WO2024002049A1

WO2024002049A1 - Composition, preparation, organic electroluminescent device, and display or illumination apparatus

Info

Publication number: WO2024002049A1
Application number: PCT/CN2023/102637
Authority: WO
Inventors: 李贵杰; 黄笛升; 佘远斌; 湛丰; 赵晓宇
Original assignee: 浙江工业大学; 浙江华显光电科技有限公司
Priority date: 2022-06-29
Filing date: 2023-06-27
Publication date: 2024-01-04
Also published as: CN115232174A

Abstract

The present invention relates to a composition, a preparation, an organic electroluminescent device, and a display or illumination apparatus. A phosphorescent material and the composition in the invention have good thermal stability, can balance hole and electron transport, and are more efficient in terms of energy transfer between a subject body and an object body. Specifically, the composition of the present invention is used as a luminescent layer of the organic electroluminescent device, and the external quantum efficiency of the luminescent device is improved. The composition has significant application prospects in the fields of OLED display and illumination.

Description

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

Technical field

The invention belongs to the field of organic electroluminescence, and specifically relates to a composition, a preparation, an organic electroluminescence device and a display or lighting device, in which the guest is a four-tooth 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 liquid crystal displays, which have shortcomings such as slow response speed, small viewing angle, need for backlight, and high energy consumption, OLED, as an autonomous light-emitting device, does not require a backlight and is energy-saving; it also has low driving voltage, fast response speed, and high resolution and contrast. , wide viewing angle, and outstanding 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, further in-depth research and development, and 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. The light-emitting materials in early OLED devices were mainly organic small molecule fluorescent materials. However, spin statistics quantum science shows that in the case of electroluminescence, the generated singlet excitons and triplet excitons (excitons) are 25% and 75% respectively. Since traditional fluorescent materials can only utilize excitons in the singlet state, ions, so its maximum theoretical internal quantum efficiency is only 25%, and the remaining 75% of triplet excitons are lost through non-radiative transitions. Professor Forrest of Princeton University and Professor Thompson of the University of Southern California discovered the phosphorescence electroluminescence phenomenon of heavy metal organic complex molecules at room temperature in 1998. Due to the strong spin-orbit coupling of heavy metal atoms, excitons can more easily undergo intersystem jump (ISC) from singlet to triplet states, allowing OLED devices to make full use of all singlet and triplet excitations generated by electrical excitation. ions, so that the theoretical internal quantum efficiency of luminescent materials can reach 100% (Nature, 1998, 395, 151).

The luminescent layer in currently applied OLED devices almost all uses the host-guest luminescent system mechanism, that is, the subject material is doped with the guest luminescent material. The energy system of the subject material is generally larger than the guest luminescent material, and the energy is transferred from the host material to the guest material. The guest material is excited and emits light. Commonly used organic phosphorescent guest materials are generally heavy metal atoms such as iridium (III), platinum (II), Pd (II), etc. The heavy metal phosphorescent organic complex molecules currently used are cyclic metal iridium (III) complex molecules, and the number is limited. The content of the metal platinum element in the earth's crust and the annual production worldwide are about ten times that of the metal iridium element. The price of IrCl ₃ ^. H ₂ O (1100 RMB/g) used to prepare iridium (III) complex phosphorescent materials is also It is much higher than the PtCl ₂ (210 RMB/g) used to prepare platinum (II) complex phosphorescent materials; in addition, the preparation of iridium (III) complex phosphorescent materials involves iridium (III) dimers, iridium (III) intermediates The four-step reaction of body-ligand exchange, synthesis of mer-iridium (III) complex and isomer conversion from mer-to fac-iridium (III) complex greatly reduces 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 and the design of the platinum salt reaction in the last step. The platinum element utilization rate 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 device efficiency and life is an important research issue. Therefore, there is an urgent need to develop new phosphorescent metal platinum (II) complexes.

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

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

Contents 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, their combinations, and organic electroluminescent devices containing the combinations.

The 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 modes of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently represented as 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, Thiol, nitro, cyano, substituted or unsubstituted amino, mono or dialkylamino, mono or diarylamino, ester group, nitrile group, isonitrile group, alkoxycarbonyl group, amido group, alkoxy group Carbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazine, substituted or Unsubstituted arylamine, substituted or unsubstituted heteroarylamino, alkylsilyl, substituted or unsubstituted arylsilyl, substituted or unsubstituted heteroarylsilyl, substituted or unsubstituted Any one of an aryloxysilyl group, a substituted or unsubstituted heteroaryloxysilyl group, a substituted or unsubstituted arylacyl group, a substituted or unsubstituted heteroarylacyl group, or a substituted or unsubstituted phosphinyl group, 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 invention provides one or more tetradentate ring metal platinum (II) or palladium (II) complex guest phosphorescent materials represented by structural formula (I) based on biphenylquinoline coordination and composed of 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 modes of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently represented as 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, Thiol, nitro, cyano, substituted or unsubstituted amino, mono or dialkylamino, mono or diarylamino, ester group, nitrile group, isonitrile group, alkoxycarbonyl group, amido group, alkoxy group Carbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazine, substituted or Unsubstituted arylamine, substituted or unsubstituted heteroarylamino, alkylsilyl, substituted or unsubstituted arylsilyl, substituted or unsubstituted heteroarylsilyl, substituted or unsubstituted Any one of an aryloxysilyl group, a substituted or unsubstituted heteroaryloxysilyl group, a substituted or unsubstituted arylacyl group, a substituted or unsubstituted heteroarylacyl group, or a substituted or unsubstituted phosphinyl group, 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 formulas (II) and (III), ^X1 , ^X2 , X3, ^X4 , ^X5 ^, ^X6 , ^X7 , ^X8 , ^X9 , ^X10 , ^X11 , ^X12 , ^X13 , ^X14 , ^X15 , ^X16 , ^X17 , ^X18 , ^X19 and ^X20 are each independently N or CH; ^Z1 , ^Z2 , ^Z3 , ^Z4 , ^Z5 , ^Z6 , ^Z7 , Z ⁸ , Z ⁹ , Z ¹⁰ , Z ¹¹ , Z ¹² and Z ¹³ are each independently N or CH, and at least 2 of them are N; L ¹ , L ² and L ³ do not exist or are selected from single bonds, 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 ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ are each independently represented as mono-substituted, di-substituted, tri-substituted, tetra-substituted or unsubstituted; 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 are each independently represented as hydrogen, deuterium, alkyl, haloalkyl group, 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 group, nitrile group, isonitrile group, alkoxy Carbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imine, sulfonyl group, carboxyl group, hydrazino group, substituted or unsubstituted arylamine group, substituted or unsubstituted heteroarylamino group, alkylsilyl group, substituted or unsubstituted arylsilyl group, substituted or unsubstituted heteroaryl group Silyl group, substituted or unsubstituted aryloxysilyl group, substituted or unsubstituted heteroaryloxysilyl group, substituted or unsubstituted arylacyl group, substituted or unsubstituted heteroarylacyl group, 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 guest phosphorescent material based on the tetradentate ring metal platinum (II) or palladium (II) complex coordinated by biphenylquinoline, the platinum (II) or Palladium(II) complexes have one of the following structures:

