CN113248426A

CN113248426A - Heterocyclic triarylamine compound and organic photoelectric device containing same

Info

Publication number: CN113248426A
Application number: CN202110371656.4A
Authority: CN
Inventors: 王鹏; 王子兴; 张迪; 高春吉; 陈清泉; 吕伯彦
Original assignee: Zhejiang Huadisplay Optoelectronics Co Ltd
Current assignee: Zhejiang Huadisplay Optoelectronics Co Ltd
Priority date: 2021-04-07
Filing date: 2021-04-07
Publication date: 2021-08-13

Abstract

The invention provides a heterocyclic triarylamine compound and an organic photoelectric device containing the same. Heterocyclic triarylamine compounds containing heterocyclic aromatic groupsAn electron withdrawing group represented by the general formula (1):

Description

Heterocyclic triarylamine compound and organic photoelectric device containing same

Technical Field

The present invention relates to a heterocyclic triarylamine compound and an organic light-emitting device in which the efficiency-enhancing layer contains such a material.

Background

With the research and development of OLED technology, the luminescent materials, hole transport materials, electron transport materials and device preparation technology used by the device are promoted in a new and different way. However, the electron mobility of the electron transport material is much lower than that of the hole transport material, which may cause unbalanced injection and transport of carriers in the OLED device, and decrease the recombination probability of holes and electrons, thereby decreasing the light emitting efficiency of the device; on the other hand, the low electron mobility of the electron transport material can cause the working voltage of the device to be increased, thereby reducing the overall power efficiency of the device and causing the energy loss.

Disclosure of Invention

Technical problem

It is an object of the present invention to provide an OLED material and an organic light emitting diode having improved driving voltage, efficiency and lifetime.

Technical scheme

The present invention provides a heterocyclic triarylamine compound represented by general formula (1):

wherein, ring A is selected from substituted or unsubstituted benzene ring, naphthalene ring;

ring B is selected from

R1, R2, R3 and R4 in the ring B are identical or different and are preferably selected from

Wherein R5, R6 and R7 are one or more of hydrogen atom, deuterium atom, halogen, C1-10 alkyl, C1-10 alkoxy, substituted or unsubstituted C6-60 aryl or heterocyclic group.

Ring C is selected from one of general formula (2) to general formula (4):

in the general formula (2), the general formula (3) and the general formula (4), Z is represented by a nitrogen atom or C (R) in the same or different manner at each occurrence; at least one Z represents a nitrogen atom; r is hydrogen atom, deuterium atom, halogen, C1-10 alkyl, C1-10 alkoxy, substituted or unsubstituted C6-60 aryl or heterocyclic radical;

n is an integer of 1 to 6.

Further, in the present invention, n is preferably 1, or 2, or 3.

Preferably, the specific structural formula of the heterocyclic triarylamine compound of the present invention is one or more of the following structures, but not limited thereto:

further, the present invention provides an organic photoelectric 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 contains the heterocyclic triarylamine compound in the general formula (1).

In addition, the present invention provides an Organic photoelectric device including an Organic photovoltaic device, an Organic Light Emitting Device (OLED), an Organic Solar Cell (OSC), 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 a display device.

In addition, the present invention provides an organic photoelectric element comprising a cathode layer, an anode layer and an organic layer, wherein the organic layer comprises 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, and any one of the layers of the element contains the heterocyclic triarylamine compound represented by the general formula (1).

In addition, the compound with the structure of the general formula (1) provided by the invention has larger electron affinity, and can be applied to an organic light-emitting diode as an electron transport layer material.

The organic photoelectric element claimed by the invention is an organic electroluminescent device, the heterocyclic triarylamine compound in the general formula (1) can be applied to a light-emitting layer, wherein the mass percentage of the heterocyclic triarylamine compound is 30-99.9%, and the guest material is not limited at all.

Furthermore, the organic photoelectric element provided by the invention is an organic electroluminescent device, and the electron transport layer contains the heterocyclic triarylamine compound disclosed in claim 1, wherein the mass percentage of the heterocyclic triarylamine compound is 1-100%.

In addition, the invention provides a display or lighting device, which comprises the organic photoelectric device. Further, the compound of the general formula (1) wherein n is preferably selected from 1, or 2, or 3 from the viewpoint of HOMO, LUMO level.

In the case of the "substituted or unsubstituted" in the present invention, the substituents are each independently selected from one or more of deuterium, an alkyl group of C1 to C15, a cycloalkyl group of C3 to C15, a heterocyclic group of C3 to C15, an alkenyl group of C2 to C15, a cycloalkenyl group of C4 to C15, an alkynyl group of C2 to C15, an alkoxy group of C1 to C15, an alkylthio group of C1 to C15, an aryl ether group of C6 to C55, an aryl thioether group of C6 to C55, an aryl group of C6 to C55, an aromatic heterocyclic group of C5 to C55, a carbonyl group, a carboxyl group, an oxycarbonyl group, a carbamoyl group, an alkylamino group of C1 to C40, or a silane group of C3 to C15 having a silicon number of 1 to 5.

In the prior patent and literature, a compound with a triarylamine structure is generally used as a hole transport layer material, but the energy level of the compound with the triarylamine structure is greatly improved by introducing a charge-absorbing group and a heterocyclic aromatic group, so that the compound is also suitable for an electron transport layer of an organic light-emitting element.

The compound of the present invention is suitable for organic electronic devices, for example, organic electroluminescent elements, organic thin film transistor lighting devices, organic thin film solar cells, organic field effect transistors, electronic artificial skin sheets, information labels, large-area sensors such as sheet scanners, electronic paper, organic EL panels, and the like. Among them, the compound of the present invention can be used as, but not limited to, an electron transport layer material.

Detailed Description

The following description is presented to enable one of ordinary skill in the art to better understand the invention with reference to the specific embodiments

And (5) explaining the steps in detail.

The synthesis of the triarylamine 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 use C-N bond formation reactions of transition metals such as zinc or copper. For example, Buchwald-Hartwig reaction using nickel or palladium, Ullman reaction using copper, but not limited to these methods. The above reaction is limited to mild reaction conditions and superior selectivity of various functional groups, and the Buchwald-Hartwig reaction is preferred. The triarylamine derivative represented by the general formula (1) in the present invention may be used alone or in combination with other materials in an organic light-emitting device.

The triarylamine derivatives of the present invention are illustrated by the following examples, but are not limited to the triarylamine derivatives and the synthesis methods illustrated in these examples.

2-bromotriphenylene, 1-bromo-9, 9-dimethyl-9H-fluorene, 1-bromonaphthalene, 4-bromophenylacetonitrile, 6-aminoquinoline, 2-amino-1, 3, 5-triazine, sodium tert-butoxide, toluene, ethyl acetate and the like are purchased from national medicine companies; various palladium catalysts, boric acid derivatives and borate derivatives, etc. were purchased from 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:

4- ((3, 5-bis (benzo-2-yl) phenyl) (pyridin-3-yl) amino) benzonitrile (Compound 8)

4- ((3, 5-bis (triphenylen-2-yl) phenyl) (pyridazin-4-yl) amino) benzonitrile (Compound 15)

4- ((3, 5-bis (benzo-2-yl) phenyl) (1,3, 5-triazin-2-yl) amino) benzonitrile (Compound 24)

4- ((3, 5-bis (benzo-2-yl) phenyl) (pyridin-3-yl) amino) isophthalonitrile (Compound 44)

4- ((3, 5-bis (benzo-2-yl) phenyl) (1,3, 5-triazin-2-yl) amino) isophthalonitrile (Compound 76)

4- ((3,6-di (triphenyl-2-yl) naphthalen-1-yl (pyridin-4 yl) amino) benzonitrile (Compound 87)

3- ((3, 6-bis (triphenylen-2-yl) naphthalen-1-yl) (pyrimidin-4-yl) amino) benzonitrile (Compound 96)

3- ((3, 6-bis (benzo-2-yl) naphthalen-1-yl) (1,3, 5-triazin-2-yl) amino) benzonitrile (Compound 101)

4- ((3, 6-bis (benzo-2-yl) naphthalen-1-yl) (pyridin-3-yl) amino) isophthalonitrile (Compound 122)

4- ((3, 5-bis (9, 9-dimethyl-9H-fluoren-1-yl) phenyl) (pyridin-3-yl) amino) benzonitrile (Compound 164)

4- ((3, 5-bis (9, 9-dimethyl-9H-fluoren-1-yl) phenyl) (1,3, 5-triazin-2-yl) amino) benzonitrile (Compound 180)

4- ((3, 5-bis (9, 9-dimethyl-9H-fluoren-1-yl) phenyl) (pyridin-3-yl) amino) isophthalonitrile (Compound 188)

4- ((3, 5-bis (9, 9-dimethyl-9H-fluoren-1-yl) phenyl) (1,3, 5-triazin-2-yl) amino) isophthalonitrile (Compound 232)

4- ((3, 5-bis (benzo-2-yl) phenyl) (quinolin-6-yl) amino) benzonitrile (Compound 237)

4- ((3, 6-bis (benzo-2-yl) naphthalen-1-yl) (quinolin-6-yl) amino) benzonitrile (Compound 279)

