a strong spin-orbit coupling effect, and the theoretical internal quantum efficiency can reach 100%. Among all phosphorescent materials, iridium complexes are the most potential organic electroluminescent materials: the iridium atomic number is larger, the strong spin orbit coupling effect is achieved, and the phosphorescence emission performance of the complex is greatly improved; the neutral complex formed by the trivalent iridium ions and the ligand has good thermal stability and film forming performance, and is beneficial to manufacturing OLED devices; in addition, the iridium complex has the advantages of short service life of an excited state, high luminous efficiency, easy adjustment of luminous color and the like. However, to meet the needs of display and lighting applications, low turn-on voltage (< 2.8V), high External Quantum Efficiency (EQE) and low efficiency roll-off are still necessary.
Carbazole (Cz) derivatives have good hole injection and hole transport properties, and thus are widely used for hole transport and host materials of organic light emitting devices. Of course, complexes of carbazole moieties with high hole mobility with Ir (III) have proven to be a good choice for efficient vacuum evaporation of OLEDs. The previously reported carbazolyl iridium complex structure is not limited due to free relaxation of the groups attached to carbazole nitrogen, which increases the non-radiative transition rate of the molecule and is unfavorable for the luminescence process.
Disclosure of Invention
Aiming at the defects of the prior art, the application aims to provide a phosphorescence iridium complex, a light-emitting layer, an organic electroluminescent device and electronic equipment.
In order to achieve the aim of the application, the application adopts the following technical scheme:
in one aspect, the present application provides a phosphorescent iridium complex having a structure represented by formula I or formula II:
wherein m=an integer of 1 to 3; l is a bidentate chelating auxiliary ligand containing lone pair electrons or a second main ligand containing lone pair electrons;
X 1 ～X 11 each independently is-CR 1 ～-CR 11 Or nitrogen atom, R 1 ～R 11 Each independently is a hydrogen atom, a deuterium atom, a fluorine atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkynyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 ring-forming carbon atoms, an amino group, an alkoxy group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, a fluoroalkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 50 ring-forming carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an arylthio group having 6 to 50 ring-forming carbon atoms, -Si (R) 101 )(R 102 )(R 103 )、-N(R 104 )(R 105 ) One of aryl groups with ring carbon number of 6-50 and heteroaryl groups with ring carbon number of 5-50;
wherein X is 1 ～X 11 Up to four N atoms, adjacent positions not being simultaneously N atoms, and adjacent substituents being optionally joined to form a ring;
y is-C (R) 106 )(R 107 )、-NR 108 、-Si(R 109 )(R 110 ) One of O, S, se;
R 101 ～R 110 each independently of the otherIs one of hydrogen atom, alkyl group with 1-20 carbon atoms, cycloalkyl group with 3-20 ring-forming carbon atoms, aryl group with 6-50 ring-forming carbon atoms and heteroaryl group with 5-50 ring-forming carbon atoms.
Preferably, the phosphorescent iridium complex has a structure shown in formula III and formula IV:
wherein the condensed position of the ring A is any condensed position on the connected ring, and the ring A is selected from any one of the formulas (1) to (6):
wherein, 1 and 2,3 and 4, 5 and 6, 7 and 8, 9 and 10, 11 and 12 respectively represent in pairs the two ring-forming carbon atoms to which ring a is bonded; x is X 12 ～X 31 Each independently is-CR 12 ～-CR 31 Or a nitrogen atom; r is R 16 ～R 35 Each independently is a hydrogen atom, a deuterium atom, a fluorine atom, a halogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkynyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 ring-forming carbon atoms, an amino group, an alkoxy group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, a fluoroalkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 50 ring-forming carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an arylthio group having 6 to 50 ring-forming carbon atoms, -Si (R) 101 )(R 102 )(R 103 )、-N(R 104 )(R 105 ) One of aryl groups with ring carbon number of 6-50 and heteroaryl groups with ring carbon number of 5-50; y and Z are each independently-C (R 106 )(R 107 )、-NR 108 、-Si(R 109 )(R 110 ) One of O, S, se, R 101 ～R 110 Each independently represents one of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 ring-forming carbon atoms, an aryl group having 6 to 50 ring-forming carbon atoms, and a heteroaryl group having 5 to 50 ring-forming atoms.