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

Among them, ^X1 , ^X2 , ^X3 , ^X4 , X5, ^X6 , ^X7 , ^X8 , ^X9 and ^X10 , ^L1 , ^L2 and ^L3 , A and ^B , ^R7 , ^R8 , R ⁹ and R ¹⁰ are the same as defined above.

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

Among them, R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ are the same as the above definitions.

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

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

The invention also relates to an organic electroluminescent device, which includes a cathode layer, an anode layer and an organic layer. The organic layer includes a hole injection layer, a hole transport layer, a light-emitting layer, a hole blocking layer, an electron injection layer, and an electron transport 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 between 0.1% and 50%.

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

The present invention relates to a composition comprising one or more formulations of Structural Formula (I) and Structural Formula (II) or Structural Formula (III) and a solvent. The solvent used is not particularly limited and can be those well known to those skilled in the art, such as Toluene, xylene, mesitylene, tetralin, decalin, dicyclohexane, n-butylbenzene, sec-butylbenzene, tert-butylbenzene and other unsaturated hydrocarbon solvents, carbon tetrachloride, chloroform, dichloro Halogenated saturated hydrocarbon solvents such as methane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, chlorobenzene, dichlorobenzene, etc. 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, which includes a cathode layer, an anode layer and an organic layer. The organic layer includes a composition, the composition includes a tetradentate based on biphenylquinoline coordination. Cyclometal 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 as shown in formula (I); the structural formula of the organic host material (II) or formula (III):

in:

In formulas (II ⁾ and (III), ^X1 , ^X2 , ^X3 , ^X4 , X35, ^X6 , ^X7 , ^X8 , ^X9 , ^X10 , ^X11 , ^X12 , ^X13 , ^X14 , ^X15 , ^X16 , ^X17 , ^X18 , ^X19 and ^X20 are each independently N or CH; ^Z1 , ^Z2 , ^Z3 , ^Z4 , ^Z5 , ^Z6 , ^Z7 , Z ⁸ , Z ⁹ , Z ¹⁰ , Z ¹¹ , Z ¹² and Z ¹³ are each independently N or CH, and at least 2 of them are N; L ¹ , L ² and L ³ do not exist or are selected from single bonds, 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 ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ are each independently represented as mono-substituted, di-substituted, tri-substituted, tetra-substituted or unsubstituted; 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 are each independently represented as hydrogen, deuterium, alkyl, haloalkyl base, Cycloalkyl, alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted aryloxy, halogen, cycloalkenyl, substituted or unsubstituted heterocyclyl, alkenyl group, alkynyl group, hydroxyl group, mercapto group, nitro group, cyano group, substituted or unsubstituted amino group, mono or dialkylamino group, mono or diarylamino group, ester group, nitrile group, isonitrile group, alkoxycarbonyl group , amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imine, sulfo, Carboxyl group, hydrazine group, substituted or unsubstituted arylamine group, substituted or unsubstituted heteroarylamino group, alkylsilyl group, substituted or unsubstituted arylsilyl group, substituted or unsubstituted heteroarylsilyl group group, substituted or unsubstituted aryloxysilyl, substituted or unsubstituted heteroaryloxysilyl, substituted or unsubstituted arylacyl, substituted or unsubstituted heteroarylacyl, substituted or unsubstituted oxygen Any one of the phosphine 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 compounds Pt1 to compounds Pt352 and compounds Pd1 to compounds Pd32.

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

Among them, ^X1 , ^X2 , ^X3 , ^X4 , ^X5 , ^{X6, X7} ^, ^X8 , ^X9 and ^X10 , ^L1 , ^L2 and ^L3 , A and B, ^R7 , ^R8 , 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 structure:

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

Preferably, the organic host material described in 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, which contains the above-mentioned organic electroluminescent device.

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

The present invention has no special limitations on the preparation method of the organic electroluminescent 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 compound, it can be prepared by using the preparation methods and materials of light-emitting devices well known to those skilled in the art.

The organic electroluminescent device of the present invention is an organic photovoltaic device, an organic light-emitting device (OLED), an organic solar cell (OSC), an electronic paper (e-paper), an organic photoreceptor (OPC), an organic thin film transistor (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 metal or conductive oxides and their alloys on the substrate to form an anode; in the prepared The surface of the anode is evaporated in sequence, with a hole injection layer, a hole transport layer, a light emitting layer, an air barrier layer and an electron transport layer, and then the cathode is prepared by evaporating the cathode. In addition to the above methods, the cathode, organic layer, and anode are sequentially evaporated on the substrate to produce an organic electroactive device. 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 according to solvent engineering (spin-coating, tape-casting, doctor-blading, and screen-printing). , inkjet printing or thermal imaging (Thermal-Imaging, etc.) instead of evaporation methods, which can reduce the number of device layers.

The materials used in the organic electroluminescent device according to the present invention can be classified into top emission, low emission or double-sided emission. The compound of the organic electroluminescent device according to the embodiment of the present invention can be applied to organic solar cells, lighting OLEDs, flexible OLEDs, organic photoreceptors, organic thin film transistors and other electroluminescent devices in the same principle as organic light-emitting devices.

Beneficial effects of the present invention: Guest platinum (II) or palladium (II) phosphorescent material molecules based on two bidentate ligands are prone to vibration and distortion, resulting in non-radiative attenuation, resulting in low phosphorescence efficiency. Compared with bidentate platinum (II) or palladium (II) complexes, the rigid structure of the tetradentate cyclic metal platinum (II) or palladium (II) complex guest phosphorescent material based on biphenylquinoline coordination can effectively suppress Non-radiative attenuation caused by molecular vibration not only achieves high-efficiency light emission, but also has 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 to make the energy transmission between the subject and the object more efficient, which is specifically manifested in the use of the present invention The external quantum efficiency of the organic electroluminescent device produced by using the composition as a light-emitting layer is improved, and the lighting voltage is reduced at the same time.

