CN115232174A - Compositions, formulations, organic electroluminescent devices and display or lighting devices - Google Patents

Abstract

The invention relates to a composition, a preparation, an organic electroluminescent device and a display or lighting device. The phosphorescent material and the composition have good thermal stability, can balance the transport of holes and electrons, and have more efficient energy transmission between a host and an object.

Description

Compositions, formulations, organic electroluminescent devices and display or lighting devices

technical field

The invention belongs to the field of organic electroluminescence, and in particular relates to a composition, a preparation, an organic electroluminescence device and a display or lighting device, wherein the guest is a tetradentate ring metal platinum (II) based on biphenylquinoline coordination ) or palladium (II) complex phosphorescent materials.

Background technique

Organic Light-Emitting Diode (OLED) is a new generation of full-color display and lighting technology. Compared with the shortcomings of liquid crystal display, such as slow response speed, small viewing angle, need for backlight source, and high energy consumption, OLED, as an autonomous light-emitting device, does not need a backlight source and saves energy; and its driving voltage is low, response speed is fast, and resolution and contrast are high. , Wide viewing angle, excellent low temperature performance; OLED devices can be made thinner and can be made into flexible structures. In addition, it also has the advantages of low production cost, simple production process, and large-area production. Therefore, OLEDs have broad and huge application prospects in high-end electronic products and aerospace; with the gradual increase in investment, the further development of research and development, and the upgrading of production equipment, OLEDs will have a very wide range of application scenarios and development in the future. prospect.

The core of OLED development is the design and development of luminescent materials. In the early OLED devices, the light-emitting materials were mainly organic small molecule fluorescent materials. However, spin statistics quantum theory shows that in the case of electroluminescence, the generated singlet excitons and triplet excitons (exciton) are 25% and 75%, respectively. Therefore, its maximum theoretical internal quantum efficiency is only 25%, and the remaining 75% of triplet excitons are lost through non-radiative transitions. In 1998, Professor Forrest of Princeton University and Professor Thompson of University of Southern California discovered the phenomenon of phosphorescence electroluminescence of heavy metal organic complex molecules at room temperature. Due to the strong spin-orbit coupling of heavy metal atoms, it is easier for excitons to transition from singlet to triplet intersystem jumping (ISC), so that OLED devices can make full use of all singlet and triplet excitations generated by electrical excitation. So that the theoretical internal quantum efficiency of the luminescent material can reach 100% (Nature, 1998, 395, 151).

Almost all of the light-emitting layers in the currently applied OLED devices use the host-guest light-emitting system mechanism, that is, doping the guest light-emitting material in the theme material, the energy system of the theme material is generally larger than that of the guest light-emitting material, and the energy is transferred from the host material to the guest material. The guest material is excited to emit light. Commonly used organic phosphorescent guest materials are generally heavy metal atoms such as iridium (III), platinum (II), Pd (II) and the like. The currently used heavy metal phosphorescent organic complex molecules cyclometal iridium (III) complex molecules are limited in number. _The content of metallic platinum in the earth's crust and the worldwide annual production are about ten times that _of metallic iridium ^. It is much higher than PtCl ₂ (210 RMB/g) for the preparation of platinum(II) complex phosphorescent materials; in addition, the preparation of iridium(III) complex phosphorescent materials involves iridium(III) dimer, iridium(III) intermediate Ligand exchange, synthesis of mer-iridium(III) complex and four-step reaction of mer- to fac-iridium(III) complex isomer conversion greatly reduced the overall yield and the raw material IrCl ₃ ^. The utilization rate of H ₂ O increases the preparation cost of iridium (III) complex phosphorescent materials. In contrast, the preparation of platinum(II) complex phosphorescent materials only involves the metallization of the ligand in the last step to design the platinum salt reaction, and the utilization rate of platinum element is high, which can further reduce the preparation cost of platinum(II) complex phosphorescent materials. To sum up, the preparation cost of platinum(II) complex phosphorescent materials is much lower than that of iridium(III) complex phosphorescent materials. However, there are still some technical difficulties in the development of platinum and palladium complex materials and devices. How to improve the efficiency and life of devices is a more important research problem. Therefore, there is an urgent need to develop new phosphorescent metal platinum(II) complexes.

At present, almost all of the light-emitting layers in organic OLED components use host-guest light-emitting systems, that is, doping guest light-emitting materials in host materials. Generally speaking, the energy system of organic host materials is larger than that of guest materials, that is, energy is transferred from the host to the host material. guest, so that the guest material is excited to emit light. The commonly used phosphorescent organic material CBP(4,4′-bis(9-carbazolyl)-biphenyl) has high efficiency and high triplet energy level, when it is used as an organic material, the triplet energy can be efficiently transferred from the light-emitting organic material to the guest Phosphorescent luminescent material. However, due to the characteristics of CBP that the holes are easily transported and the electrons are difficult to flow, the charge of the light-emitting layer is unbalanced, and the efficiency of the device is reduced as a result.

The present invention finds that the combination of a specific host material and a guest phosphorescent material can improve the external quantum efficiency of the organic electroluminescent device and reduce the operating voltage of the device.

SUMMARY OF THE INVENTION

The object of the present invention is to provide one or more guest phosphorescent materials and host materials applied to the light-emitting layer of an organic electroluminescent device, and combinations thereof, and organic electroluminescent devices comprising the combinations.

The present invention provides a metal platinum (II) or palladium (II) complex phosphorescent material, the structure of which is shown in formula (I):

In formula (I), M is Pt or Pd; Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ , Y ⁸ , Y ⁹ , Y ¹⁰ , Y ¹¹ , Y ¹² , Y ¹³ , Y ¹⁴ , Y ¹⁵ , Y ¹⁶ , Y ¹⁷ and Y ¹⁸ are each independently N or CH; the substitution patterns of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently represented as a single Substituted, disubstituted, trisubstituted or unsubstituted; R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent hydrogen, deuterium, alkyl, haloalkyl, cycloalkyl, alkoxy , substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted aryloxy, halogen, cycloalkenyl, substituted or unsubstituted heterocyclyl, alkenyl, alkynyl, hydroxyl, mercapto, nitro, cyano, substituted or unsubstituted amino, mono or dialkylamino, mono or diarylamino, ester, nitrile, isonitrile, alkoxycarbonyl, amido, alkoxy Carbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, urea, phosphoramido, imino, sulfo, carboxyl, hydrazino, substituted or Unsubstituted arylamine, substituted or unsubstituted heteroarylamine, alkylsilyl, substituted or unsubstituted arylsilyl, substituted or unsubstituted heteroarylsilyl, substituted or unsubstituted any one of aryloxysilyl, substituted or unsubstituted heteroaryloxysilyl, substituted or unsubstituted arylacyl, substituted or unsubstituted heteroarylacyl, substituted or unsubstituted phosphinyl, And two or more adjacent R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ can be selectively linked to form a fused ring.

The present invention provides one or more biphenylquinoline-coordinated-based tetradentate ring metal platinum (II) or palladium (II) complex guest phosphorescent materials represented by structural formula (I) and guest phosphorescent materials represented by structural formula (II) or The combination of one or more host materials represented by formula (III), structural formula (I) and structural formula (II) or formula (III) are as follows:

in:

In formula (I), M is Pt or Pd; Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ , Y ⁸ , Y ⁹ , Y ¹⁰ , Y ¹¹ , Y ¹² , Y ¹³ , Y ¹⁴ , Y ¹⁵ , Y ¹⁶ , Y ¹⁷ and Y ¹⁸ are each independently N or CH; the substitution patterns of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently represented as a single Substituted, disubstituted, trisubstituted or unsubstituted; R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent hydrogen, deuterium, alkyl, haloalkyl, cycloalkyl, alkoxy , substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted aryloxy, halogen, cycloalkenyl, substituted or unsubstituted heterocyclyl, alkenyl, alkynyl, hydroxyl, mercapto, nitro, cyano, substituted or unsubstituted amino, mono or dialkylamino, mono or diarylamino, ester, nitrile, isonitrile, alkoxycarbonyl, amido, alkoxy Carbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, urea, phosphoramido, imino, sulfo, carboxyl, hydrazino, substituted or Unsubstituted arylamine, substituted or unsubstituted heteroarylamine, alkylsilyl, substituted or unsubstituted arylsilyl, substituted or unsubstituted heteroarylsilyl, substituted or unsubstituted any one of aryloxysilyl, substituted or unsubstituted heteroaryloxysilyl, substituted or unsubstituted arylacyl, substituted or unsubstituted heteroarylacyl, substituted or unsubstituted phosphinyl, And two or more adjacent R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ can be selectively linked to form a fused ring;

In formulae (II) and (III), X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ , X ¹⁰ , X ¹¹ , X ¹² , X ¹³ , X ¹⁴ , X ¹⁵ , X ¹⁶ , X ¹⁷ , X ¹⁸ , X ¹⁹ and X ²⁰ are each independently N or CH; Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ , Z ⁶ , Z ⁷ , Z ⁸ , Z ⁹ , Z ¹⁰ , Z ¹¹ , Z ¹² and Z ¹³ are each independently N or CH, and at least two of them are N; L ¹ , L ² and L ³ do not exist or are selected from single bond, O, S, CR ¹⁵ R ¹⁶ , SiR ¹⁷ R ¹⁸ , NR ¹⁹ ; A, B, C and D are each independently selected from C6-C30 aryl, C2-C30 heteroaryl; R ⁷ , R ⁸ , R ⁹ , R ^{and R _ _ _ _ _ _ _ _ 7} , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ each independently represent hydrogen, deuterium, alkyl, haloalkane radical, cycloalkyl, alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted aryloxy, halogen, cycloalkenyl, substituted or unsubstituted heterocyclyl , alkenyl, alkynyl, hydroxyl, mercapto, nitro, cyano, substituted or unsubstituted amino, mono or dialkylamino, mono or diarylamino, ester, nitrile, isonitrile, alkoxy Carbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, urea, phosphoramido, imino, sulfonyl carboxyl, hydrazine, substituted or unsubstituted arylamine, substituted or unsubstituted heteroarylamine, alkylsilyl, substituted or unsubstituted arylsilyl, substituted or unsubstituted heteroaryl Silyl, substituted or unsubstituted aryloxysilyl, substituted or unsubstituted heteroaryloxysilyl, substituted or unsubstituted aryl acyl, substituted or unsubstituted heteroaryl acyl, substituted or unsubstituted Any one of the phosphinyl groups, and two or more adjacent R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ can be selectively linked to form a fused ring.

Further, the described tetradentate ring metal platinum(II) or palladium(II) complex guest phosphorescent material based on biphenylquinoline coordination, the platinum(II) or palladium(II) complex has the following A structure:

Further, the organic host material, the formula (II) is selected from the compounds described in (II)-1 to (II)-24:

Wherein, X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ and X ¹⁰ , L ¹ , L ² and L ³ , A and B, R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are the same as defined above.

Further, in the formula, A, B, C and D are selected from the groups described in the following structures:

Among them, R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ are as defined above.

Further, the host material of the present invention is selected from the following structures or the group consisting of the following structures:

Preferably, the host material of the present invention is selected from the following structures or the group consisting of the following structures:

The present invention also relates to an organic electroluminescence device, comprising a cathode layer, an anode layer and an organic layer, the organic layer comprising a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron injection layer, an electron transport layer, and a hole injection layer. At least one of the layers, wherein the light-emitting layer of the device contains the one or more guest compounds represented by structural formula I and one or more host compounds represented by structural formula (II) or structural formula (III).