4- ((3, 6-bis (benzo-2-yl) naphthalen-1-yl) (quinolin-6-yl) amino) isophthalonitrile (Compound 318)

3- ((3, 5-bis (9, 9-dimethyl-9H-fluoro-1-yl) phenyl) (quinolin-3-yl) amino) benzonitrile (Compound 323)

4- ((3, 5-bis (9, 9-dimethyl-9H-fluoren-1-yl) phenyl) (quinolin-6-yl) amino) isophthalonitrile (Compound 348)

4- ((3, 5-bis (9, 9-dimethyl-9H-fluoren-1-yl) phenyl) (quinolin-3-yl) amino) isophthalonitrile (Compound 359)

4- ((3, 6-bis (9, 9-dimethyl-9H-fluoren-1-yl) naphthalen-1-yl) (quinolin-6-yl) amino) benzonitrile (Compound 369)

4- ((3, 6-bis (9, 9-dimethyl-9H-fluoren-1-yl) naphthalen-1-yl) (quinolin-6-yl) amino) isophthalonitrile (Compound 390)

4- ((3, 6-bis (9, 9-dimethyl-9H-fluoro-1-yl) naphthalen-1-yl (quinolin-3-yl) amino) isopentanenitrile (Compound 401)

4- ((3, 5-bis (naphthalen-1-yl) phenyl) (isoquinolin-6-yl) amino) isophthalonitrile (Compound 432)

4- ((3, 5-bis (9, 9-dimethyl-9H-fluoren-1-yl) phenyl) (1, 10-phenanthrolin-3-yl) amino) benzonitrile (compound 474)

4- ((3, 5-bis (triphenylen-2-yl) phenyl) (1, 10-phenanthroline-3-yl) amino) isophthalonitrile (Compound 489)

4- ((3, 5-bis (9, 9-dimethyl-9H-fluoro-1-yl) phenyl) (1, 10-phenanthrolin-2-yl) amino) isoprenedinitrile (Compound 510)

4- ((3, 5-bis (triphenylen-2-yl) phenyl) (1, 10-phenanthroline-2-yl) amino) isophthalonitrile (Compound 516)

Example 1

Synthesis of Compound 8

27.04 g (100mmol) of 3.5-dibromochlorobenzene, 59.9 g (220mmol) of triphenylene-2-boronic acid, 200ml (300mmol) of a 1.5M aqueous solution of sodium carbonate, DME500ml, 1.4g (2mmol) of bis (triphenylphosphine) palladium (II) chloride were charged into a reaction vessel under an argon atmosphere, and the mixture was 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 washed with methanol and filtered to give 48.59 g of 2- (3-chloro-5-benzo-2-ylphenyl) triphenylene having an HPLC purity of 98.5% and a yield of 85% (based on 3, 5-dibromochlorobenzene).

¹HNMR(DMSO)：δ9.60(t，2H)，9.27(s，2H),8.37～8.30(m，6H)，8.07(d，2H)，7.82(s， 1H),7.90～7.86(m，2H)，7.70(m，4H)，7.64(m，4H),7.52(m，4H)

18.20 g (100mmol) of p-bromobenzonitrile, 9.41 g (100mmol) of m-aminopyridine, 28.83 g (300mmol) of sodium tert-butoxide, bis (vinylidene) were added to the reaction vessel under argon atmosphereBenzylacetone) palladium 288 mg (2mmol), xylene 500ml, stirred at reflux for 20 h. The reaction mixture was cooled to room temperature and the solid precipitated, filtered, and the crude product was washed 3 times with water, washed with methanol, and filtered to give 17.55 g of 4- (pyridin-3-ylamino) benzonitrile in 99.3% HPLC purity and 90% yield (p-bromobenzonitrile).

¹HNMR(DMSO)：δ9.5(s，1H)，8.04(s，1H)，7.92(m，1H)，7.48(m，2H)，7.36(m，3H)，7.15(m， 1H)

28.30 g (50mmol) of p-2- (3-chloro-5-benzo-2-ylphenyl) triphenylene, 9.76 g (50mmol) of 4- (pyridin-3-ylamino) benzonitrile, 14.4 g (150mmol) of sodium tert-butoxide, 144 mg (1mmol) of bis (benzylideneacetone) palladium and 250ml of xylene were added to a reaction vessel under argon atmosphere, and stirred at reflux for 20 hours. The reaction mixture was cooled to room temperature and the solid precipitated out, filtered and the crude product purified by column chromatography on silica gel (eluent: ethyl acetate/hexane) to give 31.1 g of compound 8, 99.3% purity by HPLC, and 80% yield (based on 2- (3-chloro-5-benzo-2-ylphenyl) triphenylene).

¹HNMR(DMSO)：δ9.60(t，2H)，9.27(s，2H),8.37～8.30(m，6H)，8.04(d，1H)，7.92(m， 1H)，7.70(m，4H)，7.60(s,1H),7.64(m，4H),7.52(m，4H)

Example 2

Synthesis of Compound 15

¹HNMR(DMSO)：δ9.60(t，2H)，9.27(s，2H),8.37～8.30(m，6H)，8.07(d，2H)，7.82(s， 1H),7.90～7.86(m，2H)，7.70(m，4H)，7.64(m，4H),7.52(m， 4H)

18.20 g (100mmol) of p-bromobenzonitrile, 13.10 g (100mmol) of 4-aminopyridazine, 28.83 g (300mmol) of sodium t-butoxide, 288 mg (2mmol) of palladium bis (benzylideneacetone), and 500ml of xylene were added to a reaction vessel under an argon atmosphere, and the mixture was stirred at reflux for 20 hours. The reaction mixture was cooled to room temperature and the solid precipitated, filtered, and the crude product was washed 3 times with water, washed with methanol, and filtered to give 17.20 g of 4- (pyridazin-4-ylamino) benzonitrile in 99.3% HPLC purity and 89% yield (p-bromobenzonitrile).

¹HNMR(DMSO)：δ9.7(s，1H)，9.26(m，1H)，9.18(m，1H)，7.48(m，2H)，7.36(m，2H)，7.06(m， 1H)

28.30 g (50mmol) of p-2- (3-chloro-5-benzo-2-ylphenyl) triphenylene, 9.76 g (50mmol) of 4- (pyridazin-4-ylamino) benzonitrile, 14.4 g (150mmol) of sodium tert-butoxide, 144 mg (1mmol) of bis (benzylideneacetone) palladium and 250ml of xylene were added to a reaction vessel under argon atmosphere, and stirred at reflux for 20 hours. The reaction mixture was cooled to room temperature, a solid precipitated, filtered and the crude product was purified by column chromatography on silica gel (eluent: ethyl acetate/hexane) to give 31.1 g of compound 15 with an HPLC purity of 99.3% and a yield of 80% (based on 2- (3-chloro-5-benzo-2-ylphenyl) triphenylene).

¹HNMR(DMSO)：δ9.60(t，2H)，9.27～9.26(m，3H),9.18(s，1H)，8.37～8.30(m，6H),8.04(d， 1H)，7.92(m，1H)，7.70(m，4H)，7.60(s,1H),7.64(m，4H),7.52(m，4H),7.37～7.35(m， 4H),7.06(m，1H)

Example 3

Synthesis of Compound 24

18.20 g (100mmol) of p-bromobenzonitrile, 13.10 g (100mmol) of 4-aminopyridazine, 28.83 g (300mmol) of sodium t-butoxide, 288 mg (2mmol) of palladium bis (benzylideneacetone), and 500ml of xylene were added to a reaction vessel under an argon atmosphere, and the mixture was stirred at reflux for 20 hours. The reaction mixture was cooled to room temperature and the solid precipitated, filtered, and the crude product was washed 3 times with water, washed with methanol, and filtered to give 17.20 g of 4- (pyridazin-4-ylamino) benzonitrile in 99.3% HPLC purity and 89% yield (based on p-bromobenzonitrile).

28.30 g (50mmol) of p-2- (3-chloro-5-benzo-2-ylphenyl) triphenylene, 9.76 g (50mmol) of 4- ((1,3, 5-triazin-2-yl) amino) benzonitrile, 14.4 g (150mmol) of sodium tert-butoxide, 144 mg (1mmol) of bis (benzylideneacetone) palladium, 250ml of xylene were added to a reaction vessel under argon atmosphere, and stirred at reflux for 20 hours. The reaction mixture was cooled to room temperature and the solid precipitated out, filtered and the crude product purified by column chromatography on silica gel (eluent: ethyl acetate/hexane) to give 31.5 g of compound 24, 99.5% purity by HPLC, and 80% yield (based on 2- (3-chloro-5-benzo-2-ylphenyl) triphenylene).

¹HNMR(DMSO)：δ9.60(t，2H)，9.28～9.26(m，4H),8.37～8.30(m，6H)，7.70(m，4H)， 7.60(s,1H),7.64(m，4H),7.52(m，4H),7.48(m,2H).