Preferably, the structure of L in formulas I and II is as shown in formula (L1):
wherein, single bond means forming covalent bond with metal center, arrow means forming coordination bond;
X 32 and X 36 Each independently is-NR 32 、-NR 36 One of O, S or Se; x is X 33 And X 35 Each independently is-C (Si) R 33 、C(Si)R 35 、-P(R 111 )(R 112 )、P(R 113 )(R 114 ) Or one of the nitrogen atoms; x is X 34 Selected from-CR 34 Or a nitrogen atom; r is R 32 ～R 36 And R is 111 ～R 114 Each independently is a hydrogen atom, a deuterium atom, a fluorine atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkynyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 ring-forming carbon atoms, an amino group, an alkoxy group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, a fluoroalkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 50 ring-forming carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an arylthio group having 6 to 50 ring-forming carbon atoms, -Si (R) 101 )(R 102 )(R 103 )、-N(R 104 )(R 105 ) One of aryl groups with ring carbon number of 6-50 and heteroaryl groups with ring atom number of 5-50.
Preferably, the structure of L in formulas I and II is as shown in formula (L2):
arrows indicate formation of coordination bonds;
wherein X is 37 One selected from carboxyl, thiocarboxyl, dithiocarboxyl, sulfonic acid group, phosphoric acid group, aryl group, imidazolyl group, triazole group and oxadiazole group; x is X 38 Is a nitrogen atom or a carbon atom; r is R 115 Is hydrogen atom, deuterium atom, fluorine atom, halogen atom, cyano group, alkyl group with 1-20 carbon atoms, alkenyl group with 1-20 carbon atoms1 to 20 alkynyl groups, cycloalkyl groups having 3 to 20 ring-forming carbon atoms, amino groups, alkoxy groups having 1 to 20 carbon atoms, fluoroalkyl groups having 1 to 20 carbon atoms, fluoroalkoxy groups having 1 to 20 carbon atoms, aryloxy groups having 6 to 50 ring-forming carbon atoms, alkylthio groups having 1 to 20 carbon atoms, arylthio groups having 6 to 50 ring-forming carbon atoms, -Si (R) 101 )(R 102 )(R 103 )、-N(R 104 )(R 105 ) One of aryl groups with ring carbon number of 6-50 and heteroaryl groups with ring atom number of 5-50.
Preferably, the structure of L in formulas I and II is as shown in formula (L3):
wherein, single bond means forming covalent bond with metal center, arrow means forming coordination bond;
R 116 ～R 118 each independently is a hydrogen atom, a deuterium atom, a fluorine atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkynyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 ring-forming carbon atoms, an amino group, an alkoxy group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, a fluoroalkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 50 ring-forming carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an arylthio group having 6 to 50 ring-forming carbon atoms, -Si (R) 101 )(R 102 )(R 103 )、-N(R 104 )(R 105 ) One of aryl groups with ring carbon number of 6-50 and heteroaryl groups with ring atom number of 5-50.
Preferably, the L is any one of the following structures:
the single bond indicates the formation of a covalent bond with the metal center and the arrow indicates the formation of a coordinate bond.
Considering the phosphorescent iridium complexes obtained by the present application comprising different combinations of tri-ligands and hetero-ligands, the present application includes, but is not limited to, complexes of yellow-green to deep-red light having a maximum emission wavelength in the range of 530-670nm:
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the iridium complexes described in the present application can be prepared by conventional methods, for example, by reacting the primary ligand with IrCl 3 Refluxing in a mixed solution of ethoxyethanol and water for 20 hours in a ratio of 2:1, cooling and filtering to obtain a chlorine bridge complex of iridium; then the chloro-bridge complex of iridium and auxiliary complex of corresponding structureThe iridium complex crude product is obtained by reacting the iridium complex in a solvent at 100-200 ℃, the pure product is obtained by column chromatography, and the luminescent material meeting the requirements of preparing devices is further obtained by sublimation and purification under the vacuum condition.
