US20190367491A1

US20190367491A1 - Compound and organic electronic device comprising the same

Info

Publication number: US20190367491A1
Application number: US16/429,160
Authority: US
Inventors: Chi-Chung Chen; Shwu-Ju Shieh
Original assignee: Shanghai Nichem Fine Chemical Co Ltd
Current assignee: Shanghai Nichem Fine Chemical Co Ltd
Priority date: 2018-06-05
Filing date: 2019-06-03
Publication date: 2019-12-05
Also published as: KR20190138613A; CN110571338A; KR102259757B1; KR20190138611A; KR20190138615A; US20190372016A1; CN110563638A; US20190372015A1; KR102243851B1; TWI699357B; US11183641B2; JP2020025080A; CN110571338B; JP6771785B2; CN110563662A; TW202003478A; US20190372014A1; CN110563707A; KR20190138612A; KR102170538B1

Abstract

Provided are a novel compound and an organic electronic device using the same. The novel compound is represented by the following Formula (I):

G¹and G²in Formula (I) are each independently selected from the group consisting of:

and G¹¹and G¹²are each a specific aryl group or heteroaryl group. The organic electronic device comprising the novel compound has the beneficial effects of improved luminous efficacy and external quantum efficiency.

Description

CROSS-REFERENCE TO RELATED APPLICATION

Pursuant to 35 U.S.C. § 119(e), this application claims the benefit of the priority to U.S. Provisional Patent Application No. 62/680,625, filed Jun. 5, 2018. The content of the prior application is incorporated herein by its entirety.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a novel compound and an organic electronic device using the same, more particularly to a novel compound as an electron transport material and an organic electronic device using the same.

2. Description of the Prior Arts

With the advance of technology, various organic electronic devices that make use of organic materials have been energetically developed. Examples of organic electronic devices include organic light emitting devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors.
OLED was initially invented and proposed by Eastman Kodak Company through a vacuum evaporation method. Dr. Ching Tang and Steven VanSlyke of Kodak Company deposited an electron transport material such as tris(8-hydroxyquinoline)aluminum(III) (abbreviated as Alq₃) on a transparent indium tin oxide glass (abbreviated as ITO glass) formed with a hole transport layer of organic aromatic diamine thereon, and subsequently deposited a metal electrode onto an electron transport layer to complete the fabrication of the OLED. OLEDs have attracted lots of attention due to their numerous advantages, such as fast response speed, light weight, compactness, wide viewing angle, high brightness, higher contrast ratio, no need of backlight, and low power consumption. However, the OLEDs still have the problems such as low efficiency.
To overcome the problem of low efficiency, one of the approaches is to interpose some interlayers between the cathode and the anode. With reference to FIG. 1, a modified OLED 1 may have a structure of a substrate 11, an anode 12, a hole injection layer 13 (abbreviated as HIL), a hole transport layer 14 (abbreviated as HTL), an emission layer 15 (abbreviated as EL), an electron transport layer 16 (abbreviated as ETL), an electron injection layer 17 (abbreviated as EIL), and a cathode 18 stacked in sequence. When a voltage is applied between the anode 12 and the cathode 18, the holes injected from the anode 12 move to the EL via HIL and HTL and the electrons injected from the cathode 18 move to the EL via EIL and ETL. Recombination of the electrons and the holes occurs in the EL to generate excitons, thereby emitting a light when the excitons decay from excited state to ground state.
Another approach is to modify the materials of ETL for OLEDs to render the electron transport materials to exhibit hole-blocking ability. Examples of conventional electron transport materials include 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), 3,3′-[5′-[3-(3-pyridinyl)phenyl][1,1′:3′,1″-terphenyl]-3,3″-diyl]bispyridine (TmPyPb), 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene (TPBi), tris(2,4,6-trimethyl-3-(pyridin-3-yl)phenyl)borane (3TPYMB), 1,3-bis(3,5-dipyrid-3-yl-phenyl)benzene (BmPyPb), and 9,10-bis(3-(pyridin-3-yl)phenyl)anthracene (DPyPA).
However, even using the foresaid electron transport materials, the luminous efficacy and external quantum efficiency (EQE) of OLEDs still need to be improved. Therefore, the present invention provides a novel compound to mitigate or obviate the problems in the prior art.