Example 4

Synthesis of Compound 44

20.7 g (100mmol) of 2, 4-dicyanobenzene, 9.41 g (100mmol) of 3-aminopyridine, 28.83 g (300mmol) of sodium tert-butoxide, 288 mg (2mmol) of bis (benzylideneacetone) palladium and 500ml of xylene were added to a reaction vessel under argon atmosphere, and the mixture was stirred at reflux for 20 hours. The reaction mixture was cooled to room temperature and the solid precipitated, filtered, and the crude product was washed 3 times with water, methanol and filtered to give 19.16 g of 4- (pyridin-3-ylamino) isophthalonitrile with an HPLC purity of 98.9% and a yield of 87% (based on 2, 4-dicyanobenzene).

¹HNMR(DMSO)：δ9.23(s，1H)，8.04(s，1H)，7.82(s，1H)，7.76(s，1H)，7.54(d，1H)， 7.47(d，1H),7.36(t，1H),7.15(d，1H)

28.30 g (50mmol) of p-2- (3-chloro-5-benzo-2-ylphenyl) triphenylene, 11.01 g (50mmol) of 4- (pyridin-3-ylamino) isophthalonitrile, 14.4 g (150mmol) of sodium tert-butoxide, 144 mg (1mmol) of bis (benzylideneacetone) palladium and 250ml of xylene were added to a reaction vessel under argon atmosphere, and the mixture was stirred under reflux for 20 hours. The reaction mixture was cooled to room temperature, a solid precipitated, filtered and the crude product was purified by column chromatography on silica gel (eluent: ethyl acetate/hexane) to give 30.1 g of compound 44 with an HPLC purity of 99.5% and a yield of 80% (based on 2- (3-chloro-5-benzo-2-ylphenyl) triphenylene).

¹HNMR(DMSO)：δ9.60(t，2H)，9.27(s，2H),8.37～8.30(m，6H)，8.04(d，1H)，7.92(m， 1H)，7.70(m，4H)，7.60(s,1H),7.64(m，4H),7.52(m，4H),7.15(m,1H)

Example 5

Synthesis of Compound 76

20.7 g (100mmol) of 2, 4-dicyanobenzene, 9.61 g (100mmol) of 2-amino-1, 3, 5-triazine, 28.83 g (300mmol) of sodium tert-butoxide, 288 mg (2mmol) of bis (benzylideneacetone) palladium and 500ml of xylene are added to a reaction vessel under argon atmosphere, and stirred at reflux for 20 hours. The reaction mixture was cooled to room temperature and the solid precipitated, filtered, and the crude product was washed 3 times with water, methanol and filtered to give 18.89 g of 4- (pyridin-3-ylamino) isophthalonitrile with an HPLC purity of 98.6% and a yield of 85% (based on 2, 4-dicyanobenzene).

¹HNMR(DMSO)：δ9.28(s，2H)，8.89(s，1H)，7.76(t，3H)，7.54(m，1H)，7.47(d，1H)

28.30 g (50mmol) of p-2- (3-chloro-5-benzo-2-ylphenyl) triphenylene, 11.11 g (50mmol) of 4- ((1,3, 5-triazin-2-yl) amino) isophthalonitrile, 14.4 g (150mmol) of sodium tert-butoxide, 144 mg (1mmol) of bis (benzylideneacetone) palladium and 250ml of xylene were added to a reaction vessel under an argon atmosphere, and stirred under reflux for 20 hours. The reaction mixture was cooled to room temperature, a solid precipitated, filtered and the crude product was purified by column chromatography on silica gel (eluent: ethyl acetate/hexane) to give 30.4 g of compound 76, 99.5% purity by HPLC, and 80% yield (based on 2- (3-chloro-5-benzo-2-ylphenyl) triphenylene).

¹HNMR(DMSO)：δ9.60(t，2H)，9.28～9.26(m，4H),8.37～8.30(m，6H)，8.04(d，1H)，7.92(m， 1H)，7.76(m，1H),7.70(m，4H)，7.60(s,1H),7.64(m，4H),7.52(m，4H),7.37(s，2H).

Example 6

Synthesis of Compound 87

32.04 g (100mmol) of 3, 6-dibromo-1-chloronaphthalene, 59.9 g (220mmol) of triphenylene-2-boronic acid, 200ml (300mmol) of a 1.5M aqueous solution of sodium carbonate, DME500ml, 1.4g (2mmol) of bis (triphenylphosphine) palladium (II) chloride were charged in a reaction vessel under an argon atmosphere, and the mixture was stirred at 80 ℃ for 15 hours. The reaction mixture was cooled to room temperature, 500ml of water were added, filtered, the crude product was washed with methanol and filtered to give 52.90 g of 2-2,2' - (4-chloronaphthalene-2, 7-diyl) triphenylene, 98.7% purity by HPLC, and 86% yield (based on 3, 5-dibromochlorobenzene).

¹HNMR(DMSO)：δ9.60(t，2H)，9.27(s，2H)，8.85(d，1H),8.37～8.30(m，6H)，8.00(m， 1H)，7.90～7.86(m，2H)，7.70(m，4H)，7.64(m，4H),7.52(m，4H)

18.20 g (100mmol) of p-bromobenzonitrile, 13.06 g (100mmol) of m-bromoaminopyridine, 28.83 g (300mmol) of sodium tert-butoxide, 288 mg (2mmol) of palladium bis (benzylideneacetone), and 500ml of xylene were added to a reaction vessel under argon atmosphere, and stirred at reflux for 20 hours. The reaction mixture was cooled to room temperature and the solid precipitated, filtered, and the crude product was washed 3 times with water, washed with methanol, and filtered to give 17.58 g of 4- (pyridin-4-ylamino) benzonitrile in 99.3% HPLC purity and 90% yield (p-bromobenzonitrile).

¹HNMR(DMSO)：δ8.46(m，2H)，7.48(m，2H)，7.36(m，2H)，7.11(s，1H)，6.99(m，2H).

30.76 g (50mmol) of p-2, 2' - (4-chloronaphthalene-2, 7-diyl) triphenylene, 11.11 g (50mmol) of 4- (pyridin-4-ylamino) benzonitrile, 14.4 g (150mmol) of sodium tert-butoxide, 144 mg (1mmol) of palladium bis (benzylideneacetone) and 250ml of xylene were added to a reaction vessel under an argon atmosphere, and the mixture was stirred under reflux for 20 hours. The reaction mixture was cooled to room temperature and the solid precipitated out, filtered and the crude product was purified by column chromatography on silica gel (eluent: ethyl acetate/hexane) to give 30.4 g of compound 76 in 99.5% HPLC purity and 80% yield (based on 2-2,2' - (4-chloronaphthalene-2, 7-diyl) triphenylene).

¹HNMR(DMSO)：δ9.60(t，2H)，9.27(s，2H)，8.56～8.46(m，2H),8.37～8.30(m，6H)，8.02(m， 1H)，7.77(m，1H),7.70～7.64(m，9H)，7.52(m，4H)，7.36(m，2H),7.19(d，1H),6.99(m， 1H)

Example 7

Synthesis of Compound 96

18.20 g (100mmol) of m-bromobenzonitrile, 9.51 g (100mmol) of 4-aminopyrimidine, 28.83 g (300mmol) of sodium tert-butoxide, 288 mg (2mmol) of bis (benzylideneacetone) palladium and 500ml of xylene are added to the reaction vessel under argon and stirred at reflux for 20 hours. The reaction mixture was cooled to room temperature and the solid precipitated, filtered, and the crude product was washed 3 times with water, methanol and filtered to give 17.61 g of 3- (pyrimidin-4-ylamino) benzonitrile in 99.2% HPLC purity and 90% yield (m-bromobenzonitrile).

¹HNMR(DMSO)：δ8.40(m，1H)，8.34(s，1H)，7.91(m，1H)，7.58(m，1H)，7.43～7.36(m， 2H),6.65(s，1H),6.44(d，1H).

30.76 g (50mmol) of p-2, 2' - (4-chloronaphthalene-2, 7-diyl) triphenylene, 11.11 g (50mmol) of 3- (pyrimidin-4-ylamino) benzonitrile, 14.4 g (150mmol) of sodium tert-butoxide, 144 mg (1mmol) of palladium bis (benzylideneacetone) and 250ml of xylene were added to a reaction vessel under an argon atmosphere, and the mixture was stirred under reflux for 20 hours. The reaction mixture was cooled to room temperature and the solid precipitated out, filtered and the crude product was purified by column chromatography on silica gel (eluent: ethyl acetate/hexane) to give 30.4 g of compound 76 in 99.5% HPLC purity and 80% yield (2-2,2' - (4-chloronaphthalene-2, 7-diyl) triphenylene as reference).

¹HNMR(DMSO)：δ9.60(t，2H)，9.27(s，2H)，8.58(d，1H),8.40～8.30(m，8H)，8.02(m， 1H)，7.77(m，1H),7.70～7.64(m，9H)，7.52(m，4H)，7.43(s，1H),7.36(m，2H),7.19(d， 1H),6.48(m，1H)

Example 8

Synthesis of Compound 101

18.20 g (100mmol) of m-bromobenzonitrile, 9.61 g (100mmol) of 2-amino-1, 3, 5-triazine, 28.83 g (300mmol) of sodium tert-butoxide, 288 mg (2mmol) of bis (benzylideneacetone) palladium and 500ml of xylene are added to a reaction vessel under argon and stirred at reflux for 20 hours. The reaction mixture was cooled to room temperature and the solid precipitated, filtered, and the crude product was washed 3 times with water, methanol and filtered to give 17.51 g of 3- ((1,3, 5-triazin-2-yl) amino) benzonitrile in 99.0% purity by HPLC and 90% yield (m-bromobenzonitrile).

¹HNMR(DMSO)：δ9.43(s，1H)，9.28(s，2H)，7.91(m，1H)，7.58(m，1H)，7.43～7.36(m， 2H).

30.76 g (50mmol) of p-2, 2' - (4-chloronaphthalene-2, 7-diyl) triphenylene, 11.11 g (50mmol) of 3- ((1,3, 5-triazin-2-yl) amino) benzonitrile, 14.4 g (150mmol) of sodium tert-butoxide, 144 mg (1mmol) of bis (benzylideneacetone) palladium and 250ml of xylene were added to a reaction vessel under an argon atmosphere, and stirred at reflux for 20 hours. The reaction mixture was cooled to room temperature and the solid precipitated out, filtered and the crude product was purified by column chromatography on silica gel (eluent: ethyl acetate/hexane) to give 30.4 g of compound 76 in 99.5% HPLC purity and 80% yield (2-2,2' - (4-chloronaphthalene-2, 7-diyl) triphenylene as reference).

¹HNMR(DMSO)：δ9.60(t，2H)，9.27(s，2H)，8.58(d，1H),8.37～8.30(m，6H)，8.02(m， 1H)，7.77(m，1H),7.70(m，4H)，7.68(m，1H),7.52(m，4H)，7.43(s，1H),7.36(m，2H), 7.19(d，1H).

Example 9

Synthesis of Compound 122

30.76 g (50mmol) of p-2, 2' - (4-chloronaphthalene-2, 7-diyl) triphenylene, 11.11 g (50mmol) of 4- (pyridine-3-amino) isophthalonitrile, 14.4 g (150mmol) of sodium tert-butoxide, 144 mg (1mmol) of bis (benzylideneacetone) palladium and 250ml of xylene were added to a reaction vessel under an argon atmosphere, and the mixture was stirred under reflux for 20 hours. The reaction mixture was cooled to room temperature and the solid precipitated out, filtered and the crude product was purified by column chromatography on silica gel (eluent: ethyl acetate/hexane) to give 30.4 g of compound 122 with an HPLC purity of 99.6% and a yield of 80% (2-2,2' - (4-chloronaphthalene-2, 7-diyl) triphenylene as reference).

¹HNMR(DMSO)：δ9.60(t，2H)，9.27(s，2H)，8.58(d，1H),8.37～8.30(m，6H)，8.04(m， 1H)，7.92(m，1H),7.70(m，4H)，7.68(m，1H),7.52(m，4H)，7.47(m，1H),7.36(m，2H), 7.19(d，1H).

Example 10

Synthesis of Compound 164

27.04 g (100mmol) of 3.5-dibromochlorobenzene, 52.38 g (220mmol) of (9, 9-dimethyl-9H-fluoren-1-yl) boronic acid, 200ml (300mmol) of a 1.5M aqueous solution of sodium carbonate, DME500ml, 1.4g (2mmol) of bis (triphenylphosphine) palladium (II) chloride were charged in 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 washed with methanol and filtered to give 41.75 g of 1,1' - (5-chloro-1, 3-phenylene) bis (9, 9-dimethyl-9H-fluorene, HPLC purity 98.9%, yield 84% (based on 3, 5-dibromochlorobenzene).

¹HNMR(DMSO)：δ8.07(s，2H)，8.00(m，2H)，7.90(m，2H),7.82(s，1H)，7.68(m，2H)，7.57～ 7.55(m，4H)，7.38(m，2H)，7.28(m，2H),1.69(s，12H)

18.20 g (100mmol) of p-bromobenzonitrile, 9.41 g (100mmol) of m-aminopyridine, 28.83 g (300mmol) of sodium tert-butoxide, 288 mg (2mmol) of bis (benzylideneacetone) palladium and 500ml of xylene were added to a reaction vessel under argon and stirred at reflux for 20 hours. The reaction mixture was cooled to room temperature and the solid precipitated, filtered, and the crude product was washed 3 times with water, washed with methanol, and filtered to give 17.55 g of 4- (pyridin-3-ylamino) benzonitrile in 99.3% HPLC purity and 90% yield (p-bromobenzonitrile).

24.86 g (50mmol) of p-1, 1'- (5-chloro-1, 3-phenylene) bis (9, 9-dimethyl-9H-fluorene), 9.76 g (50mmol) of 4- (pyridin-3-ylamino) benzonitrile, 14.4 g (150mmol) of sodium tert-butoxide, 144 mg (1mmol) of bis (benzylideneacetone) palladium, 250ml of xylene were added to a reaction vessel under argon atmosphere, the reaction mixture was stirred under reflux for 20 hours, the solid precipitated, filtered, and the crude product was purified by silica gel column chromatography (eluent: ethyl acetate/hexane) to give 26.23 g of compound 164 with an HPLC purity of 99.6% and a yield of 80% (based on 1,1' - (5-chloro-1, 3-phenylene) bis (9, 9-dimethyl-9H-fluorene).

¹HNMR(DMSO)：δ8.04～8.00(m，3H)，7.92～7.90(m，3H)，7.68(m，2H),7.60(s，1H)，7.57～ 7.55(m，4H),7.48(m，2H)，7.38(m，2H),7.37～7.36(m，5H),7.15(m，1H),1.69(s，12H).

Example 11

Synthesis of Compound 180

24.86 g (50mmol) of p-1, 1' - (5-chloro-1, 3-phenylene) bis (9, 9-dimethyl-9H-fluorene), 11.11 g (50mmol) of 4- ((1,3, 5-triazin-2-yl) amino) isophthalonitrile, 14.4 g (150mmol) of sodium tert-butoxide, 144 mg (1mmol) of bis (benzylideneacetone) palladium, 250ml of xylene were added to a reaction vessel under an argon atmosphere, the reaction mixture was stirred under reflux for 20 hours, the solid was precipitated, filtered, and the crude product was purified by silica gel column chromatography (eluent: ethyl acetate/hexane) gave 26.31 g of compound 180 in 99.6% HPLC purity and 80% yield (based on 1,1' - (5-chloro-1, 3-phenylene) bis (9, 9-dimethyl-9H-fluorene).

Example 12

Synthesis of Compound 188

24.86 g (50mmol) of p-1, 1'- (5-chloro-1, 3-phenylene) bis (9, 9-dimethyl-9H-fluorene), 9.76(50mmol) of 4- (pyridin-3-ylamino) benzonitrile, 14.4 g (150mmol) of sodium tert-butoxide, 144 mg (1mmol) of bis (benzylideneacetone) palladium, 250ml of xylene were added to a reaction vessel under argon atmosphere, the reaction mixture was stirred under reflux for 20 hours, the reaction mixture was cooled to room temperature, a solid was precipitated, filtered, and the crude product was purified by silica gel column chromatography (eluent: ethyl acetate/hexane) to give 26.29 g of compound 188, purity by HPLC 99.5%, yield 80% (based on 1,1' - (5-chloro-1, 3-phenylene) bis (9, 9-dimethyl-9H-fluorene).

¹HNMR(DMSO)：δ8.04(m，1H)，7.92～7.90(m，3H)，7.68(m，2H),7.60(s，1H)，7.57～ 7.55(m，4H),7.48(m，2H)，7.38～7.36(m，5H),7.15(m，1H),1.69(s，12H).

Example 13

Synthesis of Compound 232

To a reaction vessel under argon atmosphere was added 24.86 g (50mmol) of p-1, 1' - (5-chloro-1, 3-phenylene) bis (9, 9-dimethyl-9H-fluorene), 9.86(50mmol) of 4- ((1,3, 5-triazin-2-yl) amino) benzonitrile, 14.4 g (150mmol) of sodium tert-butoxide, 144 mg (1mmol) of bis (benzylideneacetone) palladium, 250ml of xylene, and the reaction mixture was stirred under reflux for 20 hours, cooled to room temperature, the solid was precipitated, filtered, and the crude product was purified by silica gel column chromatography (eluent: ethyl acetate/hexane) gave 28.00 g of compound 232 in 99.6% HPLC purity and 82% yield (based on 1,1' - (5-chloro-1, 3-phenylene) bis (9, 9-dimethyl-9H-fluorene).

¹HNMR(DMSO)：δ9.28(s，1H),8.00(d，2H)，7.90(d，2H)，7.76(m，1H),7.68(m，2H)， 7.60(s，1H),7.57～7.55(m，4H),7.54(d，2H)，7.38～7.37(m，4H),7.28(m，1H),1.69(s， 12H).

Example 14

Synthesis of Compound 237

18.20 g (100mmol) of p-bromobenzonitrile, 14.42 g (100mmol) of 6-aminoquinoline, 28.83 g (300mmol) of sodium tert-butoxide, 288 mg (2mmol) of palladium bis (benzylideneacetone) and 500ml of xylene were added to a reaction vessel under argon, and the mixture was stirred at reflux for 20 hours. The reaction mixture was cooled to room temperature and the solid precipitated, filtered, and the crude product was washed 3 times with water, washed with methanol, and filtered to give 21.34 g of 4- (quinolin-6-ylamino) benzonitrile in 98.6% HPLC purity and 87% yield (based on p-bromobenzonitrile).

¹HNMR(DMSO)：δ8.71(d，1H)，8.53(t，1H)，8.38(s，1H)，8.35(m，1H)，7.48～7.46(m， 3H),6.75(s，1H)

28.30 g (50mmol) of p-2- (3-chloro-5-benzo-2-ylphenyl) triphenylene, 12.27 g (50mmol) of 4- (quinolin-6-ylamino) benzonitrile, 14.4 g (150mmol) of sodium tert-butoxide, 144 mg (1mmol) of bis (benzylideneacetone) palladium and 250ml of xylene are added to a reaction vessel under argon, and stirred at reflux for 20 hours. The reaction mixture was cooled to room temperature, a solid precipitated, filtered, and the crude product was purified by silica gel column chromatography (eluent: ethyl acetate/hexane) to give 32.89 g of compound 237, purity by HPLC 99.6%, yield 85% (2- (3-chloro-5-benzo-2-ylphenyl) triphenylene as reference).

¹HNMR(DMSO)：δ9.27(s，2H)，9.19(m，2H),8.71(d，1H),8.53(d，1H),8.37～8.30(m， 5H)，7.92(m，6H),7.67(m，8H),7.48(m，3H)，7.37～7.35(m，5H),6.75(s，1H).

Example 15

Synthesis of Compound 279

30.76 g (50mmol) of p-2, 2' - (4-chloronaphthalene-2, 7-diyl) triphenylene, 12.27 g (50mmol) of 4- (quinolin-6-ylamino) benzonitrile, 14.4 g (150mmol) of sodium tert-butoxide, 144 mg (1mmol) of palladium bis (benzylideneacetone) and 250ml of xylene were added to a reaction vessel under an argon atmosphere, and the mixture was stirred under reflux for 20 hours. The reaction mixture was cooled to room temperature and a solid precipitated which was filtered and the crude product was purified by column chromatography on silica gel (eluent: ethyl acetate/hexane) to give 35.02 g of compound 279, 99.4% HPLC purity and 85% yield (2-2,2' - (4-chloronaphthalene-2, 7-diyl) triphenylene as reference).

¹HNMR(DMSO)：δ9.60(t，2H),9.27(s，2H)，9.19(m，2H),8.71(d，1H),8.53(d，1H),8.37～ 8.30(m，7H)，8.02(s，1H),7.77(m，1H),7.70(m，4H)，7.68(s，1H),7.64(m，4H),7.52(m， 4H),7.48～7.46(m，3H),7.36～7.35(m，3H),7.19(s，1H),6.75(s，1H).

Example 16

Synthesis of Compound 318

18.20 g (100mmol) of p-bromobenzonitrile, 14.42 g (100mmol) of 3-aminoquinoline, 28.83 g (300mmol) of sodium tert-butoxide, 288 mg (2mmol) of palladium bis (benzylideneacetone), and 500ml of xylene were added to a reaction vessel under argon, and the mixture was stirred at reflux for 20 hours. The reaction mixture was cooled to room temperature and the solid precipitated, filtered, and the crude product was washed 3 times with water, washed with methanol, and filtered to give 21.27 g of 4- (quinolin-3-ylamino) benzonitrile in an HPLC purity of 99.0% and a yield of 86% (based on p-bromobenzonitrile).

¹HNMR(DMSO)：δ9.77(s，1H)，8.81(s，1H)，7.96(m，1H)，7.77(m，1H)，7.48(m，2H),7.42(m， 1H),7.38(m，1H),7.36(m，2H),7.07(s，1H)

24.86 g (50mmol) of p-1, 1'- (5-chloro-1, 3-phenylene) bis (9, 9-dimethyl-9H-fluorene), 9.86(50mmol) of 4- (quinolin-3-ylamino) benzonitrile, 14.4 g (150mmol) of sodium tert-butoxide, 144 mg (1mmol) of bis (benzylideneacetone) palladium, 250ml of xylene were added to a reaction vessel under argon atmosphere, and the mixture was refluxed and stirred for 20 hours, the reaction mixture was cooled to room temperature, a solid was precipitated, filtered, and the crude product was purified by silica gel column chromatography (eluent: ethyl acetate/hexane) to give 29.30 g of compound 318, purity by HPLC 99.6%, yield 83% (based on 1,1' - (5-chloro-1, 3-phenylene) bis (9, 9-dimethyl-9H-fluorene).

¹Hnmr (dmso): δ 8.81(s, 1H),8.00(m, 2H), 7.96(m, 1H),7.90(d, 2H), 7.77(m, 1H),7.68(m, 2H), 7.60(s, 1H),7.58 to 7.55(m, 5H), 7.38 to 7.36(m, 5H),7.07(s, 1H),1.69(s, 12H). example 17

Synthesis of Compound 323

18.20 g (100mmol) of m-bromobenzonitrile, 14.42 g (100mmol) of 3-aminoquinoline, 28.83 g (300mmol) of sodium tert-butoxide, 288 mg (2mmol) of palladium bis (benzylideneacetone) and 500ml of xylene were added to the reaction vessel under argon and stirred at reflux for 20 hours. The reaction mixture was cooled to room temperature and the solid precipitated, filtered, and the crude product was washed 3 times with water, methanol and filtered to give 20.85 g of 4- (pyridin-3-ylamino) isophthalonitrile with an HPLC purity of 98.9% and a yield of 87% (based on m-bromobenzonitrile).

¹HNMR(DMSO)：δ9.77(s，1H)，8.81(s，1H)，7.96(m，1H)，7.91(m，1H)，7.77(m，1H)， 7.43～7.42(m，2H),7.38～7.36(m，2H),7.07(s，1H)

24.86 g (50mmol) of p-1, 1'- (5-chloro-1, 3-phenylene) bis (9, 9-dimethyl-9H-fluorene), 12.27 g (50mmol) of 4- (quinolin-6-ylamino) benzonitrile, 14.4 g (150mmol) of sodium tert-butoxide, 144 mg (1mmol) of bis (benzylideneacetone) palladium, 250ml of xylene were added to a reaction vessel under argon atmosphere, the reaction mixture was stirred under reflux for 20 hours, the reaction mixture was cooled to room temperature, a solid was precipitated, filtered, and the crude product was purified by silica gel column chromatography (eluent: ethyl acetate/hexane) to give 29.30 g of compound 323 with an HPLC purity of 99.7% and a yield of 83% (based on 1,1' - (5-chloro-1, 3-phenylene) bis (9, 9-dimethyl-9H-fluorene).

¹HNMR(DMSO)：δ8.71(d，1H),8.53(t，1H)，8.35(m，1H),8.00(m，2H)，7.90(m，2H),7.68(m， 2H)，7.60(s，1H),7.58～7.55(m，5H)，7.46(m，1H),7.43(m，1H),7.38～7.35(m，7H),6.75(s， 1H),1.69(s，12H).

Example 18

Synthesis of Compound 348

24.86 g (50mmol) of p-1, 1'- (5-chloro-1, 3-phenylene) bis (9, 9-dimethyl-9H-fluorene), 12.27 g (50mmol) of 4- (quinolin-6-ylamino) benzonitrile, 14.4 g (150mmol) of sodium tert-butoxide, 144 mg (1mmol) of bis (benzylideneacetone) palladium, 250ml of xylene were added to a reaction vessel under argon atmosphere, the reaction mixture was stirred under reflux for 20 hours, the reaction mixture was cooled to room temperature, a solid was precipitated, filtered, and the crude product was purified by silica gel column chromatography (eluent: ethyl acetate/hexane) to give 29.30 g of compound 348 with an HPLC purity of 99.7% and a yield of 83% (based on 1,1' - (5-chloro-1, 3-phenylene) bis (9, 9-dimethyl-9H-fluorene).

¹HNMR(DMSO)：δ8.71(d，1H),8.53(t，1H)，8.35(m，1H),8.00(m，2H)，7.90(m，2H),7.76(m， 1H)，7.68(m，2H),7.60(s，1H),7.58～7.54(m，5H),7.38～7.35(m，5H),7.28(m,2H),6.75(s， 1H),1.69(s，12H).

Example 19

Synthesis of Compound 359

20.7 g (100mmol) of 2, 4-dicyanobenzene, 14.42 g (100mmol) of 3-aminoquinoline, 28.83 g (300mmol) of sodium tert-butoxide, 288 mg (2mmol) of palladium bis (benzylideneacetone), and 500ml of xylene were added to a reaction vessel under an argon atmosphere, and the mixture was stirred at reflux for 20 hours. The reaction mixture was cooled to room temperature and the solid precipitated, filtered, and the crude product was washed 3 times with water, methanol and filtered to give 22.71 g of 4- (quinolin-3-ylamino) isophthalonitrile with an HPLC purity of 98.9% and a yield of 87% (based on 2, 4-dicyanobenzene).

¹HNMR(DMSO)：δ9.23(s，1H)，8.81(s，1H)，7.96(s，1H)，7.77～7.76(m，2H)，7.54(d， 1H)，7.47(d，1H),7.42(t，1H),7.38(t，1H)，7.07(d，1H)

24.86 g (50mmol) of p-1, 1' - (5-chloro-1, 3-phenylene) bis (9, 9-dimethyl-9H-fluorene), 13.50 g (50mmol) of 4- (quinolin-3-ylamino) isophthalonitrile, 14.4 g (150mmol) of sodium tert-butoxide, 144 mg (1mmol) of bis (benzylideneacetone) palladium, 250ml of xylene were added to a reaction vessel under an argon atmosphere, and the reaction mixture was stirred under reflux for 20 hours, 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) gave 29.15 g of compound 359 in 99.5% HPLC purity and 83% yield (based on 1,1' - (5-chloro-1, 3-phenylene) bis (9, 9-dimethyl-9H-fluorene).

¹HNMR(DMSO)：δ8.81(s，1H),8.00(m，2H)，7.96(m，1H),7.90(m，2H),7.77～7.76(m， 2H)，7.68(m，2H),7.60(s，1H),7.58～7.54(m，5H),7.47(m，1H)，7.42(m，1H),7.38～ 7.37(m，5H),7.28(m,2H),7.07(s，1H),1.69(s，12H).

Example 20

Synthesis of Compound 369

32.04 g (100mmol) of 3, 6-dibromo-1-chloronaphthalene (52.38 g (220mmol) of (9, 9-dimethyl-9H-fluoren-1-yl) boronic acid, 200ml (300mmol) of a 1.5M aqueous solution of sodium carbonate, DME500ml, 1.4g (2mmol) of bis (triphenylphosphine) palladium (II) chloride were charged in a reaction vessel under an argon atmosphere, and heated 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 washed with methanol and filtered to give 46.51 g of 1,1' - (4-chloronaphthalene-2, 7-diyl) bis (9, 9-dimethyl-9H-fluorene) having an HPLC purity of 98.9% and a yield of 84% (based on 3, 6-dibromo-1-chloronaphthalene).

¹HNMR(DMSO)：δ8.85(d，1H)，8.00(m，3H)，7.90(m，3H),7.86(s，1H)，7.68(m，2H)，7.57～ 7.55(m，5H)，7.38(m，2H)，7.28(m，2H),1.69(s，12H)

27.36 g (50mmol) of p-1, 1' - (4-chloronaphthalene-2, 7-diyl) bis (9, 9-dimethyl-9H-fluorene), 13.50 g (50mmol) of 4- (quinolin-3-ylamino) isophthalonitrile, 14.4 g (150mmol) of sodium t-butoxide, 144 mg (1mmol) of bis (benzylideneacetone) palladium and 250ml of xylene were added to a reaction vessel under an argon atmosphere, and the mixture was stirred under reflux for 20 hours. The reaction mixture was cooled to room temperature, a solid precipitated, filtered, and the crude product was purified by silica gel column chromatography (eluent: ethyl acetate/hexane) to give 31.37 g of compound 369, a HPLC purity of 99.6%, and a yield of 83% (based on 1,1' - (5-chloro-1, 3-phenylene) bis (9, 9-dimethyl-9H-fluorene).

¹HNMR(DMSO)：δ8.71(s，1H),8.53(m，2H)，8.35(s，1H),8.02(s，1H),8.00(m，2H),7.90 (m，2H),7.77(s，1H)，7.68(m，3H),7.57～7.55(m，4H),7.48(m，2H)，7.46(m，1H),7.38～ 7.35(m，5H),7.28(m,2H),7.19(s，1H),6.75(s，1H),1.69(s，12H).

Example 21

Synthesis of Compound 390

27.36 g (50mmol) of p-1, 1' - (4-chloronaphthalene-2, 7-diyl) bis (9, 9-dimethyl-9H-fluorene), 12.27 g (50mmol) of 4- (quinolin-6-ylamino) benzonitrile, 14.4 g (150mmol) of sodium tert-butoxide, 144 mg (1mmol) of bis (benzylideneacetone) palladium, and 250ml of xylene were added to a reaction vessel under an argon atmosphere, and stirred at reflux for 20 hours. The reaction mixture was cooled to room temperature, a solid precipitated, filtered, and the crude product was purified by silica gel column chromatography (eluent: ethyl acetate/hexane) to give 390.43 g of compound with an HPLC purity of 99.5% and a yield of 82% (based on 1,1' - (5-chloro-1, 3-phenylene) bis (9, 9-dimethyl-9H-fluorene).

¹HNMR(DMSO)：δ8.71(s，1H),8.53(m，2H)，8.35(s，1H),8.02(s，1H),8.00(m，2H),7.90 (m，2H),7.77～7.76(s，1H)，7.68(m，3H),7.57～7.54(m，5H),7.48(m，1H)，7.46(m， 1H),7.38(m，2H),7.35(m,1H),7.28(m，2H),7.19(s，1H)6.75(s，1H),1.69(s，12H).

Example 22

Synthesis of Compound 401

27.36 g (50mmol) of p-1, 1' - (4-chloronaphthalene-2, 7-diyl) bis (9, 9-dimethyl-9H-fluorene), 12.27 g (50mmol) of 4- (quinolin-3-ylamino) isophthalonitrile, 14.4 g (150mmol) of sodium t-butoxide, 144 mg (1mmol) of bis (benzylideneacetone) palladium and 250ml of xylene were added to a reaction vessel under an argon atmosphere, and the mixture was stirred under reflux for 20 hours. The reaction mixture was cooled to room temperature, a solid precipitated, filtered, and the crude product was purified by silica gel column chromatography (eluent: ethyl acetate/hexane) to give 31.56 g of compound 401 in 99.6% HPLC purity and 83% yield (based on 1,1' - (5-chloro-1, 3-phenylene) bis (9, 9-dimethyl-9H-fluorene).

¹HNMR(DMSO)：δ8.81(s，1H),8.53(m，1H),8.02(s，1H),8.00(m，2H),7.96(s，1H),7.90 (m，2H),7.77～7.76(m，3H)，7.68(m，3H),7.57～7.54(m，5H),7.48(m，1H)，7.46(m， 1H),7.42(m，1H),7.38(m,3H),7.28(m，2H),7.19(s，1H)6.75(s，1H),1.69(s，12H).

Example 23

Synthesis of Compound 432

27.04 g (100mmol) of 3.5-dibromochlorobenzene, 37.84 g (220mmol) of 1-naphthylboronic acid, 200ml (300mmol) of a 1.5M aqueous solution of sodium carbonate, DME500ml, 1.4g (2mmol) of bis (triphenylphosphine) palladium (II) chloride were charged into a reaction vessel under an argon atmosphere, and the mixture was 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 washed with methanol and filtered to give 31.02 g of 1,1' - (5-chloro-1, 3-phenylene) dinaphthalene in 98.9% HPLC purity and 84% yield (based on 3.5-dibromochlorobenzene).

¹HNMR(DMSO)：δ8.95(d，1H)，8.50(t，3H)，8.20(m，2H),8.09～8.07(m，4H)，7.82(s， 1H)，7.77(m，2H)，7.52(m，2H)，7.39(m，2H)

20.7 g (100mmol) of 2, 4-dicyanobenzene, 14.42 g (100mmol) of 6-aminoisoquinoline, 28.83 g (300mmol) of sodium tert-butoxide, 288 mg (2mmol) of bis (benzylideneacetone) palladium and 500ml of xylene were added to a reaction vessel under argon atmosphere, and the mixture was stirred at reflux for 20 hours. The reaction mixture was cooled to room temperature and the solid precipitated, filtered, and the crude product was washed 3 times with water, washed with methanol, and filtered to give 22.75 g of 4- (isoquinolin-6-ylamino) isophthalonitrile with an HPLC purity of 98.9% and a yield of 87% (based on 2, 4-dicyanobenzene).

¹HNMR(DMSO)：δ10.00(s，1H)，9.02(s，1H)，8.25(d，1H)，7.76(d，2H)，7.54～7.47(m， 4H)，7.37(m，1H),6.78(s，1H)

27.36 g (50mmol) of p-1, 1' - (4-chloronaphthalene-2, 7-diyl) bis (9, 9-dimethyl-9H-fluorene), 12.27 g (50mmol) of 4- (isoquinolin-6-ylamino) isophthalonitrile, 14.4 g (150mmol) of sodium tert-butoxide, 144 mg (1mmol) of bis (benzylideneacetone) palladium and 250ml of xylene were added to a reaction vessel under an argon atmosphere, and the mixture was stirred under reflux for 20 hours. The reaction mixture was cooled to room temperature, a solid precipitated, and was filtered, and the crude product was purified by silica gel column chromatography (eluent: ethyl acetate/hexane) to give 24.85 g of 432, 99.5% purity by HPLC, and 83% yield (based on 1,1' - (5-chloro-1, 3-phenylene) bis (9, 9-dimethyl-9H-fluorene).

¹HNMR(DMSO)：δ9.02(s，1H),8.95(m，2H),8.25～8.20(m，3H),8.09(m，2H),,7.77～ 7.76(m，3H)，7.60(s，1H),7.54～7.50(m，4H),7.48～7.47(m，2H),7.39～7.37(m，5H), 6.78(s，1H),1.69(s，12H).

Example 24

Synthesis of Compound 474

25.91 g (100mmol) of 3-bromo-1, 10-phenanthroline, 11.81 g (100mmol) of 4-aminobenzonitrile, 28.83 g (300mmol) of sodium tert-butoxide, 288 mg (2mmol) of bis (benzylideneacetone) palladium and 500ml of xylene are added to a reaction vessel under argon atmosphere, and the mixture is refluxed and stirred for 20 hours. The reaction mixture was cooled to room temperature, the solid precipitated, filtered, and the crude product was washed with water 3 times, methanol, and filtered to give 25.19 g of 4- ((1, 10-phenanthroline-3-yl) amino) benzonitrile, with an HPLC purity of 99.0% and a yield of 84% (based on 3-bromo-1, 10-phenanthroline).

¹HNMR(DMSO)：δ9.77(s，1H)，8.81～8.80(m，2H)，8.45(m，1H)，7.99(m，1H)，7.62(m， 1H),7.56(m，1H),7.48(m，2H)，7.36(m，2H),7.07(s，1H)

27.36 g (50mmol) of p-1, 1' - (4-chloronaphthalene-2, 7-diyl) bis (9, 9-dimethyl-9H-fluorene), 14.82 g (50mmol) of 4- ((1, 10-phenanthroline-3-yl) amino) benzonitrile, 14.4 g (150mmol) of sodium tert-butoxide, 144 mg (1mmol) of bis (benzylideneacetone) palladium, 250ml of xylene were added to a reaction vessel under an argon atmosphere, and stirred under reflux for 20 hours. The reaction mixture was cooled to room temperature and a solid precipitated, which was filtered and the crude product was purified by column chromatography on silica gel (eluent: ethyl acetate/hexane) to give 24.85 g of 474 with an HPLC purity of 99.7% and a yield of 83% (based on p-1, 1' - (4-chloronaphthalene-2, 7-diyl) bis (9, 9-dimethyl-9H-fluorene)).

¹HNMR(DMSO)：δ8.81～8.80(m，2H)，8.45(d，1H)，8.00(m，3H)，7.90(m，2H),7.60(s， 1H),7.56～7.55(m，3H),7.48(m，2H),7.38～7.36(m，6H),7.28(m，2H),7.07(s，1H),1.69(s， 12H).

Example 25

Synthesis of Compound 489

¹HNMR(DMSO)：δ9.60(t，2H)，9.27(s，2H),8.37～8.30(m，6H)，8.07(d，2H)，7.82(s，1H),7.90～7.86(m，2H)，7.70(m，4H)，7.64(m，4H),7.52(m，4H)

25.91 g (100mmol) of 3-bromo-1, 10-phenanthroline, 14.32 g (100mmol) of 4-aminoisophthalonitrile, 28.83 g (300mmol) of sodium tert-butoxide, 288 mg (2mmol) of bis (benzylideneacetone) palladium and 500ml of xylene are added to a reaction vessel under argon atmosphere, and the mixture is stirred under reflux for 20 hours. The reaction mixture was cooled to room temperature, the solid precipitated, filtered, and the crude product was washed with water 3 times, methanol, and filtered to give 25.19 g of 4- ((1, 10-phenanthroline-3-yl) amino) isophthalonitrile, with an HPLC purity of 99.0% and a yield of 84% (based on 3-bromo-1, 10-phenanthroline).

¹HNMR(DMSO)：δ9.23(s，1H)，8.81～8.80(m，2H)，8.45(m，1H)，7.99(m，1H)，7.76(m， 1H),7.62～7.47(m，4H),7.07(s，1H)

28.26 g (50mmol) of p-2- (3-chloro-5-benzo-2-ylphenyl) triphenylene, 16.07 g (50mmol) of 4- ((1, 10-phenanthroline-3-yl) amino) benzonitrile, 14.4 g (150mmol) of sodium tert-butoxide, 144 mg (1mmol) of bis (benzylideneacetone) palladium and 250ml of xylene are added to a reaction vessel under argon atmosphere, and the mixture is refluxed and stirred for 20 hours. The reaction mixture was cooled to room temperature and the solid precipitated out, filtered and the crude product was purified by column chromatography on silica gel (eluent: ethyl acetate/hexane) to give 35.70 g of compound 489 with an HPLC purity of 99.5% and a yield of 84% (based on p-1, 1' - (4-chloronaphthalene-2, 7-diyl) bis (9, 9-dimethyl-9H-fluorene)).

¹HNMR(DMSO)：δ9.60(t，2H),9.27(s，2H),8.81～8.80(m，2H)，8.45(d，1H)，8.37～8.30(m， 6H),7.99(m，1H),7.76(s，1H),7.70(m，4H),7.64(m，4H),7.62(m，1H),7.56(m，1H),7.54(m， 1H),7.52(m，4H),7.47(m，1H),7.37(s，2H),7.07(s，1H).

Example 26

Synthesis of Compound 510

25.91 g (100mmol) of 2-bromo-1, 10-phenanthroline, 14.32 g (100mmol) of 4-aminoisophthalonitrile, 28.83 g (300mmol) of sodium tert-butoxide, 288 mg (2mmol) of bis (benzylideneacetone) palladium and 500ml of xylene are added to a reaction vessel under argon atmosphere, and the mixture is stirred under reflux for 20 hours. The reaction mixture was cooled to room temperature, the solid precipitated, filtered, and the crude product was washed with water 3 times, methanol, and filtered to give 25.19 g of 4- ((1, 10-phenanthroline-2-yl) amino) isophthalonitrile, with an HPLC purity of 99.0% and a yield of 84% (based on 2-bromo-1, 10-phenanthroline).

¹HNMR(DMSO)：δ9.99(s，1H)，8.80(d，1H)，8.45(m，1H)，8.15(m，1H)，7.91(m，1H),7.76～ 7.70(m，2H),7.57～7.54(m，3H),7.47(s,1H).

In a reaction vessel under argon atmosphere, 27.36 g (50mmol) of p-1, 1' - (5-chloro-1, 3-phenylene) bis (9, 9-dimethyl-9H-fluorene), 16.07 g (50mmol) of 4- ((1, 10-phenanthroline-2-yl) amino) isophthalonitrile, 14.4 g (150mmol) of sodium tert-butoxide, 144 mg (1mmol) of bis (benzylideneacetone) palladium, 250ml of xylene were added, and the reaction mixture was stirred under reflux for 20 hours. Ethyl acetate/hexane) gave 33.23 g of compound 510 in 99.5% HPLC purity and 84% yield (based on p-2- (3-chloro-5-benzo-2-ylphenyl) triphenylene).

¹HNMR(DMSO)：δ8.80(m，1H)，8.45(d，1H)，7.90(m，2H),7.60(s，1H),7.56～7.55(m， 3H),7.48(m，2H),7.38～7.36(m，6H),7.28(m，2H),7.07(s，1H),1.69(s，12H).

Example 27

Synthesis of Compound 516

28.26 g (50mmol) of p-2- (3-chloro-5-benzo-2-ylphenyl) triphenylene, 16.07 g (50mmol) of 4- ((1, 10-phenanthroline-2-yl) amino) isophthalonitrile, 14.4 g (150mmol) of sodium tert-butoxide, 144 mg (1mmol) of bis (benzylideneacetone) palladium and 250ml of xylene are added to a reaction vessel under argon atmosphere, and the mixture is refluxed and stirred for 20 hours. The reaction mixture was cooled to room temperature and the solid precipitated out, which was filtered and the crude product was purified by column chromatography on silica gel (eluent: ethyl acetate/hexane) to give 35.61 g of compound 516 with an HPLC purity of 99.5% and a yield of 83% (based on p-2- (3-chloro-5-benzo-2-ylphenyl) triphenylene).

¹HNMR(DMSO)：δ9.60(t，2H),9.27(s，2H),8.80(m，1H)，8.45(d，1H)，8.37～8.30(m， 6H),7.91(m，1H),7.76(s，1H),7.70(m，5H),7.64(m，4H),7.60(s，1H),7.57(s，1H),7.54(m， 1H),7.52(m，4H),7.47(m，1H),7.37(s，2H).

Device embodiments

Detailed description of the preferred embodiments

The organic light emitting diode includes first and second electrodes on a substrate, and an organic material between the electrodes, the first and second electrodes including an organic layer of at least a light emitting layer therebetween.

Substrate the substrate material used for the organic light emitting display may be any substrate used in typical organic light emitting elements. 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 organic layer can comprise a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer, wherein the hole injection layer is formed on the anode layer, the hole transport layer is formed on the hole injection layer, the cathode layer is formed on the electron transport layer, and the light emitting layer is arranged between the hole transport layer and the electron transport layer; the light-emitting layer is the light-emitting layer of the organic electroluminescent device.

The anode material may be a transparent conductive material such as Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), tin dioxide (SnO2), or zinc oxide (ZnO), a metal material such as silver and an alloy thereof, aluminum and an alloy thereof, an organic conductive material such as PEDOT, or a multilayer structure of the above materials.