Description of drawings

In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, other drawings can also be obtained based on these drawings without exerting creative efforts, among which:

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

Figure 2 is the room temperature emission spectrum of the platinum complex Pt2 in dichloromethane solution in the specific embodiment;

Figure 3 is the room temperature emission spectrum of the platinum complex Pt3 in dichloromethane solution in the specific embodiment;

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

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

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

Figure 7 is the room temperature emission spectrum of the platinum complex Pt7 in 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 through 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 level comparisons 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);

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

Detailed ways

It should be pointed out that the above general description and the following detailed description are only exemplary and explanatory, 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 invention are disclosed and described, it is to be understood that they are not limited to the specific synthetic methods (otherwise indicated), or the specific reagents (otherwise indicated), as these, of course, can vary. . It is also to be understood that the terminology used herein 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. The hole transport material can be preferably selected from known or unknown materials, and is 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 contains 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 compound ET-1 to ET-13, but this does not mean that the present invention is limited to the following structure:

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 the stated 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 materials are disclosed in the present invention, and it is to be understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed, not each of the various individual and aggregate combinations and permutations of these compounds are specifically disclosed. When reference is made to specific references, each is specifically contemplated and described in the present invention. For example, if a particular compound is disclosed and discussed, and the many modifications that can be made to many molecules containing that compound are discussed, then each and every combination and permutation of that compound is specifically contemplated and that such modifications may be made. sex, otherwise it would otherwise be specifically stated to the contrary. Thus, if a class of molecules A, B, and C and a class of molecules D, E, and F, and examples of combination molecules A-D are disclosed, then each is considered to be disclosed individually and collectively 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 is also disclosed. So, for example, it should be considered that groups A-E, B-F and C-E are disclosed. These concepts apply to all aspects of the invention, including, but not limited to, the steps of methods of making and using the compositions. Therefore, if there are various additional steps that can be performed, it should be understood that each of these additional steps can be performed in a specific embodiment of the method or in a combination of embodiments.

The linking atoms used in the present invention are capable of linking two groups, for example, N and C groups. The linking atom can optionally (if valency permitting) have other attached chemical moieties. For example, in one aspect, oxygen will not have any other chemical groups attached because once bonded to two atoms (eg, N or C) the valence bond has already been satisfied. In contrast, 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, thiol, aryl, heteroaryl, cycloalkyl, and heterocyclyl.

The term "cyclic structure" or similar terms used in the present invention 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 terms, permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, and aromatic and nonaromatic substituents of organic compounds. Declarative substitution Bases 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 the organic compounds described in the present invention that satisfies the valence of the heteroatom. This disclosure is not intended to be limited in any way by the permissible substituents of organic compounds. Likewise, the term "substituted" or "substituted with" includes the implicit proviso that such substitution is consistent with the permissible valence bonds of the substituting atom and the substituent, and that the substitution results in a stable compound (e.g., one that does not spontaneously undergo transformation) For example, compounds by rearrangement, cyclization, elimination, etc.). It is also contemplated that, in certain aspects, individual substituents can further optionally be substituted (ie, further substituted or unsubstituted) unless expressly stated to the contrary.

In defining various terms, "R ¹ ", "R ² ", "R ³ ", and "R ⁴ " are used as general symbols in the present invention to represent various specific substituents. These symbols can be any substituent, not limited to those disclosed herein, and when they are qualified as certain substituents in one instance, they may be qualified in other instances as some other substituent.

The term "alkyl" used in the present invention refers to 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, half-base, nonyl, decyl, dodecyl, tetradecyl, Hexadecyl, eicosanyl, tetradecyl, etc. The alkyl group may be cyclic or acyclic. The alkyl group may be branched or unbranched. The alkyl group may 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, hydroxyl, nitro, silane as described in the present invention. group, sulfo-oxo (Sulfo-oxo) or sulfhydryl group. A "lower alkyl" group is an alkyl group containing 1 to 6 (eg, 1 to 4) carbon atoms.

Throughout this 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 substituents 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, etc. When "alkyl" is used in one context and a specific term such as "alkyl alcohol" is used in another context, it is not meant to imply that the term "alkyl" does not also refer to a specific term such as "alkyl" Alcohol" etc.

This practice also applies to other groups described in this invention. That is, when a term such as "cycloalkyl" refers to both unsubstituted and substituted cycloalkyl moieties, the substituted moiety may otherwise be specifically identified in the present invention; for example, a specifically substituted cycloalkyl group may be referred to as For example, "alkylcycloalkyl". Similarly, a substituted alkoxy group may be specifically referred to as, for example, a "halogenated alkoxy group" and a specific substituted alkenyl group may be, for example, an "enol" or the like. Likewise, the practice of using a general term such as "cycloalkyl" and 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 consisting 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" in which 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 may be substituted or unsubstituted. The cycloalkyl and heterocycloalkyl groups 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 is intended to refer to a group containing two or more CH ₂ groups linked to other identical moieties. "Polyolefin group" may be represented by -( _CH2 ) _a- , where "a" is an integer from 2 to 500.

The terms "alkoxy" and "alkoxy group", as used herein, refer to an alkyl or cycloalkyl group bonded through an ether linkage; that is, "alkoxy" may be defined as -OR ¹ , where 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 , where "a" is an integer from 1 to 200, and R ¹ , R ² and R ³ are each independently an alkyl group, a cycloalkyl group, 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 inferred that in the structural formula of the present invention, there is an asymmetric olefin, or it This can be clearly stated by the key symbol C=C. The alkenyl group may 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 "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 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" in which 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 may be substituted or unsubstituted. This cylindrite and heterothenelvide can replace one or more groups, including but not limited to the alkyl, cyclotomyl, alkyl, alumoxyl, cyclopenne, cycloprobal, ring, cyclone, cyclopyrum, cyclone, cyclone, cyclone, cyclone, cyclopae, cyclopa, Alkynyl, aryl, heteroaryl, aldehyde, amino, carboxyl, ester, halogen, hydroxyl, carbonyl, azide, nitro, silyl, sulfo-oxo or mercapto.

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

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 include, but are not limited to, cycloheptynyl, cyclooctynyl, cyclononenyl, and the like. The term "heterocycloalkynyl" is a type of cycloalkenyl as defined above and is included within the meaning of the term "cycloalkynyl" in which at least one of the carbon atoms of the ring is replaced by a heteroatom, The heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur or phosphorus. Cycloalkynyl and heterocycloalkynyl groups may be substituted or unsubstituted. Cycloalkynyl and heterocycloalkynyl can be substituted with one or more groups, and the groups include but are not limited to alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, and alkyne described in the present invention. Base, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxyl, ester, halogen, hydroxyl, carbonyl, azido, nitro, silyl, sulfo-oxo (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, anthryl, phenanthrenyl, 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 may be substituted or unsubstituted. The aryl group may 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 by a fused ring structure, as in naphthalene, or by 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 an abbreviation for carbonyl (ie, C=O).

The term "amine" or "amino" used in the present invention is represented by the formula -NR ¹ R ² , wherein R ¹ and R ² can be independently selected from hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, Choose from cycloalkynyl, aryl or heteroaryl.

The term "alkylamino" as used herein is represented by the formula -NH(-alkyl), where 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 in the present invention is represented by the formula -N(alkyl) ₂ , wherein the alkyl group is as described in the present invention. Representative examples include, but are not limited to, dimethylamino, diethylamino, dipropylamino, diisopropylamino, dibutylamino, diisobutylamino, di(sec-butyl)amino, di(tert. Butyl)amino, dipentylamino, diisopentylamino, di(tert-pentyl)amino, dihexylamino, N-ethyl-N-methyl Amino, N-methyl-N-propylamino, N-ethyl-N-propylamino, etc.

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 an alkyl group, a cycloalkyl group, an alkenyl group, or a cycloalkenyl group 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 be independently alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl according to the present invention 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" 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. base, 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 independently be alkyl, cycloalkyl, alkenyl, cycloalkenyl as described in the present invention. radical, alkynyl, cycloalkynyl, aryl, or heteroaryl and "a" is an integer from 1 to 500. Examples of polyether groups include polyoxyethylene, polyoxypropylene and polyoxybutylene.

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

The term "heterocyclyl" as used in the present invention refers to monocyclic and polycyclic non-aromatic ring systems of 3 to 30 carbon atoms, and the term "heteroaryl" as used in the present invention refers to monocyclic and polycyclic non-aromatic ring systems. Aromatic ring systems with more than 60 carbon atoms: in which at least one of the ring members is not carbon. The term includes azetidinyl, dioxanyl, furyl, 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 base, pyrrolyl, pyrrolidinyl, tetrahydrofuryl, tetrahydropyranyl, tetrazinyl including 1,2,4,5-tetrazinyl, including 1,2,3,4-tetrazolyl and 1, 2,4,5-tetrazolyl tetrazolyl, including 1,2,3-thiadiazolyl, 1,2,5-thiadiazolyl and 1,3,4-thiadiazolyl 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 triazolyl, etc.

The term "hydroxyl" as used herein 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, or alkyne as described in the present invention. group, cycloalkynyl, aryl, or heteroaryl.

The term "azido" used in the present invention is represented by the formula _-N3 .

The term "nitro" as used herein is represented by the formula _-NO2 .

The term "nitrile" as used herein 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 , where R ¹ , R ² and R ³ can independently be hydrogen or an alkyl, cycloalkyl, alkoxy group as described in the present invention. radical, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl.

The term "thio-oxo group" used in the present invention 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 an alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, cycloalkynyl group, aryl group, or heteroaryl group according to the present invention. Throughout this specification, "S(O)" is an abbreviation for S=O. The term "sulfonyl" used in the present invention refers to a thio-oxo group represented by the formula -S(O) ² R ¹ , wherein R ¹ can be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, or alkyne radical, cycloalkynyl, aryl or heteroaryl. The term "sulfone" used in the present invention is represented by the formula R ¹ S(O) ₂ R ² , where 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 "mercapto group" used in the present invention is represented by the formula -SH

“R ¹ ”, “R ² ”, “R ³ ”, and “R ⁿ ” (where n is an integer) used in the present invention may independently have one or more of the groups listed above. For example, if R ¹ is a straight chain alkyl group, then one hydrogen atom of the alkyl group may be optionally substituted with a hydroxyl group, an alkoxy group, an alkyl group, a halogen, or the like. Depending on the group chosen, the first group can be incorporated within the second group, or alternatively, the first group can be pendant, ie, attached to the second group. For example, with respect to the phrase "alkyl group containing an amino group," the amino group may be bonded within the backbone of the alkyl group. Alternatively, the amino group may be attached to the backbone of the alkyl group. selected group The nature of will determine whether the first group is embedded in or attached to the second group.

The compounds described herein may contain "optionally substituted" moieties. Generally, the term "substituted" (whether preceded by the term "optionally" or not) means that one or more hydrogens of the indicated moiety are replaced by a suitable substituent. Unless otherwise stated, an "optionally substituted" group may have a suitable substituent at each substitutable position of the group, and when more than one position in any given structure is substitutable there is more than one selected from the specified When a group is a substituent, the substituents at each position may be the same or different. Combinations of substituents contemplated by the present invention are preferably those which 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 to form a six-membered aromatic ring or heteroaromatic ring, such as benzene ring, pyridine ring, pyrazine ring, pyridazine ring, metadiaza ring etc., as well as saturated six-membered or seven-membered carbocycles or carboheterocycles, etc.

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

This is understood to be equivalent to:

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

^R1 , ^R2 , ^R3 , ^R4 , ^R5 , ^R6 , etc. are mentioned several times in the chemical structures and parts 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 referencing R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ etc. respectively or parts, unless otherwise stated.

Optoelectronic devices using organic materials are becoming increasingly urgent for several reasons. Many of the materials used to make such devices are relatively cheap, so organic optoelectronic devices have the potential to be cost-effective compared to 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 an organic light-emitting layer emits light can generally be tuned using appropriate dopants.

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

However, blue electroluminescent devices remain the most challenging area of the technology to date, and the stability of blue devices is a major issue. It has been proven that the choice of host material is very important for the stability of blue devices. However, the triplet excited state (T1) of the blue luminescent material The minimum energy is very high, which means that the minimum energy of the triplet excited state (T1) of the host material of the blue device should be higher. This makes it more difficult to develop main materials for blue devices.