SUMMARY OF THE INVENTION

An objective of the present invention is to provide a novel compound useful for an organic electronic device.
Another objective of the present invention is to provide an organic electronic device using the novel compound, so as to improve the luminous efficacy and external quantum efficiency of the organic electronic device.
To overcome the above objectives, the present invention provides a novel compound represented by the following Formula (I):
In Formula (I), G¹and G²are each independently selected from the group consisting of:
G¹and G²may be the same or different, j is an integer from 1 to 2, and k is an integer from 0 to 2.
Herein, said G¹¹and G¹²are each independently selected from the group consisting of:
wherein said G¹¹and G¹²may be the same or different;
R¹to R³are each independently selected from the group consisting of: a deuterium atom, a halo group, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and an alkynyl group having 2 to 6 carbon atoms;
n1 is an integer from 0 to 5, n2 is an integer from 0 to 4, and n3 is an integer from 0 to 7.
With said specific G¹and/or G², the novel compound is useful to improve the luminous efficacy and EQE of the organic electronic device, such that the performance of the organic electronic device can be improved.
Preferably, the compound may be represented by any one of the following Formulae (I-I) to (I-VI):
Preferably, G¹¹and G¹²are each independently selected from the group consisting of:
More preferably, G¹¹and G¹²are each independently selected from the group consisting of:
Preferably, both or either of G¹¹and G¹²is a fully deuterated substitution group such as fully deuterated phenyl group (phenyl-D₅). That is, R¹to R³are each a deuterium atom, n1 is an integer 5, n2 is an integer 4, and n3 is an integer 7.
Preferably, G¹and G²may be each independently selected from the group consisting of:
In one embodiment, j is the integer 1 and k is the integer 0. In another embodiment, j is the integer 1 and k is the integer 1.
Preferably, said halo group may be a fluoro group, a chloro group, a bromo group, or an iodo group.
Preferably, said alkyl group having 1 to 6 carbon atoms may be, but is not limited to, a methyl group, an ethyl group, a propyl group, or a butyl group. Preferably, said alkenyl group having 2 to 6 carbon atoms may be, but is not limited to, a vinyl group, a propenyl group, or a butenyl group. Preferably, said alkenyl group having 2 to 6 carbon atoms may be, but is not limited to, an ethynyl group, a propynyl group, or a butynyl group.
For example, the compound may be any one of:
The present invention also provides an organic electronic device, comprising a first electrode, a second electrode, and an organic layer disposed between the first electrode and the second electrode. The organic layer comprises the novel compound as described above. The novel compound may be, but is not limited to, any one of Compounds 1 to 404.
Preferably, the organic electronic device is an organic light emitting device (OLED).
Specifically, the organic light emitting device may comprise:
a hole injection layer formed on the first electrode;
a hole transport layer formed on the hole injection layer;
an emission layer formed on the hole transport layer;
an electron transport layer formed on the emission layer;
an electron injection layer formed between the electron transport layer and the second electrode.
In one embodiment, the organic layer may be the electron transport layer, i.e., the electron transport layer comprises an electron transport material which is the novel compound as stated above.
For example, the electron transport layer may be a single-layered configuration or a multi-layered configuration disposed between the emission layer and the electron injection layer. When the electron transport layer is the multi-layered configuration, e.g., the electron transport layer comprises a first electron transport layer and a second electron transport layer, the first electron transport material of the first electron transport layer may be made of a single novel compound and the second electron transport material of the second electron transport layer may be made of another single novel compound or any single conventional compound. Or, the first electron transport material of the first electron transport layer may be made of a novel compound in combination with another single novel compound or any single conventional compound, and so as the second electron transport material.
Said first and/or second electron transport layer comprises the novel compound such as Compounds 1 to 404. The OLEDs using the novel compound as the electron transport material can have an improved luminous efficacy and external quantum efficiency compared to the commercial OLEDs using known electron transport materials of ETL, such as BCP, TmPyPb, TPBi, 3TPYMB, BmPyPb, and DPyPA.
Preferably, the OLED comprises a hole blocking layer (HBL), formed between the electron transport layer and the emission layer, to block holes overflow from the emission layer to the electron transport layer.
In another embodiment, the organic layer may be the hole blocking layer, i.e., the hole blocking layer comprises a hole blocking material which is the novel compound as stated above. More specifically, said hole blocking layer comprises the novel compound such as Compounds 1 to 404. The OLEDs using the novel compound as the hole blocking material can have an improved efficiency compared to commercial OLEDs using known hole blocking materials of HBL, such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) and 2,3,5,6-tetramethyl-phenyl-1,4-(bis-phthalimide) (TMPP).
Preferably, the hole injection layer may be a two-layered structure, i.e., the OLED comprises a first hole injection layer and a second hole injection layer disposed between the first electrode and the hole transport layer.
Said first and second hole injection layers may be made of, for example, but not limited to: polyaniline, polyethylenedioxythiophene, 4,4′,4″-Tris[(3-methylphenyl)phenylamino]triphenylamine (m-MTDATA), or N¹,N^1′-(biphenyl-4,4′-diyl)bis(N′-(naphthalen-1-yl)-N⁴,N^4′-diphenylbenzene-1,4-diamine).
Preferably, the hole transport layer may be a two-layered structure, i.e., the OLED comprises a first hole transport layer and a second hole transport layer disposed between the two-layered hole injection layer and the emission layer.
Said first and second hole transport layers may be made of, for example, but not limited to: 1,1-bis[(di-4-tolylamino)phenylcyclohexane](TAPC), a carbazole derivative such as N-phenyl carbazole, and N⁴,N^4′-di(naphthalen-1-yl)-N⁴,N4′-diphenylbiphenyl-4,4′-diamine (NPB).
Preferably, the emission layer can be made of an emission material including a host and a dopant. The host of the emission material is, for example, but not limited to, 9-(4-(naphthalen-1-yl)phenyl)-10-(naphthalen-2-yl) anthracene.
For red OLEDs, the dopant of the emission material is, for example, but not limited to: organometallic compounds of iridium (II) having quinoline derivative ligands or isoquinoline derivative ligands; an osmium complex; or a platinum complex. For green OLEDs, the dopant of the emission material is, for example, but not limited to: diaminofluorenes; diaminoanthracenes; or organometallic compounds of iridium (II) having phenylpyridine ligands. For blue OLEDs, the dopant of the emission material is, for example, but not limited to: an aminoperylene derivative; a diaminochrysene; diaminopyrenes; or organicmetallic compounds of iridium (II) having pyridinato picolinate ligands. With various host materials of the emission layer, the OLED can emit lights in red, green or blue.
Preferably, the OLED comprises an electron blocking layer, formed between the hole transport layer and the emission layer, to block electrons overflow from the emission layer to the hole transport layer. Said electron blocking layer may be made of 9,9′-[1,1′-biphenyl]-4,4′-diylbis-9H-carbazole (CBP) or 4,4′,4″-tri(N-carbazolyl)-triphenylamine (TCTA), but it is not limited thereto.
In the presence of such a hole blocking layer and/or an electron blocking layer in an OLED, the OLED has a higher luminous efficiency compared to a typical OLED.
Said electron injection layer may be made of an electron injection material, for example, but not limited to (8-oxidonaphthalen-1-yl)lithium(II).
Said first electrode is, for example, but not limited to, an indium-doped tin oxide electrode.
Said second electrode has a work function lower than that of the first electrode. The second electrode is, for example, but not limited to, an aluminum electrode, an indium electrode, or a magnesium electrode.
Other objectives, advantages and novel features of the invention will become more apparent from the following detailed description when taken in conjunction with the accompanying drawing.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 illustrates a schematic cross-sectional view of an OLED.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Hereinafter, one person skilled in the arts can easily realize the advantages and effects of a novel compound and an organic light emitting device using the same in accordance with the present invention from the following examples. It should be understood that the descriptions proposed herein are just preferable examples only for the purpose of illustrations, not intended to limit the scope of the invention. Various modifications and variations could be made in order to practice or apply the present invention without departing from the spirit and scope of the invention.