The cathode can include but is not limited to magnesium silver mixture, metal such as LiF/Al, ITO, metal mixture, oxide device, and hole transport layer, hole injection layer between the light emitting layer and the anode.

Example 28

A glass substrate on which a thin film of Indium Tin Oxide (ITO) having a thickness of 100nm was coated was put in distilled water in which a detergent was dissolved, and ultrasonic cleaning was performed. After washing the ITO for 20 minutes, the ultrasonic washing was repeated twice with distilled water for 10 minutes each. After the completion of the washing with distilled water, the substrate was ultrasonically washed with isopropyl alcohol, acetone and methanol, then dried, and transferred to a plasma cleaner. Further, the substrate was cleaned using oxygen plasma for 5 minutes and then transferred to a vacuum depositor. On the transparent ITO electrode prepared as above, a hole injection layer was formed by thermal vacuum deposition of a compound HI at an evaporation rate of 0.04 to 0.09nm/s and a total film thickness of 60nm.

On the hole injection layer, compound HAT was vacuum-evaporated as a first hole transport layer at an evaporation rate of 0.04 to 0.09nm/s and a total film thickness of 5nm

And on the first hole transport layer, HT was deposited as a second hole transport layer by vacuum deposition. The evaporation rate is 0.04-0.09 nm/s, and the total film thickness is 50nm

Subsequently, the reaction mixture was cooled by mixing 25: 1 weight ratio of the compound BH and the compound BD were vacuum-deposited to form a light-emitting layer on the second hole transport layer. The evaporation rate is 0.04 to 0.09nm/s, and the total film thickness is 20nm.

On the light emitting layer, by adding 1: the compound 8 and the compound LiQ were vacuum deposited at a weight ratio of 1 to form an electron transport layer and an injection layer. The deposition rate was 0.1nm/s, and the total thickness of the deposited film was 35 nm.

On the electron injection and transport layer, a cathode was formed by depositing lithium fluoride (LiF) at an evaporation rate of 0.03nm/s and a total film thickness of 1nm, and then depositing aluminum at an evaporation rate of 0.2nm/s and a total film thickness of 100nm.

During the above process, the vacuum degree is kept at 1 x 10^-7To 5 x 10^-5And (4) supporting.

Example 29

The same elements as those in example 28 were evaluated except that the electron transport layer material was compound 15, and the test results are shown in Table 1.

Example 30

The same members as those in example 28 were used except that the material of the electron transport layer was compound 24, and the evaluation was made, and the test results are shown in Table 1.

Example 31

The same members as those in example 28 were used except that the electron transport layer material was the compound 44, and the evaluation was made, and the test results are shown in Table 1.

Example 32

The same members as those in example 28 were used except that the material of the electron transport layer was the compound 76, and the evaluation was made, and the test results are shown in Table 1.

Example 33

The same members as those in example 28 were used except that the material of the electron transport layer was the compound 87, and the evaluation was made, and the test results are shown in Table 1.

Example 34

The same members as those in example 28 were used except that the electron transport layer material was compound 96, and the evaluation was made, and the test results are shown in Table 1.

Example 35

The same elements as those in example 28 were used except that the material of the electron transport layer was the compound 101, and the evaluation was made, and the test results are shown in Table 1.

Example 36

The evaluation was carried out on the same members as those in example 28 except that the material of the electron transport layer was the compound 122, and the test results are shown in Table 1.

Example 37

The evaluation was carried out on the same members as those in example 28 except that the material of the electron transport layer was the compound 164, and the test results are shown in Table 1.

Example 38

The same members as those in example 28 were used except that the material of the electron transport layer was the compound 180, and the evaluation was made, and the test results are shown in Table 1.

Example 39

The same members as those in example 28 were used except that the material of the electron transport layer was the compound 188, and the evaluation was made, and the test results are shown in Table 1.

Example 40

The same members as those in example 28 were used except that the electron transport layer material was the compound 232, and the evaluation was made, and the test results are shown in Table 1.

EXAMPLE 41

The same members as those in example 28 were used except that the electron transport layer material was the compound 237, and the evaluation was made, and the test results are shown in Table 1.

Example 42

The same members as those in example 28 were used except that the material of the electron transport layer was the compound 279, and the results of the tests are shown in Table 1.

Example 43

The same members as those in example 28 were used except that the material of the electron transport layer was the compound 318, and the evaluation was made, and the test results are shown in Table 1.

Example 44

The same elements as those in example 28 were used except that the electron transport layer material was the compound 323, and evaluation was made, and the test results are shown in Table 1.

Example 45

The same members as those in example 28 were used except that the material of the electron transport layer was the compound 348, and the evaluation was made, and the test results are shown in Table 1.

Example 46

The same members as those in example 28 were used except that the electron transport layer material was the compound 359, and the evaluation was carried out, and the test results are shown in Table 1.

Example 47

The evaluation was made using the same members as those in example 28 except that the electron transport layer material was compound 369, and the test results are shown in Table 1.

Example 48

The same members as those in example 28 were used except that the material of the electron transport layer was the compound 390, and the results of the tests are shown in Table 1.

Example 49

The same members as those in example 28 were used except that the material of the electron transport layer was the compound 401, and the evaluation was made, and the test results are shown in Table 1.

Example 50

The same members as those in example 28 were used except that the electron transport layer material was the compound 432, and the evaluation was made, and the test results are shown in Table 1.

Example 51

The same members as those in example 28 were used except that the material of the electron transport layer was the compound 474, and the results of the tests are shown in Table 1.

Example 52

The same members as those in example 28 were used except that the electron transport layer material was the compound 489, and the evaluation was made, and the test results are shown in Table 1.

Example 53

The same members as those in example 28 were used except that the electron transport layer material was the compound 510, and the evaluation was made, and the test results are shown in Table 1.

Example 54

The evaluation was carried out on the same members as those in example 28 except that the material of the electron transport layer was compound 516, and the test results are shown in Table 1.

Comparative example 1

The evaluation was carried out using the same members as those in example 28 except that the electron transport layer material was compound ET1, and the test results are shown in Table 1.

Comparative example 2

The evaluation was carried out using the same members as those in example 28 except that the electron transport layer material was compound ET2, and the test results are shown in Table 1.

The voltage and efficiency of each of the organic light emitting devices of the examples and comparative examples were measured at a current density of 10mA/cm2, and the performance results are shown in Table 1.

TABLE 1

In device examples 28 to 54, in the same situation as in comparative example 1 and comparative example 2 as other materials in the organic electroluminescent device structure, the series of compounds of the present invention can replace the commercialized electron transport material ET-1 in the device comparative example 1, and thus the technical effects of voltage reduction and current efficiency improvement can be achieved. The voltage was also relatively lower and the efficiency higher than that of the electron transport material ET2 in comparative device example 2. The results show that the novel organic material is an organic luminescent functional material with good performance as an electron transport material of an organic electroluminescent device, and is expected to be popularized and applied commercially.

The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.

It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.

In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims

1. A material of heterocyclic triarylamine, characterized in that: having the following general formula (1)

ring B is selected from

In ring B, wherein R1, R2, R3, R4, which may be the same or different, are independently selected from one of the following structures:

wherein R5, R6 and R7 are one or more of hydrogen atom, deuterium atom, halogen, C1-10 alkyl, C1-10 alkoxy, substituted or unsubstituted C6-60 aryl or heterocyclic group;

ring C is independently selected from one of general formula (2) to general formula (4):

in the general formula (2), the general formula (3), the general formula (4), Z is represented, identically or differently at each occurrence, as a nitrogen atom or C (R), and at least one Z is represented as a nitrogen atom; r is hydrogen atom, deuterium atom, halogen, C1-10 alkyl, C1-10 alkoxy, substituted or unsubstituted C6-60 aryl or heterocyclic radical; n is an integer of 1 to 6.

2. The method according to claim 1, wherein n is 1, or 2, or 3.

3. A heterocyclic triarylamine compound according to claim 1 wherein the specific structural formula of the heterocyclic triarylamine compound is one or more of the following structures:

4. an organic optoelectronic device, comprising:

a first electrode;

a second electrode facing the first electrode;

wherein the organic functional layer comprises a heterocyclic triarylamine compound according to any one of claims 1 to 3.

5. The Organic optoelectronic device according to claim 4, 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.

6. 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: a device comprising in any one of the layers a heterocyclic triarylamine compound according to any one of claims 1 to 4.

7. The organic photoelectric element according to claim 4 or 6, wherein the triarylamine compound according to claim 1 is contained in the electron transport layer.

8. The organic photoelectric element according to claim 4 or 6, which is an organic electroluminescent device, wherein the light-emitting layer contains the heterocyclic triarylamine compound according to claim 1 and a corresponding guest material, wherein the heterocyclic triarylamine compound is present in an amount of 30 to 99.9% by mass, and the guest material is not limited thereto.

9. The organic photoelectric element according to claim 4 or 6, wherein the electron transport layer contains the heterocyclic triarylamine compound according to claim 1, wherein the triarylamine compound is present in an amount of 1 to 100% by mass.

10. A display or lighting device comprising the organic photoelectric element according to any one of claims 4 to 9.