1. A triphenylene derivative having the following general formula (1)

Wherein R1 is selected from the group consisting of substituted and unsubstituted substituents

Wherein R2 and R3 are selected from the following substituted or unsubstituted substituents

Wherein R4, R5, R6 and R7 are independently selected from hydrogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C4-C30 heteroaryl, or a combination thereof.

2. The triphenylene derivative of claim, wherein the triphenylene derivative is selected from the following structures:

3. an organic optoelectronic device, comprising:

a first electrode;

a second electrode facing the first electrode;

the organic functional layer is clamped between the first electrode and the second electrode;

wherein the organic functional layer comprises a triphenylene derivative described in claims 1 to 2.

4. The Organic optoelectronic device according to claim 3, wherein the Organic optoelectronic device 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 an Organic Memory device (Organic Memory Element), a lighting and display device.

5. An organic photoelectric element comprising a cathode layer, an anode layer and an organic layer, the organic layer comprising at least one of a hole injection layer, a hole transport layer, a light emitting layer or an active layer, an electron injection layer, and an electron transport layer, wherein: any layer of the device contains the triphenylene derivative described in claims 1-2.

6. The organic photoelectric element according to claim 3 or 5, wherein the light-emitting layer contains the organic compound and a corresponding guest material, wherein the organic compound is contained in an amount of 1 to 99% by mass, and the guest material is not limited at all.

7. The organic photoelectric element according to claim 3 or 5, wherein the organic compound is contained in the electron transport layer, and the mass percentage of the organic compound is 1% to 100%.

8. A display or lighting device comprising the organic photoelectric element according to any one of claims 3 to 7.

Background

An Organic Light-Emitting Diode (OLED) is used. The light emitting device has a feature of being thin and capable of emitting light with high luminance at a low driving voltage and emitting light in multiple colors by selecting a light emitting material, and thus attracts attention.

Since the research revealed that the organic thin film element can emit light with high brightness by c.w.tang et al of kodak corporation, a lot of research and progress has been made on its application by a large number of researchers in the OLED industry. Organic thin film light emitting devices are widely used in various main displays and the like, and their practical use has been advanced.

Although the research on organic electroluminescence is rapidly progressing, there are still many problems to be solved, such as improvement of External Quantum Efficiency (EQE), design and synthesis of new materials with excellent purity and high efficiency for electron transport/hole blocking, and so on. For the organic electroluminescent device, the luminous quantum efficiency of the device is the comprehensive reflection of various factors and is an important index for measuring the quality of the device.

Electroluminescence can be generally classified into fluorescence and phosphorescence. In fluorescence emission, an organic molecule in a singlet excited state transits to a ground state, thereby emitting light. On the other hand, in phosphorescence, organic molecules in a triplet excited state transition to a ground state, thereby emitting light.

At present, some organic electroluminescent materials have been commercially used due to their excellent properties, but as host materials in organic electroluminescent devices, it is more important to have good hole transport properties in addition to the triplet energy level higher than that of the guest materials to prevent the energy reverse transfer of exciton transition release. Currently, materials having both a high triplet level and good hole mobility in the host material are still lacking. Therefore, how to design a new host material with better performance is a problem to be solved by those skilled in the art.

Disclosure of Invention

[ problem to be solved by the invention ]

As described above, designing a new better-performing host material is a problem to be solved at present.

The present invention relates to a triphenylene derivative for an organic light-emitting element, a light-emitting device material containing the triphenylene derivative, and a light-emitting device, and more particularly, to a soluble organic compound having excellent color purity, high luminance, and light-emitting efficiency, and an OLED device using the same.

The present invention provides a triphenylene derivative having the following general formula (1)

Wherein R1 is selected from the group consisting of substituted and unsubstituted substituents

Wherein R2 and R3 are selected from the following substituted or unsubstituted substituents

Wherein R4, R5, R6 and R7 are independently selected from hydrogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C4-C30 heteroaryl or the combination thereof;

in a further preferred mode, the organic compound is independently selected from the following compounds

The invention also provides application of the triphenylene-containing derivative in an organic light-emitting device.

Preferably, the organic light emitting device comprises an anode, a cathode and a plurality of organic functional layers located between the anode and the cathode, wherein the organic functional layers contain the triphenylene derivative.

The invention has the beneficial effects that:

the invention provides a triphenylene derivative which has a structure shown in a general formula (1), wherein the triphenylene structure has a medium triplet state energy level, and a bipolar material is designed by adjusting substituent groups, so that hole transmission capacity and electron transmission capacity of the triphenylene derivative are balanced, and the performance of a device is improved. In addition, the planar structure of triphenylene is beneficial to the accumulation of molecules, is beneficial to reducing unnecessary vibration energy loss, and realizes high-efficiency luminous performance. The triphenylene derivative disclosed by the invention is simple in preparation method, easy in raw material obtaining and capable of meeting the industrial requirements.

The organic electroluminescent device comprises a luminescent element containing a triphenylene derivative, wherein the luminescent element comprises a substrate, a first electrode, an organic layer, a second electrode and a covering layer.

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 as the structure of the organic layer. The organic layer of the light-emitting element may be formed of a single-layer structure, or may be formed of 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 element of the present invention, any material known in the art for the layer can be used for the other layers except that the light-emitting layer contains the triphenylene derivative of the present invention.

In the light-emitting element of the present invention, any substrate used in a typical organic light-emitting element can be used as a substrate material. The substrate can be sodium glass or alkali-free glass or a transparent flexible substrate, can also be a substrate made of opaque materials such as silicon or stainless steel, and can also 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 the triphenylene derivative provided by the present invention, a dopant material (also referred to as a guest material) may be used and may contain a plurality of dopant materials. 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 dopant may be a fluorescent material or a 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 dopant material that can be used in the present invention may include: fused polycyclic aromatic derivatives, styrylamine derivatives, fused ring amine derivatives, boron-containing compounds, pyrrole derivatives, indole derivatives, carbazole derivatives, and the like, but are not limited thereto. Phosphorescent dopant materials useful in the present invention may include: heavy metal complexes, phosphorescent rare earth metal complexes, and the like, but are 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 energy levels are preferable. Electron transport materials that can be used in the present invention include: 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, but are not limited thereto.

The electron transport material of the present invention is preferably a substance having an ability to transport electrons, has an effect of injecting electrons from a cathode, and has an excellent ability to form a thin film. Electron injection materials that can be used as the present invention include: alkali metal compounds such as lithium oxide, lithium fluoride, lithium 8-hydroxyquinoline, lithium boron oxide, cesium carbonate, cesium 8-hydroxyquinoline, potassium silicate, calcium fluoride, calcium oxide, magnesium fluoride, magnesium oxide; a fluorenone; nitrogen-containing five-membered ring derivatives, for example, oxazole derivatives, oxadiazole derivatives, imidazole derivatives; a metal complex; 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 LiO₂and/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 formation 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 formation alone, a single layer laminated structure by film mixing, a single layer formed by film formation alone, and a single layer laminated structure by film mixing, but not limited thereto. The organic electroluminescent device according to the present invention can be manufactured by sequentially laminating 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 light-emitting 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.

Detailed Description

The synthesis of the triphenylene derivative represented by the above general formula (1) can be carried out by a known method. For example, a cross-coupling reaction of a transition metal such as nickel or palladium is used. 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 triphenylene derivatives of the present invention are illustrated by the following examples, but are not limited to the triphenylene derivatives and the synthesis methods illustrated by these examples.

The initial raw materials and the solvent of the invention are purchased from Chinese medicine, and some common 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.

¹H-NMR data were determined using a JEOL (400MHz) nuclear magnetic resonance apparatus; HPLC data were determined using a Shimadzu LC-20AD HPLC.

The substances used in the examples and comparative examples were:

(Compound 1)3, 6-bis (dibenzofuran-3-yl) -11, 13-diphenylphenanthroline

(Compound 20)3, 6-bis (9, 9-dimethyl-9H-fluoren-1-yl) -11, 13-diphenylphenanthroline

(Compound 28)3- (9, 9-dimethyl-9H-fluoren-4-yl) -6,11, 13-triphenylphenanthroline

(Compound 50)6- (Naphthalen-1-yl) -3- (Naphthalen benzofuran-8-yl) -11, 13-Diphenylphenanthroline

(Compound 67)3, 6-bis (Naphthol benzofuran-10-yl) -11, 13-diphenylphenanthroline

(Compound 109)3, 6-bis (benzonaphtholthiophen-9-yl) -11, 13-diphenylphenanthroline

(Compound 135)11, 13-Diphenyl-3, 6-bis (7-phenyl-7H-benzocarbazol-8-yl) phenanthrenequinazoline

(Compound 155)10- (6- (Naphthalen-2-yl) -11, 13-Diphenylphenanthrolin-3-yl) -10H-benzoxazines

(Compound 179)3- (dibenzofuran-2-yl) -6- (naphthalen-2-yl) -11, 13-diphenylphenanthroline

(Compound 181)3- (Dibenzothien-4-yl) -6- (naphthalen-2-yl) -11, 13-diphenylphenanthroline

(Compound 203)11, 13-Diphenyl-3, 6-bis (9-phenyl-9H-carbazol-2-yl) phenanthroquinazoline

(Compound 239)3, 6-bis (naphthobenzofuran-4-yl) -11, 13-diphenylphenanthroline

(Compound 270)3, 6-bis (benzonaphtholthiophen-8-yl) -11, 13-diphenylphenanthroline

(Compound 315)3, 6-bis (9H-carbazol-9-yl) -11, 13-diphenylphenanthroline

Example 1

Synthesis of Compound 1

Under argon atmosphere, a reaction flask was charged with 50.5 g (100mmol) of N- (7, 10-dibromoterphenyl-2-yl) benzamide and 300ml of 2-chloropyridine 12.5 g (120mmol) of dichloromethane, cooled to-78 ℃, then 31.0 g (110mmol) of trifluoromethanesulfonic anhydride was added, the reaction mixture was placed in an ice-water bath and heated to 0 ℃, and 11 g (110mmol) of benzonitrile was added. The reaction mixture was heated to 45 ℃ for 6 hours, cooled to room temperature and neutralized with triethylamine. The volatiles were removed under reduced pressure and flash column chromatography (eluent: 10% ethyl acetate in hexanes) was used to give 51.9 g of 3, 6-dibromo-11, 13-diphenylphenanthroline in 88% yield and 99.6% HPLC purity.

¹HNMR(DMSO)：δ9.10(s，1H)，8.93(s，1H)，8.81(d,1H),8.35(m，2H),8.29(s，1H),8.12(s，1H),8.05～7.99(m，3H),7.80(d,2H),7.65(t，2H),7.50～7.49(m,4H)

59.0g (100mmol) of 3, 6-dibromo-11, 13-diphenylphenanthroline, 50.8g (240mmol) of dibenzofuran-3-ylboronic acid, 1.16g (1.0mmol) of tetrakis (triphenylphosphine) palladium, 200ml (300mmol) of a 1.5M aqueous solution of sodium carbonate and 800ml of ethylene glycol dimethyl ether (DME) were charged into a reactor under an argon atmosphere, and the mixture was stirred at 80 ℃ overnight. After cooling to room temperature, 500ml of water was added, a solid precipitated and was filtered, and the obtained solid was washed with ethanol to give 65.0g of compound 1, yield 85%, and HPLC purity 99.3%.

¹Hnmr (dmso): δ 9.11(d, 2H), 8.93(s, 1H),8.46 to 8.43(m,4H),8.35(d, 2H),8.12(s,1H),8.03 to 7.98(m,4H),7.82 to 7.76(m,6H),7.54 to 7.49(m, 6H),7.39 to 7.31(m,4H) example 2

Synthesis of Compound 20

Under argon atmosphere, a reaction flask was charged with 50.5 g (100mmol) of N- (7, 10-dibromoterphenyl-2-yl) benzamide and 300ml of 2-chloropyridine 12.5 g (120mmol) of dichloromethane, cooled to-78 ℃, then 31.0 g (110mmol) of trifluoromethanesulfonic anhydride was added, the reaction mixture was placed in an ice-water bath and heated to 0 ℃, and 11 g (110mmol) of benzonitrile was added. The reaction mixture was heated to 45 ℃ for 6 hours, cooled to room temperature and neutralized with triethylamine. The volatiles were removed under reduced pressure and flash column chromatography (eluent: 10% ethyl acetate in hexanes) was used to give 51.9 g of 3, 6-dibromo-11, 13-diphenylphenanthroline in 88% yield and 99.6% HPLC purity.