Preparation of Intermediate A

Intermediate A, which was used to synthesize the novel compounds, could be purchased or synthesized by the following Scheme I through steps A-1 to A-4.

Step A-1: Synthesis of Intermediate A-1

A mixture of dibenzosuberone (86 g, 1.0 eq), N-bromosuccinimide (NBS, 106 g, 1.4 eq), and benzyl peroxide (0.7 g, 0.01 eq) in carbon tetrachloride (CCl₄, 430 ml) was heated to 85° C. The reaction was monitored by HPLC. After completion of the reaction, the precipitate was separated by filtration and washed with MeOH, then purified by recrystallization. The purified product was concentrated to dryness, whereby a white solid product was obtained in an amount of 144 g and a yield of 92.3%.
The purified product was identified as Intermediate A-1 by a field desorption mass spectroscopy (FD-MS) analysis. FD-MS analysis C₁₅H₁₀Br₂O: theoretical value of 366.05 and observed value of 366.05.

Step A-2: Synthesis of Intermediate A-2

The obtained Intermediate A-1 (96.0 g, 1.0 eq) was dissolved in 960 ml of furan/tetrahydrofuran(THF) (v/v=2/1), and the reaction was cooled to 0° C. and then treated with KO-t-Bu (87.8 g, 3.0 eq). The reaction was allowed to stir for 1 hour (h) at 0° C. prior to raise up to room temperature (rt) and stirred for additional 12 h. After completion of the reaction, the solution was quenched by DI water and the organic layer was recovered by solvent extraction and dried over sodium sulfate. The solvent was removed from the organic layer by distillation under reduced pressure, and the resulting residue was purified by silica gel column chromatography. The purified product was concentrated to dryness, whereby a light yellow solid product was obtained in an amount of 46.8 g in a yield of 51.1%.
The light yellow solid product was identified as Intermediate A-2 by FD-MS analysis. FD-MS analysis: C₁₉H₁₂O₂: theoretical value of 272.3 and observed value of 272.3.

Step A-3: Synthesis of Intermediate A-3

A suspension of the obtained Intermediate A-2 (41.5 g, 1.0 eq) and 5% Pd/C (8.1 g, 0.025 eq) in 535 ml ethyl acetate (EA) was stirred for 3 h to 6 h under a hydrogen atmosphere provided by a balloon of hydrogen. The resulting mixture was filtered through a pad of celite and washed with EA, and the filtrate was concentrated under reduced pressure to obtain 41.8 g (100%) of Intermediate A-3 as a yellow solid. The obtained compound, Intermediate A-3, was directly used in the subsequent reaction without further purification.

Step A-4: Synthesis of Intermediate A

The obtained Intermediate A-3(41 g, 1.0 eq) and p-toluenesulfonic acid (PTSA, 55 g, 2.0 eq) in 530 ml of toluene was heated to reflux for 12 h. The reaction mixture was cooled to rt and then quenched with a saturated aqueous solution of NaHCO₃and extracted with CH₂Cl₂. The organic layer was washed with water, brine and dried with anhydrous Na₂SO₄subsequently. Then the resulting solution was concentrated under reduced pressure and purified by column chromatography on silica gel with CH₂Cl₂/hexane (v/v=1/1) as eluent. 46.0 g of Intermediate A was obtained as light yellow solids in a yield of 91.5%.
The purified product was identified as Intermediate A by FD-MS analysis. FD-MS analysis C₁₉H₁₂O: theoretical value of 256.3 and observed value of 256.3.