The metal complexes of the present invention can be customized 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 with ligands with electron-donating substituents or electron-withdrawing substituents can often exhibit different optical properties in emission and absorption spectra. The color of metal complexes can be adjusted by modifying the conjugated groups on the fluorescent emitters and ligands.

The emission of the complexes of the invention can be modulated, for example from ultraviolet to near infrared, by changing the ligand or phosphor structure. A phosphor is a group of atoms in an organic molecule that can absorb energy to produce a singlet excited state, where singlet excitons rapidly decay to produce instantaneous light emission. In one aspect, the complexes of the present invention provide emission across a large portion of the visible spectrum. In specific examples, the complex of the present invention can emit light in the wavelength range of visible light or near-infrared light. On the other hand, the complexes of the present invention have improved stability and efficiency relative to traditional emissive complexes. Additionally, the complexes of the 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 compounds or composite complexes containing platinum. The terms compound or complex are used interchangeably herein. Additionally, the compounds disclosed herein have a neutral charge.

The compounds disclosed herein can exhibit desired properties and have emission and/or absorption spectra that can be modulated by selection of appropriate ligands. In another aspect, the invention may exclude any compound or 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 compatible light absorption and emission, and Used as markers for biological applications.

As stated 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 are useful in a variety of applications. As a luminescent 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 traditional materials, the compounds of the present invention are used in light-emitting devices (such as OLEDs), which can improve the luminous efficiency and the operating 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.

Compounds disclosed herein may 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. In another aspect, the compounds disclosed herein can be delayed fluorescent emitters and phosphorescent emitters.

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

The compound provided by the embodiment of the present invention can be used in a light-emitting device such as an OLED. The device includes at least one cathode, at least one anode and at least one luminescent layer. At least one of the luminescent layers includes the above Tetradentate cyclometal 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, light emitting layer, and electron transport layer are all organic layers, and the anode and cathode are electrically connected.

Synthesis Example

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

The following examples provide methods for the preparation of new compounds, 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 modify and prepare, the methods listed below or other methods can be used for their preparation. The following examples are only examples and are not intended to limit the scope of protection of this patent. The temperature, catalyst, concentration, reactants and reaction process can be changed to select different conditions for different reactants to prepare the compound.

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

synthetic route

Example 1: Platinum complex Pt1 can be synthesized according to the following route:

Synthesis of L1: To a schlenk tube with a magnetic rotor, add Cl-1 (440 mg, 1.49 mmol, 1.00 equivalent), Pin-1 (576 mg, 1.49 mmol, 1.00 equivalent), Pd ₂ (dba) ₃ (40.8 mg , 0.05mmol, 0.03 equivalent), tricyclohexylphosphorus (25mg, 0.09mmol, 0.06 equivalent), potassium phosphate (631mg, 2.97mmol, 2.00 equivalent), replace nitrogen three times and add 8mL of 1,4-dioxane by injection. Add 2 mL of water and raise the temperature to 85°C. Reaction 24h. The reaction mixture was quenched with water, extracted three times with ethyl acetate, the organic phases were combined, dried over anhydrous sodium sulfate, and the crude product obtained was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate) = 10:1 , the solvent was distilled off under reduced pressure to obtain 670 mg of white solid, with a yield of 87%. ¹ H NMR (500MHz, CDCl ₃ ): δ1.46 (s, 9H), 7.38 (dd, J = 8.5, 4.5Hz, 1H), 7.58 (t, J = 7.5Hz, 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 equivalent) and platinum dichloride (113 mg, 0.42 mmol, 1.10 equivalent) to a 50 mL three-necked flask with a magnetic rotor in sequence, replace nitrogen three times, and add benzene 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 through silica gel column chromatography. The eluent (petroleum ether/ethyl acetate = 20:1) was used to remove the solvent by distillation under reduced pressure to obtain 110 mg of yellow solid, which was collected. The rate is 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 according to the following route:

Synthesis of L2: To a schlenk tube with a magnetic rotor, add Cl-2 (166 mg, 0.47 mmol, 1.05 equivalent), Pin-2 (200 mg, 0.45 mmol, 1.00 equivalent), Pd ₂ (dba) ₃ (12.4 mg , 0.01mmol, 0.03 equivalent), tricyclohexylphosphorus (7.6mg, 0.03mmol, 0.06 equivalent), potassium phosphate (200mg, 0.95mmol, 2.10 equivalent), replace nitrogen three times and then add 1,4-dioxane by injection. 6 mL and 1.5 mL of water, and raise the temperature to 85°C. Reaction 24h. The reaction mixture was quenched with water, extracted three times with ethyl acetate, the organic phases were combined, dried over anhydrous sodium sulfate, and the crude product obtained was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate) = 10:1 , the solvent was distilled off under reduced pressure to obtain 240 mg of white solid, with a yield of 84%. ¹ H NMR (400MHz, CDCl ₃ ): δ1.44 (s, 9H), 1.47 (s, 9H), 7.38 (dd, J = 8.4, 4.4Hz, 1H), 7.69 (t, J = 1.6Hz, 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 (120 mg, 0.19 mmol, 1.00 equivalent) and platinum dichloride (55 mg, 0.20 mmol, 1.10 equivalent) to a 50 mL three-necked flask with a magnetic rotor in sequence, replace nitrogen three times, and add benzene by injection. 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 through silica gel column chromatography. The eluent (petroleum ether/ethyl acetate = 20:1) was used to remove the solvent by distillation under reduced pressure to obtain 70 mg of red solid, which was collected. The rate is 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: Platinum complex Pt3 can be synthesized according to the following route:

Synthesis of L3: To a schlenk tube with a magnetic rotor, add Cl-2 (159 mg, 0.45 mmol, 1.05 equivalent), Pin-3 (200 mg, 0.43 mmol, 1.00 equivalent), Pd ₂ (dba) ₃ (11.8 mg , 0.01mmol, 0.03 equivalent), tricyclohexylphosphorus (7.2mg, 0.03mmol, 0.06 equivalent), potassium phosphate (191mg, 0.90mmol, 2.1 equivalent), replace nitrogen three times and then add 1,4-dioxane by injection. 6 mL and 1.5 mL of water, and raise the temperature to 85°C. Reaction 24h. The reaction mixture was quenched with water, extracted three times with ethyl acetate, the organic phases were combined, dried over anhydrous sodium sulfate, and the crude product obtained was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate) = 10:1 , the solvent was distilled off under reduced pressure to obtain 237 mg of white solid, with a yield of 84%. ¹ H NMR (400MHz, CDCl ₃ ): δ1.43(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 (180 mg, 0.28 mmol, 1.00 equivalent) and platinum dichloride (81 mg, 0.30 mmol, 1.1 equivalent) to a 50 mL three-necked flask with a magnetic rotor in sequence, replace nitrogen three times, and add benzene 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 by distillation under reduced pressure. 49 mg of red solid was obtained, with a yield of 21%. ¹ H NMR(400 MHz, 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＝4.8,1.2 Hz,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 according to the following route:

Synthesis of L4: To a schlenk tube with a magnetic rotor, add Cl-3 (143 mg, 0.45 mmol, 1.05 equivalent), Pin-3 (200 mg, 0.43 mmol, 1.00 equivalent), Pd ₂ (dba) ₃ (11.8 mg , 0.01mmol, 0.03 equivalent), tricyclohexylphosphorus (7.2mg, 0.03mmol, 0.06 equivalent), potassium phosphate (191mg, 0.90mmol, 2.1 equivalent), replace nitrogen three times and then add 1,4-dioxane by injection. 6 mL and 1.5 mL of water, and raise the temperature to 85°C. Reaction 24h. The reaction mixture was quenched with water, extracted three times with ethyl acetate, the organic phases were combined, dried over anhydrous sodium sulfate, and the crude product obtained was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate) = 10:1 , the solvent was distilled off under reduced pressure to obtain 210 mg of white solid, with a yield of 82%. ¹ H NMR (400MHz, CDCl ₃ ): δ1.44 (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 equivalent) and platinum dichloride (44.8 mg, 0.16 mmol, 1.1 equivalent) to a 50 mL three-necked flask with a magnetic rotor in sequence, replace nitrogen three times, and add benzene by injection. Carbonitrile 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 eluent (petroleum ether/ethyl acetate/dichloromethane=6:1:1) was used to remove the solvent by distillation under reduced pressure. 85 mg of red solid was obtained, with a yield of 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).

Example 5: Complex Pt5 was 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 equivalent), Pin-1 (150 mg, 0.39 mmol, 1.00 equivalent), Pd (PPh ₃ ) ₄ (13.4 mg, 0.01mmol, 0.03 equivalent), potassium carbonate (106mg, 0.77mmol, 2.0 equivalent), replace nitrogen three times, add 5mL of 1,4-dioxane and 1mL of water by injection, and raise the temperature to 85°C. Reaction 24h. The reaction mixture was quenched with water, extracted three times with ethyl acetate, the organic phases were combined, dried over anhydrous sodium sulfate, and the crude product obtained was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate) = 20:1 , the solvent was distilled off under reduced pressure to obtain 140 mg of white solid, with a yield of 78%. ¹ H NMR (500MHz, CDCl ₃ ): δ1.46 (s, 9H), 7.38 (dd, J＝8.0, 4.0Hz, 1H), 7.42 (dd, J＝8.5, 4.5Hz, 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).

Pt5 synthesis: Add L5 (130 mg, 0.28 mmol, 1.00 equivalent) and platinum dichloride (81.9 mg, 0.31 mmol, 1.1 equivalent) to a 50 mL three-necked flask with a magnetic rotor in sequence, replace nitrogen three times, and add benzene 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 by distillation under reduced pressure. 68 mg of red solid was obtained, with a yield of 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).

Example 6: Complex Pt6 was 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 equivalent), Pin-3 (171 mg, 0.39 mmol, 1.00 equivalent), Pd (PPh ₃ ) ₄ (13.4 mg, 0.01mmol, 0.03 equivalent), potassium carbonate (106mg, 0.77mmol, 2.0 equivalent), replace nitrogen three times, add 5mL of 1,4-dioxane and 1mL of water by injection, and raise the temperature to 85°C. Reaction 24h. The reaction mixture was quenched with water, extracted three times with ethyl acetate, the organic phases were combined, dried over anhydrous sodium sulfate, and the crude product obtained was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate) = 40:1 , the solvent was distilled off under reduced pressure to obtain 160 mg of white solid, with a yield of 80%. ¹ H NMR (500MHz, CDCl ₃ ): δ1.44 (s, 9H), 1.46 (s, 9H), 7.38 (dd, J = 8.0, 4.0Hz, 1H), 7.42 (dd, J = 8.5, 4.5Hz ,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).

Pt6 synthesis: Add L6 (130 mg, 0.25 mmol, 1.00 equivalent) and platinum dichloride (73 mg, 0.28 mmol, 1.1 equivalent) to a 50 mL three-necked flask with a magnetic rotor in sequence, replace 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 by distillation under reduced pressure. 85 mg of red solid was obtained, with a yield of 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: Platinum complex Pt7 can be synthesized according to the following route:

Synthesis of L7: To a schlenk tube with a magnetic rotor, add Cl-3 (150 mg, 0.47 mmol, 1.00 equivalent), Pin-1 (184 mg, 0.47 mmol, 1.00 equivalent), Pd ₂ (dba) ₃ (13.04 mg , 0.01mmol, 0.03 equivalent), tricyclohexylphosphorus (7.99mg, 0.03mmol, 0.06 equivalent), potassium phosphate (211mg, 0.99mmol, 2.1 equivalent), replace nitrogen three times and then add 1,4-dioxane by injection. 6mL and water 1.5mL, The temperature rises to 85°C. Reaction 24h. The reaction mixture was quenched with water, extracted three times with ethyl acetate, the organic phases were combined, dried over anhydrous sodium sulfate, and the crude product obtained was separated and purified by silica gel column chromatography, eluent (petroleum ether/ethyl acetate) = 10:1 , the solvent was distilled off under reduced pressure to obtain 240 mg of white solid, with a yield of 93%. ¹ H NMR (500MHz, CDCl ₃ ): δ1.47 (s, 9H), 7.38–7.44 (m, 2H), 7.46 (dd, J = 8.0, 4.0Hz, 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, 2.0Hz, 1H), 8.96 (dd, J = 4.0, 2.0Hz, 1H).

Synthesis of Pt7: Add L7 (150 mg, 0.27 mmol, 1.00 equivalent) and platinum dichloride (77.5 mg, 0.29 mmol, 1.05 equivalent) to a 50 mL three-necked flask with a magnetic rotor in sequence, replace nitrogen three times, and add benzene by injection. Carbonitrile 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 by distillation under reduced pressure. 40 mg of red solid was obtained, with a yield of 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).

Photophysical tests and theoretical calculations explained

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

It can be seen from Figures 1 to 7 that the above-mentioned platinum (II) complex can emit strong light in dichloromethane solution, and its solution quantum efficiency is 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

Table 2: Frontline orbital energy levels of some metal complexes

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 level of platinum (II) complexes can be adjusted by regulating the ligand structure.

As can be seen from Figure 8, based on the symmetrical structure of the mother core, its frontline orbital electron cloud distribution also has a certain degree of symmetry. Its HOMO is mainly distributed on the central metal atom and the biphenyl group, while the LUMO is mainly distributed on the two quinolyl groups. On the regiment. In Pt9, the tert-butyl group introduced at position 6 of the 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 into the phenyl group. Due to the large dihedral angle between the introduced phenyl group and the molecular core structure, the HOMO distribution is not significantly delocalized to the introduced phenyl ring. The introduction of the phenyl group It can well improve the electron transport performance of platinum complexes. Pd1 replaces the central metal atom from platinum to palladium, and it can be observed that the energy level difference becomes significantly larger, so it is expected that its emission spectrum will be blue-shifted. Pt12 can improve the solubility and electron transport capabilities of the complex without significantly changing the molecular electron cloud distribution.

As can be seen from Figure 9, the tert-butyl group introduced into the quinoline ring in Pt13 has little contribution to the frontier orbital, while the introduced phenyl group can significantly delocalize its LUMO distribution to the right. By introducing multiple tert-butyl groups, the thermal stability of the molecule can be greatly improved and intermolecular π-π stacking suppressed, which is beneficial to the sublimation of the complex. Pt15 and Pt16 introduced multiple substituents into the biphenyl group and found that their HOMO changes were very small. Therefore, it is speculated that functional substituents can be introduced into the biphenyl group to improve the molecular structure.

As can be seen from Figure 10, the introduction of tert-butyl and isopropyl groups into the biphenyl group in Pt18 increases its HOMO energy level, and can well improve the thermal stability of the platinum complex and inhibit intermolecular π-π stacking. In Pt19, on the acene group on the left phenyl group, the conjugated structure increases, and its HOMO delocalizes to the introduced phenyl group, and its HOMO energy level increases significantly. Therefore, its HOMO energy level can be controlled by generating conjugation. In Pt20, due to the formation of a fused ring on the right side, conjugation occurs, resulting in a reduction in the LUMO distribution on the right side.

As can be seen from Figure 11, when tert-butyl and cycloalkyl groups are introduced on both sides, the electron cloud distribution changes are small. The cycloalkyl group can also improve the thermal stability of the molecule and inhibit intermolecular π-π stacking. The introduction of benzofuran into Pt23 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 rate. In Figure 12, Pt28 introduces a trifluoromethyl group in the upper right corner, and it can be clearly observed that its LUMO energy level is significantly delocalized to the trifluoromethyl side, and the LUMO energy level is significantly reduced. because The LUMO energy level can be controlled by introducing an electron-withdrawing group on one side.

The host materials involved in the present invention are obtained by known synthesis 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 2 mm × 2 mm, or mix the p-doped materials with the surface at a concentration of 1% to 50%. The compounds described in are co-evaporated to form a hole injection layer (HIL) of 5-100 nm, a hole transport layer (HTL) of 5-200 nm, and then an emitting layer (EML) of 10-100 nm is formed on the hole transport layer ( can contain the described compound), and finally use the described compound to form the electron transport layer (ETL) 20-200nm and the cathode 50-200nm in sequence. If necessary, add an electron blocking layer (EBL) between the HTL and EML layers. An electron injection layer (EIL) is added between the cathode and the cathode to create an organic light-emitting element. The OLEDs described were tested by standard methods, listed in Table 3.

table 3

As can be seen from Table 3, compared with the comparative device 1 using the traditional host material CBP, 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 and simultaneously reduce the driving voltage.

In summary, the introduction of functional substituents into the biphenyl group can improve the molecular structure and have less impact on the frontier orbital distribution of the molecule. In particular, the introduction of tert-butyl groups on the biphenyl group can effectively suppress intermolecular π-π stacking. Similarly, introducing conjugated groups such as acene or benzofuran into the biphenyl group can delocalize 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 and adjust its photophysical properties.

Claims

A metal platinum (II) or palladium (II) complex phosphorescent material whose structure 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 modes of R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently represented as 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, Thiol, nitro, cyano, substituted or unsubstituted amino, mono or dialkylamino, mono or diarylamino, ester group, nitrile group, isonitrile group, alkoxycarbonyl group, amido group, alkoxy group Carbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazine, substituted or Unsubstituted arylamine, substituted or unsubstituted heteroarylamino, alkylsilyl, substituted or unsubstituted arylsilyl, substituted or unsubstituted heteroarylsilyl, substituted or unsubstituted Any one of an aryloxysilyl group, a substituted or unsubstituted heteroaryloxysilyl group, a substituted or unsubstituted arylacyl group, a substituted or unsubstituted heteroarylacyl group, or a substituted or unsubstituted phosphinyl group, 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.
A composition, characterized by comprising a tetradentate ring metal platinum (II) or palladium (II) complex phosphorescent material based on biphenylquinoline coordination and an organic host material, wherein the metal platinum (II) or The structural formula of the palladium (II) complex phosphorescent material is shown as formula (I); the structural formula (II) or formula (III) of the organic host material is shown:

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 modes of R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently represented as 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, Thiol, nitro, cyano, substituted or unsubstituted amino, mono or dialkylamino, mono or diarylamino, ester group, nitrile group, isonitrile group, alkoxycarbonyl group, amido group, alkoxy group Carbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazine, substituted or Unsubstituted arylamine, substituted or unsubstituted heteroarylamino, alkylsilyl, substituted or unsubstituted arylsilyl, substituted or unsubstituted heteroarylsilyl, substituted or unsubstituted Any one of an aryloxysilyl group, a substituted or unsubstituted heteroaryloxysilyl group, a substituted or unsubstituted arylacyl group, a substituted or unsubstituted heteroarylacyl group, or a substituted or unsubstituted phosphinyl group, 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 formulas (II ) and (III), X1 , X2 , X3 , X4 , X35, X6 , X7 , X8 , X9 , X10 , X11 , X12 , X13 , X14 , X15 , X16 , X17 , X18 , X19 and X20 are each independently N or CH; Z1 , Z2 , Z3 , Z4 , Z5 , Z6 , Z7 , Z 8 , Z 9 , Z 10 , Z 11 , Z 12 and Z 13 are each independently N or CH, and at least 2 of them are N; L 1 , L 2 and L 3 do not exist or are selected from single bonds, 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 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 are each independently represented as mono-substituted, di-substituted, tri-substituted, tetra-substituted or unsubstituted; 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, 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 group, cyano group, substituted or unsubstituted amino, mono or dialkylamino, mono or diarylamino, ester group, nitrile group, isonitrile group, alkoxycarbonyl group, amido group, alkoxycarbonylamino group, Aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazine, substituted or unsubstituted Arylamine group, substituted or unsubstituted heteroarylamino group, alkylsilyl group, substituted or unsubstituted arylsilyl group, substituted or unsubstituted heteroarylsilyl group, substituted or unsubstituted aryloxy group Any one of silicon group, substituted or unsubstituted heteroaryloxysilyl group, substituted or unsubstituted arylacyl group, substituted or unsubstituted heteroarylacyl group, substituted or unsubstituted phosphinyl group, and two Or multiple adjacent R 1 , R 2 , R 3 , R 4 , R 5 and R 6 can be selectively linked to form a fused ring.
The composition according to claim 2, wherein the platinum (II) or palladium (II) complex has one of the following structures:
The composition according to claim 1, wherein formula (II) is selected from the compounds described in (II)-1 to (II)-24:

Among them, X1 , X2 , X3 , X4 , X5, X6 , X7 , X8 , X9 and X10 , L1 , L2 and L3 , A and B , R7 , R8 , R 9 and R 10 are the same as claim 1.
The composition according to claim 1, wherein A, B, C and D are selected from the group consisting of the following structures:

Among them, R 15 , R 16 , R 17 , R 18 and R 19 are the same as claim 1 .
The composition according to any one of claims 2 to 3, characterized in that the organic host material described in formula (II) or formula (III) is selected from one of the following representative structures:
A preparation, characterized in that it contains the composition according to any one of claims 2-6 and at least one solvent.
A preparation according to claim 7, characterized in that the composition and solvent form a preparation, and the solvent used 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, dicyclohexane, n-butylbenzene, sec-butylbenzene or tert-butylbenzene; the halogenation Saturated hydrocarbon solvents are carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane or bromine Cyclohexane; the halogenated unsaturated hydrocarbon solvent is chlorobenzene, dichlorobenzene or trichlorobenzene; the ether solvent is tetrahydrofuran or tetrahydropyran; the ester solvent is alkyl benzoate.
An organic electroluminescent device, characterized by comprising: a first electrode; a second electrode facing the first electrode; an organic functional layer sandwiched between the first electrode and the second electrode between; wherein, the light-emitting layer includes the composition according to any one of claims 2 to 6.
The organic electroluminescent device according to claim 9, characterized in that the light-emitting layer contains the biphenylquinoline-based coordination A four-tooth ring metal platinum (II) or palladium (II) complex phosphorescent material and an organic host material, wherein the four-tooth ring metal platinum (II) or palladium (II) complex based on biphenylquinoline coordination The mass percentage of phosphorescent material ranges from 1% to 50%.
The organic electroluminescent device according to claim 10, characterized in that the device is a full-color display, a photovoltaic device, a light-emitting display device or an organic light-emitting diode.
An organic electroluminescent device, which includes a cathode layer, an anode layer and an organic layer, the organic layer includes a composition, the composition includes a tetradental ring metal platinum (II) based on biphenylquinoline coordination ) 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 as formula (I); the structural formula (II) or formula of the organic host material (III) shown:

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 modes of R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently represented as 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, Thiol, nitro, cyano, substituted or unsubstituted amino, mono or dialkylamino, mono or diarylamino, ester group, nitrile group, isonitrile group, alkoxycarbonyl group, amido group, alkoxy group Carbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imino, sulfo, carboxyl, hydrazine, take Substituted or unsubstituted arylamine group, substituted or unsubstituted heteroarylamino group, alkylsilyl group, substituted or unsubstituted arylsilyl group, substituted or unsubstituted heteroarylsilyl group, substituted or unsubstituted heteroarylsilyl group, Any one of a substituted aryloxysilyl group, a substituted or unsubstituted heteroaryloxysilyl group, a substituted or unsubstituted arylacyl group, a substituted or unsubstituted heteroarylacyl group, or a substituted or unsubstituted phosphinyl group species, 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 formulas (II ) and (III), X1 , X2 , X3 , X4 , X35, X6 , X7 , X8 , X9 , X10 , X11 , X12 , X13 , X14 , X15 , X16 , X17 , X18 , X19 and X20 are each independently N or CH; Z1 , Z2 , Z3 , Z4 , Z5 , Z6 , Z7 , Z 8 , Z 9 , Z 10 , Z 11 , Z 12 and Z 13 are each independently N or CH, and at least 2 of them are N; L 1 , L 2 and L 3 do not exist or are selected from single bonds, 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 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 are each independently represented as mono-substituted, di-substituted, tri-substituted, tetra-substituted or unsubstituted; 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 are each independently represented as hydrogen, deuterium, alkyl, haloalkyl group, 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 group, nitrile group, isonitrile group, alkoxy Carbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imine, sulfonyl group, carboxyl group, hydrazino group, substituted or unsubstituted arylamine group, substituted or unsubstituted heteroarylamino group, alkylsilyl group, substituted or unsubstituted arylsilyl group, substituted or unsubstituted heteroaryl group Silyl group, substituted or unsubstituted aryloxysilyl group, substituted or unsubstituted heteroaryloxysilyl group, substituted or unsubstituted arylacyl group, substituted or unsubstituted heteroarylacyl group, 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.
A display or lighting device, characterized in that the display or lighting device contains the organic electroluminescent device according to claims 9 to 11.
Use of the composition according to any one of claims 2 to 6 in the production of organic light-emitting devices.