The mass percentage of the guest material in the light-emitting layer composition of the organic electroluminescent device of the present invention is 0.1%-50%.

When the combination of two compounds in the structural formula (II) or structural formula (III) of the present invention is used as the host material, the volume ratio of them is 1:99 to 99:1.

The present invention relates to a composition comprising structural formula (I) and one or more formulations of structural formula (II) or structural formula (III) and a solvent. Toluene, xylene, mesitylene, tetralin, decalin, bicyclohexane, n-butylbenzene, sec-butylbenzene, tert-butylbenzene and other unsaturated hydrocarbon solvents, carbon tetrachloride, chloroform, dichloride Halogenated saturated hydrocarbon solvents such as methane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, chlorobenzene, dichloromethane Halogenated unsaturated hydrocarbon solvents such as chlorobenzene and trichlorobenzene, ether solvents such as tetrahydrofuran and tetrahydropyran, and ester solvents such as alkyl benzoate.

The present invention also provides an organic electroluminescent device comprising a cathode layer, an anode layer and an organic layer, the organic layer comprising a composition comprising a biphenylquinoline-coordinated tetradentate Cyclometallic platinum (II) or palladium (II) complex phosphorescent material and organic host material, wherein the structural formula of the metal platinum (II) or palladium (II) complex phosphorescent material is shown in formula (I); the structural formula of the organic host material (II) or formula (III):

in:

In formula (I), M is Pt or Pd; Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ , Y ⁸ , Y ⁹ , Y ¹⁰ , Y ¹¹ , Y ¹² , Y ¹³ , Y ¹⁴ , Y ¹⁵ , Y ¹⁶ , Y ¹⁷ and Y ¹⁸ are each independently N or CH; the substitution patterns of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently represented as a single Substituted, disubstituted, trisubstituted or unsubstituted; R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent hydrogen, deuterium, alkyl, haloalkyl, cycloalkyl, alkoxy , substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted aryloxy, halogen, cycloalkenyl, substituted or unsubstituted heterocyclyl, alkenyl, alkynyl, hydroxyl, mercapto, nitro, cyano, substituted or unsubstituted amino, mono or dialkylamino, mono or diarylamino, ester, nitrile, isonitrile, alkoxycarbonyl, amido, alkoxy Carbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, urea, phosphoramido, imino, sulfo, carboxyl, hydrazino, substituted or Unsubstituted arylamine, substituted or unsubstituted heteroarylamine, alkylsilyl, substituted or unsubstituted arylsilyl, substituted or unsubstituted heteroarylsilyl, substituted or unsubstituted any one of aryloxysilyl, substituted or unsubstituted heteroaryloxysilyl, substituted or unsubstituted arylacyl, substituted or unsubstituted heteroarylacyl, substituted or unsubstituted phosphinyl, And two or more adjacent R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ can be selectively linked to form a fused ring;

In formulae (II) and (III), X ¹ , X ² , X ³ , X ⁴ , X 3 ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ , X ¹⁰ , X ¹¹ , X ¹² , X ¹³ , X ¹⁴ , X ¹⁵ , X ¹⁶ , X ¹⁷ , X ¹⁸ , X ¹⁹ and X ²⁰ are each independently N or CH; Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ , Z ⁶ , Z ⁷ , Z ⁸ , Z ⁹ , Z ¹⁰ , Z ¹¹ , Z ¹² and Z ¹³ are each independently N or CH, and at least two of them are N; L ¹ , L ² and L ³ do not exist or are selected from single bond, O, S, CR ¹⁵ R ¹⁶ , SiR ¹⁷ R ¹⁸ , NR ¹⁹ ; A, B, C and D are each independently selected from C6-C30 aryl, C2-C30 heteroaryl; R ⁷ , R ⁸ , R ⁹ , R ^{and R _ _ _ _ _ _ _ _ 7} , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ each independently represent hydrogen, deuterium, alkyl, haloalkane radical, cycloalkyl, alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted aryloxy, halogen, cycloalkenyl, substituted or unsubstituted heterocyclyl , alkenyl, alkynyl, hydroxyl, mercapto, nitro, cyano, substituted or unsubstituted amino, mono or dialkylamino, mono or diarylamino, ester, nitrile, isonitrile, alkoxy Carbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, urea, phosphoramido, imino, sulfonyl carboxyl, hydrazine, substituted or unsubstituted arylamine, substituted or unsubstituted heteroarylamine, alkylsilyl, substituted or unsubstituted arylsilyl, substituted or unsubstituted heteroaryl Silyl, substituted or unsubstituted aryloxysilyl, substituted or unsubstituted heteroaryloxysilyl, substituted or unsubstituted aryl acyl, substituted or unsubstituted heteroaryl acyl, substituted or unsubstituted Any one of the phosphinyl groups, and two or more adjacent R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ can be selectively linked to form a fused ring.

Preferably, the above-mentioned platinum(II) or palladium(II) complex is any one of the above-mentioned compound Pt1 to compound Pt352 and compound Pd1 to compound Pd32.

Preferably, the above formula (II) is selected from the compounds described in (II)-1 to (II)-24:

Wherein, X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ and X ¹⁰ , L ¹ , L ² and L ³ , A and B, R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are the same as claim 1 .

Preferably, A, B, C and D in the above formula are selected from the groups described in the following structures:

Wherein, R15, R16, R17, R18 and R19 are the same as claim 1.

Preferably, the organic host material of the above formula (II) or formula (III) is selected from the above compounds 0-1 to 33-80.

The present invention also provides a display or lighting device, wherein the display or lighting device includes the above organic electroluminescence device.

The invention also provides the application of the tetradentate ring metal platinum (II) or palladium (II) complex phosphorescent material based on the coordination of biphenylquinoline in the preparation of organic light-emitting devices.

The present invention has no particular limitation on the preparation method of the organic electrical device, except that one or more guest compounds represented by structural formula I and one or more hosts represented by structural formula (II) or structural formula (III) are used. In addition to the compounds, the preparation methods and materials of light-emitting devices well known to those skilled in the art can be used to prepare them.

The organic electro-devices described in the present invention are organic photovoltaic devices, organic light-emitting devices (OLED), organic solar cells (OSC), electronic paper (e-paper), organic photoreceptors (OPC), organic thin film transistors (OTFT) and Any of organic memory elements, lighting and display devices.

In the present invention, the organic optoelectronic device can use sputter coating, electron beam evaporation, vacuum evaporation and other methods to evaporate metals or conductive oxides and their alloys on the substrate to form an anode; A hole injection layer, a hole transport layer, a light-emitting layer, an air blocking layer and an electron transport layer are sequentially evaporated on the surface of the anode, and then the cathode is evaporated later. The organic electric device is fabricated by sequentially vapor-depositing a cathode, an organic layer and an anode on a substrate other than the above method. The organic layer may also include a multi-layer structure such as a hole injection layer, a hole transport layer, a light-emitting layer, a hole blocking layer, and an electron transport layer. In the present invention, the organic layer is made of polymer materials by solvent engineering (spin-coating, tape-casting, doctor-blading, screen-printing) , inkjet printing or thermal imaging (Thermal-Imaging, etc.) instead of evaporation method, which can reduce the number of device layers.

The materials used in the organic electro-device according to the present invention can be classified into top emission, low emission or double-sided emission. The organic electro-device compounds according to the embodiments of the present invention can be applied to organic solar cells, lighting OLEDs, flexible OLEDs, organic photoreceptors, organic thin-film transistors and other electro-devices with similar principles of organic light-emitting devices.

Beneficial effects of the present invention: the guest platinum (II) or palladium (II) phosphorescent material molecules based on two bidentate ligands are easily vibrated and twisted to cause non-radiative attenuation, resulting in low phosphorescence efficiency. Compared with bidentate platinum(II) or palladium(II) complexes, the rigid structure of tetradentate ring metal platinum(II) or palladium(II) complex guest phosphorescent materials based on biphenylquinoline coordination can effectively inhibit the The non-radiative attenuation caused by molecular vibration can not only achieve high-efficiency light emission, but also have good thermal stability; in addition, both the guest material and the host material involved in the present invention have good thermal stability, and the host material composition can Balance the transport of holes and electrons, so that the energy transfer between the host and the guest is more efficient, which is embodied in the improvement of the external quantum efficiency of the organic electroluminescent device made by using the composition of the present invention as the light-emitting layer, and the lighting at the same time. Voltage drops.

Description of drawings

In order to illustrate the technical solutions in the embodiments of the present invention more clearly, the following briefly introduces the accompanying drawings used in the description of the embodiments. Obviously, the accompanying drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, under the premise of no creative work, other drawings can also be obtained from these drawings, wherein:

Fig. 1 is the room temperature emission spectrum of platinum complex Pt1 in the dichloromethane solution in the specific embodiment;

Fig. 2 is the room temperature emission spectrum of platinum complex Pt in the specific embodiment in dichloromethane solution;

Fig. 3 is the room temperature emission spectrum of platinum complex Pt in the specific embodiment in dichloromethane solution;

Fig. 4 is the room temperature emission spectrum of platinum complex Pt4 in the dichloromethane solution in the specific embodiment;

Fig. 5 is the room temperature emission spectrum of platinum complex Pt5 in the dichloromethane solution in the specific embodiment;

Fig. 6 is the room temperature emission spectrum of platinum complex Pt6 in the dichloromethane solution in the specific embodiment;

Fig. 7 is the room temperature emission spectrum of platinum complex Pt7 in the dichloromethane solution in the specific embodiment;

Figure 8 shows the HOMO and LUMO orbital distributions and energy level comparisons of Pt9, Pt10, Pd1 and Pt12 calculated by density functional theory (DFT);

Figure 9 shows the HOMO and LUMO orbital distributions and energy level comparisons of Pt13, Pd2, Pt15 and Pt16 calculated by density functional theory (DFT);

Figure 10 shows the HOMO and LUMO orbital distributions and energy levels of Pt17, Pt18, Pt19 and Pt20 calculated by density functional theory (DFT);

Figure 11 shows the HOMO and LUMO orbital distributions and energy level comparisons of Pt21, Pt22, Pt23 and Pt24 calculated by density functional theory (DFT);

Figure 12 shows the HOMO and LUMO orbital distributions and energy level comparisons of Pt25, Pt26, Pt27 and Pt28 calculated by density functional theory (DFT);

13 is a structural layer diagram of the organic electroluminescent diode device of the present invention, wherein 110 represents a substrate, 120 represents an anode, 130 represents a hole injection layer, 140 represents a hole transport layer, 150 represents a light emitting layer, and 160 represents a hole blocking layer , 170 denotes the electron transport layer, 180 denotes the electron injection layer, and 190 denotes the cathode.

Detailed ways

It should be pointed out that both the above general description and the following detailed description are exemplary and explanatory only and are not restrictive.

The present disclosure may be more readily understood by reference to the following detailed description and the examples contained therein.

Before the compounds, devices and/or methods of the present invention are disclosed and described, it is to be understood that they are not limited to specific synthetic methods (otherwise indicated), or specific reagents (otherwise indicated), as this can, of course, vary . It is also to be understood that the terminology used in the present invention is for the purpose of describing particular aspects only and is not intended to be limiting. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing, exemplary methods and materials are described below.

In a preferred embodiment of the present invention, the OLED device of the present invention contains a hole transport layer, and the hole transport material can be preferably selected from known or unknown materials, particularly preferably selected from the following structures, but does not represent the present invention Limited to the following structures:

In a preferred embodiment of the present invention, the hole transport layer contained in the OLED device of the present invention comprises one or more p-type dopants. The preferred p-type dopant of the present invention has the following structure, but it does not mean that the present invention is limited to the following structure:

In a preferred embodiment of the present invention, the electron transport layer can be selected from at least one of compounds ET-1 to ET-13, but it does not mean that the present invention is limited to the following structures:

As used herein, the terms "optional" or "optionally" mean that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.

Components useful in preparing the compositions described herein are disclosed, as well as the compositions themselves to be used in the methods disclosed herein. These and other species are disclosed herein, and it should be understood that when combinations, subsets, interactions, groups, etc. of these species are disclosed, each individual and total combination and permutation of these compounds cannot be specifically disclosed When specific references are made, each is specifically contemplated and described in the present invention. For example, if a particular compound is disclosed and discussed, and a number of modifications that can be made to a number of molecules comprising the compound are discussed, then every and every combination and permutation of the compound is specifically contemplated, and the modifications may be made sex, otherwise specifically stated to the contrary. Thus, if an instance of a class of molecules A, B, and C and a class of molecules D, E, and F, and a combination of molecules A-D is disclosed, it is contemplated that each individually and collectively is disclosed even if each is not individually recited Expected meaning combinations, A-E, A-F, B-D, B-E, B-F, C-D, C-E, and C-F. Likewise, any subset or combination of these are also disclosed. Thus, for example, the disclosure of groups A-E, B-F and C-E should be considered. These concepts apply to all aspects of the invention, including but not limited to steps in methods of making and using the compositions. Thus, if there are various additional steps that can be performed, it is understood that each of these additional steps can be performed in a specific embodiment of the method or in a combination of embodiments.

Linking atoms used in the present invention are capable of linking two groups, eg, N and C groups. The linking atom can optionally (if the valence allows) have other attached chemical moieties. For example, in one aspect, oxygen will not have any other chemical groups attached since the valence bond has been satisfied once bonded to two atoms (eg, N or C). Conversely, when carbon is the linking atom, two additional chemical moieties can be attached to the carbon atom. Suitable chemical moieties include, but are not limited to, hydrogen, hydroxy, alkyl, alkoxy, =O, halogen, nitro, amine, amide, mercapto, aryl, heteroaryl, cycloalkyl, and heterocyclyl.

The term "cyclic structure" or similar terms as used herein refers to any cyclic chemical structure including, but not limited to, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclyl, carbene, and N-heterocyclyl Ring Carbine.

The term "substituted" as used herein is intended to encompass all permissible substituents of organic compounds. In broad aspects, permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, and aromatic and non-aromatic substituents of organic compounds. Illustrative substituents include, for example, those described below. For suitable organic compounds, the permissible substituents may be one or more, the same or different. For the purposes of the present invention, a heteroatom (eg nitrogen) can have a hydrogen substituent and/or any permissible substituent of an organic compound described herein that satisfies the valency of the heteroatom. This disclosure is not intended to limit in any way the permissible substituents of organic compounds. Likewise, the terms "substituted" or "substituted with" include the implied condition that the substitution complies with the substituted atom and the permissible valency of the substituent, and that the substitution results in a stable compound (e.g., that does not spontaneously undergo transformation ( Compounds such as by rearrangement, cyclization, elimination, etc.). It is also contemplated that, in certain aspects, unless explicitly stated to the contrary, individual substituents can be further optionally substituted (ie, further substituted or unsubstituted).

^In defining various terms, "R1", " ^R2 ", " ^R3 " and " ^R4 " are used in the present invention as general symbols to denote various specific substituents. These symbols can be any substituents, not limited to those disclosed herein, and when they are defined in one instance as certain substituents, they may be defined as some other substituents in other instances.

The term "alkyl" as used herein is a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl base, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, hexyl, heptyl, hemiyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, etc. The alkyl group can be cyclic or acyclic. The alkyl group can be branched or unbranched. The alkyl group can also be substituted or unsubstituted. For example, the alkyl group may be substituted with one or more groups including, but not limited to, optionally substituted alkyl, cycloalkyl, alkoxy, amino, halogen, hydroxy, nitro, silane described herein thio-oxo (Sulfo-oxo) or sulfhydryl. A "lower alkyl" group is an alkyl group containing from 1 to 6 (eg, 1 to 4) carbon atoms.

Throughout the specification, "alkyl" is generally used to refer to both unsubstituted and substituted alkyl groups; however, substituted alkyl groups are also specifically referred to herein by identifying the specific substituent on the alkyl group. For example, the term "halogenated alkyl" or "haloalkyl" specifically refers to an alkyl group substituted with one or more halogens (eg, fluorine, chlorine, bromine, or iodine). The term "alkoxyalkyl" specifically refers to an alkyl group substituted with one or more alkoxy groups, as described below. The term "alkylamino" specifically refers to an alkyl group substituted with one or more amino groups, as described below, and the like. When "alkyl" is used in one instance and a specific term such as "alkyl alcohol" is used in another, it is not meant to imply that the term "alkyl" does not simultaneously refer to a specific term such as "alkyl alcohol" Alcohol" etc.

This practice also applies to other groups described herein. That is, when terms such as "cycloalkyl" refer to both unsubstituted and substituted cycloalkyl moieties, that substituted moiety may otherwise be specifically identified in the present invention; for example, a specifically substituted cycloalkyl may be referred to as For example "alkylcycloalkyl". Similarly, substituted alkoxy groups can be specifically referred to as, for example, "halogenated alkoxy groups," and specific substituted alkenyl groups can be, for example, "enols," and the like. Likewise, the practice of using a general term such as "cycloalkyl" with a specific term such as "alkylcycloalkyl" is not intended to imply that the general term does not also encompass that specific term.

The term "cycloalkyl" as used herein is a non-aromatic carbon-based ring composed of at least three carbon atoms. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclononyl, and the like. The term "heterocycloalkyl" is a class of cycloalkyl groups as defined above and is included within the meaning of the term "cycloalkyl" wherein at least one ring carbon atom is replaced by a heteroatom such as but not limited to nitrogen, oxygen, sulfur or phosphorus replace. The cycloalkyl and heterocycloalkyl groups can be substituted or unsubstituted. The cycloalkyl and heterocycloalkyl may be substituted with one or more groups, including but not limited to alkyl, cycloalkyl, alkoxy, amino, halogen, hydroxyl, nitro, methyl, as described in the present invention Silyl, sulfo-oxo or mercapto.

The term "polyolefin group" as used herein refers to a group containing two or more _CH2 groups attached to other identical moieties. A "polyolefin group" may be represented as -( _CH2 ) _a- , where "a" is an integer from 2 to 500.

The terms "alkoxy" and "alkoxy group" as used herein to refer to an alkyl or cycloalkyl group bonded through an ether linkage; that is, "alkoxy" may be defined as -OR ¹ , wherein R ¹ is alkyl or cycloalkyl as defined above. "Alkoxy" also includes polymers of the alkoxy groups just described; that is, the alkoxy group may be a polyether such as -OR ¹ -OR ² or -OR ¹ -(OR ² ) _a -OR ³ , wherein "a" is an integer from 1 to 200, and R ¹ , R ² and R ³ are each independently alkyl, cycloalkyl, or a combination thereof.

The term "alkenyl" as used herein is a hydrocarbon group of 2 to 30 carbon atoms whose structural formula contains at least one carbon-carbon double bond. Asymmetric structures such as (R ¹ R ² )C=C(R ³ R ⁴ ) are intended to encompass both E and Z isomers. This can be presumed in the structural formula of the present invention, where the asymmetric olefin is present, or it can be explicitly represented by the bond symbol C=C. The alkenyl can be substituted with one or more groups, including but not limited to the alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, Heteroaryl, aldehyde, amino, carboxyl, ester, halogen, hydroxyl, carbonyl, azido, nitro, silyl, sulfo-oxo or mercapto.

The term "cycloalkenyl" as used herein is a non-aromatic carbon-based ring consisting of at least 3 carbon atoms and containing at least one carbon-carbon double bond, ie, C=C. Examples of cycloalkenyl groups include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, norbornenyl, and the like. The term "heterocycloalkenyl" is a class of cycloalkenyl groups as defined above and is included within the meaning of the term "cycloalkenyl" wherein at least one carbon atom of the ring is replaced by a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur , or phosphorus substitution. Cycloalkenyl and heterocycloalkenyl groups can be substituted or unsubstituted. The cycloalkenyl and heterocycloalkenyl may be substituted with one or more groups, including but not limited to the alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkenyl, and cycloalkenyl groups described in the present invention. Alkynyl, aryl, heteroaryl, aldehyde, amino, carboxyl, ester, halogen, hydroxy, carbonyl, azido, nitro, silyl, sulfo-oxo or mercapto.

The term "alkynyl" as used in the present invention is a hydrocarbon group having 2 to 30 carbon atoms having a structural formula containing at least one carbon-carbon triple bond. Alkynyl can be unsubstituted or substituted with one or more groups, including but not limited to alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl described in the present invention , cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxyl, ester, halogen, hydroxyl, carbonyl, azide, nitro, silyl, sulfo-oxo or Sulfhydryl.

The term "cycloalkynyl," as used herein, is a non-aromatic carbon-based ring containing at least seven carbon atoms and containing at least one carbon-carbon triple bond. Examples of cycloalkynyl groups include, but are not limited to, cycloheptynyl, cyclooctynyl, cyclononynyl, and the like. The term "heterocycloalkynyl" is a type of cycloalkenyl as defined above and is included within the meaning of the term "cycloalkynyl" wherein at least one of the carbon atoms of the ring is replaced by a heteroatom, so Such heteroatoms are, for example, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. Cycloalkynyl and heterocycloalkynyl groups can be substituted or unsubstituted. Cycloalkynyl and heterocycloalkynyl can be substituted with one or more groups, including but not limited to alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkyne described in the present invention radical, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxyl, ester, halogen, hydroxyl, carbonyl, azide, nitro, silyl, sulfo-oxo or thiol.

The term "aryl" as used herein is a group containing any carbon-based aromatic group including, but not limited to, phenyl, naphthyl, phenyl, biphenyl, Phenoxyphenyl, anthracenyl, phenanthryl, etc. The term "aryl" also includes "heteroaryl", which is defined as a group containing an aromatic group having at least one heteroatom introduced into the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Likewise, the term "non-heteroaryl" (which is also included in the term "aryl") defines a group containing an aromatic group that does not contain heteroatoms. Aryl groups can be substituted or unsubstituted. Aryl can be substituted with one or more groups, including but not limited to alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, Aryl, heteroaryl, aldehyde, amino, carboxyl, ester, halogen, hydroxyl, carbonyl, azide, nitro, silyl, sulfo-oxo or mercapto. The term "biaryl" is a specific type of aryl group and is included in the definition of "aryl". Biaryl refers to two aryl groups joined together through a fused ring structure, as in naphthalene, or two aryl groups joined through one or more carbon-carbon bonds, as in biphenyl.

The term "aldehyde" as used herein is represented by the formula -C(O)H. Throughout the specification, "C(O)" is a shorthand for carbonyl (ie, C=O).

^The term "amine" or "amino" as used herein is represented by the ^{formula -NR1R2} , wherein R1 and R2 can be independently selected from ^hydrogen , alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, selected from cycloalkynyl, aryl or heteroaryl.

The term "alkylamino" as used herein is represented by the formula -NH(-alkyl), wherein the alkyl group is as described herein. Representative examples include, but are not limited to, methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, (sec-butyl)amino, (tert-butyl)amino, pentylamino , isopentylamino, (tert-amyl)amino, hexylamino, etc.

The term "dialkylamino" as used herein is represented by the formula -N(alkyl) ₂ , wherein the alkyl group is as described herein. Representative examples include, but are not limited to, dimethylamino, diethylamino, dipropylamino, diisopropylamino, dibutylamino, diisobutylamino, di(sec-butyl)amino, di(tert- Butyl)amino, dipentylamino, diisoamylamino, di(tert-amyl)amino, dihexylamino, N-ethyl-N-methylamino, N-methyl-N-propylamino, N-ethyl-N-propylamino and the like.

The term "carboxylic acid" as used herein is represented by the formula -C(O)OH.

The term "ester" used in the present invention is represented by the formula -OC(O)R ¹ or -C(O)OR ¹ , wherein R ¹ can be alkyl, cycloalkyl, alkenyl, cycloalkenyl as described in the present invention , alkynyl, cycloalkynyl, aryl or heteroaryl. The term "polyester" as used herein is represented by the formula -(R ¹ O(O)CR ² -C(O)O) _a - or -(R ¹ O(O)CR ² -OC(O)) _a - , wherein R ¹ and R ² can independently be alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl as described herein and "a" is 1 an integer up to 500. The term "polyester" is used to describe groups produced by the reaction between a compound having at least two carboxyl groups and a compound having at least two hydroxyl groups.

The term "ether" as used in the present invention is represented by the formula R ¹ OR ² , wherein R ¹ and R ² can independently be alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkyne as described in the present invention aryl, aryl or heteroaryl. The term "polyether" used in the present invention is represented by the formula -(R ¹ OR ² O) _a -, wherein R ¹ and R ² can be independently alkyl, cycloalkyl, alkenyl, cycloalkene as described in the present invention alkynyl, alkynyl, cycloalkynyl, aryl, or heteroaryl and "a" is an integer from 1 to 500. Examples of polyether groups include polyethylene oxide, polypropylene oxide and polybutylene oxide.

The term "halogen" as used herein refers to the halogens fluorine, chlorine, bromine and iodine.

The term "heterocyclyl" as used herein refers to monocyclic and polycyclic non-aromatic ring systems of 3 to 30 carbon atoms, and "heteroaryl" as used herein refers to monocyclic and polycyclic non-aromatic Aromatic ring systems of more than 60 carbon atoms: wherein at least one of the ring members is not carbon. The term includes azetidinyl, dioxanyl, furanyl, imidazolyl, isothiazolyl, isoxazolyl, morpholinyl, oxazolyl, including 1,2,3-oxadiazolyl, 1,2,5-oxadiazolyl and 1,3,4-oxadiazolyl oxazolyl, piperazinyl, piperidinyl, pyrazinyl, pyrazolyl, pyridazinyl, pyridyl, pyrimidine pyrrolyl, pyrrolyl, pyrrolidinyl, tetrahydrofuranyl, tetrahydropyranyl, tetrazinyl including 1,2,4,5-tetrazinyl, including 1,2,3,4-tetrazolyl and 1, Tetrazolyl of 2,4,5-tetrazolyl, thiadiazolyl including 1,2,3-thiadiazolyl, 1,2,5-thiadiazolyl and 1,3,4-thiadiazolyl azolyl, thiazolyl, thienyl, triazinyl including 1,3,5-triazinyl and 1,2,4-triazinyl, including 1,2,3-triazolyl and 1,3,4 -triazolyl of triazolyl, etc.

The term "hydroxyl" as used in the present invention is represented by the formula -OH.

The term "ketone" used in the present invention is represented by the formula R ¹ C(O)R ² , wherein R ¹ and R ² can independently be alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkyne as described in the present invention alkynyl, cycloalkynyl, aryl, or heteroaryl.

The term "azido" used in the present invention is represented by the formula -N ₃ .

The term "nitro" as used in the present invention is represented by the formula -NO ₂ .

The term "nitrile" as used in the present invention is represented by the formula -CN.

The term "silyl" used in the present invention is represented by the formula —SiR ¹ R ² R ³ , wherein R ¹ , R ² and R ³ can be independently hydrogen or alkyl, cycloalkyl, alkoxy as described in the present invention alkenyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl.

The term "thio-oxo group" as used herein is represented by the formula -S(O)R ¹ , -S(O) ² R ¹ , -OS(O) ² R ¹ or -OS(O) ² OR ¹ , wherein R ¹ can be hydrogen or alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl as described in the present invention. Throughout this specification, "S(O)" is a shorthand for S=O. The term "sulfonyl" as used herein refers to a thio-oxo group represented by the formula -S(O) ² R ¹ , wherein R ¹ can be alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkyne alkynyl, cycloalkynyl, aryl or heteroaryl. The term "sulfone" used in the present invention is represented by the formula R ¹ S(O) ₂ R ² , wherein R ¹ and R ² can independently be alkyl, cycloalkyl, alkenyl, cycloalkenyl, Alkynyl, cycloalkynyl, aryl or heteroaryl. The term "sulfoxide" used in the present invention is represented by the formula R ¹ S(O)R ² , wherein R ¹ and R ² can independently be alkyl, cycloalkyl, alkenyl, cycloalkenyl, Alkynyl, cycloalkynyl, aryl or heteroaryl.

The term "thiol" used in the present invention is represented by the formula -SH

"R1", "R2", " ^R3 ", " ^Rn " (where ⁿ is an integer ⁾ as used herein may independently have one or more of the above-listed groups. For example, if R1 is ^a straight chain alkyl group, then one hydrogen atom of the alkyl group may be optionally substituted with a hydroxy, alkoxy, alkyl, halo, and the like. Depending on the group chosen, the first group may be incorporated within the second group, or alternatively, the first group may be pendant, ie, attached to the second group. For example, for the phrase "an alkyl group containing an amino group," the amino group may be incorporated within the backbone of the alkyl group. Alternatively, the amino group can be attached to the backbone of the alkyl group. The nature of the selected group will determine whether the first group is embedded or attached to the second group.

The compounds of the present invention may contain "optionally substituted" moieties. Generally, the term "substituted" (whether or not the term "optional" is preceded by the term "optional") means that one or more hydrogens of the indicated moiety have been replaced with a suitable substituent. Unless otherwise specified, an "optionally substituted" group may have suitable substituents at each substitutable position of the group, and when in any given structure more than one position may be substituted with more than one selected from the group consisting of In the case of substituents of a group, the substituents at each position may be the same or different. Substituent combinations contemplated by the present invention are preferably those that form stable or chemically feasible compounds. In certain aspects, unless expressly indicated to the contrary, it is also contemplated that each substituent may be further optionally substituted (ie, further substituted or unsubstituted).

The term "fused ring" used in the present invention means that two adjacent substituents can be fused into a six-membered aromatic ring, a heteroaromatic ring, such as a benzene ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a meta-diaza ring etc., and saturated six- or seven-membered carbocyclic or carboheterocycles, etc.

The structure of the compound can be represented by the following formula:

It is understood to be equivalent to the following formula:

where n is usually an integer. That is, R ⁿ is understood to represent the five individual substituents R ^{a(1 )} , R ^a(2) , R ^a(3) , R ^a(4) , R ^{a (5)} . "Individual substituents" means that each R substituent may be independently defined. For example, if in one instance ^Ra(m) is halogen, then ^Ra(n) in that instance is not necessarily halogen.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , etc. are mentioned several times in the chemical structures and moieties disclosed and described herein. Any description ^of R ¹ , R ² , ^{R 3} , R ⁴ , R ⁵ , R ^{6 etc.} in the ^{specification applies to} any structure or section, unless otherwise stated.

The term "fused ring" used in the present invention means that two adjacent substituents can be fused into a six-membered aromatic ring, a heteroaromatic ring, such as a benzene ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a meta-diaza ring etc., and saturated six- or seven-membered carbocyclic or carboheterocycles, etc.

Optoelectronic devices using organic materials are becoming increasingly urgent for several reasons. Many of the materials used to make such devices are relatively inexpensive, so organic optoelectronic devices have the potential for cost advantages of inorganic devices. Furthermore, the inherent properties of organic materials, such as their flexibility, can make them well suited for special applications such as fabrication on flexible substrates. Examples of organic optoelectronic devices include organic light emitting devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, organic materials may have performance advantages over conventional materials. For example, the wavelength at which the organic light-emitting layer emits light can often be tuned with appropriate dopants.

The excitons decay from the singlet excited state to the ground state to produce instant luminescence, which is fluorescence. If excitons decay from the triplet excited state to the ground state to produce light emission, this is phosphorescence. Phosphorescent metal complexes such as platinum complexes have been shown to simultaneously utilize singlet states due to the strong spin-orbit coupling of heavy metal atoms between singlet and triplet excited states, which effectively enhances intersystem crossing (ISC). and triplet exciton potential to achieve 100% internal quantum efficiency. Therefore, phosphorescent metal complexes are good candidates for dopants in the emissive layer of organic light-emitting devices (OLEDs) and have gained great attention in both academic and industrial fields. Over the past decade, many results have been achieved leading to lucrative applications of this technology, for example, OLEDs have been used in advanced displays for smartphones, TVs and digital cameras.

However, blue electroluminescent devices are still the most challenging field in this technology so far, and the stability of blue devices is a major issue. The choice of host material has been shown to be very important for the stability of blue devices. However, the triplet excited state (T1) minimum energy of the blue light-emitting material is very high, which means that the triplet excited state (T1) minimum energy of the host material of the blue device should be higher. This makes the development of host materials for blue devices more difficult.

The metal complexes of the present invention can be tailored or tuned to specific applications where specific emission or absorption properties are desired. The optical properties of the metal complexes disclosed herein can be tuned by changing the structure of the ligand surrounding the metal center or by changing the structure of the fluorescent emitter on the ligand. For example, metal complexes of ligands with electron-donating substituents or electron-withdrawing substituents can often exhibit different optical properties in emission and absorption spectra. The color of the metal complexes can be tuned by modifying the fluorescent emitters and the conjugated groups on the ligands.

The emission of the complexes of the invention can be tuned, for example, by changing the ligand or fluorescent emitter structure, eg from ultraviolet to near infrared. A fluorescent emitter is a group of atoms in an organic molecule that can absorb energy to produce a singlet excited state, and the singlet excitons rapidly decay to produce instant light emission. In one aspect, the complexes of the present invention can provide emission in most of the visible spectrum. In specific examples, the complexes of the present invention can emit light in the visible or near-infrared wavelength range. On the other hand, the complexes of the present invention have improved stability and efficiency relative to conventional emission complexes. In addition, the complexes of the present invention can be used as luminescent labels, for example, in biological applications, anticancer agents, emitters in organic light emitting diodes (OLEDs), or combinations thereof. In another aspect, the complexes of the present invention can be used in light emitting devices such as compact fluorescent lamps (CFLs), light emitting diodes (LEDs), incandescent lamps, and combinations thereof.

Disclosed herein are platinum-containing compounds or complex complexes. The terms compound or complex are used interchangeably herein. Additionally, the compounds disclosed herein have a neutral charge.

The compounds disclosed herein can exhibit desirable properties and possess emission and/or absorption spectra that can be tuned by selection of appropriate ligands. In another aspect, the invention may exclude any one or more of the compounds, structures, or portions thereof specifically recited herein.

The compounds disclosed herein are suitable for use in a wide variety of optical and electro-optical devices, including but not limited to light absorbing devices such as solar and photosensitive devices, organic light emitting diodes (OLEDs), light emitting devices or devices capable of light absorption and emission compatible and Used as a marker for biological applications.

As noted above, the disclosed compounds are platinum complexes. At the same time, the compounds disclosed herein can be used as host materials for OLED applications, such as full-color displays.

The compounds disclosed herein can be used in a variety of applications. As a light-emitting material, the compound can be used in organic light-emitting diodes (OLEDs), light-emitting devices and displays, and other light-emitting devices.

In addition, compared with conventional materials, the compounds of the present invention can be used in light-emitting devices (such as OLEDs), which can improve the light-emitting efficiency and the operation time of the device.

The compounds of the present invention can be prepared using a variety of methods, including but not limited to those described in the Examples provided herein.

The compounds disclosed herein can be delayed fluorescent and/or phosphorescent emitters. In one aspect, the compounds disclosed herein can be delayed fluorescent emitters. In one aspect, the compounds disclosed herein can be phosphorescent emitters. On the other hand, the compounds disclosed herein can be delayed fluorescent emitters and phosphorescent emitters.

The compounds disclosed in the embodiments of the present invention are suitable for use in a wide variety of optical and electro-optical devices, including but not limited to light absorbing devices such as solar and light sensitive devices, organic light emitting diodes (OLEDs), light emitting devices or existing light absorbing devices There are also light-emitting devices and markers for biological applications.

The compounds provided by the embodiments of the present invention can be used in a light-emitting device such as an OLED, the device comprising at least one cathode, at least one anode and at least one light-emitting layer, at least one of the light-emitting layers comprising the above-mentioned Tetradentate ring metal platinum complexes based on phenylcarbazole. Specifically, the light emitting device may include an anode, a hole transport layer, a light emitting layer, an electron transport layer and a cathode formed by sequential deposition. The hole transport layer, the light-emitting layer and the electron transport layer are all organic layers, and the anode and the cathode are electrically connected.

Synthesis Example

The following examples of compound synthesis, compositions, devices or methods are only to provide a general approach to the industry, and are not intended to limit the scope of protection of this patent. For the data (quantity, temperature, etc.) mentioned in the patent as much as possible is guaranteed to be accurate, but there may be some errors. Unless otherwise specified, the weighing is carried out separately, the temperature is ℃ or normal temperature, and the pressure is close to normal pressure.

Methods for the preparation of novel compounds are provided in the following examples, but the preparation of such compounds is not limited to this method. In this professional technical field, since the compounds protected in this patent are easy to be modified and prepared, the methods listed below or other methods can be adopted for their preparation. The following examples are only used as examples, and are not intended to limit the protection scope of this patent. Temperatures, catalysts, concentrations, reactants, and reaction procedures can all be varied to select different conditions for the preparation of the compounds for different reactants.

¹ H NMR (500MHz), ¹ H NMR (400MHz), ¹³ C NMR (126MHz) spectra were measured on an ANANCE III (500M) nuclear magnetic resonance spectrometer; unless otherwise specified, DMSO-d ₆ or 0.1% NMR was used for nuclear magnetic resonance. The CDCl ₃ of TMS is used as the solvent, and if CDCl ₃ is used as the solvent in the ¹ H NMR spectrum, TMS (δ=0.00ppm) is used as the internal standard; when DMSO-d ₆ is used as the solvent, TMS (δ=0.00ppm) or The residual DMSO peak (δ=2.50 ppm) or the residual water peak (δ=3.33 ppm) was used as the internal standard. In the ¹³ C NMR spectrum, CDCl ₃ (δ=77.00 ppm) or DMSO-d ₆ (δ=39.52 ppm) was used as an internal standard. HPLC-MS was determined on an Agilent 6210TOF LC/MS mass spectrometer; HRMS spectra were determined on an Agilent 6210TOF LC/MS liquid chromatography-time-of-flight mass spectrometer. In the ¹ H NMR spectral data: s=singlet, d=doublet, t=triplet, q=quartet, p=quintet, m=multiplet, br=broad.

synthetic route

Example 1: The platinum complex Pt1 can be synthesized as follows:

Synthesis of L1: To a schlenk tube with a magnetic rotor, add Cl-1 (440 mg, 1.49 mmol, 1.00 equiv), Pin-1 (576 mg, 1.49 mmol, 1.00 equiv), Pd ₂ (dba) ₃ (40.8 mg , 0.05 mmol, 0.03 equiv), tricyclohexyl phosphorus (25 mg, 0.09 mmol, 0.06 equiv), potassium phosphate (631 mg, 2.97 mmol, 2.00 equiv), after three nitrogen purges, 1,4-dioxane 8 mL was added by injection and 2 mL of water, and the temperature was increased to 85 °C. Reaction for 24h. The reaction mixture was quenched by adding water, extracted three times with ethyl acetate, and the organic phases were combined, dried over anhydrous sodium sulfate, and the obtained crude product was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate)=10:1 , and the solvent was distilled off under reduced pressure to obtain 670 mg of white solid with a yield of 87%. ¹ H NMR (500 MHz, CDCl ₃ ): δ 1.46 (s, 9H), 7.38 (dd, J=8.5, 4.5 Hz, 1H), 7.58 (t, J=7.5 Hz, 1H), 7.71-7.75 (m ,3H),7.87(d,J＝2.0Hz,1H),7.97(t,J＝1.5Hz,1H),8.17(dd,J＝8.0,1.5Hz,1H),8.89(dd,J＝4.0, 2.0Hz, 1H).

Synthesis of Pt1: add L1 (200 mg, 0.38 mmol, 1.00 equiv.) and platinum dichloride (113 mg, 0.42 mmol, 1.10 equiv.) to a 50 mL three-necked flask with a magnetic rotor in turn, and purge nitrogen three times. Add benzyl by injection. Nitrile 15mL. After bubbling with nitrogen for 30 minutes, the temperature was raised to 180°C, and the reaction was carried out for 48 hours. The reaction mixture was distilled under reduced pressure to remove benzonitrile, and then the reaction mixture was separated and purified by silica gel column chromatography. The solvent was distilled off under reduced pressure with the eluent (petroleum ether/ethyl acetate = 20:1) to obtain 110 mg of a yellow solid, which was collected rate 41%. ¹ H NMR (400MHz, DMSO-d6): δ1.54 (s, 9H), 7.17 (t, J=8.0Hz, 1H), 7.47 (d, J=7.2Hz, 1H), 7.61 (dd, J= 8.0, 5.2Hz, 1H), 7.81(d, J=8.0Hz, 1H), 8.08(d, J=2.0Hz, 1H), 8.31(d, J=4.8, 1.2Hz, 1H), 8.65(d, J=1.6Hz, 1H), 8.83 (dd, J=8.4, 1.2Hz, 1H).

Example 2: The platinum complex Pt2 can be synthesized as follows:

Synthesis of L2: To a schlenk tube with a magnetic rotor, add Cl-2 (166 mg, 0.47 mmol, 1.05 equiv), Pin-2 (200 mg, 0.45 mmol, 1.00 equiv), Pd ₂ (dba) ₃ (12.4 mg , 0.01 mmol, 0.03 equiv), tricyclohexyl phosphorus (7.6 mg, 0.03 mmol, 0.06 equiv), potassium phosphate (200 mg, 0.95 mmol, 2.10 equiv), after three nitrogen purges, 1,4-dioxane was added by injection 6mL and 1.5mL of water, heated to 85°C. The reaction was carried out for 24h. The reaction mixture was quenched by adding water, extracted three times with ethyl acetate, and the organic phases were combined, dried over anhydrous sodium sulfate, and the obtained crude product was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate)=10:1 , and the solvent was distilled off under reduced pressure to obtain 240 mg of white solid with a yield of 84%. ¹ H NMR (400 MHz, CDCl ₃ ): δ 1.44 (s, 9H), 1.47 (s, 9H), 7.38 (dd, J=8.4, 4.4 Hz, 1H), 7.69 (t, J=1.6 Hz, 1H) , 7.74–7.77 (m, 3H), 7.89 (d, J=2.4Hz, 1H), 8.17 (dd, J=8.0, 1.6Hz, 1H), 8.89 (dd, J=4.0, 1.6Hz, 1H).

Synthesis of Pt2: Add L2 (120mg, 0.19mmol, 1.00 equiv), platinum dichloride (55mg, 0.20 mmol, 1.10 equiv) to a 50mL three-necked flask with a magnetic rotor in turn, replace nitrogen three times, and inject benzyl Nitrile 12mL. After bubbling with nitrogen for 30 minutes, the temperature was raised to 180°C, and the reaction was carried out for 48 hours. The reaction mixture was distilled under reduced pressure to remove benzonitrile, and then the reaction mixture was separated and purified by silica gel column chromatography. The solvent was distilled off under reduced pressure with the eluent (petroleum ether/ethyl acetate = 20:1) to obtain 70 mg of red solid, which was collected rate 45%. ¹ H NMR (400MHz, DMSO-d6): δ1.46(s, 9H), 1.54(s, 9H), 7.58–7.62(m, 2H), 7.71(d, J=0.8Hz, 1H), 8.07( d, J=2.0Hz, 1H), 8.33 (dd, J=5.2, 2.0Hz, 1H), 8.61 (d, J=1.6Hz, 1H), 8.81 (dd, J=8.4, 2.0Hz, 1H).

Example 3: The platinum complex Pt3 can be synthesized as follows:

Synthesis of L3: To a schlenk tube with a magnetic rotor, add Cl-2 (159 mg, 0.45 mmol, 1.05 equiv), Pin-3 (200 mg, 0.43 mmol, 1.00 equiv), Pd ₂ (dba) ₃ (11.8 mg , 0.01 mmol, 0.03 equiv), tricyclohexyl phosphorus (7.2 mg, 0.03 mmol, 0.06 equiv), potassium phosphate (191 mg, 0.90 mmol, 2.1 equiv), after three purges of nitrogen, 1,4-dioxane was added by injection 6mL and 1.5mL of water, heated to 85°C. Reaction for 24h. The reaction mixture was quenched by adding water, extracted three times with ethyl acetate, and the organic phases were combined, dried over anhydrous sodium sulfate, and the obtained crude product was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate)=10:1 , and the solvent was distilled off under reduced pressure to obtain 237 mg of white solid with a yield of 84%. ¹ H NMR (400 MHz, CDCl ₃ ): δ 1.43 (s, 9H), 1.44 (s, 9H), 1.47 (s, 9H), 7.37–7.45 (m, 3H), 7.49–7.53 (m, 2H) ,7.70–7.79(m,8H),7.84–7.85(m,1H),7.89(d,J=2.0Hz,1H),8.02(d,J=2.0Hz,1H),8.09(d,J=2.0 Hz,1H),8.17(dd,J＝8.4,1.6Hz,1H),8.26(dd,J＝8.4,1.6Hz,1H),8.89(dd,J＝4.4,1.6Hz,1H),8.95(dd , J=4.4, 1.6Hz, 1H).

Synthesis of Pt3: add L3 (180mg, 0.28mmol, 1.00 equiv.), platinum dichloride (81 mg, 0.30 mmol, 1.1 equiv.) to a 50mL three-necked flask with a magnetic rotor in turn, purge nitrogen three times, and add benzyl by injection Nitrile 15mL. After bubbling with nitrogen for 30 minutes, the temperature was raised to 180°C, and the reaction was carried out for 48 hours. The reaction mixture was distilled under reduced pressure to remove benzonitrile, and then the reaction mixture was separated and purified by silica gel column chromatography. The eluent (petroleum ether/ethyl acetate/dichloromethane=5:1:1) was used to remove the solvent under reduced pressure. 49 mg of red solid were obtained, the yield was 21%. ¹ H NMR (400MHz, DMSO-d6): δ1.45(s, 9H), 1.46(s, 9H), 1.54(s, 9H), 7.52(t, J=7.6Hz, 1H), 7.60–7.68( m,6H),7.72(s,1H),7.82–7.85(m,1H),8.00(d,J=7.6Hz,2H),8.08(d,J=2.0Hz,1H),8.35(dd,J =4.8,1.2Hz,1H),8.40–8.43(m,2H),8.62(d,J=1.6Hz,1H),8.78(d,J=1.6Hz,1H),8.83(dd,J=8.0, 1.2Hz, 1H), 8.90 (dd, J=8.4, 1.2Hz, 1H).

Example 4: The platinum complex Pt4 can be synthesized as follows:

Synthesis of L4: To a schlenk tube with a magnetic rotor, add Cl-3 (143 mg, 0.45 mmol, 1.05 equiv), Pin-3 (200 mg, 0.43 mmol, 1.00 equiv), Pd ₂ (dba) ₃ (11.8 mg , 0.01 mmol, 0.03 equiv), tricyclohexyl phosphorus (7.2 mg, 0.03 mmol, 0.06 equiv), potassium phosphate (191 mg, 0.90 mmol, 2.1 equiv), after three purges of nitrogen, 1,4-dioxane was added by injection 6mL and 1.5mL of water, heated to 85°C. Reaction for 24h. The reaction mixture was quenched by adding water, extracted three times with ethyl acetate, and the organic phases were combined, dried over anhydrous sodium sulfate, and the obtained crude product was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate)=10:1 , and the solvent was distilled off under reduced pressure to obtain 210 mg of a white solid with a yield of 82%. ¹ H NMR (400 MHz, CDCl ₃ ): δ 1.44 (s, 9H), 7.38-7.46 (m, 4H), 7.48-7.52 (m, 4H), 7.60 (t, J=7.6Hz, 1H), 7.73 –7.78(m,8H),7.87(t,J=1.6Hz,1H),8.00–8.03(m,3H),8.08(t,J=2.8Hz,2H),8.26(ddd,J=8.4,3.2 , 1.6Hz, 2H), 8.94 (ddd, J=6.0, 4.4, 2.0Hz, 2H).

Synthesis of Pt4: add L3 (100 mg, 0.15 mmol, 1.00 equiv), platinum dichloride (44.8 mg, 0.16 mmol, 1.1 equiv) to a 50 mL three-necked flask with a magnetic rotor in turn, purge nitrogen three times, and add benzene by injection Formonitrile 12mL. After bubbling with nitrogen for 30 minutes, the temperature was raised to 180°C, and the reaction was carried out for 48 hours. The reaction mixture was distilled under reduced pressure to remove benzonitrile, and then the reaction mixture was separated and purified by silica gel column chromatography. The solvent was distilled off under reduced pressure with the eluent (petroleum ether/ethyl acetate/dichloromethane=6:1:1), 85mg of red solid was obtained, the yield was 65%. ¹ H NMR (400MHz, DMSO-d6): δ1.45(s, 9H), 7.19(t, J=7.6Hz, 1H), 7.50-7.72(m, 10H), 7.85(s, 1H), 7.96( d, J=8.4Hz, 1H), 8.00–8.05 (m, 4H), 8.41–8.46 (m, 4H), 8.80 (d, J=1.2Hz, 1H), 8.86 (d, J=1.6Hz, 1H) ), 8.91–8.93 (m, 2H).

Embodiment 5: The complex Pt5 is synthesized according to the following route:

L5 synthesis: To a schlenk tube with a magnetic rotor, add Br-1 (113 mg, 0.39 mmol, 1.00 equiv), Pin-1 (150 mg, 0.39 mmol, 1.00 equiv), Pd(PPh ₃ ) ₄ (13.4 mg, 0.01 mmol, 0.03 equiv.), potassium carbonate (106 mg, 0.77 mmol, 2.0 equiv.), purge nitrogen three times, inject 5 mL of 1,4-dioxane and 1 mL of water, and heat at 85°C. Reaction for 24h. The reaction mixture was quenched by adding water, extracted three times with ethyl acetate, and the organic phases were combined, dried over anhydrous sodium sulfate, and the obtained crude product was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate)=20:1 , and the solvent was distilled off under reduced pressure to obtain 140 mg of a white solid with a yield of 78%. ¹ H NMR (500 MHz, CDCl ₃ ): δ 1.46 (s, 9H), 7.38 (dd, J=8.0, 4.0 Hz, 1H), 7.42 (dd, J=8.5, 4.5 Hz, 1H), 7.57-7.63 (m, 3H), 7.70–7.73 (m, 4H), 7.75 (d, J=2.0Hz, 1H), 7.80 (dd, J=6.0, 1.5Hz, 1H), 7.84 (dd, J=8.0, 1.5 Hz, 1H), 7.87 (d, J=2.5Hz, 1H), 7.96–7.98 (m, 2H), 8.17 (dd, J=8.5, 2.0Hz, 1H), 8.21 (dd, J=8.0, 1.5Hz) , 1H), 8.89 (dd, J=4.0, 1.5Hz, 1H), 8.95 (dd, J=4.0, 1.5Hz, 1H).

Synthesis of Pt5: add L5 (130mg, 0.28mmol, 1.00 equiv), platinum dichloride (81.9 mg, 0.31 mmol, 1.1 equiv) to a 50mL three-necked flask with a magnetic rotor in turn, purge nitrogen three times, and add benzyl by injection Nitrile 15mL. After bubbling with nitrogen for 30 minutes, the temperature was raised to 180°C, and the reaction was carried out for 48 hours. The reaction mixture was distilled under reduced pressure to remove benzonitrile, and then the reaction mixture was separated and purified by silica gel column chromatography. The eluent (petroleum ether/ethyl acetate/dichloromethane=10:2:1) was used to remove the solvent under reduced pressure. 68 mg of red solid was obtained, the yield was 37%. ¹ H NMR (500MHz, DMSO-d6): δ1.53(s, 9H), 7.13-7.18(m, 2H), 7.47(d, J=2.5Hz, 2H), 7.61-7.65(m, 2H), 7.81(t,J＝8.0Hz,2H),7.88(t,J＝8.0Hz,1H),8.08(d,J＝2.0Hz,1H),8.13–8.15(m,1H),8.31(dd,J =5.0,1.5Hz,1H),8.38(dd,J=5.0,1.5Hz,1H),8.65(d,J=2.0Hz,1H),8.67(d,J=7.0Hz,1H),8.83(dd , J=8.5, 1.5Hz, 1H), 8.85 (dd, J=8.5, 1.5Hz, 1H).

Embodiment 6: The complex Pt6 is synthesized according to the following route:

L6 synthesis: To a schlenk tube with a magnetic rotor, add Br-1 (113 mg, 0.39 mmol, 1.00 equiv), Pin-3 (171 mg, 0.39 mmol, 1.00 equiv), Pd(PPh ₃ ) ₄ (13.4 mg, 0.01 mmol, 0.03 equiv.), potassium carbonate (106 mg, 0.77 mmol, 2.0 equiv.), purge nitrogen three times, inject 5 mL of 1,4-dioxane and 1 mL of water, and heat at 85°C. Reaction for 24h. The reaction mixture was quenched by adding water, extracted three times with ethyl acetate, and the organic phases were combined, dried over anhydrous sodium sulfate, and the obtained crude product was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate)=40:1 , and the solvent was distilled off under reduced pressure to obtain 160 mg of a white solid with a yield of 80%. ¹ H NMR (500 MHz, CDCl ₃ ): δ 1.44 (s, 9H), 1.46 (s, 9H), 7.38 (dd, J=8.0, 4.0 Hz, 1H), 7.42 (dd, J=8.5, 4.5 Hz , 1H), 7.56–7.59 (m, 1H), 7.61–7.64 (m, 1H), 7.70 (d, J=1.5Hz, 1H), 7.71–7.74 (m, 3H), 7.74 (d, J=2.5 Hz,1H),7.78–7.81(m,2H),7.84(dd,J=8.0,1.0Hz,1H),7.87(d,J=2.0Hz,1H),7.95(t,J=1.5Hz,1H) ),8.17(dd,J＝8.5,2.0Hz,1H),8.21(dd,J＝8.0,1.5Hz,1H),8.88(dd,J＝4.5,2.0Hz,1H),8.96(dd,J＝ 4.0, 2.0Hz, 1H).

Synthesis of Pt6: add L6 (130 mg, 0.25 mmol, 1.00 equiv), platinum dichloride (73 mg, 0.28 mmol, 1.1 equiv) to a 50 mL three-necked flask with a magnetic rotor in turn, purge nitrogen three times, and add benzonitrile by injection 15mL. After bubbling with nitrogen for 30 minutes, the temperature was raised to 180°C, and the reaction was carried out for 48 hours. The reaction mixture was distilled under reduced pressure to remove benzonitrile, and then the reaction mixture was separated and purified by silica gel column chromatography. The eluent (petroleum ether/ethyl acetate/dichloromethane=10:2:1) was used to remove the solvent under reduced pressure. 85mg of red solid was obtained, the yield was 48%. ¹ H NMR (500MHz, DMSO-d6): δ1.44 (s, 9H), 1.54 (s, 9H), 7.15 (t, J=7.5Hz, 1H), 7.52 (d, J=6.0Hz, 1H) ,7.55(d,J＝1.5Hz,1H),7.62(dd,J＝5.0,1.0Hz,1H),7.64(dd,J＝5.0,1.0Hz,1H),7.71–7.71(m,1H), 7.81(d,J＝8.0Hz,1H),7.87(t,J＝7.5Hz,1H),8.08(d,J＝2.0Hz,1H),8.13-8.14(m,1H),8.32(dd,J ＝5.5,1.5Hz,1H),8.40(dd,J＝5.5,1.5Hz,1H),8.61(d,J＝2.0Hz,1H),8.67(d,J＝2.5Hz,1H),8.83(dd , J=8.5, 3.5Hz, 1H), 8.83 (dd, J=8.0, 1.0Hz, 1H).

Example 7: The platinum complex Pt7 can be synthesized as follows:

Synthesis of L7: To a schlenk tube with a magnetic rotor, add Cl-3 (150 mg, 0.47 mmol, 1.00 equiv), Pin-1 (184 mg, 0.47 mmol, 1.00 equiv), Pd ₂ (dba) ₃ (13.04 mg , 0.01 mmol, 0.03 equiv), tricyclohexyl phosphorus (7.99 mg, 0.03 mmol, 0.06 equiv), potassium phosphate (211 mg, 0.99 mmol, 2.1 equiv), 1,4-dioxane was added after pumping nitrogen three times 6mL and 1.5mL of water, heated to 85°C. Reaction for 24h. The reaction mixture was quenched by adding water, extracted three times with ethyl acetate, and the organic phases were combined, dried over anhydrous sodium sulfate, and the obtained crude product was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate)=10:1 , and the solvent was distilled off under reduced pressure to obtain 240 mg of white solid with a yield of 93%. ¹ H NMR (500 MHz, CDCl ₃ ): δ 1.47 (s, 9H), 7.38–7.44 (m, 2H), 7.46 (dd, J=8.0, 4.0 Hz, 1H), 7.50–7.53 (m, 2H), 7.59–7.63 (m, 2H), 7.72–7.80 (m, 7H), 7.89 (d, J=2.0Hz, 1H), 8.00 (t, J=2.0Hz, 1H), 8.04–8.05 (m, 2H) ,8.09(d,J＝2.0Hz,1H),8.19(dd,J＝8.0,1.5Hz,1H),8.28(dd,J＝8.0,1.5Hz,1H),8.90(dd,J＝4.5,2.0 Hz, 1H), 8.96 (dd, J=4.0, 2.0 Hz, 1H).

Synthesis of Pt7: add L7 (150 mg, 0.27 mmol, 1.00 equiv), platinum dichloride (77.5 mg, 0.29 mmol, 1.05 equiv.) to a 50 mL three-necked flask with a magnetic rotor in turn, purge nitrogen three times, and add benzene by injection Formonitrile 15mL. After bubbling with nitrogen for 30 minutes, the temperature was raised to 180°C, and the reaction was carried out for 48 hours. The reaction mixture was distilled under reduced pressure to remove benzonitrile, and then the reaction mixture was separated and purified by silica gel column chromatography. The eluent (petroleum ether/ethyl acetate/dichloromethane=10:3:1) was used to remove the solvent under reduced pressure. 40 mg of red solid was obtained, the yield was 20%. ¹ H NMR (500MHz, DMSO-d6): δ1.54 (s, 9H), 7.16–7.19 (m, 2H), 7.48–7.53 (m, 3H), 7.60–7.68 (m, 4H), 7.82 (d) ,J=8.0Hz,1H),7.95(d,J=8.0Hz,1H),8.03–8.05(m,2H),8.09(d,J=2.0Hz,1H),8.34(dd,J=5.0, 1.5Hz, 1H), 8.38 (dd, J=5.5, 1.5Hz, 1H), 8.45 (d, J=2.0Hz, 1H), 8.66 (d, J=2.0Hz, 1H), 8.83–8.86 (m, 2H), 8.91 (dd, J=8.5, 1.5Hz, 1H).

Description of Photophysical Tests and Theoretical Calculations

Steady-state emission experiments and lifetime measurements were performed on a Horiba Jobin Yvon FluoroLog-3 spectrometer. Theoretical calculations for the Pt(II) complexes were performed using the Titan software package. The geometry of the ground state (S ₀ ) molecule was optimized using density functional theory (DFT). DFT calculations were performed using the B3LYP functional with the 6-31G(d) basis set for C, H, O, and N atoms and the LANL2DZ basis set for Pt atoms.

It can be seen from Figures 1 to 7 that the above platinum (II) complexes can strongly emit light in dichloromethane solution, and their solution quantum efficiencies are all greater than 50%. As shown in Table 1 below, the thermogravimetric analysis (TGA) data of some platinum (II) complexes show that they have high thermal stability, and the 5% mass loss temperature is above 430°C.

Table 1

Platinum(II) complex Decomposition temperature (5% mass loss temperature) Pt1 434℃ Pt5 435℃ Pt6 438℃

Table 2: Frontier orbital energy levels of some metal complexes

metal complex HOMO/eV LUMO/eV Gap/eV Pt9 -4.61 -1.98 2.63 Pt10 -4.65 -2.06 2.59 Pt12 4.62 -2.02 2.60 Pt13 -4.56 -2.03 2.53 Pt15 -4.49 -1.96 2.53 Pt16 -4.51 -1.88 2.63 Pt17 -4.31 -1.87 2.44 Pt18 -4.53 -1.91 2.62 Pt19 -4.44 -2.02 2.42 Pt20 -4.60 -1.94 2.66 Pt21 -4.57 -1.90 2.67 Pt22 -4.52 -1.91 2.61 Pt23 -4.56 -2.00 2.56 Pt24 -4.72 -2.17 2.55 Pt25 -4.88 -2.07 2.81 Pt26 -4.29 -1.81 2.48 Pt27 -4.57 -2.06 2.51 Pt28 -4.62 -2.16 2.68 Pd1 -4.75 -1.95 2.80 Pd2 -4.72 -1.96 2.76

The theoretical calculation data of some platinum(II) complexes are listed in Table 2. It can be seen from the table that the frontier orbital energy levels of platinum(II) complexes can be adjusted by manipulating the structure of the ligands.

It can be seen from Figure 8 that, based on the symmetrical structure of the parent nucleus, the distribution of the frontier orbital electron cloud also has a certain symmetry. The HOMO is mainly distributed on the central metal atom and the biphenyl group, while the LUMO is mainly distributed on the two quinoline groups. on the group. In Pt9, the tert-butyl group introduced at position 6 of quinoline hardly participates in the distribution of frontier orbitals, but can increase its steric hindrance and improve the thermal stability of the molecule. In Pt10, a phenyl group is introduced on the phenyl group. Due to the large dihedral angle between the introduction of the phenyl group and the molecular core structure, the HOMO distribution of Pt10 does not significantly delocalize to the introduced phenyl ring, and the introduction of the phenyl group The electron transport properties of platinum complexes can be well improved. Pd1 replaces the central metal atom from platinum with palladium, and its energy level difference can be observed to be significantly larger, so its emission spectrum is expected to have a blue shift. Pt12 can improve the solubility and electron transport ability of the complexes without significantly changing the molecular electron cloud distribution.

It can be seen from Figure 9 that the tert-butyl group introduced on the quinoline ring in Pt13 hardly contributes to the frontier orbital, while the introduced phenyl group can make the LUMO distribution significantly delocalized to the right. By introducing multiple tert-butyl groups, the thermal stability of the molecule can be well improved and the intermolecular π-π stacking can be suppressed, which is beneficial to the sublimation of the complex. Pt15 and Pt16 introduced a number of substituents on the biphenyl group, and found that their HOMO changed little, so it was speculated that functional substituents could be introduced into the biphenyl group to improve the molecular structure.

It can be seen from Figure 10 that the introduction of tert-butyl and isopropyl groups into biphenyl groups in Pt18 increases its HOMO level, and can well improve the thermal stability of platinum complexes and inhibit intermolecular π-π stacking. In Pt19, the acyl group on the left phenyl group increases the conjugated structure, and its HOMO is delocalized to the introduced phenyl group, and its HOMO energy level is significantly increased, so its HOMO energy level can be regulated by conjugation. In Pt20, the conjugation occurs due to the formation of a condensed ring on the right side, resulting in a decrease in the LUMO distribution on the right side.

It can be seen from Figure 11 that when tert-butyl groups and cycloalkyl groups are introduced on both sides, the changes in the electron cloud distribution are small, and the cycloalkyl groups can also improve the thermal stability of the molecule and inhibit the intermolecular π-π stacking. The introduction of Pt23 into benzofuran delocalizes the HOMO distribution and slightly increases its HOMO energy level. The introduction of a conjugated system can enhance the molecular rigidity, and has little effect on the electron cloud distribution, which can improve the exciton utilization. In Figure 12, a trifluoromethyl group is introduced into the upper right corner of Pt28, and it can be clearly observed that its LUMO energy level is obviously delocalized to the trifluoromethyl side, and the LUMO energy level is significantly reduced. Therefore, its LUMO energy level can be regulated by introducing electron withdrawing groups on one side.

The host materials involved in the present invention are obtained by known synthetic methods.

Preparation of OLED devices: Evaporate p-doped materials P-1 to P-5 on the surface or anode of ITO glass with a light-emitting area of 2mm × 2mm, or use the p-doped materials at a concentration of 1% to 50% with the table. The compounds described in co-evaporated to form a 5-100 nm hole injection layer (HIL), a 5-200 nm hole transport layer (HTL), followed by a 10-100 nm light emitting layer (EML) on the HTL ( can contain the compound), and finally use the compound to form an electron transport layer (ETL) 20-200nm and a cathode 50-200nm, if necessary, add an electron blocking layer (EBL) between the HTL and EML layers. An electron injection layer (EIL) was added between the cathode and the organic light emitting element. The OLEDs were tested by standard methods and are listed in Table 3.

table 3

It can be seen from Table 3 that, compared with the comparative device 1 using the traditional host material CBP, the device examples 1 to 7 using the compound combination provided by the present invention as the host can significantly improve the current efficiency of the OLED device while reducing the driving voltage.

In conclusion, the introduction of functional substituents into the biphenyl group can improve the molecular structure and have less marketing to the frontier orbital distribution of the molecule. In particular, the introduction of tert-butyl groups on biphenyl groups can well suppress intermolecular π-π stacking. Similarly, the introduction of conjugated groups such as acene or benzofuran into the biphenyl group can delocalize the HOMO and regulate the HOMO energy level. Replacing the central metal atom from platinum to palladium can significantly change the energy level difference, which is expected to blue-shift the emission spectrum of the molecule, which can tune its photophysical properties.

Claims (14)

1. A metal platinum (II) or palladium (II) complex phosphorescent material has a structure shown in a formula (I):

in formula (I), M is Pt or Pd; y is ¹ 、Y ² 、Y ³ 、Y ⁴ 、Y ⁵ 、Y ⁶ 、Y ⁷ 、Y ⁸ 、Y ⁹ 、Y ¹⁰ 、Y ¹¹ 、Y ¹² 、Y ¹³ 、Y ¹⁴ 、Y ¹⁵ 、Y ¹⁶ 、Y ¹⁷ And Y ¹⁸ Each independently is N or CH; r ¹ 、R ² 、R ³ 、R ⁴ 、R ⁵ And R ⁶ Each independently represents mono-, di-, tri-or no substitution; r ¹ 、R ² 、R ³ 、R ⁴ 、R ⁵ And R ⁶ Each independently represents any one of hydrogen, deuterium, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted aryloxy group, a halogen, a cycloalkenyl group, a substituted or unsubstituted heterocyclic group, an alkenyl group, an alkynyl group, a hydroxyl group, a mercapto group, a nitro group, a cyano group, a substituted or unsubstituted amino group, a mono-or dialkylamino group, a mono-or diarylamino group, an ester group, a nitrile group, an isonitrile group, an alkoxycarbonyl group, an amido group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, a sulfinyl group, a ureido group, a phosphoramido group, an imino group, a sulfo group, a carboxyl group, a hydrazino group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted heteroarylamino group, an alkylsilyl group, a substituted or unsubstituted arylsilyl group, a substituted or unsubstituted heteroarylsilyl group, a substituted or unsubstituted arylsilyl group, a substituted or unsubstituted arylacyl group, a substituted or unsubstituted heteroaryloxy group, and two or more adjacent R groups ¹ 、R ² 、R ³ 、R ⁴ 、R ⁵ And R ⁶ May be selectively linked to form fused rings.

2. The composition is characterized by comprising a tetradentate ring metal platinum (II) or palladium (II) complex phosphorescent material based on biphenyl quinoline coordination and an organic host material, wherein the structural formula of the metal platinum (II) or palladium (II) complex phosphorescent material is shown as a formula (I); the organic host material has a structural formula (II) or (III):

wherein:

in formula (I), M is Pt or Pd; y is ¹ 、Y ² 、Y ³ 、Y ⁴ 、Y ⁵ 、Y ⁶ 、Y ⁷ 、Y ⁸ 、Y ⁹ 、Y ¹⁰ 、Y ¹¹ 、Y ¹² 、Y ¹³ 、Y ¹⁴ 、Y ¹⁵ 、Y ¹⁶ 、Y ¹⁷ And Y ¹⁸ Each independently is N or CH; r ¹ 、R ² 、R ³ 、R ⁴ 、R ⁵ And R ⁶ Each independently represents mono-, di-, tri-or unsubstituted; r ¹ 、R ² 、R ³ 、R ⁴ 、R ⁵ And R ⁶ Each independently represents any one of hydrogen, deuterium, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted aryloxy group, halogen, a cycloalkenyl group, a substituted or unsubstituted heterocyclic group, an alkenyl group, an alkynyl group, a hydroxyl group, a mercapto group, a nitro group, a cyano group, a substituted or unsubstituted amino group, a mono-or dialkylamino group, a mono-or diarylamino group, an ester group, a nitrile group, an isonitrile group, an alkoxycarbonyl group, an amido group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, a sulfinyl group, a ureido group, a phosphoramido group, an imino group, a sulfo group, a carboxyl group, a hydrazine group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted heteroarylamino group, an alkylsilyl group, a substituted or unsubstituted arylsilyl group, a substituted or unsubstituted heteroarylsilyl group, a substituted or unsubstituted arylsilyl group, a substituted or unsubstituted heteroaryloxy group, and two or more adjacent R ¹ 、R ² 、R ³ 、R ⁴ 、R ⁵ And R ⁶ May be optionally linked to form fused rings;

in the formulae (II) and (III), X ¹ 、X ² 、X ³ 、X ⁴ 、X3 ⁵ 、X ⁶ 、X ⁷ 、X ⁸ 、X ⁹ 、X ¹⁰ 、X ¹¹ 、X ¹² 、X ¹³ 、X ¹⁴ 、X ¹⁵ 、X ¹⁶ 、X ¹⁷ 、X ¹⁸ 、X ¹⁹ And X ²⁰ Each independently is N or CH; z ¹ 、Z ² 、Z ³ 、Z ⁴ 、Z ⁵ 、Z ⁶ 、Z ⁷ 、Z ⁸ 、Z ⁹ 、Z ¹⁰ 、Z ¹¹ 、Z ¹² And Z ¹³ Each independently is N or CH, and at least 2 are N; l is ¹ 、L ² And L ³ Absent or selected from single bonds, O, S, CR ¹⁵ R ¹⁶ 、SiR ¹⁷ R ¹⁸ 、NR ¹⁹ (ii) a A. B, C and D are each independently selected from C6-C30 aryl, C2-C30 heteroaryl; r is ⁷ 、R ⁸ 、R ⁹ 、R ¹⁰ 、R ¹¹ 、R ¹² 、R ¹³ 、R ¹⁴ 、R ¹⁵ 、R ¹⁶ 、R ¹⁷ 、R ¹⁸ And R ¹⁹ Each independently represents mono-, di-, tri-, tetra-, or unsubstituted; and R is ⁷ 、R ⁸ 、R ⁹ 、R ¹⁰ 、R ¹¹ 、R ¹² 、R ¹³ 、R ¹⁴ 、R ¹⁵ 、R ¹⁶ 、R ¹⁷ 、R ¹⁸ And R ¹⁹ Each independently represents any one of hydrogen, deuterium, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted aryloxy group, a halogen, a cycloalkenyl group, a substituted or unsubstituted heterocyclic group, an alkenyl group, an alkynyl group, a hydroxyl group, a mercapto group, a nitro group, a cyano group, a substituted or unsubstituted amino group, a mono-or dialkylamino group, a mono-or diarylamino group, an ester group, a nitrile group, an isonitrile group, an alkoxycarbonyl group, an amido group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, a sulfinyl group, a ureido group, a phosphoramido group, an imino group, a sulfo group, a carboxyl group, a hydrazino group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted heteroarylamino group, an alkylsilyl group, a substituted or unsubstituted arylsilyl group, a substituted or unsubstituted heteroarylsilyl group, a substituted or unsubstituted arylsilyl group, a substituted or unsubstituted arylacyl group, a substituted or unsubstituted heteroaryloxy group, and two or more adjacent R groups ¹ 、R ² 、R ³ 、R ⁴ 、R ⁵ And R ⁶ Can be selectively linked to form thickAnd (4) a ring.

3. The composition of claim 2, wherein the platinum (II) or palladium (II) complex has a structure of one of:

4. the composition of claim 1, wherein formula (II) is selected from the group consisting of (II) -1 to (II) -24:

wherein, X ¹ 、X ² 、X ³ 、X ⁴ 、X ⁵ 、X ⁶ 、X ⁷ 、X ⁸ 、X ⁹ And X ¹⁰ ，L ¹ 、L ² And L ³ A and B, R ⁷ 、R ⁸ 、R ⁹ And R ¹⁰ The same as in claim 1.

5. The composition of claim 1, wherein A, B, C and D are selected from the group of structures:

wherein R is ¹⁵ 、R ¹⁶ 、R ¹⁷ 、R ¹⁸ And R ¹⁹ The same as in claim 1.

6. The composition of any one of claims 2 to 3, wherein the organic host material of formula (II) or formula (III) is selected from one of the following representative structures:

7. a formulation comprising a composition according to any one of claims 2 to 6 and at least one solvent.

8. A formulation according to claim 7, wherein the composition and solvent form a formulation in which the solvent is an unsaturated hydrocarbon solvent, a halogenated saturated hydrocarbon solvent, a halogenated unsaturated hydrocarbon solvent, an ether solvent or an ester solvent; wherein the unsaturated hydrocarbon solvent is toluene, xylene, mesitylene, tetralin, decalin, bicyclohexane, n-butylbenzene, sec-butylbenzene or tert-butylbenzene; the halogenated saturated hydrocarbon solvent is carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane or bromocyclohexane; the halogenated unsaturated hydrocarbon solvent is chlorobenzene, dichlorobenzene or trichlorobenzene; the ether solvent is tetrahydrofuran or tetrahydropyran; the ester solvent is alkyl benzoate.

9. An organic electroluminescent device, comprising: a first electrode; a second electrode facing the first electrode; the organic functional layer is clamped between the first electrode and the second electrode; wherein the light-emitting layer comprises the composition of any one of claims 2 to 6.

10. The organic electroluminescent device according to claim 9, wherein the luminescent layer contains the biphenylquinoline coordinated tetradentate ring metal platinum (II) or palladium (II) complex phosphorescent material and an organic host material, wherein the mass percentage of the biphenylquinoline coordinated tetradentate ring metal platinum (II) or palladium (II) complex phosphorescent material is 1 to 50%.

11. The organic electroluminescent device according to claim 10, wherein the device is a full-color display, a photovoltaic device, a light-emitting display device, or an organic light-emitting diode.

12. An organic electroluminescent device comprises a cathode layer, an anode layer and an organic layer, wherein the organic layer comprises a composition, the composition comprises a tetradentate ring metal platinum (II) or palladium (II) complex phosphorescent material based on biphenyl quinoline coordination and an organic host material, and the structural formula of the metal platinum (II) or palladium (II) complex phosphorescent material is shown as the formula (I); the organic host material has a structural formula (II) or (III):

wherein:

in formula (I), M is Pt or Pd; y is ¹ 、Y ² 、Y ³ 、Y ⁴ 、Y ⁵ 、Y ⁶ 、Y ⁷ 、Y ⁸ 、Y ⁹ 、Y ¹⁰ 、Y ¹¹ 、Y ¹² 、Y ¹³ 、Y ¹⁴ 、Y ¹⁵ 、Y ¹⁶ 、Y ¹⁷ And Y ¹⁸ Each independently is N or CH; r ¹ 、R ² 、R ³ 、R ⁴ 、R ⁵ And R ⁶ Each independently represents mono-, di-, tri-or no substitution; r ¹ 、R ² 、R ³ 、R ⁴ 、R ⁵ And R ⁶ Each independently represents hydrogen, deuterium, alkyl, haloalkyl, cycloalkyl, alkoxy, substituted or unsubstitutedSubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted aryloxy, halogen, cycloalkenyl, substituted or unsubstituted heterocyclyl, alkenyl, alkynyl, hydroxyl, mercapto, nitro, cyano, substituted or unsubstituted amino, mono-or dialkylamino, mono-or diarylamino, ester, nitrile, isonitrile, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphonamido, imino, sulfo, carboxyl, hydrazino, substituted or unsubstituted arylamino, substituted or unsubstituted heteroarylamino, alkylsilyl, substituted or unsubstituted arylsilyl, substituted or unsubstituted heteroarylsilyl, substituted or unsubstituted aryloxysilyl, substituted or unsubstituted heteroaryloxysilyl, substituted or unsubstituted arylacyloxy, substituted or unsubstituted arylacyl, substituted or unsubstituted heteroarylacyl, substituted or unsubstituted phosphinyl, and two or more adjacent R' s ¹ 、R ² 、R ³ 、R ⁴ 、R ⁵ And R ⁶ May be optionally linked to form fused rings;

in the formulae (II) and (III), X ¹ 、X ² 、X ³ 、X ⁴ 、X3 ⁵ 、X ⁶ 、X ⁷ 、X ⁸ 、X ⁹ 、X ¹⁰ 、X ¹¹ 、X ¹² 、X ¹³ 、X ¹⁴ 、X ¹⁵ 、X ¹⁶ 、X ¹⁷ 、X ¹⁸ 、X ¹⁹ And X ²⁰ Each independently is N or CH; z ¹ 、Z ² 、Z ³ 、Z ⁴ 、Z ⁵ 、Z ⁶ 、Z ⁷ 、Z ⁸ 、Z ⁹ 、Z ¹⁰ 、Z ¹¹ 、Z ¹² And Z ¹³ Each independently is N or CH, and at least 2 are N; l is ¹ 、L ² And L ³ Absent or selected from a single bond, O, S, CR ¹⁵ R ¹⁶ 、SiR ¹⁷ R ¹⁸ 、NR ¹⁹ (ii) a A. B, C and D are each independently selected from C6-C30 aryl, C2-C30 heteroaryl; r ⁷ 、R ⁸ 、R ⁹ 、R ¹⁰ 、R ¹¹ 、R ¹² 、R ¹³ 、R ¹⁴ 、R ¹⁵ 、R ¹⁶ 、R ¹⁷ 、R ¹⁸ And R ¹⁹ Each independently represents mono-, di-, tri-, tetra-, or unsubstituted; and R is ⁷ 、R ⁸ 、R ⁹ 、R ¹⁰ 、R ¹¹ 、R ¹² 、R ¹³ 、R ¹⁴ 、R ¹⁵ 、R ¹⁶ 、R ¹⁷ 、R ¹⁸ And R ¹⁹ Each independently represents any one of hydrogen, deuterium, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted aryloxy group, a halogen, a cycloalkenyl group, a substituted or unsubstituted heterocyclic group, an alkenyl group, an alkynyl group, a hydroxyl group, a mercapto group, a nitro group, a cyano group, a substituted or unsubstituted amino group, a mono-or dialkylamino group, a mono-or diarylamino group, an ester group, a nitrile group, an isonitrile group, an alkoxycarbonyl group, an amido group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, a sulfinyl group, a ureido group, a phosphoramido group, an imino group, a sulfo group, a carboxyl group, a hydrazino group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted heteroarylamino group, an alkylsilyl group, a substituted or unsubstituted arylsilyl group, a substituted or unsubstituted heteroarylsilyl group, a substituted or unsubstituted arylsilyl group, a substituted or unsubstituted arylacyl group, a substituted or unsubstituted heteroaryloxy group, and two or more adjacent R groups ¹ 、R ² 、R ³ 、R ⁴ 、R ⁵ And R ⁶ May be selectively linked to form fused rings.

13. A display or lighting device comprising the organic electroluminescent element as claimed in any one of claims 9 to 11.

14. Use of a composition according to any one of claims 2 to 6 in the manufacture of an organic light emitting device.

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