Preparation of Intermediate Bn

Intermediate Bn, including Intermediates B1 to B4, which was used to synthesize the novel compounds, could be purchased or synthesized by the following Scheme II.
The main difference of the preparation of Intermediates B1 to B4 was the material of Reactant An (Reactants A1 to A4) as listed in Table 1.

TABLE 1

the chemical structures, names, and CAS No. of Reactants Al to A4.

	Chemical
	Structure of
Reactant An	Reactant An	Name	CAS No.

Reactant A1	2-bromo-4′-chlorobiphenyl	179526-95-5

Reactant A2	2-bromo-3′-chlorobiphenyl	154407-17-7

Reactant A3	2,2′-dibromobiphenyl	13029-09-9

Reactant A4	2-bromo-5,3′-dichlorobiphenyl	—

Synthesis of Reactant A4

A solution of 1-bromo-2-chloro-4-iodobenzene (1.0 eq), 4-chlorophenylboronic acid (1.1 eq), Pd(OAc)₂(0.95 g, 0.01 eq), PPh₃(4.45 g, 0.04 eq), and 3.0 M K₂CO₃aqueous solution (58.6 g, 2.0 eq in 144 ml H₂O) in toluene (730 mL) was heated under nitrogen at 65° C. for 12 h. After cooling to room temperature, the solvent was then removed using a rotary evaporator, and the remaining substance was purified with column chromatography to obtain Reactant A4. The purified product was identified as Reactant A4 by FD-MS analysis. FD-MS analysis C₈H₇BrCl₂: theoretical value of 301.99 and observed value of 301.99.

Synthesis of Intermediate B1

Take the Intermediate B1 as an example, it was synthesized by the above Scheme II through steps B-1 and B-2 as described below.

Step B-1: Synthesis of Spiro Alcohol

To the Reactant A1 (1.0 eq) in anhydrous THF (0.4 M), n-BuLi (1 eq) was added dropwise and stirred at −78° C. After stirring for 20 min, Intermediate A (0.7 eq) was added to the mixture and the reaction mixture was allowed to warm to room temperature. The reaction was monitored by HPLC. After completion of the reaction, the reaction solution was quenched with water, and a water layer was extracted with ethyl acetate. The extracted solution and an organic layer were combined and washed with saturated saline, and then dried with magnesium sulfate. After drying, this mixture was subjected to suction filtration, and then the filtrate was concentrated. 65 g of spiro alcohol was obtained as a light yellow, powdery solid and was directly used in step B-2 without further purification.

Step B-2: Synthesis of Intermediate B1

To the obtained spiro alcohol (1 eq), acetic acid (w/v=1/3 to the reactant) and H₂SO₄(5 drops) were added, and the mixture was stirred at 110° C. for 6 h. The reaction was monitored by HPLC. After completion of the reaction, the precipitate was separated by filtration. The remaining substance was purified with column chromatography to obtain 58 g of white solid in a yield of 93.0%.
The white solid product was identified as Intermediate B1 by FD-MS analysis. FD-MS analysis C₃₁H₁₉Cl: theoretical value 426.94, observed value 426.94.

Synthesis of Intermediates B2 to B4

The procedures for preparing the Intermediates B2 to B4 were similar to that for Intermediate B1, except for the material of Reactant An. The obtained intermediates B2 to B4 were present in white solids. The yields and MS analysis data of the intermediates B1 to B4 are also listed in the following Table 2.

TABLE 2

the material of Reactant An used to prepare Intermediate Bn, chemical
structures of spiro alcohol and Intermediate Bn, and yields, formulae, and mass
(M⁺) analyzed by FD-MS of Intermediate Bn.

Material of	Chemical Structure		Yield	Formula/
Reactant An	of Spiro Alcohol	Intermediate Bn	(%)	Mass(M⁺)

			93.0	C₃₁H₁₉Cl/ 426.94

			89.1	C₃₁H₁₉Cl/ 426.94

			83.2	C₃₁H₁₉Br/ 471.39

			75.4	C₃₁H₁₈Cl₂/ 461.38

Modifications of Intermediates Bn

In addition to the Intermediates B1 to B4, one person skilled in the art can adopt other Reactants An similar to Reactants A1 to A4 to react with Intermediate A to synthesize other desired Intermediates Bn through Scheme II. Applicable modifications of Intermediate Bn may be, for example, but are not limited to, Intermediates B5 to B7 as follows.

Preparation of Intermediate Cn

Intermediate Cn, including Intermediates C1 to C4, could be purchased or synthesized by the following Scheme III.
A mixture of Intermediate Bn (1.0 eq), bis(pinacolato)diboron (1.20 eq), tris(dibenzylideneacetone)dipalladium[Pd₂(dba)₃] (0.015 eq), dicyclohexyl(2′,6′-dimethoxy-[1,1′-biphenyl]-2-yl)phosphine (SPhos), and potassium acetate (KOAc) (3.0 eq) in anhydrous 1,4-dioxane (100 mL) was stirred at 110° C. for 8 h under nitrogen atmosphere. After cooling to room temperature, the solvent was then removed under reduced pressure, and the residue was purified with column chromatography to obtain a pale yellow solid product. The yield was listed in Table 3.
Each of the pale yellow solid products was identified as Intermediate Cn by a FD-MS analysis. The chemical structures, yield, formulae, and mass analyzed by FD-MS of Intermediate Cn were listed in Table 3.