The iridium complex molecule carbazolothiophene and other groups provided by the application are beneficial to regulating and controlling the luminescent color of the material, can effectively regulate and control the carrier transmission performance, increase the stability of the material, improve the efficiency of the device and reduce the roll-off of the efficiency. The iridium complex provided by the application has very high photoluminescence quantum yield and short excited state life. The device prepared by the iridium complex has excellent performance, high external quantum efficiency, low starting voltage and low efficiency roll-off, and has potential application value in the field of OLED illumination and display.
In a second aspect, the present application provides a light-emitting layer comprising a phosphorescent iridium complex as described in the first aspect.
In a third aspect, the present application provides an organic electroluminescent device comprising a light-emitting layer comprising a phosphorescent iridium complex as described in the first aspect.
Preferably, the organic electroluminescent device comprises a substrate, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a metal electrode from bottom to top.
In a fourth aspect, the present application provides an electronic device comprising an organic electroluminescent device as described in the third aspect.
Compared with the prior art, the application has the following beneficial effects:
according to the application, the energy level structure of the iridium complex is reasonably regulated, so that the phosphorescence generated by the iridium complex mainly comprises LC state emission, and the contribution of the MLCT emission state is reduced. Unlike the traditional iridium complex based on LC emission state, the structure such as indolothiophene enhances the rigidity of the structure, inhibits the non-radiative transition of the complex to a certain extent, and enhances the luminescence performance of the complex. OLED devices prepared from the luminescent materials show higher external quantum efficiency, slow efficiency attenuation and lower starting voltage, and have potential application value in the field of OLED illumination and display.
Drawings
Fig. 1 is a schematic structural diagram of an organic electroluminescent device according to the present application, wherein 1 is a substrate, 2 is a hole injection layer, 3 is a hole transport layer, 4 is a light emitting layer, 5 is an electron transport layer, 6 is an electron injection layer, and 7 is a metal electrode.
Detailed Description
The technical scheme of the application is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the application and are not to be construed as a specific limitation thereof.
The chemical reagent raw materials involved in the embodiments of the present application are all purchased from related material manufacturers.
EXAMPLE 1 yellow phosphorescent Complex Ir-13
The synthesis route is as follows:
carbazole (10.0 g,60mmol,1.0 eq), 2, 3-dibromothiophene (19.0 g,180mmol,3.0 eq), anhydrous copper sulfate (CuSO) 4 0.5g,3.0mmol,0.05 eq), potassium carbonate (K 2 CO 3 16.5g,120mmol,2.0 eq) under nitrogen at 200℃for 5 hours. After the reaction was completed, the temperature was lowered to room temperature, a sample was prepared by adding silica gel, and the crude product was purified by column chromatography using petroleum ether: further purification was performed with methylene chloride (80:20). 15.7g of pale yellow solid P-1 was obtained in 80% yield. 1 H NMR (500 MHz, deuterated chloroform) δ8.55 (dd, j=7.3, 1.6hz, 1H), 8.24-8.15 (m, 1H), 7.52 (dd, j=7.3, 1.6hz, 1H), 7.44-7.37 (m, 1H), 7.23-7.14 (m, 3H), 7.11 (td, j=7.4, 1.6hz, 1H), 7.07 (d, j=7.5 hz, 1H), 6.98 (d, j=7.5 hz, 1H).
Intermediate P-1 (13.1 g,40mmol,1.0 eq) was reacted under nitrogen with palladium (II) acetate ([ Pd (OAc)) 2 ]0.9g,4mmol,0.1 eq), tri-tert-butylphosphine (tBu) 3 P,1.6g,8mmol,0.2 eq), cesium carbonate (Cs 2 CO 3 A mixture of 26.0g,80mmol,2.0 eq) was dispersed in 80mL of N, N' -dimethylacetamide (DMAc) and reacted at 140℃for 12 hours. After the reaction is finished, a large amount of water is added, the filter cake is leached for 2 times by water, ethanol and petroleum ether respectively, and 7.9g of white solid P-2 is obtained after drying, and the yield is 80%. 1 H NMR (500 MHz, deuterated chloroform) δ8.55 (dd, j=7.3, 1.6hz, 1H), 8.24-8.15 (m, 1H), 7.52 (dd, j=7.3, 1.6hz, 1H), 7.44-7.37 (m, 1H), 7.23-7.14 (m, 3H), 7.11 (td, j=7.4, 1.6hz, 1H), 7.07 (d, j=7.5 hz, 1H), 6.98 (d, j=7.5 hz, 1H).
Intermediate P-2 (7.9 g,32mmol,1.0 eq) was dispersed in 100mL of methylene chloride under nitrogen atmosphere, and N-bromosuccinimide (NBS, 6.8g,38.4mmol,1.2 eq) was added in 6 portions at room temperature and reacted for 5 hours. After the reaction is finished, concentrating a dichloromethane solvent, adding a large amount of methanol for ultrasonic treatment, precipitating white precipitate, directly performing suction filtration to obtain white precipitate, washing 3 times with methanol, and drying in a vacuum drying oven to obtain 9.9g of product P-3, wherein the yield is 94%. 1 H NMR (500 MHz, deuterated chloroform) delta 8.46-7.93 (m, 2H), 7.72 (dd, j=7.5, 1.4hz, 1H), 7.67-7.24 (m, 1H), 7.24-7.13 (m, 2H), 7.10 (t, j=7.5 hz, 1H), 6.88 (s, 1H).
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Intermediate P-3 (9.7 g,30mmol,1.0 eq), pinacol biborate (Bpin, 14.0g,33mmol,1.1 eq), dichloro [1,1' -bis (diphenylphosphine) ferrocene]Palladium (Pd (dppf) Cl) 2 1.1g,1.5mmol,0.05 eq), potassium acetate (CH 3 COOK,11.8g,120mmol,4.0 eq) was dispersed in 300mL dioxane (1, 4-dioxane), and after 3 times of nitrogen purging, the reaction was refluxed for 12h. Cooling to room temperature after the raw materials are reacted completely, adding water into the reaction solution for quenching, and extracting for 3 times by using dichloromethane and water. The organic phases were combined and concentrated on a column and the crude product was chromatographed on column using petroleum ether: further purification was performed with methylene chloride (80:20). 9.5g of white color was obtainedSolid P-4, yield 85%. 1 H NMR (500 MHz, deuterated chloroform) delta 8.23-8.14 (m, 2H), 7.72 (dd, j=15.0, 2.9hz, 1H), 7.43-7.36 (m, 1H), 7.25-7.14 (m, 2H), 7.10 (t, j=14.9 hz, 1H), 6.90 (s, 1H), 1.14 (s, 12H).
Intermediate P-4 (7.6 g,20mmol,1.0 eq), 2-bromopyridine (3.7 g,24mmol,1.2 eq), tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 1.1g,1.0mmol,0.05 eq), potassium carbonate (K 2 CO 3 4.1g,30mmol,1.5 eq) in 50mL Tetrahydrofuran (THF) and 15mL water, nitrogen was purged 3 times and then the reaction was refluxed for 12h. Cooling to room temperature after the raw materials are reacted completely, adding water into the reaction solution for quenching, and extracting for 3 times by using dichloromethane and water. The organic phases were combined and concentrated on a column and the crude product was chromatographed on column using petroleum ether: further purification was performed with methylene chloride (50:50). 6.0g of white solid L1 was obtained in a yield of 90%. 1 H NMR (500 MHz, deuterated chloroform) δ8.47 (dd, j=7.5, 1.4hz, 1H), 8.24-8.14 (m, 2H), 7.81 (td, j=7.5, 1.5hz, 1H), 7.76-7.67 (m, 2H), 7.44-7.39 (m, 1H), 7.37 (s, 1H), 7.24-7.14 (m, 3H), 7.10 (t, j=7.5 hz, 1H).
Iridium trichloride (IrCl) 3 1.4g,4.8mmol,1 eq) and ligand L1 (3.0 g,10mmol,2.1 eq) were dispersed in 30mL ethylene glycol ethyl ether (EtOH) 2 CH 2 OH) and 10mL of water, and after 3 times of nitrogen gas pumping, reflux reaction is carried out for 12h. After the reaction is finished, the temperature is reduced to room temperature, a large amount of water is added, suction filtration is carried out, a filter cake is collected, petroleum ether is used for leaching for 2 times, 3.8g of orange solid P-5 is obtained after drying, and the yield is 95%.
P-5 (1.7 g,1.0mmol,1.0 eq.) auxiliary ligand 3, 7-diethylnonane-4, 6-dione (0.6 g,3.0mmol,3.0 eq.) potassium carbonate (K 2 CO 3 0.69g,5.0mmol,5.0 eq) in 20mL ethylene glycol ethyl ether (EtOH) 2 CH 2 OH), nitrogen was purged 3 times, and then reacted at 120℃for 12 hours. After the reaction is finished, the temperature is reduced to room temperature, a large amount of water is added, after the extraction is carried out for 3 times by methylene dichloride, an organic phase is collected, and then the separation and the purification are carried out by column chromatography and chromatography, petroleum ether:dichloromethane (20:80). 1.1g of orange iridium complex Ir-13 was obtained in a yield of 50%. 1 H NMR (500 MHz, deuterated chloroform) δ9.25 (t, j=7.5 hz, 2H), 8.59 (dd, j=7.5, 1.4hz, 2H), 8.24-8.14 (m, 4H), 7.72 (dd, j=7.5, 1.4hz, 2H), 7.46-7.35 (m, 2H), 7.30 (dd, j=7.5, 1.6hz, 2H), 7.22-7.14 (m, 4H), 7.10 (t, j=7.5 hz, 2H), δ5.05 (s, 1H), 2.15-1.90 (m, 2H), 1.65-1.34 (m, 8H), 0.94 (t, j=13.3 hz, 12H).
The compounds in table 1 were prepared with reference to the above compound preparation methods, and elemental analysis and molecular weight analysis of the compounds were performed, and the results are shown in table 1.
TABLE 1 elemental analysis and molecular weight analysis of light-emitting Compounds of examples 1 to 11
Compounds of formula (I) Elemental analysis (%) Molecular weight
Example 1 Ir-1 C,65.33；H,2.88；N,7.50 1162.20
Example 2 Ir-5 C,67.80；H,4.50；N,6.32 1330.40
Example 3 Ir-13 C,62.95；H,4.32；N,5.40；O,3.05 1050.26
Example 4 Ir-20 C,63.40；H,3.60；N,5.40；O,3.16 1042.30
Example 5 Ir-25 C,60.51；H,4.04；N,5.79；O,3.40 972.59
Example 6 Ir-30 C,63.58；H,3.20；N,5.40；O,3.10 1038.16
Example 7 Ir-40 C,65.66；H,3,90；N,6.15 916.50
Example 8 Ir-50 C,70.88；H,4.20；N,5.40；O,1.52 1052.38
Example 9 Ir-55 C,65.77；H,4.29；N,4.87；O,2.78 1150.35
Example 10 Ir-58 C,63.74；H,3.91；N,4.44；O,2.53 1262.24
Example 11 Ir-59 C,60.96；H,3.90；N,4.82；O,2.75 1162.25
Example 12 Ir-62 C,62.69；H,4.01；N,4.96；O,5.66 1130.28
Example 13 Ir-64 C,65.28；H,4.04；N,4.99；O,2.85 1122.30
Example 14 Ir-66 C,65.28；H,4.04；N,4.99；O,2.85 1122.35
Example 15 Ir-69 C,65.77；H,4.29；N,4.87；O,2.78 1150.50
Example 16 Ir-72 C,60.96；H,3.90；N,4.82；O,2.75 1162.35
Example 17 Ir-75 C,64.33；H,5.20；N,4.87；O,2.80 1150.40
Example 18 Ir-79 C,67.22；H,4.29；N,4.87；O,2.81 1150.33
Example 19 Ir-81 C,66.55；H,5.57；N,6.19；O,4.32 1356.80
Example 20 Ir-85 C,69.55；H,4.79；N,4.37；O,2.63 1282.60
Example 21 Ir-88 C,58.51；H,2.71；N,7.55；O,2.78 1152.20
Example 22 Ir-90 C,64.88；H,3.91；N,4.50；O,2.53 1262.28
Example 23 Ir-92 C,68.22；H,5.22；N,4.70；O,2.88 1375.20
Example 24 Ir-95 C,57.14；H,3.41；N,3.86；O,2.21 1450.80
Example 25 Ir-99 C,66.32；H,4.18；N,9.48；O,2.88 1182.80
Example 26 Ir-104 C,69.82；H,4.93；N,8.28 1231.80
Example 27 Ir-105 C,65.95；H,3.16；N,8.55 1147.80
Device example 1
The device structure includes, as shown in fig. 1, a substrate 1, a hole injection layer 2, a hole transport layer 3, a light emitting layer 4, an electron transport layer 5, an electron injection layer 6, and a metal electrode 7 in this order from bottom to top.
The transparent ITO glass is used as a substrate for preparing the electroluminescent device, firstly, the substrate is treated by 5% ITO washing liquid for 30min in an ultrasonic way, then distilled water (2 times), acetone (2 times) and isopropanol (2 times) are sequentially washed in an ultrasonic way, and finally, the ITO glass is stored in the isopropanol. Each time useBefore, the ITO glass surface is carefully wiped by acetone cotton balls and isopropanol cotton balls, and after the isopropanol is washed, the ITO glass surface is dried, and then O is used 2 Plasma (Plasma) treatment for 5min under conditions of chamber pressure of 100mTorr, RF power of 7W, gas flow rate of 100cm 3 min -1 . The preparation of the device is completed by vacuum coating equipment by adopting a vacuum evaporation process, and when the vacuum degree of a vacuum evaporation system reaches 5 multiplied by 10 -4 And starting evaporation when Pa is lower, wherein the deposition rate is measured by an Saint film thickness meter, and sequentially depositing various organic layers, liF electron injection layers and metal Al electrodes on ITO glass by using a vacuum evaporation process (the specific device structure is shown in the following application examples). The characteristics of current, voltage, brightness, luminescence spectrum and the like of the device are synchronously tested by adopting a PR655 spectrum scanning luminance meter and a Keithley K2400 digital source meter system, and the performance test of the device is carried out in air. The materials used for each layer are as follows.
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In the organic electroluminescent device, HATCN is a hole injection layer, TAPC is a hole transport layer, tmPyPB is an electron transport layer, and LiF is an electron injection layer. The EML represents a light-emitting layer, the light-emitting layer takes 26DCzPPy as a main body, the light-emitting compound (Ir-13) prepared by the method is taken as a guest material, and the doping weight percentage of the light-emitting compound in the host material is 8%. The electroluminescent device structure is [ ITO/HATCN (6 nm)/TAPC (50 nm)/EML (20 nm)/TmPyPB (60 nm)/LiF (1 nm)/Al (100 nm) ].
Device examples 2 to 27
The procedure and conditions were the same as in device example 1, except that light-emitting compound (Ir-1) was used as the guest material of the light-emitting layer.
The performance of the organic electroluminescent device prepared by the embodiment of the device is tested under the same condition, and the characteristics of current, voltage, brightness, luminescence spectrum and the like of the device are synchronously tested by adopting a PR655 spectrum scanning luminance meter and a Keithley K2400 digital source meter system, and the performance test of the device is carried out in air. The performance test results are shown in table 2:
table 2 electroluminescent device performance test
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As can be seen from Table 2, the phosphorescent iridium complex of the application enables the electroluminescent device to have lower driving voltage (lower than 2.8V), the external quantum efficiency of the device is up to more than 22%, and the brightness is 1000cd m -2 The external quantum efficiency of the device can reach more than 18 percent. As can be seen by comparison with the results of the comparison (Niu Zhi-gansetc, iridium (III) complexes adopting thienylpyridine derivatives for yellow-to-deep red OLEDs with low efficiency roll-off, dyes and Pigments 2019,162,863), after the absence of the carbazole-structure retaining ring, (thp) 2 Ir (tpip) exhibits a higher starting voltage (3.9V) and lower external quantum efficiency (11.3%), illustrating the beneficial effects of the structure of the present application.
The applicant states that the phosphorescent iridium complex, the light-emitting layer, the organic electroluminescent device and the electronic device of the present application are described by the above embodiments, but the present application is not limited to the above embodiments, i.e., it does not mean that the present application must be implemented depending on the above embodiments. It should be apparent to those skilled in the art that any modification of the present application, equivalent substitution of selected raw materials, addition of auxiliary components, selection of specific modes, etc. fall within the scope of the present application and the scope of disclosure.

Claims (10)

1. A phosphorescent iridium complex, characterized in that the phosphorescent iridium complex has a structure represented by formula I or formula II:
wherein m=an integer of 1 to 3; l is a bidentate chelating auxiliary ligand containing lone pair electrons or a second main ligand containing lone pair electrons;
X 1 ～X 11 each independently is-CR 1 ～-CR 11 Or nitrogen atom, R 1 ～R 11 Each independently is a hydrogen atom, a deuterium atom, a fluorine atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkynyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 ring-forming carbon atoms, an amino group, an alkoxy group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, a fluoroalkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 50 ring-forming carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an arylthio group having 6 to 50 ring-forming carbon atoms, -Si (R) 101 )(R 102 )(R 103 )、-N(R 104 )(R 105 ) One of aryl groups with ring carbon number of 6-50 and heteroaryl groups with ring carbon number of 5-50;
wherein X is 1 ～X 11 Up to four selected from the group consisting of N atoms, adjacent positions being not simultaneously N atoms, and adjacent substituents optionally being joined to form a ring;
y is-C (R) 106 )(R 107 )、-NR 108 、-Si(R 109 )(R 110 ) One of O, S, se;
R 101 ～R 110 each independently represents one of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 ring-forming carbon atoms, an aryl group having 6 to 50 ring-forming carbon atoms, and a heteroaryl group having 5 to 50 ring-forming atoms.
2. The phosphorescent iridium complex according to claim 1, wherein the phosphorescent iridium complex has structures represented by formula III and formula IV:
wherein the condensed position of the ring A is any condensed position on the connected ring, and the ring A is selected from any one of the formulas (1) to (6):
wherein, 1 and 2,3 and 4, 5 and 6, 7 and 8, 9 and 10, 11 and 12 respectively represent in pairs the two ring-forming carbon atoms to which ring a is bonded; x is X 12 ～X 31 Each independently is-CR 12 ～-CR 31 Or a nitrogen atom; r is R 16 ～R 35 Each independently is a hydrogen atom, a deuterium atom, a fluorine atom, a halogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkynyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 ring-forming carbon atoms, an amino group, an alkoxy group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, a fluoroalkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 50 ring-forming carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an arylthio group having 6 to 50 ring-forming carbon atoms, -Si (R) 101 )(R 102 )(R 103 )、-N(R 104 )(R 105 ) One of aryl groups with ring carbon number of 6-50 and heteroaryl groups with ring carbon number of 5-50; y and Z are each independently-C (R 106 )(R 107 )、-NR 108 、-Si(R 109 )(R 110 ) One of O, S, se, R 101 ～R 110 Each independently represents one of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 ring-forming carbon atoms, an aryl group having 6 to 50 ring-forming carbon atoms, and a heteroaryl group having 5 to 50 ring-forming atoms.
3. Phosphorescent iridium complex according to claim 1 or 2, characterized in that the structure of L in formulae I and II is represented by formula (L1):
wherein, single bond means forming covalent bond with metal center, arrow means forming coordination bond;
X 32 and X 36 Each independently is-NR 32 、-NR 36 One of O, S or Se; x is X 33 And X 35 Each independently is-C (Si) R 33 、C(Si)R 35 、-P(R 111 )(R 112 )、P(R 113 )(R 114 ) Or one of the nitrogen atoms; x is X 34 Selected from-CR 34 Or a nitrogen atom; r is R 32 ～R 36 And R is 111 ～R 114 Each independently is a hydrogen atom, a deuterium atom, a fluorine atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkynyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 ring-forming carbon atoms, an amino group, an alkoxy group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, a fluoroalkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 50 ring-forming carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an arylthio group having 6 to 50 ring-forming carbon atoms, -Si (R) 101 )(R 102 )(R 103 )、-N(R 104 )(R 105 ) One of aryl groups with ring carbon number of 6-50 and heteroaryl groups with ring atom number of 5-50.
4. Phosphorescent iridium complex according to claim 1 or 2, characterized in that the structure of L in formulae I and II is represented by formula (L2):
arrows indicate formation of coordination bonds;
wherein X is 37 One selected from carboxyl, thiocarboxyl, dithiocarboxyl, sulfonic acid group, phosphoric acid group, aryl group, imidazolyl group, triazole group and oxadiazole group; x is X 38 Is a nitrogen atom or a carbon atom; r is R 115 Is hydrogen atom, deuterium atom, fluorine atom, halogen atom, cyano group, alkyl group with 1-20 carbon atoms, alkenyl group with 1-20 carbon atoms, alkynyl group with 1-20 carbon atoms, cycloalkyl group with 3-20 ring-forming carbon atoms, amino group, alkoxy group with 1-20 carbon atoms, fluoroalkyl group with 1-20 carbon atoms, fluoroalkoxy group with 1-20 carbon atoms, aryloxy group with 6-50 ring-forming carbon atoms, alkylthio group with 1-20 carbon atoms, arylthio group with 6-50 ring-forming carbon atoms, -Si (R) 101 )(R 102 )(R 103 )、-N(R 104 )(R 105 ) One of aryl groups with ring carbon number of 6-50 and heteroaryl groups with ring atom number of 5-50.
5. Phosphorescent iridium complex according to claim 1 or 2, characterized in that the structure of L in formulae I and II is represented by formula (L3):
wherein, single bond means forming covalent bond with metal center, arrow means forming coordination bond;
R 116 ～R 118 each independently is a hydrogen atom, a deuterium atom, a fluorine atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkynyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 ring-forming carbon atoms, an amino group, an alkoxy group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, a fluoroalkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 50 ring-forming carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an arylthio group having 6 to 50 ring-forming carbon atoms, -Si (R) 101 )(R 102 )(R 103 )、-N(R 104 )(R 105 ) One of aryl groups with ring carbon number of 6-50 and heteroaryl groups with ring atom number of 5-50.
Preferably, the L is any one of the following structures:
the single bond indicates the formation of a covalent bond with the metal center and the arrow indicates the formation of a coordinate bond.
6. Phosphorescent iridium complex according to any one of claims 1 to 5, characterized in that it is any one of the following complexes:
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7. a light-emitting layer comprising the phosphorescent iridium complex according to any one of claims 1 to 6.
8. An organic electroluminescent device comprising a light-emitting layer comprising the phosphorescent iridium complex according to any one of claims 1 to 6.
9. The organic electroluminescent device of claim 8, comprising, in order from bottom to top, a substrate, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a metal electrode.
10. An electronic device, characterized in that it comprises an organic electroluminescent device as claimed in any one of claims 1-6.
CN202311223194.7A 2023-09-20 2023-09-20 Phosphorescent iridium complex, light-emitting layer, organic electroluminescent device and electronic equipment Pending CN117088918A (en)

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