CN113817462B

CN113817462B - Host material, organic photoelectric device and display or lighting device

Info

Publication number: CN113817462B
Application number: CN202111132490.7A
Authority: CN
Inventors: 王鹏; 王子兴; 高春吉
Original assignee: Zhejiang Huadisplay Optoelectronics Co Ltd
Current assignee: Zhejiang Huadisplay Optoelectronics Co Ltd
Priority date: 2021-09-27
Filing date: 2021-09-27
Publication date: 2022-09-30
Anticipated expiration: 2041-09-27
Also published as: CN113817462A

Abstract

The present invention provides a host material comprising at least one first host compound and at least one second host compound, wherein the first host compound is represented by formula i and the second host compound is represented by formula ii:

Description

Host material, organic photoelectric device, and display or lighting device

Technical Field

The invention relates to a main body material. And more particularly, to a host material, an organic optoelectronic device, and a display or lighting device.

Background

Organic Light-Emitting devices (OLEDs) are attracting attention because they are thin and capable of Emitting Light with high luminance at low driving voltages and Emitting Light in multiple colors by selecting Light-Emitting materials.

Organic opto-electronic devices (e.g., organic electroluminescent devices) convert electrical energy into light by applying a voltage across the device. The organic electroluminescent device includes an anode, a cathode, and organic layers between the anode and the cathode, which may include a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer (including a host material and a dopant material), an electron buffer layer, a hole blocking layer, an electron transport layer, an electron injection layer, and the like. Materials constituting the organic layer may be classified into a hole injection material, a hole transport material, an electron blocking material, a light emitting material, an electron buffer material, a hole blocking material, an electron transport material, a hole blocking material, and the like according to the function of the material. When a bias is applied to the device, holes are injected from the anode into the light-emitting layer, electrons are injected from the cathode into the light-emitting layer, the holes and the electrons meet to form excitons, and the excitons recombine to emit light, wherein the influence of the light-emitting layer on the performance of the organic light-emitting device is most critical. The light emitting layer material is required to have characteristics of high quantum efficiency, high electron mobility, high hole mobility, and the like, and the light emitting layer material may use a combination of a host material and a dopant material to improve color purity, light emitting efficiency, and stability. In order to obtain an organic optoelectronic device with higher efficiency, longer service life, etc., it is important to select a suitable matching combination of host material and dopant material. Japanese patent application laid-open No. 2001-23777 discloses an organic electroluminescent device in which a nitrogen-containing 5-membered heteroaryl group is condensed on an intermediate benzene ring compound of a phenanthrene skeleton as a host material, wherein the organic electroluminescent device comprising the above compound disclosed therein has excellent color purity characteristics of blue. However, the above compounds still need to be improved in terms of driving voltage, current efficiency, and driving life.

Disclosure of Invention

In order to overcome the defects in the prior art, the invention provides a host material, an organic photoelectric device and a display or lighting device. The organic photoelectric device has high current efficiency and long service life.

In order to realize the purpose of the invention, the technical scheme of the invention is as follows:

wherein, X ₁ -X ₈ Each independently selected from a CR or N atom, wherein R is selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl or heteroaryl;

X ₁ -X ₈ are the same or different from each other;

L ₁ 、L ₂ and L ₃ Each independently selected from a single bond or a substituted or unsubstituted aryl group;

R ₁ 、R ₂ and R ₃ Each independently selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C4-C30 heteroaryl or bonded to adjacent atoms to form a ring, wherein R is ₁ 、R ₂ And R ₃ At least one of which is selected from the following substituted or unsubstituted groups:

wherein R is ₄ -R ₁₀ Each independently selected from hydrogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted C4-C30 heteroaryl;

when X is present ₁ -X ₈ When none is N atom, R ₁ 、R ₂ And R ₃ Not all of which are the same or all of which are different;

wherein Ar is ₁ 、Ar ₂ And Ar ₃ Each independently selected from substituted or unsubstituted C6-C30 aryl or substituted or unsubstituted C3-C30 heteroaryl;

Z ₁ 、Z ₂ and Z ₃ Each independently selected from carbon or nitrogen;

Y ₁ and Y ₂ Each independently selected from NR ₁ Or oxygen, wherein R ₁ Is substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C6-30 aryl or substituted or unsubstituted C3-C30 heteroaryl;

R ₁₁ is hydrogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C30 aryl or substituted or unsubstituted C4-C30 heteroaryl.

Preferably, wherein the compound represented by formula i is selected from the group consisting of:

preferably, formula ii is selected from the following compounds:

Z ₁ 、Z ₂ and Z ₃ Each independently selected from carbon or nitrogen;

R ₁₁ is hydrogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C30 aryl or substituted or unsubstituted C4-C30 heteroaryl. More preferably, wherein the compound represented by formula ii is selected from the group consisting of:

the invention also provides an organic photoelectric device which comprises a cathode layer, an anode layer and an organic layer, wherein the organic layer is at least one of a hole injection layer, a hole transport layer, a light emitting layer, an electron injection layer or an electron transport layer, and the light emitting layer contains the main body material.

Preferably, wherein the organic layer is a light-emitting layer, the light-emitting layer further comprises a dopant, and the mass ratio of the host material to the dopant is 1: 99-99: 1. preferably, wherein the mass ratio of the first host compound to the second host compound is 1: 99-99: 1.

preferably, wherein the organic optoelectronic device is an organic photovoltaic device, an organic light emitting device, an organic solar cell, electronic paper, an organic photoreceptor, an organic thin film transistor, or an organic memory device.

The invention further provides a display or lighting device comprising the organic optoelectronic device.

The tricarbazole compound represented by the general formula I has a high triplet state energy level, and therefore, has good hole transport capacity. The derivative compounds of phenanthrothiazole, oxazole, furan, thiophene, etc. represented by general formula ii of the present invention inherently have high electronegativity and electron-rich groups, and the compounds represented by the two general formulas have rigid characteristics due to a structure in which tricarbazole, phenanthrene and oxazole, phenanthrene and thiazole, phenanthrene and furan, or phenanthrene and thiophene, etc. are condensed, so that the two derivatives of the present invention promote charge transition between molecules. In addition, the derivatives of the tricarbazole derivative, phenanthrene and oxazole, phenanthrene and thiazole, phenanthrene and furan, phenanthrene and thiophene and the like have good planarity, can enhance the intermolecular stacking of the two types, and can more easily realize horizontal molecular orientation, thereby enabling rapid electron current characteristics. An organic electroluminescent device having high efficiency and long life can be realized.

Detailed Description

Hereinafter, the present invention will be described in detail. However, the following description is intended to explain the invention and is not meant to limit the scope of the invention in any way.

The invention provides an application of the host material in an organic photoelectric device.

The organic photoelectric device comprises a deposited anode, a hole injection layer, a hole transport layer, a luminescent layer, an electron transport layer, an electron injection layer and a cathode in sequence.

The organic photoelectric device comprises an anode, a cathode and a plurality of organic layers positioned between the anode and the cathode, wherein the organic layers contain the main material.

The organic photoelectric device comprises a substrate, a first electrode, an organic layer, a second electrode and a covering layer, wherein the first electrode is positioned on the substrate, the organic layer is positioned on the first electrode, the second electrode is positioned on the organic layer, and the covering layer is positioned on the outer side of the second electrode.

The organic layer of the present invention may include a light emitting layer, a hole injection layer, a hole transport layer, an electron transport layer, and an electron injection layer. The organic layer may have a single-layer structure or a stack of layers (a multilayer structure including a light-emitting layer, a hole-injecting layer, a hole-transporting layer, an electron-transporting layer, and an electron-injecting layer). Meanwhile, the organic layer may further include one or more layers, for example, the hole transport layer may include a first hole transport layer and a second hole transport layer. In the light-emitting device of the present invention, any material known in the art for a layer may be used for the layer, except that the light-emitting layer includes the plurality of host materials of the present invention.

In the light emitting device of the present invention, the substrate material may be any substrate used in a typical organic light emitting device, and may be soda glass, alkali-free glass, or a transparent flexible substrate, or may be a substrate made of an opaque material such as silicon or stainless steel, or may be a flexible polyimide film. Different substrate materials have different properties and different application directions. The hole transport layer of the present invention can be formed by a method of stacking or mixing one or two or more kinds of hole transport materials, or a method of using a mixture of a hole transport material and a polymer binder. Since the hole transport material needs to transport holes from the positive electrode efficiently between electrodes to which an electric field is applied, it is desirable that the hole transport material has high hole injection efficiency and can transport injected holes efficiently. Therefore, a hole transport material is required to have an appropriate ionization potential, an appropriate energy level, and a large hole mobility, to be excellent in material stability, and to be less likely to generate impurities that become traps during manufacturing and use. The substance satisfying such conditions is not particularly limited, and examples thereof include carbazole derivatives, triarylamine derivatives, biphenyldiamine derivatives, fluorene derivatives, phthalocyanine compounds, hexacarbonitrile hexaazatriphenylene compounds, quinacridone compounds, perylene derivatives, anthraquinone compounds, F4-TCNQ, polyaniline, polythiophene, and polyvinylcarbazole, but are not limited thereto.

As the light-emitting layer material of the present invention, in addition to containing a plurality of host materials provided by the present invention, a dopant material (also referred to as a guest material) may be used, and a plurality of dopant materials may be contained. The compound represented by formula i may serve as a first host compound for a plurality of host materials, and the compound represented by formula ii may serve as a second host compound for a plurality of host materials. The mass ratio of the first host compound to the second host compound is about 1: 99 to about 99: 1. preferably about 1: 9 to about 9: 1. more preferably about 3: 7 to 7: 3. even more preferably about 2: 3 to about 3: 2. and more preferably about 1: 1. when the light-emitting layer contains two or more materials, the layers may be formed by mixed evaporation, or may be simultaneously co-evaporated. In addition, the light-emitting layer can be a single light-emitting layer or a composite light-emitting layer which is overlapped together in the transverse direction or the longitudinal direction. The selection of the type of the doped material can be fluorescent material or phosphorescent material; the amount of the dopant is preferably 0.1 to 70% by mass, more preferably 0.1 to 30% by mass, even more preferably 1 to 20% by mass, and particularly preferably 1 to 10% by mass.