TABLE 3

Intermediate Bn used for preparing Intermediate Cn, chemical
structures, yields, formulae, and mass analyzed by FD-MS of Intermediate Cn

Intermediate Cn

Intermediate Bn		Yield	Formula/
Chemical Structure	Chemical Structure	(%)	Mass (M⁺)

		82	C₃₇H₃₁BO₂/ 518.45

		85	C₃₇H₃₁BO₂/ 518.45

		90	C₃₇H₃₁BO₂/ 518.45

Modifications of Intermediates Cn

In addition to the Intermediates C1 to C3, one person skilled in the art can undergo a similar reaction of Scheme III to synthesize other desired Intermediates Cn, for example, but are not limited to, Intermediates C4 to C7. Said Intermediates C4 to C7 may be obtained from Intermediates B4 to B7 through a reaction of Scheme III, respectively.

Preparation of Reactants Bn

Reactants Bn, such as Reactants B1 to B20, applicable to prepare a novel compound were listed in Table 4. Most of Reactants B1 to B7, B9 to B18 and B20 were purchased from Sigma-Aldrich.

TABLE 4

chemical structures and the CAS No. of the Reactants B1 to B20

Reactant	Reactant B1	Reactant B2	Reactant B3
Bn

Chemical structure

CAS No.	3842-55-5	1205748-61-3	1616231-57-2

Reactant	Reactant B4	Reactant B5	Reactant B6
Bn

Chemical structure

CAS No.	29509-91-9	2142681-84-1	1618107-00-8

Reactant	Reactant B7	Reactant B8	Reactant B9
Bn

Chemical structure

CAS No.	1300115-09-6	—	1588407-97-9

Reactant	Reactant B10	Reactant B11	Reactant B12
Bn

Chemical structure

CAS No.	1421599-34-9	3114-52-1	774-53-8

Reactant	Reactant B13	Reactant B14	Reactant B15
Bn

Chemical structure

CAS No.	307929-32-4	1472062-94-4	1883265-32-4

Reactant	Reactant B16	Reactant B17	Reactant B18
Bn

Chemical structure

CAS No.	1624289-88-8	2226747-73-3	2286234-09-9

Reactant	Reactant B19	Reactant B20
Bn

Chemical structure

CAS No.	—	2304744-50-9

Synthesis of Reactant B8

Reactant B8 could be synthesized by Scheme IV.
2,4-dichloro-6-phenyl-pyrimidine (1.0 eq), pyridinylphenylboronic acid (1.05 eq, CAS No. 170230-28-1), Pd(PPh₃)₄(0.012 eq), Na₂CO₃(2.0 eq, 3 M) in THF (0.3 M) was heated at 60° C. for 16 h. After completion of the reaction, the volatiles were removed under vacuum, and the resulting solution was extracted with CH₂Cl₂. The combined organic extract was washed with brine solution, dried over Na₂SO₄. Then the resulting solution was concentrated under reduced pressure and purified by column chromatography to obtain Reactant B8 in a yield of 68%. The purified product was identified as Reactant B8 by FD-MS analysis. FD-MS analysis C₂₁H₁₄ClN₃: theoretical value of 343.81 and observed value of 343.81.

Preparation of Claimed Compounds

Each of the foresaid Intermediates, e.g., Intermediates Bn and Cn could be reacted with various Reactants Bn to synthesize various claimed novel compounds. The general synthesis pathway of the claimed novel compound was summarized in Scheme V.
In the above Scheme V, “Intermediate Cn” may be any one of the foresaid Intermediates C1 to C3 as listed in Table 3 and Intermediates C4 to C7, and “Reactant Bn” may be any one of Reactants B1 to B20 as listed in Table 4, but it is not limited thereto.
Intermediate Cn (1.0 eq), Reactant Bn (1.2 eq), Pd(OAc)₂(0.01 eq), and 2-(dicyclohexylphosphino)biphenyl[P(Cy)₂(2-biPh)] (0.04 eq) were stirred in a mixed solution of toluene/ethanol (0.5M, v/v=10/1), and 3.0 M of K₂CO₃aqueous solution. The reaction mixture was heated to about 100° C. and stirred for 12 h under nitrogen atmosphere. After completion of the reaction, water and toluene were added to the reaction mixture. Subsequently, the organic layer was recovered by solvent extraction operation and dried over sodium sulfate. The solvent was then removed under reduced pressure, and the resulting residue was purified by silica gel column chromatography. The obtained residue was recrystallized with toluene to obtain a white solid product as the claimed novel compound.
Intermediates Cn and Reactants Bn adopted to synthesize Compounds 1 to 7 were listed in Table 5. The obtained Compounds 1 to 7 were identified by H¹-NMR (500 MHz, CDCl₃) and FD-MS, and the chemical structure, yield, formula and mass of each of Compounds 1 to 7 were also listed in Tables 5 and 6. From the data of Table 6, it indicated that Compounds 4 to 7 each had two stereoisomers existing therein.