¹HNMR(DMSO)：δ9.10(s，1H)，8.93(s，1H)，8.81(d,1H),8.35(m，2H),8.29(s，1H),8.12(s，1H),8.05～7.99(m，3H),7.80(d,2H),7.65(t，2H),7.50～7.49(m,4H)

59.0g (100mmol) of 3, 6-dibromo-11, 13-diphenylphenanthroline, 57.1g (240mmol) of (9, 9-dimethyl-9H-fluoren-1-yl) boronic acid, 1.16g (1.0mmol) of tetrakis (triphenylphosphine) palladium, 200ml (300mmol) of a 1.5M aqueous sodium carbonate solution and 800ml of ethylene glycol dimethyl ether (DME) were charged into a reactor under an argon atmosphere, and heated and stirred overnight at 80 ℃. After cooling to room temperature, 500ml of water was added, a solid precipitated and was filtered, and the obtained solid was washed with ethanol to obtain 71.9g of compound 20, yield 88%, and HPLC purity 99.5%.

¹HNMR(DMSO)：δ9.11(d，2H)，8.93(s，1H),8.46～8.43(m,4H),8.35(d，2H),8.12(s,1H),8.00(d,2H),7.90(d,2H),7.80(d,2H),7.68～7.65(m,4H),7.57～7.55(m,4H),7.50～7.49(m，4H),7.38(m,4H),7.28(m,4H),1.69(s,12H).

Example 3

Synthesis of Compound 28

Under argon, a reaction flask was charged with 46.0 g (100mmol) of N- (7-bromo-10-chlorobenzo-2-yl) benzamide and 300ml of 2-chloropyridine 12.5 g (120mmol) of dichloromethane, cooled to-78 deg.C, then 31.0 g (110mmol) of trifluoromethanesulfonic anhydride was added, the reaction mixture was placed in an ice-water bath and heated to 0 deg.C, and 11 g (110mmol) of benzonitrile was added. The reaction mixture was heated to 45 ℃ for 6 hours, cooled to room temperature and neutralized with triethylamine. The volatiles were removed under reduced pressure and flash column chromatography (eluent: 10% ethyl acetate in hexanes) was used to give 46.3 g of 6-bromo-3-chloro-11, 13-diphenylphenanthroline in 85% yield and 99.4% HPLC purity.

¹HNMR(DMSO)：δ9.10(s，1H)，8.93(s，1H)，8.81(d,1H),8.35(m，2H),8.29(s，1H),8.12(s，1H),8.05～7.99(m，3H),7.80(d,2H),7.65(t，2H),7.50～7.49(m,4H)

Under an argon atmosphere, 54.6g (100mmol) of 6-bromo-3-chloro-11, 13-diphenylphenanthroline, 12.1g (100mmol) of phenylboronic acid, 1.16g (1.0mmol) of tetrakis (triphenylphosphine) palladium, 200ml (300mmol) of 1.5M aqueous sodium carbonate solution and 800ml of ethylene glycol dimethyl ether (DME) were added to a reactor, and the mixture was stirred with heating at 80 ℃ overnight. Cooling to room temperature, adding 500ml water, precipitating solid, filtering, washing the obtained solid with ethanol to obtain 40.7g of 3-chloro-6, 11, 13-triphenylphenanthroline, yield is 75%, and HPLC purity is 99.1%.

¹HNMR(DMSO)：δ9.11(d，2H)，8.93(s，1H),8.86(d,1H),8.46～8.43(m,2H),8.35(d，2H),8.13～8.12(d,2H),7.89(d,1H),7.80～7.75(m,4H),7.50～7.49(m，6H),7.41(m,1H).

Under an argon atmosphere, 54.3g (100mmol) of 3-chloro-6, 11, 13-triphenylphenanthroline, 28.6g (120mmol) of (9, 9-dimethyl-9H-fluoren-4-yl) boronic acid, 1.16g (1.0mmol) of tetrakis (triphenylphosphine) palladium, 200ml (300mmol) of 1.5M aqueous sodium carbonate solution and 800ml of ethylene glycol dimethyl ether (DME) were added to a reactor, and the mixture was stirred at 80 ℃ overnight. After cooling to room temperature, 500ml of water was added, a solid precipitated and was filtered, and the obtained solid was washed with ethanol to obtain 55.3g of compound 28, yield 79%, and HPLC purity 99.7%.

¹HNMR(DMSO)：δ9.11(d，2H)，8.93(s，1H),8.46～8.43(m,4H),8.35(d，2H),8.12(s,1H),7.90(d,1H),7.80～7.75(m,5H),7.65(m,3H),7.55～7.49(m,7H),7.47～7.41(m,2H),1.69(s,6H).

Example 4

Synthesis of Compound 50

Under argon, a reaction flask was charged with 46.0 g (100mmol) of N- (7-bromo-10-chlorobenzo-2-yl) benzamide and 300ml of 2-chloropyridine 12.5 g (120mmol) of dichloromethane, cooled to-78 deg.C, then 31.0 g (110mmol) of trifluoromethanesulfonic anhydride was added, the reaction mixture was placed in an ice-water bath and heated to 0 deg.C, and 11 g (110mmol) of benzonitrile was added. The reaction mixture was heated to 45 ℃ for 6 hours, cooled to room temperature and neutralized with triethylamine. The volatiles were removed under reduced pressure and flash column chromatography (eluent: 10% ethyl acetate in hexanes) was used to give 46.3 g of 6-bromo-3-chloro-11, 13-diphenylphenanthroline in 85% yield and 99.4% HPLC purity.

¹HNMR(DMSO)：δ9.10(s，1H)，8.93(s，1H)，8.81(d,1H),8.35(m，2H),8.29(s，1H),8.12(s，1H),8.05～7.99(m，3H),7.80(d,2H),7.65(t，2H),7.50～7.49(m,4H)

Under argon atmosphere, 54.6g (100mmol) of 6-bromo-3-chloro-11, 13-diphenylphenanthroline, 172.0g (100mmol) of 1-naphthalene boronic acid, 1.16g (1.0mmol) of tetrakis (triphenylphosphine) palladium, 200ml (300mmol) of 1.5M aqueous sodium carbonate solution and 800ml of ethylene glycol dimethyl ether (DME) are added to a reactor, and the mixture is heated and stirred overnight at 80 ℃. Cooling to room temperature, adding 500ml water, precipitating solid, filtering, washing the obtained solid with ethanol to obtain 42.7g of 3-chloro-6- (naphthalene-1-yl) -11, 13-diphenyl phenanthroline, yield 72%, HPLC purity 99.1%.