The fluorescent doping material that can be used in the present invention includes a condensed polycyclic aromatic derivative, a styrylamine derivative, a condensed cyclic amine derivative, a boron-containing compound, a pyrrole derivative, an indole derivative, a carbazole derivative, and the like, but is not limited thereto. Can be used in the present inventionThe phosphorescent dopant material of (2) may include a heavy metal complex, a phosphorescent rare earth metal complex, and the like, but is not limited thereto. Examples of the heavy metal complex include iridium complexes, platinum complexes, osmium complexes, and the like; examples of the rare earth metal complex include, but are not limited to, terbium complexes and europium complexes. As the electron transport material of the present invention, a material having good electron mobility and suitable HOMO and LUMO levels are preferable. The electron transport material that can be used in the present invention includes, but is not limited to, metal complexes, oxathiazole derivatives, oxazole derivatives, triazole derivatives, azabenzene derivatives, phenanthroline derivatives, diazene derivatives, silicon-containing heterocycles, boron-containing heterocycles, cyano compounds, quinoline derivatives, benzimidazole derivatives, and the like. The electron injection material of the present invention is preferably a substance having an electron transporting ability, and has an effect of injecting electrons from a cathode, and has an excellent thin film forming ability. The electron injecting material that can be used in the present invention includes alkali metal compounds such as lithium oxide, lithium fluoride, lithium 8-quinolinolato, lithium boron oxide, cesium carbonate, cesium 8-quinolinolato, potassium silicate, calcium fluoride, calcium oxide, magnesium fluoride, magnesium oxide; a fluorenone; nitrogen-containing five-membered ring derivatives such as oxazole derivatives, oxadiazole derivatives, imidazole derivatives, metal complexes, anthraquinone dimethane, diphenoquinone, anthrone derivatives, and the like, but are not limited thereto, and these compounds may be used alone or in combination with other materials. As the cathode material of the present invention, a material having a low work function is preferable in order to easily inject electrons into the organic layer. Cathode materials useful in the present invention include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, aluminum, silver, tin, lead, or alloys thereof; and multilayer materials, e.g. LiF/Al or LiO ₂ and/Al, but not limited thereto.

When the organic layer materials of the present invention are used, they may be formed into a single layer structure by film-forming alone, or may be mixed with other materials to form a single layer structure, or may be formed into a single layer laminated structure by film-forming alone, a single layer laminated structure by film-mixing, a single layer formed alone, and a single layer laminated structure by film-mixing, but not limited thereto. The organic electroluminescent device of the present invention can be manufactured by sequentially stacking the above-described structures. The production method may employ a known method such as a dry film formation method or a wet film formation method. Specific examples of the dry film formation method include a vacuum deposition method, a sputtering method, a plasma method, an ion plating method, and the like; specific examples of the wet film formation method include various coating methods such as a spin coating method, a dipping method, a casting method, and an ink jet method, but are not limited thereto. The organic photoelectric device can be widely applied to the fields of panel display, lighting sources, flexible OLEDs, electronic paper, organic solar cells, organic photoreceptors or organic thin film transistors, signs, signal lamps and the like.

Examples

The compounds represented by the above general formula I or II can be synthesized by a method known in the art, for example, a cross-coupling reaction using a transition metal such as nickel or palladium. Other synthesis methods are C-C, C-N coupling reactions using transition metals such as magnesium or zinc. The above reaction is limited to mild reaction conditions, superior selectivity of various functional groups, and the like, and Suzuki and Buchwald reactions are preferred.

The multi-host compounds of the present invention are illustrated by the following examples, but are not limited to the compounds and synthetic methods illustrated by these examples.

The initial raw materials and the solvent of the invention are purchased from Chinese medicine, and part of commonly used products such as OLED intermediates and the like are purchased from domestic OLED intermediate manufacturers; various palladium catalysts, ligands, etc. are available from sigma-Aldrich.

¹ H-NMR data were determined using a JEOL (400MHz) nuclear magnetic resonance apparatus;

HPLC data were determined using a Shimadzu LC-20AD HPLC.

Example 1

Synthesis of Compound 2

1) Synthesis of intermediate 2-2

Under an argon atmosphere, a reaction vessel was charged with 648 mg of the compound 2-145.1 g (100mmol), (2-nitrophenyl) boronic acid 36.7g (220mmol), [1, 3-bis (2, 6-di-isopropylphenyl) -4, 5-dihydroimidazol-2-ylidene ] chloro ] [ 3-phenylallyl ] palladium (II) catalyst, 200ml (300mmol) of 1.5M aqueous sodium carbonate solution and 1000ml of ethylene glycol dimethyl ether (DME), and stirred at 80 ℃ overnight. Cooled to room temperature, 800ml of water was added, a solid was precipitated, filtered, and the crude product was purified by silica gel column chromatography (eluent: ethyl acetate/hexane) to obtain 42.3g of compound 2-2, yield 79%, and HPLC purity 99.1%.

2) Synthesis of intermediates 2-3

In a reaction vessel, 2 to 253.6 g (100mmol) of the compound was added under an argon atmosphere, and dissolved in 100ml of chlorobenzene, and 7.9 g of triphenylphosphine was added thereto, and the mixture was stirred overnight at 180 ℃. Cooled to room temperature, filtered, and the filtrate was freed of the solvent under reduced pressure, and the crude product obtained was purified by column chromatography on silica gel (eluent: ethyl acetate/hexane) to give 35.4g of compound 2-3 in 75% yield and 98.7% purity by HPLC.

3) Synthesis of Compound 2

26.9 g (240mmol) of potassium tert-butoxide, 62.7g (220mmol) of [1, 3-bis (2, 6-di-isopropylphenyl) -4, 5-dihydroimidazol-2-ylidene ] chloro ] [ 3-phenylallyl ] palladium (II) catalyst 648 mg (1 mmol%) of 2-bromo-3-phenylquinoline, 2-347.2 g (100mmol) of the compound and 1000mL of ethylene glycol dimethyl ether (DME) were charged into a reaction vessel under an argon atmosphere, and stirred at 80 ℃ for 15 hours. The reaction mixture was cooled to room temperature, 500ml of water was added, filtered and the crude product was purified by column chromatography on silica gel (eluent: ethyl acetate/hexane) to give 70.4 g of compound 2, 99.5% purity by HPLC, 80% yield.

¹ HNMR(DMSO)：δ8.55(d，2H)，8.40(d，4H),8.03(m，3H),7.94(d，2H),7.83(s,1H),7.80(d,4H),7.67(m,4H),7.59～7.57(m,8H),7.47(s，4H),7.35(m,2H),7.16(m,2H).

Example 2

Synthesis of Compound 4

1) Synthesis of intermediate 4-2

Same as example 1 except that the starting material was changed to 4-1

2) Synthesis of intermediate 4-3

Same as example 1 except that the starting material was changed to 4-2

3) Synthesis of Compound 4

The procedure was as in example 1 except that the starting materials were replaced with compounds 4-3 and 2-bromonaphthalene.

¹ HNMR(DMSO)：δ8.55(d，2H)，8.40(d，2H),8.03(m，6H),7.94(m，2H),7.83(s,2H),7.80(d,2H),7.67(m,2H),7.59～7.57(m,7H),7.47(s，4H),7.35(m,3H),7.16(m,2H).

Example 3

Synthesis of Compound 12

1) Synthesis of intermediate 12-2

The reaction was conducted in the same manner as in example 1 except that the starting material was changed to Compound 12-1.

2) Synthesis of intermediate 12-3

The reaction was conducted in the same manner as in example 1 except that the starting material was changed to compound 12-2.

3) Synthesis of Compound 12

Same as example 1 except that the starting materials were changed to 12-3 and m-bromopyridine

¹ HNMR(DMSO)：δ8.71(s，2H),8.55(d,2H),8.46(m，2H),7.94(d，2H),

7.87(d,2H),7.62(m,2H),7.58(s,1H),7.48(m,2H),7.47(s,4H),7.35(t,2H),7.16(m,2H)..

Example 4

Synthesis of Compound 18

1) Synthesis of intermediate 18-2

Same as in example 1.

2) Synthesis of intermediate 18-3

Same as in example 1.

3) Synthesis of Compound 18

The procedure of example 1 was repeated, except that the starting materials were changed to 19-3 and 3-bromo-1, 2, 4-oxadiazole.

¹ HNMR(DMSO)：δ8.90(s,2H),8.55(d，2H),8.03(m，3H),7.94(d，2H),7.83(s,1H),7.59(m,2H),7.47(s,4H),7.35(m,3H),7.16(m,2H).

Example 5

Synthesis of Compound 22

1) Synthesis of intermediate 22-2

The procedure was as in example 1 except that the starting materials were replaced with compound 22-1 and (5- (tert-butyl) -2-nitrophenyl) boronic acid.

2) Synthesis of intermediate 22-3

The procedure was repeated in the same manner as in example 1 except that the starting material was changed to 22-2.

3) Synthesis of Compound 22

The procedure of example 1 was repeated, except that the starting materials were replaced with o-bromopyridine and 22-3.

¹ HNMR(DMSO)：δ8.95(s,2H),8.65(d，3H),8.15(m，3H),8.02(d，3H),7.86(d,2H),7.47(s,4H),7.36(m,3H),7.11(d,2H),1.43(s.18H).

Example 6

Synthesis of Compound 30

1) Synthesis of intermediate 30-2

The procedure was as in example 1 except that the starting materials were replaced with compound 30-1 and (5- (tert-butyl) -2-nitrophenyl) boronic acid.

1) Synthesis of intermediate 30-3

The reaction was carried out in the same manner as in example 1 except that the starting material was changed to compound 30-2.

2) Synthesis of Compound 30

The procedure of example 1 was repeated, except that the starting materials were replaced with 30-3 and 2-bromobenzothiazole.

¹ HNMR(DMSO)：δ8.95(s,2H),8.18(d，2H),8.02(d，2H),7.86(d,2H),7.72(m,2H),

7.53(m,2H),7.51(m,2H),7.47(s,4H),7.39(d,2H),7.11(d,2H),1.43(s.18H).

Example 7

Synthesis of Compound 37

1) Synthesis of intermediate 37-2

The procedure was as in example 1, except that the starting materials were replaced with compound 37-1 and (3-nitropyridin-2-yl) boronic acid.

2) Synthesis of intermediate 37-3

The reaction was conducted in the same manner as in example 1 except that the starting material was changed to compound 37-2.

3) Synthesis of Compound 37

The procedure of example 1 was repeated, except that the starting material was changed to m-bromopyridine and compound 37-3.

¹ HNMR(DMSO)：δ8.71(s，3H),8.46(m,3H),8.43(d，2H),7.97(d，2H),7.87(d,2H),7.55(s,2H),7.48(d,3H),7.40(s,2H),7.22(m,2H)

Example 8

Synthesis of Compound 44

1) Synthesis of intermediate 44-2

The procedure was as in example 1 except that the starting materials were replaced with compound 41-1 and (3-nitropyridin-2-yl) boronic acid.

2) Synthesis of intermediate 44-3

The reaction was conducted in the same manner as in example 1 except that the starting material was changed to Compound 43-2.

3) Synthesis of Compound 44

The procedure was as in example 1 except that the starting material was changed to 2-bromobenzoxazole and compound 44-3.

¹ HNMR(DMSO)：δ8.43(d,2H),8.18(d,2H),8.02(d,3H),7.97(d，2H),7.55(s,2H),7.53(d，3H),7.51(d,3H),7.40(s,2H),7.22(m,2H).

Example 9

Synthesis of Compound 47

1) Synthesis of intermediate 47-2

The procedure was as in example 1 except that the starting materials were replaced with compound 47-1 and (4-nitropyridin-3-yl) boronic acid.

2) Synthesis of intermediate 47-3

The procedure of example 1 was repeated, except that the starting material was changed to 47-2.

3) Synthesis of Compound 47

The procedure of example 1 was repeated, except that the starting materials were changed to 47-3 and 3-bromoquinoline.

¹ HNMR(DMSO)：δ9.34(s,2H),8.93(s，3H),8.35(d，2H),8.12(s,3H),8.11(d,3H),8.00(d,3H),7.69(m,3H),7.57(m,3H),7.51(d,2H),7.47(s,4H)

Example 10

Synthesis of Compound 53

1) Synthesis of intermediate 53-2

The procedure was as in example 1 except that the starting material was changed to 53-1.

2) Synthesis of intermediate 53-3

The procedure was as in example 1 except that the starting material was changed to 53-2.

3) Synthesis of Compound 53

The procedure was repeated in the same manner as in example 1 except that the starting material was changed to 53-3.

¹ HNMR(DMSO)：δ9.34(s，2H),9.25(s，3H),8.52(d,2H),8.35(d,2H),8.07(d,3H),7.75(m,3H),7.69(m,3H),7.63(d,3H),7.51(d,2H),7.47(s,4H).

Example 11

Synthesis of Compound 67

1) Synthesis of intermediate 67-2

The procedure was as in example 1 except that the starting materials were replaced with compound 67-1 and (5-cyano-2-nitrophenyl) boronic acid.

2) Synthesis of intermediate 67-3

The reaction was carried out in the same manner as in example 1 except that the starting material was changed to compound 67-2.

3) Synthesis of Compound 67

The procedure was as in example 1 except that the starting material was changed to 67-3.

¹ HNMR(DMSO)：δ8.71(s，3H),8.46(d,3H),8.12(d，2H),7.87(d，3H),7.80(s,2H),7.48(m,3H),7.47(s,4H),7.33(d,2H).

Example 12

Synthesis of Compound 87

1) Synthesis of intermediate 87-2

The procedure was as in example 1, except that the starting materials were replaced with Compound 87-1 and (3-nitropyridin-2-yl) boronic acid.

2) Synthesis of intermediate 87-3

The reaction was conducted in the same manner as in example 1 except that the starting material was changed to compound 87-2.

3) Synthesis of Compound 87

The procedure of example 1 was repeated, except that the starting materials were changed to 87-3 and 2-bromopyrazine.

¹ HNMR(DMSO)：δ8.83(d，3H),8.82(d，3H),8.76(m，3H),8.43(d,2H),7.97(d,2H),7.55(s,2H),7.40(s,2H),7.22(m,2H).

Example 13

Synthesis of Compound 94

1) Synthesis of intermediate 94-2

The procedure was as in example 1 except that the starting materials were replaced with compound 94-1 and (3-nitropyridin-2-yl) boronic acid.

2) Synthesis of intermediate 94-3

The reaction was conducted in the same manner as in example 1 except that the starting material was changed to compound 94-2.

3) Synthesis of Compound 94

The procedure of example 1 was repeated, except that the starting materials were replaced with Compound 94-3 and 3- (4-bromophenyl) pyridine.

¹ HNMR(DMSO)：δ9.24(s，3H),8.70(d，3H),8.43(d,2H),8.42(d,3H),7.97(d,2H),7.92(d,6H),7.91(d,6H),7.57(m,3H),7.55(s,2H),7.40(s,2H),7.22(m,2H).

Example 14

Synthesis of Compound 146

1) Synthesis of intermediate 146-2

The procedure of example 1 was repeated, except that the starting material was changed to 146-1.

2) Synthesis of intermediate 146-3

The procedure of example 1 was repeated, except that the starting material was changed to 146-2.

3) Synthesis of Compound 146

The process was the same as in example 1, except that the starting materials were replaced with bromobenzene and 146-3 and bromobenzene.

¹ Hnmr (dmso): δ 8.93(s, 1H),8.80(d,1H),8.55(d,2H),8.45(d,1H),8.14(d,1H),8.12(s,1H),7.94(d,2H),7.89(d,1H),7.62(m,4H),7.58(m,2H),7.56(m,1H),7.50(m,4H),7.47(s,4H),7.35(m,2H),7.16(m,2H). example 15

Synthesis of Compound 149

1) Synthesis of intermediate 149-2

The procedure was as in example 1 except that the starting materials were changed to the compound 149-1 and 5-methoxy-2-nitrophenyl) boronic acid.

2) Synthesis of intermediate 149-3

The reaction was conducted in the same manner as in example 1 except that the starting material was changed to the compound 149-2.

3) Synthesis of Compound 149

The procedure of example 1 was repeated, except that the starting materials were replaced with 149-3 and bromobenzene.

¹ HNMR(DMSO)：δ8.93(s，1H),8.80(d,1H),8.45(d,1H),8.24(s,2H),8.14(d,1H),8.12(s,1H),7.89(d,1H),7.62(m,4H),7.58(m,2H),7.56(m,1H),7.50(m,4H),7.47(s,4H),7.33(m,2H),6.60(m,2H),3.81(s,9H).

Example 16

Synthesis of Compound 183

1) Synthesis of intermediate 183-2

The reaction was conducted in the same manner as in example 1 except that the starting material was changed to compound 183-1.

2) Synthesis of intermediate 183-3

The reaction was carried out in the same manner as in example 1 except that the starting material was changed to the compound 183-2.

3) Synthesis of Compound 183

The procedure was repeated as in example 1 except that the starting materials were replaced with 183-3 and 2-bromonaphthalene.

¹ HNMR(DMSO)：δ8.82(d,1H),8.55(d,2H),8.44(d,1H),8.21(s,1H),

8.03(m,6H),7.83(s,2H),7.90(d,1H),7.85(m,1H),7.83(s,2H),7.68(m,1H),7.60(m,1H),7.59(m,2H),7.58(m,2H),7.47(s,5H),7.35(m,3H),7.16(m,2H).

Example 17

Synthesis of Compound E-1

Under an argon atmosphere, compound E-1-1(33.0g, 100mmol), (4, 6-diphenyl-1, 3, 5-triazin-2-yl) boronic acid (38.8g, 110mmol), palladium bis (dibenzylideneacetone) (1.15g, 2mmol), tri-tert-butylphosphine tetrafluoroborate (1.16g, 4mmol), 1.5M cesium carbonate (200mL, 300mmol), and 800mL o-xylene were added to a reaction vessel and heated under reflux for 20 hours. After completion of the reaction, the mixture was cooled to room temperature, and a solid was precipitated, filtered, and the crude product was purified by silica gel column chromatography (eluent: ethyl acetate/hexane) to obtain 38.6g of compound E-1 in a yield of 64% and a purity of 99.2% by HPLC.

¹ HNMR(DMSO)：δ9.08(d，1H),8.92(d，1H),8.36(d，2H),8.29(m,1H),8.18(d,2H),8.15(d,1H),7.96(d,2H),7.88(d,1H),7.75(d,2H),7.70(s,2H),7.65(d,2H),7.62(m,1H),7.50(m,3H),7.49(m,2H),7.41(m,1H),7.25(d,2H).

Example 18

Synthesis of Compound E-13

The reaction was conducted in the same manner as in example 17 except that the starting material was changed to the compound E-13-2.

¹ HNMR(DMSO)：δ9.08(d，1H),8.95(d，1H),8.92(d,1H),8.50(d,1H),8.29(m，1H),7.96(d,4H),7.88(d,1H),7.77(m,1H),7.75(d,2H),7.70(s,1H),7.65(m,2H),7.62(m,1H),7.52(m,1H),7.49(m,2H),7.41(m,1H),7.39(m,1H),7.25(d,4H).

Example 19

Synthesis of Compound E-32

The reaction was conducted in the same manner as in example 17 except that the starting material was changed to the compound E-32-2.

¹ HNMR(DMSO)：δ9.08(d，1H),8.95(d，1H),8.92(d,1H),8.38(d,1H),8.29(m，1H),8.20(d,1H),8.18(d,2H),8.15(d,1H),8.09(d,1H),7.96(d,2H),7.94(s,1H),7.88(d,1H),7.75(d,2H),7.73(m,1H),7.70(s,2H),7.65(m,2H),7.62(m,1H),7.61(d,1H),7.52(m,1H),7.49(m,2H),7.41(m,1H),7.39(m,1H),7.25(d,2H).

Example 20

Synthesis of Compound E-39

The reaction was conducted in the same manner as in example 17 except that the starting material was changed to the compound E-39-2.

¹ HNMR(DMSO)：δ9.08(d，1H),8.92(d,1H),8.36(d，2H),8.29(m,1H),8.18(d,2H),8.15(d,1H),8.08(d,1H),7.88(d,2H),7.70(s,2H),7.65(m,2H),7.62(m,1H),7.54(d,1H),7.51(m,1H),7.50(m,3H),7.39(m,1H),7.31(m,1H).

Example 21

Synthesis of Compound E-54

The reaction was conducted in the same manner as in example 1 except that the starting material was changed to the compound E-54-2.

¹ HNMR(DMSO)：δ9.08(d，1H),8.92(d，1H),8.29(m,1H),8.18(d,2H),8.15(m，1H),8.09(d,1H),8.06(d,1H),7.99(d,1H),7.98(d,1H),7.96(d,2H),7.88(d,1H),7.82(d,1H),7.70(s,2H),7.69(d,1H),7.65(m,2H),7.63(m,1H),7.62(m,1H),7.57(m,1H),7.55(s,1H),7.54(d,1H),7.39(m,1H),7.38(d,1H),7.31(m,1H),7.25(d,2H).

Example 22

Synthesis of Compound E-69

The reaction was conducted in the same manner as in example 17 except that the starting material was changed to the compound E-69-2.

¹ HNMR(DMSO)：δ9.08(d，1H),8.92(d，1H),8.29(m,1H),8.18(d，2H),8.09(d,1H),8.06(d,1H),7.99(d,1H),7.98(d,1H),7.96(d,2H),7.88(d,1H),7.82(d,1H),7.70(s,2H),7.69(d,1H),7.65(m,2H),7.63(m,1H),7.62(m,1H),7.60(m,1H),7.57(m,1H),7.55(s,1H),7.54(d,1H),7.39(m,1H),7.38(d,1H),7.31(m,1H),7.25(d,2H).

Example 23

Synthesis of Compound E-77

The reaction was conducted in the same manner as in example 17 except that the starting material was changed to the compound E-77-2.

¹ HNMR(DMSO)：δ9.08(d，1H),8.92(d，1H),8.55(d,1H),8.31(d,1H),8.29(m,1H),8.18(d,2H),8.15(m,1H),7.96(d,2H),7.94(d,1H),7.91(d,1H),7.88(d,1H),7.75(d,2H),7.74(s,1H),7.70(s,2H),7.65(m,1H),7.62(m,3H),7.58(m,1H),7.50(d,2H),7.49(m,2H),7.35(m,1H),7.25(d,2H),7.16(m,1H).

Example 24

Synthesis of Compound E-94

The reaction was conducted in the same manner as in example 17 except that the starting material was changed to the compound E-94-2.

¹ HNMR(DMSO)：δ9.08(d，1H),8.92(d,1H),8.29(m,1H),8.18(d，2H),8.15(d,1H),7.96(d,4H),7.88(m,1H),7.75(d,4H),7.70(s,2H),7.65(m,2H),7.62(m,1H),7.49(m,4H),7.41(m,2H),7.25(d,4H).

Example 25

Synthesis of Compound E-125

The reaction was conducted in the same manner as in example 17 except that the starting material was changed to the compound E-125-2.

¹ HNMR(DMSO)：δ9.08(d，1H),8.92(d，1H),8.38(d,1H),8.29(m,1H),8.18(d,2H),8.15(d，1H),8.09(d,1H),8.06(d,1H),7.99(d,1H),7.96(d,2H),7.94(s,1H),7.88(d,1H),7.75(d,2H),7.73(m,1H),7.65(m,2H),7.63(m,1H),7.62(m,1H),7.61(d,1H),7.60(m,1H),7.55(s,1H),7.49(m,2H),7.41(m,1H),7.38(d,1H),7.25(d,2H).

Example 26

Synthesis of Compound E-142

The reaction was conducted in the same manner as in example 17 except that the starting material was changed to the compound E-142-2.

¹ HNMR(DMSO)：δ9.08(d，1H),8.92(d，1H),8.29(d,1H),8.18(d,2H),8.15(d，1H),8.09(d,1H),8.06(d,1H),7.99(d,1H),7.98(d,1H),7.96(d,2H),7.88(d,2H),7.83(s,1H),7.79(d,1H),7.70(s,2H),7.65(m,2H),7.63(m,1H),7.62(m,1H),7.55(s,1H),7.54(d,1H),7.39(m,1H),7.38(d,1H),7.31(m,1H),7.25(d,2H).

Example 27

Synthesis of Compound E-160

The reaction was conducted in the same manner as in example 17 except that the starting material was changed to the compound E-160-2.

¹ HNMR(DMSO)：δ9.08(d，1H),8.92(d，1H),8.29(m,1H),8.18(d,2H),8.15(d，1H),8.09(d,1H),8.06(d,1H),7.99(d,1H),7.98(d,1H),7.96(d,2H),7.88(d,2H),7.83(s,1H),7.79(d,1H),7.70(s,1H),7.65(m,2H),7.63(m,1H),7.62(m,1H),7.60(m,1H),7.55(s,1H),7.54(d,1H),7.39(m,1H),7.31(m,1H),7.25(d,2H).

Example 28

Synthesis of Compound E-180

The procedure was as in example 1 except that the starting material was changed to compound E-180-2.

¹ HNMR(DMSO)：δ9.08(d，1H),8.92(d，1H),8.55(d,1H),8.29(m,1H),8.18(d,2H),8.15(d,1H),8.09(d,1H),8.06(d,1H),7.99(d，1H),7.96(d,2H),7.94(d,1H),7.91(d,1H),7.70(s,2H),7.68(d,1H),7.65(m,2H),7.63(m,1H),7.62(m,2H),7.60(m,1H),7.58(m,1H),7.56(m,1H),7.55(s,1H),7.50(d,2H),7.38(d,1H),7.35(m,1H),7.25(d,2H),7.16(m,1H).

Example 29

Synthesis of Compound E-220

The procedure was as in example 17 except that the starting materials were replaced with the compounds E-220-1 and E-220-2.

¹ HNMR(DMSO)：δ9.27(s,1H),8.92(d，1H),8.52(d,1H),8.18(d,2H),8.15(d,1H),7.98(d,1H),7.96(d,2H),7.92(m,1H),7.88(d,2H),7.83(d,1H),7.79(d,1H),7.75(d,2H),7.70(d,1H),7.65(m,2H),7.62(m,1H),7.54(d,1H),7.49(d,2H),7.41(m,1H),7.39(m,1H),7.31(m,1H),7.25(d,2H).

Example 30

Synthesis of Compound E-251

The same procedures used in example 17 except that the starting materials were replaced with the compounds E-251 and E-251-2

¹ HNMR(DMSO)：δ9.27(s，1H),8.92(d，1H),8.52(d,1H),8.18(d,2H),8.15(d，1H),8.09(d,2H),8.06(d,1H),7.99(d,1H),7.96(d,2H),7.92(d,1H),7.90(d,1H),7.89(d,1H),7.88(d,1H),7.70(s,1H),7.65(m,2H),7.63(m,1H),7.62(m,1H),7.60(m,1H),7.55(d,2H),7.38(m,1H),7.28(m,1H),7.25(d,2H).

Example 31

Synthesis of Compound E-305

The same procedures used in example 17 except that the starting materials were replaced with the compounds E-305-1 and E-305-2

¹ HNMR(DMSO)：δ9.27(s，1H),8.92(d，1H),8.52(d,1H),8.38(d,1H),8.18(d，2H),8.15(d,1H),8.09(d,1H),8.06(d,1H),7.99(d,1H),7.96(d,2H),7.94(s,1H),7.92(d,1H),7.75(d,2H),7.73(m,1H),7.70(d,1H),7.65(m,2H),7.63(m,1H),7.62(m,1H),7.61(d,1H),7.60(m,1H),7.55(s,1H),7.49(d,2H),7.41(m,1H),7.25(d,2H).

Example 32

Synthesis of Compound E-350

The same procedures used in example 17 except that the starting materials were replaced with the compounds E-350-1 and E-350-2

¹ HNMR(DMSO)：δ9.27(s，1H),9.09(s，1H),8.92(d,1H),8.55(d,1H),8.52(d，1H),8.49(d,1H),8.31(d,1H),8.18(d,2H),8.16(d,1H),8.15(d,1H),8.08(d,1H),7.94(d,1H),7.92(d,1H),7.91(d,1H),7.88(d,1H),7.74(d,1H),7.70(d,1H),7.65(m,2H),7.62(m,2H),7.61(m,1H),7.59(m,1H),7.50(m,2H),7.35(m,1H),7.16(m,1H).

Device embodiments

Evaluation of organic opto-electronic devices

The compounds of the respective organic layers used in the device examples are as follows:

example 33

The basic structural model of an organic optoelectronic device is: ITO/HAT-CN (10nm)/TAPC (40nm)/TCTA (10nm)/EML (host material of the present invention: RD (Ir complex)) (40nm) ═ 98: 2/ETL (30nm)/LiF (1nm)/Al (80nm)

The method for manufacturing the organic photoelectric device comprises the following steps:

(1) carrying out ultrasonic cleaning on a transparent anode Indium Tin Oxide (ITO)20(10 omega/sq) glass substrate by using acetone, ethanol and distilled water in sequence, and then treating for 15 minutes by using ozone plasma;

(2) after an ITO substrate is arranged on a substrate fixer of vacuum vapor deposition equipment, the system pressure is controlled to be 10 ^-6 Sequentially evaporating HAT-CN with the thickness of 10nm, TAPC with the thickness of 40nm and TCTA with the thickness of 10nm on the ITO substrate;

(3) evaporating a light-emitting layer (EML) with the thickness of 40nm (wherein, the mass ratio of the host material to RD is 98: 2, and the mass ratio of the first host compound to the second host compound is 2: 3);

(4) evaporating an Electron Transport Layer (ETL) material with the thickness of 30 nm;

(5) evaporating LiF with the thickness of 1nm as an electron injection layer;

(6) and finally, evaporating Al with the thickness of 80nm as a cathode, and packaging the device by using a glass packaging cover.

The test results of the organic photoelectric device of the present invention are shown in table 1.

Example 34

The same devices as those in example 33 were evaluated except that the EML material was changed to compounds 4 and E-13, and the test results are shown in Table 1.

Example 35

The same devices as those in example 33 were fabricated and evaluated except that the EML materials were compound 12 and E-32, and the test results are shown in table 1.

Example 36

The same devices as those in example 33 were fabricated and evaluated except that the EML materials were compound 18 and E-39, and the test results are shown in table 1.

Example 37

The same devices as those in example 33 were evaluated except that the EML materials were Compound 22 and E-54, and the test results are shown in Table 1.

Example 38

The same devices as those in example 33 were fabricated and evaluated except that the EML materials were compound 30 and E-69, and the test results are shown in table 1.

Example 39

The same devices as those in example 33 were evaluated except that the EML materials were compound 37 and E-77, and the test results are shown in Table 1.

Example 40

The same devices as those in example 33 were evaluated except that the EML materials were compound 44 and E-94, and the test results are shown in Table 1.

EXAMPLE 41

The same devices as those in example 33 were evaluated except that the EML materials were Compound 47 and E-125, and the test results are shown in Table 1.

Example 42

The same devices as those prepared in example 33 were evaluated except that the EML materials were compound 53 and E-142, and the test results were as shown in table 1.

Example 43

The same devices as those in example 33 were evaluated except that the EML materials were the compounds 67 and E-160, and the test results are shown in Table 1.

Example 44

The same devices as those prepared in example 33 were evaluated except that the EML materials were Compound 87 and E-180, and the test results are shown in Table 1.

Example 45

The same devices as those in example 33 were evaluated except that the EML materials were compound 94 and E-220, and the test results are shown in Table 1.

Example 46

The same devices as those in example 33 were evaluated except that the EML materials were the compound 146 and E-251, and the test results are shown in Table 1.

Example 47

The same devices as those in example 33 were evaluated except that the EML materials were the compounds 149 and E-305, and the test results are shown in Table 1.

Example 48

The same devices as those in example 33 were evaluated except that the EML materials were the compounds 183 and E-350, and the test results are shown in Table 1.

Comparative example 1

The same devices as those prepared in example 33 were evaluated except that the EML material was CBP compound, and the test results are shown in table 1.

Comparative example 2

The same devices as those prepared in example 33 were evaluated except that the EML material was the compounds Ref-1 and Ref-2, and the test results are shown in Table 1.

TABLE 1

As can be seen from Table 1, the organic photoelectric device structure is consistent except that the light-emitting layer is different, and based on the device performance of comparative example 1 and comparative example 2 as reference, the current efficiency of the device after the host material of the invention is applied to the light-emitting layer is remarkably improved, and the service life of the device is also improved. Therefore, the host material has great application value in organic photoelectric devices (such as organic light emitting diodes).

The foregoing has described the general principles, principal features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the present invention, and that various changes and modifications may be made without departing from the spirit and scope of the invention as defined by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims

1. A host material comprising at least one first host compound and at least one second host compound, wherein the first host compound is selected from the group consisting of:

wherein the second host compound is selected from the group consisting of:

2. an organic optoelectronic device comprising a cathode layer, an anode layer and an organic layer, wherein the organic layer is at least one of a hole injection layer, a hole transport layer, a light emitting layer, an electron injection layer or an electron transport layer, and wherein the light emitting layer comprises the host material of claim 1.

3. The organic optoelectronic device of claim 2, wherein the organic layer is a light emitting layer further comprising a dopant, wherein the mass ratio of the host material to the dopant is 1: 99-99: 1.

4. the organic optoelectronic device of claim 3, wherein the mass ratio of the first host compound to the second host compound is 1: 99-99: 1.

5. the organic optoelectronic device according to claim 2, wherein the organic optoelectronic device is an organic photovoltaic device, an organic light emitting device, electronic paper, an organic photoreceptor, an organic thin film transistor, or an organic memory device.

6. A display or lighting device comprising the organic optoelectronic device of claim 2.