TABLE 5

Intermediates Cn and Reactant Bn adopted to prepare Compounds 1 to
7 and their yields, formulae, and FD-MS data

Claimed Compound

		Chemical	Yield	Formula/
Intermediate Cn	Reactant Bn	Structure	(%)	Mass (M⁺)

			85	C₄₆H₂₉N₃/ 623.74

			76	C₅₈H₃₇N₃/ 775.93

			65	C₅₈H₃₇N₃/ 775.93

			81	C₄₆H₂₉N3/ 623.74

			77	C₅₈H₃₇N₃/ 775.93

			82	C₅₈H₃₇N₃/ 775.93

			78	C₅₂H₃₁N₃O/ 713.82

TABLE 6

H¹-NMR results of Compounds 1 to 7.

Compound	H¹-NMR

	δ 9.01 ppm (d, 1H), 8.99 ppm (s, 1H), 8.75 ppm (d, 4H), 8.65 ppm (d, 1H), 8.05 ppm (d, 1H), 7.7 ppm (t, 2H), 7.60-7.58 ppm (m, 8H), 7.35-7.31 ppm (m, 4H), 7.29-7.05 ppm (m, 5H), 6.70 ppm (t, 1H), 5.85 ppm (d, 1H)

	δ 8.97 ppm (s, 3H), 8.84 ppm (s, 1H), 8.81 ppm (d, 1H), 8.77 ppm (d, 1H), 8.06 ppm (m, 2H), 7.80-7.76 ppm (m, 6H), 7.62-7.49 ppm (m, 12H), 7.47-7.41 ppm (m, 4H), 7.34-7.24 ppm (m, 3H), 7.09-7.05 ppm (m, 2H), 6.68 ppm (t, 1H), 5.87 ppm (d, 1H)

	δ 9.01 ppm (s, 2H), 8.89 ppm (s, 1H), 8.74 ppm (d, 2H), 8.07 ppm (d, 1H), 7.84 ppm (dd, 2H), 7.76-7.68 ppm (m, 6H), 7.66-7.57 ppm (m, 6H),, 7.52-7.46 ppm (m, 5H) 7.44-7.39 ppm (m, 3H), 7.36-7.30 ppm (m, 4H), 7.16 ppm (t, 1H), 7.11-7.06 ppm (m, 2H), 6.70 ppm (t, 1H), 5.89 ppm (d, 1H)

	δ 9.23 ppm (s, 1H), 8.93 ppm (d, 1H), 8.92 ppm (s, 1H), 8.86 ppm (d, 4H), 8.70 ppm (d, 4H), 8.13 ppm (d, 1H), 8.05 ppm (d, 1H), 7.85 ppm (d, 1H), 7.79 ppm (d, 1H), 7.69-7.54 ppm (m, 27H), 7.32 ppm (t, 4H), 7.18-7.13 ppm (m, 5H), 7.06 ppm (tt, 4H), 6.68 ppm (t, 1H), 6.03 ppm (d, 1H), 5.86 ppm (d, 1H)

	δ 9.23 ppm (s, 1H), 9.08 ppm (s, 2H), 8.96 ppm (d, 1H), 8.92 ppm (s, 2H), 8.85 ppm (d, 2H), 8.69 ppm (d, 2H), 8.10 ppm (d, 1H), 8.02 ppm (d, 1H), 7.85-7.76 ppm (m, 11H), 7.73-7.67 ppm (m, 10H), 7.64-7.58 ppm (m, 12H), 7.53 ppm (dd, 8H), 7.44 ppm (t, 4H), 7.34 ppm (t, 4H), 7.19-7.12 ppm (m, 6H), 7.05 ppm (t, 4H), 6.69 ppm (t, 1H), 6.05 ppm (d, 1H), 5.85 ppm (d, 1H)

	δ 9.23 ppm (s, 1H), 9.04 ppm (s, 2H), 8.94 ppm (d, 1H), 8.92 ppm (s, 1H), 8.88 ppm (s, 2H), 8.86 ppm (d, 2H), 8.73 ppm (d, 2H) 8.10 ppm (d, 1H), 8.19 ppm (s, 1H), 8.02 ppm (d, 1H), 8.00 ppm (s, 1H)7.83 ppm (d, 6H), 7.78 ppm (d, 4H), 7.70 ppm (dd, 4H), 7.70-7.51 ppm (m, 25H), 7.46 ppm (t, 4H), 7.34 ppm (t, 4H), 7.20-7.13 ppm (m, 5H), 7.08-7.04 ppm (m, 4H), 6.68 ppm (t, 1H), 6.05 ppm (dd 1H), 5.88 ppm (dd, 1H)

	δ 9.19 ppm (s, 1H), 9.00 ppm (s, 1H), 8.89 ppm (d, 1H), 8.85 ppm (s, 1H) 8.83 ppm (m, 3H), 8.70 ppm (s, 1H), 870-8.68 ppm (m, 3H), 8.12 ppm (d, 1H), 8.06 ppm (d, 1H), 8.04-7.95 ppm (m, 4H), 7.897.82 ppm (dd, 2H), 7.73 ppm (m, 4H), 7.67-7.45 ppm (m, 21H), 7.34-7.37 ppm (m, 6H), 7.26-7.19 ppm (m, 5H), 7.12 ppm (t, 4H), 6.71 ppm (t, 1H), 6.03 ppm (d, 1H), 5.91 ppm (d, 1H)

Modifications of Compounds 1 to 7

In addition to the Compounds 1 to 7, one person skilled in the art can react any Intermediate Bn or Intermediate Cn with any Reactant Bn through a reaction mechanism similar to Scheme V to synthesize other desired claimed novel compounds.