¹HNMR(DMSO)：δ9.11(d，2H)，8.95～8.93(m，2H),8.86(d,1H),8.50(d，1H)，8.46～8.43(m,2H),8.35(d，2H),8.20(d,1H),8.13～8.12(d,2H),8.09(d,1H),7.89(d,1H),7.80～7.77(m,3H),7.65(m,2H),7.52～7.49(m,5H),7.39(d,1H).

To a reactor, 59.3g (100mmol) of 3-chloro-6- (naphthalen-1-yl) -11, 13-diphenylphenanthroline, 31.4g (120mmol) of naphtho [1,2-b ] benzofuran-8-ylboronic acid, 1.16g (1.0mmol) of tetrakis (triphenylphosphine) palladium, 200ml (300mmol) of a 1.5M aqueous solution of sodium carbonate, and 800ml of ethylene glycol dimethyl ether (DME) were added under an argon atmosphere, and the mixture was stirred with heating at 80 ℃ overnight. After cooling to room temperature, 500ml of water was added, a solid precipitated and was filtered, and the obtained solid was washed with ethanol to give 62.8g of compound 50, yield 81%, and HPLC purity 99.5%.

¹HNMR(DMSO)：δ9.11(d，2H)，8.95～8.93(m，2H),8.50(d，1H)，8.46～8.43(m,4H),8.35(d，2H),8.20～8.16(m,2H),8.12～8.11(d,2H),8.09(d,1H),7.88～7.83(m,3H),7.80～7.77(m,4H),7.69～7.65(m,4H),7.52～7.48(m,6H),7.39(m,1H).

Example 5

Synthesis of Compound 67

Under argon atmosphere, a reaction flask was charged with 50.5 g (100mmol) of N- (7, 10-dibromoterphenyl-2-yl) benzamide and 300ml of 2-chloropyridine 12.5 g (120mmol) of dichloromethane, cooled to-78 ℃, then 31.0 g (110mmol) of trifluoromethanesulfonic anhydride was added, the reaction mixture was placed in an ice-water bath and heated to 0 ℃, and 11 g (110mmol) of benzonitrile was added. The reaction mixture was heated to 45 ℃ for 6 hours, cooled to room temperature and neutralized with triethylamine. The volatiles were removed under reduced pressure and flash column chromatography (eluent: 10% ethyl acetate in hexanes) was used to give 51.9 g of 3, 6-dibromo-11, 13-diphenylphenanthroline in 88% yield and 99.6% HPLC purity.

¹HNMR(DMSO)：δ9.10(s，1H)，8.93(s，1H)，8.81(d,1H),8.35(m，2H),8.29(s，1H),8.12(s，1H),8.05～7.99(m，3H),7.80(d,2H),7.65(t，2H),7.50～7.49(m,4H)

Under an argon atmosphere, 59.0g (100mmol) of 3, 6-dibromo-11, 13-diphenylphenanthroline, 62.9g (240mmol) of naphthobenzofuran-10-ylboronic acid, 1.16g (1.0mmol) of tetrakis (triphenylphosphine) palladium, 200ml (300mmol) of a 1.5M aqueous solution of sodium carbonate and 800ml of ethylene glycol dimethyl ether (DME) were charged into a reactor, and the mixture was heated and stirred at 80 ℃ overnight. After cooling to room temperature, 500ml of water was added, a solid precipitated and was filtered, and the obtained solid was washed with ethanol to obtain 72.7g of compound 67, yield 84%, and HPLC purity 99.3%.

¹HNMR(DMSO)：δ9.11(d，2H)，8.93(s，1H),8.46～8.43(m,4H),8.35(d，2H),8.16(d,2H),8.12～8.11(m,3H),8.08(d,2H),8.02(m,2H),7.84～7.80(m,4H),7.69～7.67(m,4H),7.65(d,2H),7.51～7.48(m,8H).

Example 6

Synthesis of Compound 109

Under argon atmosphere, a reaction flask was charged with 50.5 g (100mmol) of N- (7, 10-dibromoterphenyl-2-yl) benzamide and 300ml of 2-chloropyridine 12.5 g (120mmol) of dichloromethane, cooled to-78 ℃, then 31.0 g (110mmol) of trifluoromethanesulfonic anhydride was added, the reaction mixture was placed in an ice-water bath and heated to 0 ℃, and 11 g (110mmol) of benzonitrile was added. The reaction mixture was heated to 45 ℃ for 6 hours, cooled to room temperature and neutralized with triethylamine. The volatiles were removed under reduced pressure and flash column chromatography (eluent: 10% ethyl acetate in hexanes) was used to give 51.9 g of 3, 6-dibromo-11, 13-diphenylphenanthroline in 88% yield and 99.6% HPLC purity.

¹HNMR(DMSO)：δ9.10(s，1H)，8.93(s，1H)，8.81(d,1H),8.35(m，2H),8.29(s，1H),8.12(s，1H),8.05～7.99(m，3H),7.80(d,2H),7.65(t，2H),7.50～7.49(m,4H)

Under argon atmosphere, 59.0g (100mmol) of 3, 6-dibromo-11, 13-diphenylphenanthroline, 66.8g (240mmol) of benzonaphthol thiophen-9-ylboronic acid, 1.16g (1.0mmol) of tetrakis (triphenylphosphine) palladium, 200ml (300mmol) of 1.5M aqueous sodium carbonate solution and 800ml of ethylene glycol dimethyl ether (DME) were added to a reactor, and the mixture was heated and stirred at 80 ℃ overnight. After cooling to room temperature, 500ml of water was added, a solid precipitated and was filtered, and the obtained solid was washed with ethanol to obtain 74.5g of compound 109, yield 83%, HPLC purity 99.4%.

¹HNMR(DMSO)：δ9.11(d，2H)，8.93(s，1H),8.54(m,2H),8.46～8.43(m，4H),8.35(d,2H),8.24～8.17(m,6H),7.99(d,2H),7.80～7.78(m,6H),7.65～7.61(m,4H),7.53～7.50(m,5H).

Example 7

Synthesis of Compound 135

Under argon atmosphere, a reaction flask was charged with 50.5 g (100mmol) of N- (7, 10-dibromoterphenyl-2-yl) benzamide and 300ml of 2-chloropyridine 12.5 g (120mmol) of dichloromethane, cooled to-78 ℃, then 31.0 g (110mmol) of trifluoromethanesulfonic anhydride was added, the reaction mixture was placed in an ice-water bath and heated to 0 ℃, and 11 g (110mmol) of benzonitrile was added. The reaction mixture was heated to 45 ℃ for 6 hours, cooled to room temperature and neutralized with triethylamine. The volatiles were removed under reduced pressure and flash column chromatography (eluent: 10% ethyl acetate in hexanes) was used to give 51.9 g of 3, 6-dibromo-11, 13-diphenylphenanthroline in 88% yield and 99.6% HPLC purity.

¹HNMR(DMSO)：δ9.10(s，1H)，8.93(s，1H)，8.81(d,1H),8.35(m，2H),8.29(s，1H),8.12(s，1H),8.05～7.99(m，3H),7.80(d,2H),7.65(t，2H),7.50～7.49(m,4H)

Under argon atmosphere, 59.0g (100mmol) of 3, 6-dibromo-11, 13-diphenylphenanthroline, 80.9g (240mmol) of (7-phenyl-7H-benzocarbazol-8-yl) boric acid, 1.16g (1.0mmol) of tetrakis (triphenylphosphine) palladium, 200ml (300mmol) of 1.5M aqueous sodium carbonate solution and 800ml of ethylene glycol dimethyl ether (DME) are added into a reactor, and the mixture is heated and stirred at 80 ℃ overnight. After cooling to room temperature, 500ml of water was added, a solid precipitated and was filtered, and the obtained solid was washed with ethanol to give 87.4g of compound 135 with a yield of 86% and a HPLC purity of 99.5%.

¹HNMR(DMSO)：δ9.11(d，2H)，8.93(s，1H),8.54(m,2H),8.46～8.43(m，4H),8.35(d,2H),8.29(d,2H),8.12(s,1H),8.06～7.94(m,8H),7.80(d,2H),7.65～7.61(m,7H),7.58(d,2H),7.53(d,2H),7.50(m,7H),7.48(m,2H).

Example 8

Synthesis of Compound 155

Under argon, a reaction flask was charged with 46.0 g (100mmol) of N- (7-bromo-10-chlorobenzo-2-yl) benzamide and 300ml of 2-chloropyridine 12.5 g (120mmol) of dichloromethane, cooled to-78 deg.C, then 31.0 g (110mmol) of trifluoromethanesulfonic anhydride was added, the reaction mixture was placed in an ice-water bath and heated to 0 deg.C, and 11 g (110mmol) of benzonitrile was added. The reaction mixture was heated to 45 ℃ for 6 hours, cooled to room temperature and neutralized with triethylamine. The volatiles were removed under reduced pressure and flash column chromatography (eluent: 10% ethyl acetate in hexanes) was used to give 46.3 g of 6-bromo-3-chloro-11, 13-diphenylphenanthroline in 85% yield and 99.4% HPLC purity.

¹HNMR(DMSO)：δ9.10(s，1H)，8.93(s，1H)，8.81(d,1H),8.35(m，2H),8.29(s，1H),8.12(s，1H),8.05～7.99(m，3H),7.80(d,2H),7.65(t，2H),7.50～7.49(m,4H)

Under argon atmosphere, 54.6g (100mmol) of 6-bromo-3-chloro-11, 13-diphenylphenanthroline, 172.0g (100mmol) of 2-naphthalene boronic acid, 1.16g (1.0mmol) of tetrakis (triphenylphosphine) palladium, 200ml (300mmol) of 1.5M aqueous sodium carbonate solution and 800ml of ethylene glycol dimethyl ether (DME) were added to a reactor, and the mixture was heated and stirred overnight at 80 ℃. Cooling to room temperature, adding 500ml water, precipitating solid, filtering, washing the obtained solid with ethanol to obtain 42.7g of 3-chloro-6- (naphthalene-1-yl) -11, 13-diphenyl phenanthroline, yield 72%, HPLC purity 99.1%.

¹HNMR(DMSO)：δ9.11(d，2H)，8.93(d，1H),8.86(d,1H),8.46～8.43(m,2H),8.35(d,2H),8.13～8.12(m,2H),8.09～7.99(m,3H),7.89(m,1H),7.80(m,2H),7.65～7.63(m,3H),7.60(m,1H),7.55(d,1H),7.50～7.49(m,4H),7.38(d,1H).

26.9 g (240mmol) of potassium tert-butoxide, [1, 3-bis (2, 6-di-isopropylphenyl) -4, 5-dihydroimidazol-2-ylidene ] chloro ] [ 3-phenylallyl ] palladium (II) catalyst 648 mg (1 mmol%) of 3-chloro-6- (naphthalen-1-yl) -11, 13-diphenylphenanthroline 59.3g (100mmol), 22.0 g (120mmol) of 10H-benzoxazine and 1000mL of ethylene glycol dimethyl ether (DME) were charged to 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 were added, filtered and the crude product was purified by column chromatography on silica gel (eluent: ethyl acetate/hexane) to give 59.9 g of compound 155, 99.3% HPLC purity, 81% yield.

¹HNMR(DMSO)：δ9.11(d，2H)，8.93(d，1H),8.88(d,1H),8.46～8.43(m,2H),8.35(d,2H),8.12(s,1H),8.09～8.06(m,2H),7.99(d,1H),7.90(s,1H),7.80(d,2H),7.66～7.63(m,4H),7.60(m,1H),7.50～7.49(m,4H),7.38(d,1H),7.14(d,2H),7.01～6.96(m,6H).

Example 9

Synthesis of Compound 179

Under argon, a reaction flask was charged with 46.0 g (100mmol) of N- (7-bromo-10-chlorobenzo-2-yl) benzamide and 300ml of 2-chloropyridine 12.5 g (120mmol) of dichloromethane, cooled to-78 deg.C, then 31.0 g (110mmol) of trifluoromethanesulfonic anhydride was added, the reaction mixture was placed in an ice-water bath and heated to 0 deg.C, and 11 g (110mmol) of benzonitrile was added. The reaction mixture was heated to 45 ℃ for 6 hours, cooled to room temperature and neutralized with triethylamine. The volatiles were removed under reduced pressure and flash column chromatography (eluent: 10% ethyl acetate in hexanes) was used to give 46.3 g of 6-bromo-3-chloro-11, 13-diphenylphenanthroline in 85% yield and 99.4% HPLC purity.

¹HNMR(DMSO)：δ9.10(s，1H)，8.93(s，1H)，8.81(d,1H),8.35(m，2H),8.29(s，1H),8.12(s，1H),8.05～7.99(m，3H),7.80(d,2H),7.65(t，2H),7.50～7.49(m,4H)

Under argon atmosphere, 54.6g (100mmol) of 6-bromo-3-chloro-11, 13-diphenylphenanthroline, 172.0g (100mmol) of 2-naphthalene boronic acid, 1.16g (1.0mmol) of tetrakis (triphenylphosphine) palladium, 200ml (300mmol) of 1.5M aqueous sodium carbonate solution and 800ml of ethylene glycol dimethyl ether (DME) were added to a reactor, and the mixture was heated and stirred overnight at 80 ℃. Cooling to room temperature, adding 500ml water, precipitating solid, filtering, washing the obtained solid with ethanol to obtain 42.7g of 3-chloro-6- (naphthalene-1-yl) -11, 13-diphenyl phenanthroline, yield 72%, HPLC purity 99.1%.

¹HNMR(DMSO)：δ9.11(d，2H)，8.93(d，1H),8.86(d,1H),8.46～8.43(m,2H),8.35(d,2H),8.13～8.12(m,2H),8.09～7.99(m,3H),7.89(m,1H),7.80(m,2H),7.65～7.63(m,3H),7.60(m,1H),7.55(d,1H),7.50～7.49(m,4H),7.38(d,1H).

3-chloro-6- (naphthalen-1-yl) -11, 13-diphenylphenanthroline 59.3g (100mmol), dibenzofuran-2-ylboronic acid 25.4g (120mmol), [1, 3-bis (2, 6-di-isopropylphenyl) -4, 5-dihydroimidazol-2-ylidene ] are introduced into a reaction vessel under argon]Chlorine][ 3-Phenylallyl group]648 mg of palladium (II) catalyst, 200ml (300mmol) of 1.5M aqueous sodium carbonate solution and 1000ml of ethylene glycol dimethyl ether (DME), and stirring overnight at 80 ℃. Cooling to room temperature, adding 800ml of water, solidifyingThe precipitate was filtered off, the solid obtained was washed with ethanol and recrystallized from 500ml of toluene to give 58.0g of 179, 80% yield and 99.5% purity by HPLC.¹HNMR(DMSO)：δ9.11(d，2H)，8.93(d，1H),8.46～8.43(m,2H),8.35(d,2H),

8.12(s,1H),8.09～7.99(m,3H),7.98(d,1H),7.88～7.83(m,2H),7.80～7.79(m,3H),7.65～7.63(m,3H),7.60(m,1H),7.50～7.49(m,4H),7.39～7.38(m,2H),7.31(m,1H).

Example 10

Synthesis of Compound 181

Under argon, a reaction flask was charged with 46.0 g (100mmol) of N- (7-bromo-10-chlorobenzo-2-yl) benzamide and 300ml of 2-chloropyridine 12.5 g (120mmol) of dichloromethane, cooled to-78 deg.C, then 31.0 g (110mmol) of trifluoromethanesulfonic anhydride was added, the reaction mixture was placed in an ice-water bath and heated to 0 deg.C, and 11 g (110mmol) of benzonitrile was added. The reaction mixture was heated to 45 ℃ for 6 hours, cooled to room temperature and neutralized with triethylamine. The volatiles were removed under reduced pressure and flash column chromatography (eluent: 10% ethyl acetate in hexanes) was used to give 46.3 g of 6-bromo-3-chloro-11, 13-diphenylphenanthroline in 85% yield and 99.4% HPLC purity.

¹HNMR(DMSO)：δ9.10(s，1H)，8.93(s，1H)，8.81(d,1H),8.35(m，2H),8.29(s，1H),8.12(s，1H),8.05～7.99(m，3H),7.80(d,2H),7.65(t，2H),7.50～7.49(m,4H)

Under argon atmosphere, 54.6g (100mmol) of 6-bromo-3-chloro-11, 13-diphenylphenanthroline, 172.0g (100mmol) of 2-naphthalene boronic acid, 1.16g (1.0mmol) of tetrakis (triphenylphosphine) palladium, 200ml (300mmol) of 1.5M aqueous sodium carbonate solution and 800ml of ethylene glycol dimethyl ether (DME) were added to a reactor, and the mixture was heated and stirred overnight at 80 ℃. Cooling to room temperature, adding 500ml water, precipitating solid, filtering, washing the obtained solid with ethanol to obtain 42.7g of 3-chloro-6- (naphthalene-1-yl) -11, 13-diphenyl phenanthroline, yield 72%, HPLC purity 99.1%.

¹HNMR(DMSO)：δ9.11(d，2H)，8.93(d，1H),8.86(d,1H),8.46～8.43(m,2H),8.35(d,2H),8.13～8.12(m,2H),8.09～7.99(m,3H),7.89(m,1H),7.80(m,2H),7.65～7.63(m,3H),7.60(m,1H),7.55(d,1H),7.50～7.49(m,4H),7.38(d,1H).

59.3g (100mmol) of 3-chloro-6- (naphthalen-1-yl) -11, 13-diphenylphenanthroline, 27.3g (120mmol) of dibenzothiophen-4-ylboronic acid, [1, 3-bis (2, 6-di-isopropylphenyl) -4, 5-dihydroimidazol-2-ylidene ] chloro ] [ 3-phenylallyl ] palladium (II) as catalyst, 200ml (300mmol) of 1.5M aqueous sodium carbonate solution and 1000ml of ethylene glycol dimethyl ether (DME) were charged into a reaction vessel under argon atmosphere, and stirred at 80 ℃ overnight. After cooling to room temperature, 800ml of water were added, the solid precipitated and filtered, the solid obtained was washed with ethanol and recrystallized from 500ml of toluene to give 63.0g of compound 181, yield 85%, purity 99.3% by HPLC.

¹HNMR(DMSO)：δ9.11(d，2H)，8.93(d，1H),8.55(m,1H),8.46～8.43(m,5H),8.35～8.32(m,3H),8.12(s,1H),8.09～7.99(m,3H),7.93(d,1H),7.80(m,2H),7.70(m,1H),7.65～7.63(m,3H),7.60(m,1H),7.56～7.55(m,2H),7.50～7.49(m,5H),7.38(d,1H).

Example 11

Synthesis of Compound 203

Under argon atmosphere, a reaction flask was charged with 50.5 g (100mmol) of N- (7, 10-dibromoterphenyl-2-yl) benzamide and 300ml of 2-chloropyridine 12.5 g (120mmol) of dichloromethane, cooled to-78 ℃, then 31.0 g (110mmol) of trifluoromethanesulfonic anhydride was added, the reaction mixture was placed in an ice-water bath and heated to 0 ℃, and 11 g (110mmol) of benzonitrile was added. The reaction mixture was heated to 45 ℃ for 6 hours, cooled to room temperature and neutralized with triethylamine. The volatiles were removed under reduced pressure and flash column chromatography (eluent: 10% ethyl acetate in hexanes) was used to give 51.9 g of 3, 6-dibromo-11, 13-diphenylphenanthroline in 88% yield and 99.6% HPLC purity.

¹HNMR(DMSO)：δ9.10(s，1H)，8.93(s，1H)，8.81(d,1H),8.35(m，2H),8.29(s，1H),8.12(s，1H),8.05～7.99(m，3H),7.80(d,2H),7.65(t，2H),7.50～7.49(m,4H)

59.0g (100mmol) of 3, 6-dibromo-11, 13-diphenylphenanthroline, 68.9g (240mmol) of (9-phenyl-9H-carbazol-2-yl) boric acid, 1.16g (1.0mmol) of tetrakis (triphenylphosphine) palladium, 200ml (300mmol) of 1.5M aqueous sodium carbonate solution and 800ml of ethylene glycol dimethyl ether (DME) are added to a reactor under an argon atmosphere, and the mixture is heated and stirred at 80 ℃ overnight. After cooling to room temperature, 500ml of water was added, a solid precipitated and was filtered, and the obtained solid was washed with ethanol to obtain 73.2g of compound 203 with a yield of 80% and a HPLC purity of 99.3%.

¹HNMR(DMSO)：δ9.11(d，2H)，8.93(s，1H),8.55(d,2H),8.46～8.43(m，4H),8.35(d,2H),8.31(d,2H),8.12(s,1H),7.94～7.91(m,4H),7.80(d,2H),7.74(s,2H),7.65～7.62(m,6H),7.58(m,2H),7.50～7.49(m,8H),7.35(d,2H),7.16(d,2H).

Example 12

Synthesis of Compound 239

Under argon atmosphere, a reaction flask was charged with 50.5 g (100mmol) of N- (7, 10-dibromoterphenyl-2-yl) benzamide and 300ml of 2-chloropyridine 12.5 g (120mmol) of dichloromethane, cooled to-78 ℃, then 31.0 g (110mmol) of trifluoromethanesulfonic anhydride was added, the reaction mixture was placed in an ice-water bath and heated to 0 ℃, and 11 g (110mmol) of benzonitrile was added. The reaction mixture was heated to 45 ℃ for 6 hours, cooled to room temperature and neutralized with triethylamine. The volatiles were removed under reduced pressure and flash column chromatography (eluent: 10% ethyl acetate in hexanes) was used to give 51.9 g of 3, 6-dibromo-11, 13-diphenylphenanthroline in 88% yield and 99.6% HPLC purity.

¹HNMR(DMSO)：δ9.10(s，1H)，8.93(s，1H)，8.81(d,1H),8.35(m，2H),8.29(s，1H),8.12(s，1H),8.05～7.99(m，3H),7.80(d,2H),7.65(t，2H),7.50～7.49(m,4H)

Under an argon atmosphere, 59.0g (100mmol) of 3, 6-dibromo-11, 13-diphenylphenanthroline, 62.9g (240mmol) of naphthobenzofuran-4-ylboronic acid, 1.16g (1.0mmol) of tetrakis (triphenylphosphine) palladium, 200ml (300mmol) of a 1.5M aqueous solution of sodium carbonate and 800ml of ethylene glycol dimethyl ether (DME) were charged into a reactor, and the mixture was heated and stirred at 80 ℃ overnight. After cooling to room temperature, 500ml of water was added, the solid precipitated and was filtered, and the resulting solid was washed with ethanol to give 70.9g of compound 239 in 82% yield and 99.5% purity by HPLC.

¹HNMR(DMSO)：δ9.11(d，2H)，8.93(s，1H),8.46～8.43(m,4H),8.35(d，2H),8.28(d,2H),8.12(s,1H),8.11～8.02(m,6H),7.80(d,2H),7.75(d，2H),7.51～7.50(m,5H),7.49(s,2H),7.42(s,2H).

Example 13

Synthesis of Compound 270

Under argon atmosphere, a reaction flask was charged with 50.5 g (100mmol) of N- (7, 10-dibromoterphenyl-2-yl) benzamide and 300ml of 2-chloropyridine 12.5 g (120mmol) of dichloromethane, cooled to-78 ℃, then 31.0 g (110mmol) of trifluoromethanesulfonic anhydride was added, the reaction mixture was placed in an ice-water bath and heated to 0 ℃, and 11 g (110mmol) of benzonitrile was added. The reaction mixture was heated to 45 ℃ for 6 hours, cooled to room temperature and neutralized with triethylamine. The volatiles were removed under reduced pressure and flash column chromatography (eluent: 10% ethyl acetate in hexanes) was used to give 51.9 g of 3, 6-dibromo-11, 13-diphenylphenanthroline in 88% yield and 99.6% HPLC purity.

¹HNMR(DMSO)：δ9.10(s，1H)，8.93(s，1H)，8.81(d,1H),8.35(m，2H),8.29(s，1H),8.12(s，1H),8.05～7.99(m，3H),7.80(d,2H),7.65(t，2H),7.50～7.49(m,4H)

Under an argon atmosphere, 59.0g (100mmol) of 3, 6-dibromo-11, 13-diphenylphenanthroline, 66.8g (240mmol) of naphthobenzofuran-4-ylboronic acid, 1.16g (1.0mmol) of tetrakis (triphenylphosphine) palladium, 200ml (300mmol) of a 1.5M aqueous solution of sodium carbonate and 800ml of ethylene glycol dimethyl ether (DME) were charged into a reactor, and the mixture was heated and stirred at 80 ℃ overnight. After cooling to room temperature, 500ml of water was added, a solid precipitated and was filtered, and the obtained solid was washed with ethanol to give 74.5g of compound 270, yield 83%, HPLC purity 99.5%.

¹HNMR(DMSO)：δ9.11(d，2H)，8.93(s，1H),8.55～8.54(m,4H),8.46～8.43(m,4H),8.35(d，2H),8.32(d,2H),8.12(s,1H),7.99(m,2H),7.80(m,4H),7.78(d,2H),7.70(d,2H),7.65～7.61(m,4H),7.53(m,2H),7.50(m,3H).

Example 14

Synthesis of Compound 315

Under argon atmosphere, a reaction flask was charged with 50.5 g (100mmol) of N- (7, 10-dibromoterphenyl-2-yl) benzamide and 300ml of 2-chloropyridine 12.5 g (120mmol) of dichloromethane, cooled to-78 ℃, then 31.0 g (110mmol) of trifluoromethanesulfonic anhydride was added, the reaction mixture was placed in an ice-water bath and heated to 0 ℃, and 11 g (110mmol) of benzonitrile was added. The reaction mixture was heated to 45 ℃ for 6 hours, cooled to room temperature and neutralized with triethylamine. The volatiles were removed under reduced pressure and flash column chromatography (eluent: 10% ethyl acetate in hexanes) was used to give 51.9 g of 3, 6-dibromo-11, 13-diphenylphenanthrene [9,10-g ] quinazoline in 88% yield and 99.6% HPLC purity.

¹HNMR(DMSO)：δ9.10(s，1H)，8.93(s，1H)，8.81(d,1H),8.35(m，2H),8.29(s，1H),8.12(s，1H),8.05～7.99(m，3H),7.80(d,2H),7.65(t，2H),7.50～7.49(m,4H)

26.9 g (240mmol) of potassium tert-butoxide, [1, 3-bis (2, 6-di-isopropylphenyl) -4, 5-dihydroimidazol-2-ylidene ] chloro ] [ 3-phenylallyl ] palladium (II) catalyst 648 mg (1 mmol%) of 3, 6-dibromo-11, 13-diphenylphenanthrene [9,10-g ] quinazoline 59.0g (100mmol), 40.1 g (200mmol) of carbazole 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, filtration was carried out, and the crude product was purified by silica gel column chromatography (eluent: ethyl acetate/hexane) to give 61.0 g of 3, 6-bis (9H-carbazol-9-yl) -11, 13-diphenylphenanthrene [9,10-g ] quinazoline, HPLC purity 99.5%, yield 80%.

¹HNMR(DMSO)：δ9.05(d，2H)，8.93(s,1H),8.55(d,2H),8.35(d,2H),8.25～8.24(m，2H),8.19(m,2H),8.11(m，3H),8.00(m,1H),7.94(d,2H),7.80(m,2H)7.65(m,2H),7.58(m,2H),7.50～7.49(m,6H),7.35(d,2H),7.20(d,2H),7.16(d,2H).

Device embodiments

Evaluation of luminescent Material devices

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

example 15

The preparation method of the device comprises the following steps:

the basic structural model of the device is as follows: ITO/HAT-CN (10nm)/TAPC (40nm)/TCTA (10 nm)/EML: RD (Ir complex) (40nm) ═ 94: 6/ETL (30nm)/LiF (1nm)/Al (80nm)

A transparent anodic Indium Tin Oxide (ITO)20(10 Ω/sq) glass substrate was subjected to ultrasonic cleaning using acetone, ethanol, and distilled water in this order, and then treated with ozone plasma for 15 minutes.

Then, an ITO substrate was mounted on a substrate holder of a vacuum vapor deposition apparatus. In the evaporation equipment, the system pressure is controlled at 10^-6And (4) supporting. And evaporating the hole transport layer material HAT-CN with the thickness of 60nm onto the ITO substrate.

Then the light emitting layer material EML (compound 1) was evaporated to a thickness of 40nm, in which different mass fractions of RD metal iridium complex dopant were doped.

The electron transport layer material ETL was then evaporated to a thickness of 30 nm.

Then, LiF with a thickness of 1nm was evaporated to form an electron injection layer.

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

Example 16

The evaluation was carried out using the same elements as those in example 20 except that the EML material was compound 20, and the test results are shown in table 1.

Example 17

The same elements as in example 20 were used for evaluation except that the EML material was compound 28, and the test results are shown in table 1.

Example 18

The same elements as in example 20 were used for evaluation except that the EML material was compound 50, and the test results are shown in table 1.

Example 19

The same elements as in example 20 were used for evaluation, except that the EML material was compound 67, and the test results are shown in table 1.

Example 20

The same elements as in example 20 were used for evaluation except that the EML material was compound 109, and the test results are shown in table 1.

Example 21

The same elements as in example 20 were used for evaluation, except that the EML material was compound 135, and the test results are shown in table 1.

Example 22

The same elements as in example 20 were used for evaluation, except that the EML material was compound 155, and the test results are shown in table 1.

Example 23

The evaluation was carried out using the same elements as those in example 20 except that the EML material was compound 179, and the test results are shown in Table 1.

Example 24

The same elements as in example 20 were used for evaluation except that the EML material was compound 181, and the test results are shown in table 1.

Example 25

The same elements as in example 20 were used for evaluation except that the EML material was compound 203, and the test results are shown in table 1.

Example 26

The same elements as those in example 20 were evaluated except that the EML material was the compound 239, and the test results are shown in Table 1.

Example 27

The evaluation was carried out using the same elements as those in example 20 except that the EML material was compound 270, and the test results are shown in table 1.

Example 28

The same elements as in example 20 were used for evaluation, except that the EML material was compound 315, and the test results are shown in table 1.

Comparative example 1

The same elements as in example 20 were evaluated except that the EML material was the compound RH-01, and the test results are shown in Table 1.

Comparative example 2

The same elements as those in example 20 were evaluated except that the EML material was RH-02, and the results are shown in Table 1.

[ TABLE 1 ]

Serial number	Host material	Current (mA/cm)2)	Current efficiency (cd/A)	LT98(hr)
					Example 15	1	10	16.8	11.0
Example 16	20	10	16.1	11.8
					Example 17	28	10	16.7	12.1
Example 18	50	10	15.9	13.3
					Example 19	67	10	14.8	12.3
Example 20	109	10	16.5	14.2
					Example 21	135	10	15.9	11.9
Example 22	155	10	14.7	12.3
					Example 23	179	10	16.9	11.8
Example 24	181	10	17.1	12.8
					Example 25	203	10	16.3	11.7
Example 26	239	10	15.4	11.6
					Example 27	270	10	15.9	12.3
Example 28	315	10	15.3	12.6
					Comparative example 1	RH01	10	9.7	10.8
Comparative example 2	RH02	10	8.2	10.7

The device structure is different except for the light emitting layer, the other structures are consistent, the current efficiency of the triphenylene derivative is remarkably improved by taking the device performance of RH-01 and RH-02 as reference, and the service life of the device is also prolonged. In conclusion, the novel triphenylene derivative organic material prepared by the invention has a great application value in organic light-emitting diodes.