Preparation of OLED Devices

A glass substrate coated with ITO layer (abbreviated as ITO substrate) in a thickness of 1500 Å was placed in distilled water containing a detergent dissolved therein, and was ultrasonically washed. The detergent was a product manufactured by Fischer Co., and the distilled water was distilled water filtered twice through a filter (Millipore Co.). After the ITO layer had been washed for 30 minutes, it was ultrasonically washed twice with distilled water for 10 minutes. After the completion of washing, the glass substrate was ultrasonically washed with isopropyl alcohol, acetone and methanol solvents and then dried, after which it was transported to a plasma cleaner. Then the substrate was cleaned with oxygen plasma for 5 min, and then transferred to a vacuum evaporator.
After that, various organic materials and metal materials were sequentially deposited on the ITO substrate to obtain the OLED device of Examples and Comparative Examples as stated above. The vacuum degree during the deposition was maintained at 1×10⁻⁶to 3×10⁻⁷torr. Herein, the ITO substrate was deposited with a first hole injection layer (HIL-1), a second hole injection layer (HIL-2), a hole transporting layer (HTL), a blue/green/red emission layer (BEL/GEL/REL), an electron transporting layer (ETL), an electron injection layer (EIL), and a cathode (Cthd).
Herein, HI and HI-D were materials for forming HIL-1; HI was a material for forming HIL-2; HT was a material for forming HTL; novel compounds of the present invention were materials for forming ETL; Liq was a material for forming ETL and EIL. RH/GH/BH were each a host material for forming REL/GEL/BEL, and RD/GD/BD were each a dopant for forming REL/GEL/BEL. The detailed chemical structures of foresaid commercial materials used in the OLED devices were listed in Table 7.

TABLE 7

chemical structures of commercial materials for OLED devices.

The main difference of the OLED devices between Examples and Comparative Examples was that the material of ETL of OLED in the following Comparative Example was made of reference compound as shown in Table 7 but the material of ETL of OLED in the following Examples was made of the novel compounds of the present invention listed in Table 5. Specifically, the materials of ETL of Examples 1 to 21 were listed in Table 5.

Preparation of Red OLED Devices

To prepare the red OLED device, multiple organic layers were respectively deposited on the ITO substrate according to the sequence as listed in Table 8, and the materials and the thicknesses of the organic layers in red OLED devices were also listed in Table 8.

TABLE 8

coating sequence, materials and thickness of
the organic layers in red OLED device

Coating
Sequence	Layer	Material	Thickness

1	HIL-1	HI doped with 3.0 wt % of HI-D	100 Å
2	HIL-2	HI	2200 Å
4	HTL	HT	100 Å
5	REL	RH doped with 3.5 wt % of RD	300 Å
6	ETL	novel compounds/reference	350 Å
		compound doped with 35.0 wt %
		of Liq
7	EIL	Liq		15 Å
8	Cthd	Al	1500 Å

Preparation of Green OLED Devices

To prepare the green OLED device, multiple organic layers were respectively deposited on the ITO substrate according to the sequence as listed in Table 9, and the materials and the thicknesses of the organic layers in the green OLED devices were also listed in Table 9.

TABLE 9

coating sequence, materials and thickness of the
layers in green OLED device

Coating
Sequence	Layer	Material	Thickness

1	HIL-1	HI doped with 3.0 wt % of HI-D	100 Å
2	HIL-2	HI	1400 Å
4	HTL	HT	100 Å
5	GEL	GH doped with 10.0 wt % of GD	400 Å
6	ETL	novel compounds/reference	350 Å
		compound doped with 35.0 wt %
		of Liq
7	EIL	Liq		15 Å
8	Cthd	Al	1500 Å

Preparation of Blue OLED Devices

To prepare the blue OLED device, multiple organic layers were respectively deposited on the ITO substrate according to the sequence as listed in Table 10, and the materials and the thicknesses of the organic layers in the blue OLED devices were also listed in Table 10.

TABLE 10

coating sequence, materials and thickness of the
layers in blue OLED device

Coating
Sequence	Layer	Material	Thickness

1	HIL-1	HI doped with 3.0 wt % of HI-D	100 Å
2	HIL-2	HI	850 Å
4	HTL	HT	100 Å
5	BEL	BH doped with 3.5 wt % of BD	250 Å
6	ETL	novel compounds/reference	250 Å
		compound doped with 35.0 wt %
		of Liq
7	EIL	Liq		15 Å
8	Cthd	Al	1500 Å

Performance of OLED Device

To evaluate the performance of OLED devices, red, green, and blue OLED devices were measured by PR650 as photometer and Keithley 2400 as power supply. Color coordinates (x,y) were determined according to the CIE chromaticity scale (Commission Internationale de L'Eclairage, 1931). The results were shown in Table 11. For the blue OLED devices, the data were collected at 1000 nits. For the green OLED devices, the data were collected at 3000 nits. And for the red OLED devices, the data were collected at 3000 nits.

TABLE 11

materials of ETL, colors, CIEs, luminous efficacy, and EQE of
OLED devices of Examples 1 to 21 (E1 to E21) and Comparative
Examples 1 to 3 (C1 to C3)

				Luminous
Example	Material			efficacy	EQE
No.	of ETL	Color	CIE (x, y)	(lm/W)	(%)

E1	Compound 1	B	(0.130, 0.148)	8.41	7.13
E2		G	(0.311, 0.637)	50.6	17.51
E3		R	(0.656, 0.342)	17.8	20.68
E4	Compound 2	B	(0.129, 0.156)	7.89	7.57
E5		G	(0.310, 0.640)	48.8	17.99
E6		R	(0.657, 0.340)	17.5	21.03
E7	Compound 3	B	(0.129, 0.158)	8.06	7.06
E8		G	(0.319, 0.636)	54.1	18.55
E9		R	(0.657, 0.340)	17.4	20.86
E10	Compound 4	B	(0.129, 0.164)	6.94	7.54
E11		G	(0.313, 0.639)	54.4	18.14
E12		R	(0.658, 0.339)	13.1	20.44
E13	Compound 5	B	(0.128, 0.161)	7.3	7.16
E14		G	(0.322, 0.634)	43.5	18.45
E15		R	(0.659, 0.338)	15.1	20.62
E16	Compound 6	B	(0.129, 0.168)	7.23	7.1
E17		G	(0.327, 0.630)	45.20	18.79
E18		R	(0.656, 0.341)	15.3	20.26
E19	Compound 7	B	(0.132, 0.138)	6.58	7.00
E20		G	(0.320, 0.632)	52.1	18.18
E21		R	(0.660, 0.338)	18.5	17.97
C1	Reference	B	(0.129, 0.149)	4.66	5.92
C2	Compound	G	(0.316, 0.639)	31.2	17.41
C3		R	(0.657, 0.341)	10.10	12.12

As shown in Table 11, adopting the novel compounds of the present invention as the electron transport material can effectively improve both luminous efficacy and EQE of the red, green, or blue OLEDs.
Even though numerous characteristics and advantages of the present invention have been set forth in the foregoing description, together with details of the structure and features of the invention, the disclosure is illustrative only. Changes may be made in the details, especially in matters of shape, size, and arrangement of parts within the principles of the invention to the full extent indicated by the broad general meaning of the terms in which the appended claims are expressed.

Claims

What is claimed is:

1. A compound represented by the following Formula (I):

wherein,

G¹¹and G¹²are each independently selected from the group consisting of:

R¹to R³are each independently selected from the group consisting of: a deuterium atom, a halo group, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and an alkynyl group having 2 to 6 carbon atoms;

J is an integer from 1 to 2;

k is an integer from 0 to 2; and

n1 is an integer from 0 to 5, n2 is an integer from 0 to 4, and n3 is an integer from 0 to 7.

2. The compound as claimed in claim 1, wherein the compound is represented by the following Formulae (I-I) to (I-VI):

3. The compound as claimed in claim 1, wherein G¹¹and G¹²are each independently selected from the group consisting of:

4. The compound as claimed in claim 1, wherein G¹and G²are each independently selected from the group consisting of:

5. The compound as claimed in claim 1, wherein G¹and G²are the same.

6. The compound as claimed in claim 1, wherein j is the integer 1 and k is the integer 0.

7. The compound as claimed in claim 1, wherein j is the integer 1 and k is the integer 1.

8. The compound as claimed in claim 1, wherein the compound is selected from the group consisting of:

9. An organic electronic device, comprising a first electrode, a second electrode, and an organic layer disposed between the first electrode and the second electrode, wherein the organic layer comprises the compound as claimed in claim 1.

10. The organic electronic device as claimed in claim 9, wherein the organic electronic device is an organic light emitting device.

11. The organic electronic device as claimed in claim 10, wherein the organic light emitting device comprises:

a hole injection layer formed on the first electrode;

a hole transport layer formed on the hole injection layer;

an emission layer formed on the hole transport layer;

an electron transport layer formed on the emission layer, wherein the organic layer is the electron transport layer;

an electron injection layer formed between the electron transport layer and the second electrode.

12. The organic electronic device as claimed in claim 10, wherein the organic light emitting device comprises:

a hole injection layer formed on the first electrode;

a hole transport layer formed on the hole injection layer;

an emission layer formed on the hole transport layer;

a hole blocking layer formed on the emission layer, wherein the organic layer is the hole blocking layer;

an electron transport layer formed on the hole blocking layer;

13. The organic electronic device as claimed in claim 9, wherein the organic layer comprises the compound as claimed in claim 3.

14. The organic electronic device as claimed in claim 9, wherein the organic layer comprises the compound as claimed in claim 4.

15. The organic electronic device as claimed in claim 9, wherein the compound is selected from the group consisting of: