阅读说明：本技术 可产生发光激基复合物的有机发光器件 (Organic light-emitting device capable of generating light-emitting exciplex ) 是由 黄贺隆 赵登志 赖振昌 殷力嘉 林祺臻 洪文谊 汪根欉 张敏忠 孙杰 于 2018-08-02 设计创作，主要内容包括：一种可产生发光激基复合物的有机发光器件,系包括：阳极；阴极；以及介于该阴极与阳极之间的发光层,且该发光层包括具式(I)之杂环化合物及具式(II)之三嗪衍生物,以提升其有机发光器件之性能,<Image he="283" wi="700" file="DDA0001752665300000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>其中,X、L1、Ar1、Ar2、A1及Y系如同说明书中之定义。(An organic light-emitting device capable of producing a light-emitting exciplex, comprising: an anode; a cathode; and a light-emitting layer between the cathode and the anode, wherein the light-emitting layer comprises a heterocyclic compound of formula (I) and a triazine derivative of formula (II) to improve the performance of the organic light-emitting device, wherein X, L1, Ar1, Ar2, A1 and Y are defined as in the specification.)

1. An organic light-emitting device capable of producing a light-emitting exciplex, comprising:

a cathode;

an anode; and

a light-emitting layer interposed between the cathode and the anode, and the light-emitting layer includes a heterocyclic compound of formula (I) and a triazine derivative of formula (II),

wherein X represents S or O;

L₁represents a C6-C30 arylene group;

Ar₁and Ar₂Are the same or different and each Ar₁And Ar₂Independently represent a C6-C15 aryl group substituted or unsubstituted with a C6-C9 aryl group, a di- (C6-C9) arylamine group, or at least one C1-C30 alkyl group, or Ar₂N and L₁Taken together to form a carbazole moiety substituted or unsubstituted with a (C6-C15) aryl group; and

Ar₁and Ar₂At least one of which has an aromatic hydrocarbon moiety of C10-C15;

wherein each A₁Are the same or different and independently represent a substituted or unsubstituted C6-C20 arylene group, a substituted or unsubstituted arylene group containing a group selected from the group consisting of N, O, andc3-20 heteroarylene of at least one heteroatom from the group consisting of S;

each Y is the same or different and is independently selected from the group consisting of halo, nitro, carbonyl, pyridyl, cyano, pyrazolyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted

2. The organic light emitting device according to claim 1, wherein Ar of the heterocyclic compound of formula (I)₁And Ar₂Each independently represents a phenyl group, a naphthyl group, a biphenyl group, a dimethylfluorenyl group or a (diphenylamino) phenyl group.

3. The organic light-emitting device of claim 1, wherein the carbazole moiety of the heterocyclic compound of formula (I) is 2, 9-carbazole or 3, 9-carbazole.

4. The organic light-emitting device of claim 3, wherein the heterocyclic compound of formula (I) is selected from the group consisting of:

5. the organic light emitting device according to claim 1, wherein L of the heterocyclic compound of formula (I)₁It represents a phenylene group.

6. The organic light emitting device of claim 5, wherein the heterocyclic compound of formula (I) is selected from the group consisting of:

7. the organic light emitting device according to claim 1, wherein A of the triazine derivative of formula (II)₁Are all biphenylene.

8. The organic light emitting device of claim 7, wherein the triazine derivative of formula (II) is selected from the group consisting of:

9. the organic light emitting device according to claim 1, wherein A of the triazine derivative of formula (II)₁Are all phenylene, and Y is bonded to A in relation to the triazine ring₁The neutral position.

10. The organic light emitting device of claim 9, wherein the triazine derivative of formula (II) is selected from the group consisting of:

11. the organic light emitting device according to claim 1, wherein the weight ratio of the heterocyclic compound of formula (I) and the triazine derivative of formula (II) is 3: 7 to 8: 2.

12. the organic light emitting device of claim 1, wherein the light emitting layer further comprises a guest emitter, wherein the guest emitter is a phosphorescent dopant, and the content of the phosphorescent dopant is 1 wt% to 3 wt%.

13. The organic light emitting device of claim 12, wherein the light emitting layer emits red light.

14. The organic light emitting device of claim 12, wherein the phosphorescent dopant comprises an organometallic complex of at least one metal selected from the group consisting of ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum, and gold.

15. The organic light emitting device according to claim 14, wherein the phosphorescent dopant system is tris [ 1-phenylisoquinoline-C2, N ] iridium (iii).

16. The organic light emitting device of claim 1, wherein the thickness of the light emitting layer is 200 to 300 angstroms.

Technical Field

The present invention relates to an organic light emitting device, and more particularly, to an organic light emitting device capable of generating a light emitting exciplex.

Background

Organic Light Emitting Devices (OLEDs) are expected to be applied to full color displays or portable electronic devices because of their features of lightness, thinness, wide viewing angle, high contrast, low power consumption, high response speed, full color, flexibility, etc.

Typically, the OLED is a multi-layer thin film structure formed by sequentially depositing an anode, a hole transport layer, a light emitting layer, an electron transport layer and a cathode by a vacuum deposition method or a coating method. When a current is applied, the anode injects holes and the cathode injects electrons into the organic layer or layers, and the injected holes and electrons each migrate to the oppositely charged electrode. When electrons and holes are confined to the same molecule, an "exciton (exiton)" is formed, which has a confined electron-hole pair in an excited energy state that relaxes by a light-emitting mechanism to emit light.

To improve the device efficiency of OLED, the Anda Qiaohi (Chihaya Adachi) at the university of Jiuzhou island of Japan is designed by proper molecular structure to make the energy level difference (Delta E) between singlet and triplet excited states_ST) Narrowing, increasing Reverse Inter-System Crossing (Reverse Inter-System Crossing; RISC), a thermally activated Delayed Fluorescence (thermally activated Delayed Fluorescence; TADF) allows triplet excitons, which originally have lost energy in a thermal motion, to return to the singlet state and emit light, thereby achieving a 100% internal quantum efficiency theoretically equivalent to that of phosphorescent materials.

In addition, low Δ E can be achieved by forming exciplex (exiplex) at the contact interface by two independent materials with charge transport_STHowever, korean j.j.kim teaches that an exciplex is used as a common host material to prepare an organic light emitting device, and the difference between the Highest Occupied Molecular Orbital (HOMO) of the charge donor and the Lowest Unoccupied Molecular Orbital (LUMO) of the charge acceptor is formed to have characteristics similar to the energy of the singlet excited state and the triplet excited state, so that the energy of the singlet and triplet states is completely transferred to the dopant material, thereby greatly reducing the charge injection barrier.

Therefore, there is a need to develop an organic light emitting device with improved performance to meet the requirement of practical display applications.

Disclosure of Invention

The present invention provides an organic light emitting device with improved current efficiency, external quantum efficiency, and light emitting efficiency, reduced operating voltage, and prolonged service life.

The present invention provides an organic light emitting device capable of generating a light emitting exciplex, comprising: a cathode; an anode; and a light-emitting layer interposed between the cathode and the anode, and including a heterocyclic compound of formula (I) and a triazine derivative of formula (II),

wherein X represents S or O; l is₁Represents a C6-C30 arylene group; ar (Ar)₁And Ar₂Are the same or different and each Ar₁And Ar₂Independently represent a C6-C15 aryl group substituted or unsubstituted with a C6-C9 aryl group, a di- (C6-C9) arylamine group, or at least one C1-C30 alkyl group, or Ar₂N and L₁Taken together to form a carbazole moiety substituted or unsubstituted with a (C6-C15) aryl group; and Ar₁And Ar₂At least one of which has an aromatic hydrocarbon moiety of C10-C15;

wherein each A₁Are the same or different and independently represent a substituted or unsubstituted C6-C20 arylene, a substituted or unsubstituted C3-20 heteroarylene containing at least one heteroatom selected from the group consisting of N, O, and S;

each Y is the same or different and is independently selected from the group consisting of halo, nitro, carbonyl, pyridyl, cyano, pyrazolyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted

A diazolyl group, a substituted or unsubstituted aryl sulfone group, a substituted or unsubstituted di- (C6-C20) aryl-phosphinoxy group and a substituted or unsubstituted C6-C20 aryl sulfoxide group.

The present invention provides an organic light emitting device capable of generating a light emitting exciplex, which emits light due to its light emissionA luminescence exciplex formed by a heterocyclic compound of formula (I) and a triazine derivative of formula (II) in the layer, so that the energy level difference (Delta E) between the singlet excited state and the triplet excited state_ST) And the reduction is carried out to effectively improve the performance of the whole assembly and improve the service life of the organic light-emitting device.

Drawings

The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:

FIG. 1 is a schematic cross-sectional view of one embodiment of an organic light emitting device of the present invention;

FIG. 2 is a schematic cross-sectional view of another embodiment of an organic light emitting device of the present invention; and

FIG. 3 is a schematic cross-sectional view of another embodiment of an organic light emitting device of the present invention.

Wherein the figures include the following reference numerals:

100. 200, 300 organic light emitting devices;

110. 210, 310 substrates;

120. 220, 320 anodes;

130. 230, 330 hole injection layer;

140. 240, 340 hole transport layers;

150. 250, 350 light emitting layer;

160. 260, 360 electron transport layers;

170. 270, 370 electron injection layers;

180. 280, 380 cathodes;

245 an electron blocking layer;

355 a hole blocking layer.

Detailed Description

The following description is provided to illustrate the embodiments of the present invention by way of specific examples, and the advantages and effects of the present invention will be apparent to those skilled in the art from the description. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present disclosure. Moreover, all ranges and values herein are inclusive and combinable. Any number or point within the ranges set forth herein, e.g., any integer, may be considered a minimum or maximum value to derive a lower range, etc.

The present invention provides an organic light emitting device capable of generating a light emitting exciplex, comprising: a cathode; an anode; and a light-emitting layer interposed between the cathode and the anode, and including a heterocyclic compound of formula (I) and a triazine derivative of formula (II),

wherein X represents S or O; l is₁Represents a C6-C30 arylene group; ar (Ar)₁And Ar₂Are the same or different and each Ar₁And Ar₂Independently represent a C6-C15 aryl group substituted or unsubstituted with a C6-C9 aryl group, a di- (C6-C9) arylamine group, or at least one C1-C30 alkyl group, or Ar₂N and L₁Taken together to form a carbazole moiety substituted or unsubstituted with a (C6-C15) aryl group; and Ar₁And Ar₂At least one of which has an aromatic hydrocarbon moiety of C10-C15;

wherein each A₁Are the same or different and independently represent a substituted or unsubstituted C6-C20 arylene, a substituted or unsubstituted C3-20 heteroarylene containing at least one heteroatom selected from the group consisting of N, O, and S;

each Y is the same or different and is independently selected from the group consisting of halo, nitro, carbonyl, pyridyl, cyano, pyrazolyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted

Oxadiazolyl, menstrual crampSubstituted or unsubstituted aryl sulfone group, substituted or unsubstituted di- (C6-C20) aryl-phosphino group and substituted or unsubstituted C6-C20 aryl sulfoxide group.

As used herein, "aryl" means aryl or (arylene) which means monocyclic or fused polycyclic derived from aromatic hydrocarbons and includes, but is not limited to, phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthryl, phenylphenanthryl, anthryl, indenyl, terphenylidene, pyrenyl, tetracenyl, perylenyl, Kuai yl, naphthonaphthyl, propadienefluorenyl and the like.

As used herein, "heteroaryl" means heteroaryl or heteroarylene, which means an aryl group containing a ring backbone atom containing at least one heteroatom selected from the group consisting of N, O and S, and may be a monocyclic ring such as furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl and the like, or a condensed ring condensed with at least one benzene ring such as benzofuryl, benzothienyl, isobenzofuryl, dibenzofuryl, dibenzothienyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, isothiazolyl, thiadiazolyl, thia, Phenanthreneoxazolyl, phenanthridinyl, benzodiacenaphthenyl, dihydroacridinyl, and the like.

As used herein, "substituted" in the expression "substituted or unsubstituted" means that a hydrogen atom in a functional group is replaced with another atom or group (i.e., substituent). Each of the substituents is independently selected from at least one of the group consisting of: deuterium, halogen, C1-C30 alkyl, C1-C30 alkoxy, C6-C30 aryl, C5-C30 heteroaryl, C5-C30 heteroaryl substituted with C6-C30 aryl, benzimidazolyl, C30-C30 cycloalkyl, C30-C30 heterocycloalkyl, tri- (C30-C30) alkylsilyl, tri- (C30-C30) arylsilyl, di- (C30-C30) alkyl- (C30-C30) arylsilyl, C30-C30 alkyl di- (C30-C30) arylsilyl, C30-C30 alkenyl, C30-C30 alkynyl, cyano, di- (C30-C30) alkylamino, di- (C30-C30) arylboronyl, di- (C30) alkylboronyl, C30-C30 alkyl, C30-C30 alkyl, C1-C30 alkyl C6-C30 aryl, carboxyl, nitro and hydroxyl.

The organic light-emitting device capable of generating light-emitting exciplex is formed by combining the heterocyclic compound of formula (I) and the triazine derivative of formula (II), so that triplet excitons which dissipate energy in a thermal motion mode can return to a singlet state and emit light, thereby improving the quantum efficiency of the whole component.

As used herein, the term "exciplex" refers to a complex of excited states formed at a contact interface by two separate charge transporting materials, and the phenomenon of light emission through the exciplex is referred to as "light-emitting exciplex".

In one embodiment, in the light emitting layer of the organic light emitting device, the weight ratio of the heterocyclic compound of formula (I) and the triazine derivative of formula (II) is 3: 7 to 8: 2, wherein the weight ratio of the heterocyclic compound of the formula (I) and the triazine derivative of the formula (II) is in particular 1: 1 to 4: preferably 1.

A heterocyclic compound of formula (I):

in one embodiment, Ar of the heterocyclic compound of formula (I) is₁And Ar₂Each independently represents a substituted or unsubstituted C6-C15 aryl group.

The substituted Ar₁And Ar₂The substituents are each independently selected from C6-C9 aryl, di- (C6-C9) arylamino, or at least one C1-C30 alkyl.

In another embodiment, the C1-C30 alkyl group is methyl, the C6-C9 aryl group is phenyl, and the di- (C6-C9) arylamino group is diphenylamino.

The substituents may be linked through any position of the substituted group. However, the di- (C6-C9) arylamine group is not linked to the C6-C15 aryl group via an ortho-position.

In one embodiment, Ar of the heterocyclic compound of formula (I)₁And Ar₂Each independently represents a phenyl group, a naphthyl group, a biphenyl group, a dimethylfluorenyl group or a (diphenylamino) phenyl group.

In one embodiment, Ar₁And Ar₂At least one of which has a C10-C15 aromatic hydrocarbon moiety.

In one embodiment, Ar₁Represents phenyl, naphthyl, biphenyl, dimethylfluorenyl or (diphenylamino) phenyl; and Ar₂N and L₁Are bonded together to form a substituted or unsubstituted carbazole moiety.

In another embodiment, the carbazole moiety is substituted with a (C6-C15) aryl group. Preferably, the carbazole moiety is substituted with phenyl, naphthyl or biphenyl.

In yet another embodiment, the carbazole moiety of the heterocyclic compound of formula (I) is 2, 9-carbazole or 3, 9-carbazole.

In one embodiment, when Ar is₁When represents (diphenylamino) phenyl, Ar₂Represented by phenyl, naphthyl or biphenyl.

In one embodiment, L of the heterocyclic compound of formula (I)₁It represents phenylene or biphenylene.

In one embodiment, L of the heterocyclic compound of formula (I)₁Is phenylene or biphenylene and Ar₁And Ar₂When are the same, Ar₁And Ar₂Having a C10-C15 aromatic hydrocarbon moiety. Wherein, Ar is₁And Ar₂Further preferred are biphenyl or naphthyl groups.

Preferred embodiments of the aforementioned heterocyclic compounds of formula (I) are selected from Table 1, but are not limited thereto.

TABLE 1

One of the typical synthetic routes for heterocyclic compounds of formula (I) is described below, which obeys the conditions of Suzuki coupling (Suzuki coupling) and Hardwig amination (Hartwig amination) mentioned in the literature.

The following synthetic examples describe in more detail the synthetic procedures of the heterocyclic compounds of formula (I) of the present invention with reference to the above; however, the present invention should not be limited to those exemplified in the embodiments.

Synthesis example 1

In a 250mL flask, a mixture of 4- (4' -bromophenyl) dibenzo [ b, d ] furan (10g), tetrahydrofuran (90mL) was stirred and cooled to-78 ℃ under a nitrogen atmosphere, n-butyllithium solution (18.8mL, 2.5M in n-hexane) was injected at-78 ℃ and stirred for 2 hours at-78 ℃. After 2 hours, trimethyl borate (16g) was injected and the reaction allowed to equilibrate to room temperature overnight, and the reaction was monitored by thin layer chromatography. After completion of the reaction, 2N hydrochloric acid solution (60mL) was added to the reaction mixture and stirred for 1 hour, the reaction mixture was quenched with water (50mL), and extracted with ethyl acetate (70mL), the organic layer was extracted with water (3 × 50mL) and dried over anhydrous sodium sulfate. Subsequently, the ethyl acetate layer was evaporated to dryness in a rotary evaporator under vacuum to give 4- (dibenzofuran-4' -yl) phenylboronic acid (5 g).

A mixture of 4- (dibenzofuran-4' -yl) phenylboronic acid (5g), 2-bromocarbazole (4.7g), tetrakis (triphenylphosphine) palladium (1g), toluene (64mL), ethanol (7mL), water (20mL) and potassium carbonate (6.6g) was stirred at reflux and the reaction was monitored by thin layer chromatography. After completion of the reaction, the reaction mixture was quenched with water (100mL) and extracted with ethyl acetate (100mL), the organic layer was extracted with water (3 × 30mL) and dried over anhydrous sodium sulfate. The collected ethyl acetate layer was further purified by celite column chromatography. The ethyl acetate layer was then evaporated to dryness in a rotary evaporator under vacuum to yield compound 1-1(1g, 39%) with an HPLC purity of over 99%.

The melting point of compound 1-1 is 246.35 ℃ and the glass transition temperature is 95.24 ℃.

1H NMR(CDCl₃,δ)：8.34-8.27(m,1H)；8.26-8.02(m,3H)；7.98-7.88(m,2H)；7.86-7.80(m,1H)； 7.58-7.66(d,2H)；7.60-7.40(m,7H)；7.38-7.30(m,1H)；7.29-7.21(m,7H)；7.20-7.10(m,1H)。

Synthesis example 2

In a 250mL flask, a mixture of dibenzo [ b, d ] thiophen-4-ylboronic acid (5g, 20.31mmol), 3-bromocarbazole (4.9g, 21.33mmol), tetrakis (triphenylphosphine) palladium (1.2g, 1.01mmol), toluene (60mL), ethanol (8mL), H2O (20mL) and potassium carbonate (7.4g, 53.33mmol) was stirred at reflux for 5 hours, and the reaction was monitored by thin layer chromatography. After completion of the reaction, the reaction mixture was quenched with water (30mL) and extracted with ethyl acetate (50mL), the organic layer was extracted with water (3 × 30mL) and dried over anhydrous sodium sulfate. The collected ethyl acetate layer was further purified by celite column chromatography. Subsequently, the ethyl acetate layer was evaporated to dryness in a rotary evaporator under vacuum to give 2- (dibenzo [ b, d ] thiophen-4-yl) -9H-carbazole (3 g).

A mixture of 2- (dibenzo [ b, d ] thiophen-4-yl) -9H-carbazole (2g, 58.72mmol), 2-bromonaphthalene (1.3g, 6.29mmol), bis (dibenzylideneacetone) palladium (0) (0.1g, 0.17mmol), sodium tert-butoxide (1.1g, 11.44mmol), toluene (30ml), and tri (tert-butyl) phosphine (0.09g, 0.45 mmol) was refluxed under nitrogen atmosphere, and the reaction was monitored by thin layer chromatography. After completion of the reaction, the reaction mixture was quenched with water (20mL) and extracted with ethyl acetate (50mL), the organic layer was extracted with water (3 × 20mL) and dried over anhydrous sodium sulfate. The collected ethyl acetate layer was further purified by celite column chromatography. Subsequently, the ethyl acetate layer was evaporated to dryness under vacuum using a rotary evaporator. The residue was further precipitated by adding 200mL of methanol, filtered and dried under vacuum. 1g of compound 1-4 (36%) are obtained in a yellow solid with an HPLC purity of more than 99%.

The melting point of the compound 1-4 is 187.51 ℃ and the glass transition temperature is 101.31 ℃.

1H NMR(CDCl₃,δ)：8.56-8.53(d,1H)；8.25-8.14(m,3H)；7.13-7.09(m,2H)；8.02-7.92(m,2H)； 7.85-7.79(m,2H)；7.76-7.72(m,1H)；7.64-7.57(m,5H)；7.53-7.42(m,4H)；7.37-7.31(m,1H)。

Synthesis example 3

In a 150mL flask, a mixture of 2- (dibenzo [ b, d ] furan-4-yl) -9H-carbazole (3.5g), 4-bromotriphenylamine (3.7g), bis (dibenzylideneacetone) palladium (0) (0.18g), sodium tert-butoxide (2g), toluene (53mL), tris (tert-butyl) phosphine (0.17g) was refluxed under a nitrogen atmosphere, and the reaction was monitored by thin layer chromatography. After completion of the reaction, the reaction mixture was quenched with water (30mL) and extracted with ethyl acetate (50mL), the organic layer was extracted with water (3 × 30mL) and dried over anhydrous sodium sulfate. The collected ethyl acetate layer was further purified by celite column chromatography. Subsequently, the ethyl acetate layer was evaporated to dryness under vacuum using a rotary evaporator. The residue was further precipitated by adding methanol, filtered and dried under vacuum. 3.5g of compounds 1-7 (57%) are obtained in an HPLC purity of more than 99% and as yellow solid.

The melting point of the compounds 1-7 was 283.3 ℃ and the glass transition temperature was 94.64 ℃.

1H NMR(CDCl₃,δ)：8.29-8.27(d,1H)；8.20-8.18(d,1H)；8.01-8.00(m,2H)；7.95-7.94(m,1H)； 7.85-7.83(d,1H)；7.71-7.69(m,1H)；7.55-7.54(d,1H)；7.50-7.43(m,7H)；7.39-7.36(t,1H)； 7.31-7.20(m,10H)；7.08-7.07(t,2H)。

Synthesis example 4

A mixture of dibenzothiophene-4-boronic acid (10g (g)), 1, 4-dibromobenzene (9.4g), tetrakis (triphenylphosphine) palladium (2.42g), toluene (120 mL (mL)), ethanol (16 mL (mL)), water (46mL), and potassium carbonate (14.44g) was stirred at 80 ℃ for 5 hours. Monitoring the reaction by thin layer chromatography; after completion of the reaction, the reaction mixture was quenched with water (100mL) and extracted with ethyl acetate (100mL), the organic layer was extracted with water (3 × 30mL), and dried over anhydrous sodium sulfate. The collected ethyl acetate layer was subjected to celite column chromatography for further purification. Subsequently, the ethyl acetate layer was evaporated to dryness in a rotary evaporator under vacuum to give 13.52g of 4- (4' -bromophenyl) dibenzothiophene. A mixture of 4- (4' -bromophenyl) dibenzothiophene (10g), bis (4-biphenyl) amino (13.08g), bis (dibenzylideneacetone) palladium (0) (0.152g), sodium tert-butoxide (6.52g), toluene (125ml), tris (tert-butyl) phosphine (0.274g) was added together and refluxed under a nitrogen atmosphere, and the reaction was monitored by thin layer chromatography. After completion of the reaction, the reaction mixture was quenched with water (50ml), and extracted with ethyl acetate (100 ml). The organic layer was extracted with water (3 × 30ml) and dried over anhydrous sodium sulfate. The collected ethyl acetate layer was subjected to celite column chromatography for further purification. Subsequently, the ethyl acetate layer was evaporated to dryness under vacuum using a rotary evaporator. The residue was further precipitated by adding 200mL of methanol, filtered and dried under vacuum. 10.38g of compounds 1-12 (44%) are obtained in an HPLC purity of more than 99% and as a yellow solid.

The melting point of compounds 1-12 is 278.3 ℃ and the glass transition temperature is 102.9 ℃.

1H NMR(CDCl₃,δ)：8.16-8.11(m,2H)；7.79-7.77(m,1H)；7.58-7.39(m,18H)；7.33-7.22(m, 8H)。

Synthesis example 5

In a 250mL flask, a mixture of 4- (4' -bromophenyl) dibenzothiophene (10g), N-phenyl-2-naphthylamine (N-phenylnaphthalene-2-amine, 7.75g), bis (dibenzylideneacetone) palladium (0) (0.59g), sodium tert-butoxide (6.5g), toluene (150mL), and tris (tert-butyl) phosphine (0.55g) was refluxed under a nitrogen atmosphere, and the reaction was monitored by thin layer chromatography. After completion of the reaction, the reaction mixture was quenched with water (50mL) and extracted with ethyl acetate (70 mL). The organic layer was extracted with water (3 × 50mL) and dried over anhydrous sodium sulfate. The collected ethyl acetate layer was subjected to celite column chromatography for further purification. Subsequently, the ethyl acetate layer was evaporated to dryness under vacuum using a rotary evaporator. The residue was further precipitated into methanol (100ml), filtered and dried under vacuum. 7g of compounds 1-14 (49%) are obtained in a yellow solid with an HPLC purity of more than 99%.

The melting point of compounds 1-14 is 202.21 ℃ and the glass transition temperature is 82.08 ℃.

1H NMR(CDCl₃,δ)：8.30-8.17(m,1H)；8.16-8.10(m,1H)；7.88-7.83(m,1H)；7.82-7.76(m,2H)； 7.68-7.63(m,3H)；7.58-7.30(m,9H)；7.29-7.22(m,5H)；7.14-7.08(m,1H)。

Synthesis example 6

A mixture of 4-dibenzofuranboronic acid (13.3g), 1, 4-dibromobenzene (10g), tetrakis (triphenylphosphine) palladium (3.02g), toluene (158mL), ethanol (65mL), water (65mL) and potassium carbonate (21.69g) was stirred at 80 ℃ for 5 hours, and the reaction was monitored by thin layer chromatography. After completion of the reaction, the reaction mixture was quenched with water (100mL) and extracted with ethyl acetate (100 mL). The organic layer was extracted with water (3 × 30ml) and dried over anhydrous sodium sulfate. The collected ethyl acetate layer was further purified by celite column chromatography. Subsequently, the ethyl acetate layer was evaporated to dryness in a rotary evaporator under vacuum to give 13.7g of 4- (4' -bromophenyl) dibenzofuran.

In a 500mL flask, a mixture of 4- (4' -bromophenyl) dibenzofuran (10g), bis (4-biphenyl) amino (12.7g), bis (dibenzylideneacetone) palladium (0) (0.62g), sodium tert-butoxide (6.9g), xylene (150mL), and tris (tert-butyl) phosphine (0.58g) was refluxed under a nitrogen atmosphere, and the reaction was monitored by thin layer chromatography. After completion of the reaction, the reaction mixture was quenched with water (50mL) and extracted with ethyl acetate (70 mL). The organic layer was extracted with water (3 × 50mL) and dried over anhydrous sodium sulfate. The collected ethyl acetate layer was further purified by celite column chromatography. Subsequently, the ethyl acetate layer was evaporated to dryness under vacuum using a rotary evaporator. The residue was further precipitated into methanol (100ml), filtered and dried under vacuum. 7.67g of compounds 1-18 (44%) were obtained with an HPLC purity of over 99% and as a pale yellow solid.

The glass transition temperature of compounds 1-18 was 96.57 ℃.

1H NMR(CDCl₃,δ)：8.00(d,1H)；7.98-7.87(m,3H)；7.63-7.53(m,10H)；7.49-7.38(m,15H)。

Synthesis example 7

In a 500mL flask, a mixture of 4- (4' -bromophenyl) dibenzofuran (4.2g), N- (4-biphenyl) - (9, 9-dimethylafluoren-2-yl) amino (5g), bis (dibenzylideneacetone) palladium (0) (0.24g), sodium t-butoxide (2.65g), toluene (75mL), and tris (tert-butyl) phosphine (0.22g) was refluxed under a nitrogen atmosphere. After completion of the reaction, the reaction mixture was quenched with water (50mL) and extracted with ethyl acetate (70 mL). The organic layer was extracted with water (3 × 50mL) and dried over anhydrous sodium sulfate. The collected ethyl acetate layer was further purified by celite column chromatography. Subsequently, the ethyl acetate layer was evaporated to dryness under vacuum using a rotary evaporator to obtain 3.45g of compounds 1-24 (44%) with HPLC purity of over 99% as a yellow solid.

The glass transition temperature of the compounds 1-24 is 110.5 ℃.

1H NMR(CDCl₃,δ)：8.01-7.99(d,1H)；7.92-7.88(m,3H)；7.69-7.55(m,11H)；7.49-7.26(m, 17H)；7.20-7.18(dd,1H)。

Synthesis example 8

A mixture of 4-dibenzofuranboronic acid (13.3g), 1, 3-dibromobenzene (10g), tetrakis (triphenylphosphine) palladium (3.02g), toluene (158mL), ethanol (65mL), water (65mL) and potassium carbonate (21.69g) was stirred at 80 ℃ for 5 hours, and the reaction was monitored by thin layer chromatography. After completion of the reaction, the reaction mixture was quenched with water (100mL) and extracted with ethyl acetate (100 mL). The organic layer was extracted with water (3 × 30mL) and dried over anhydrous sodium sulfate. The collected ethyl acetate layer was further purified by celite column chromatography. Subsequently, the ethyl acetate layer was evaporated to dryness in a rotary evaporator under vacuum to give 13.7g of 4- (3' -bromophenyl) dibenzofuran.

A mixture of 4- (3' -bromophenyl) dibenzofuran (7.4g), N- (4-biphenyl) - (9, 9-dimethylfluoren-2-yl) amino (10g), bis (dibenzylideneacetone) palladium (0) (0.46g), sodium tributyrate (5.1g), toluene (110mL), and tri (tert-butyl) phosphine (0.43g) was refluxed under a nitrogen atmosphere, and the reaction was monitored by thin layer chromatography. After completion of the reaction, the reaction mixture was quenched with water (50mL) and extracted with ethyl acetate (70mL), the organic layer was extracted with water (3 × 50mL) and dried over anhydrous sodium sulfate. The collected ethyl acetate layer was further purified by celite column chromatography. Subsequently, the ethyl acetate layer was evaporated to dryness under vacuum using a rotary evaporator to obtain 6.12g of compounds 1-28 (44%) with HPLC purity of over 99% as a yellow solid.

The glass transition temperature of compounds 1-28 was 103.11 ℃.

1H NMR(CDCl₃,δ)：8.09-7.93(d,1H)；7.92-7.89(d,1H)；7.73-7.72(t,1H)；7.71-7.60(m,6H)； 7.57-7.30(m,22H)；7.29-7.2(dd,2H)。

Synthesis example 9

A mixture of dibenzo [ b, d ] thiophen-4-ylboronic acid (10g, 38.4 mmol), 1, 3-dibromobenzene (9.5g, 40.33mmol), tetrakis (triphenylphosphine) palladium (2.3g, 2.01mmol), toluene (130ml), ethanol (17ml), H2O (45ml) and potassium carbonate (13.9g, 100mmol) was stirred at 80 ℃ for 5H and the reaction was monitored by thin layer chromatography. After completion of the reaction, the reaction mixture was quenched with water (100mL) and extracted with ethyl acetate (100mL), the organic layer was extracted with water (3 × 30mL) and dried over anhydrous sodium sulfate. The collected ethyl acetate layer was further purified by celite column chromatography. Subsequently, the ethyl acetate layer was evaporated to dryness in a rotary evaporator under vacuum to give 4- (3-bromophenyl) dibenzo [ b, d ] thiophene (8.2 g).

A mixture of 4- (3-bromophenyl) dibenzo [ b, d ] thiophene (8.2g) (3.5g, 10.31mmol), bis (4-biphenylyl) amino (3.48g, 10.83mmol), bis (dibenzylideneacetone) palladium (0) (0.19g, 0.32mmol), sodium trifluorobutoxide (2g, 21.65mmol), xylene (40ml), tributylphosphine (0.17g, 0.86 mmol) was refluxed under nitrogen atmosphere, and the reaction was monitored by thin layer chromatography. After completion of the reaction, the reaction mixture was quenched with water (30mL) and extracted with ethyl acetate (50mL), the organic layer was extracted with water (3 × 30mL) and dried over anhydrous sodium sulfate. The collected ethyl acetate layer was further purified by celite column chromatography. Subsequently, the ethyl acetate layer was evaporated to dryness under vacuum using a rotary evaporator to obtain 3.0g of compound 1-32 (50%) as a yellow solid with an HPLC purity of over 99%.

The melting point of the compounds 1-32 is 191.22 ℃ and the glass transition temperature is 93.21 ℃.

1H NMR(CDCl₃,δ)：8.18-8.10(m,2H)；7.82-7.78(m,1H)；7.62-7.49(m,6H)；7.48-7.38(m, 11H)；7.34-7.22(m,9H)。

Synthesis example 10

In a 250mL flask, a mixture of 4- (3' -bromophenyl) dibenzothiophene (5g), N- (4-biphenyl) - (9, 9-dimethylfluoren-2-yl) amino (6.39g), bis (dibenzylideneacetone) palladium (0) (0.29g), sodium tributoxide (3.27g), toluene (95mL), and tris (tributyl) phosphine (0.28g) was refluxed under a nitrogen atmosphere, and the reaction was monitored by thin layer chromatography. After completion of the reaction, the reaction mixture was quenched with water (50mL) and extracted with ethyl acetate (70mL), the organic layer was extracted with water (3 × 50mL) and dried over anhydrous sodium sulfate. The collected ethyl acetate layer was further purified by celite column chromatography. Subsequently, the ethyl acetate layer was evaporated to dryness under vacuum using a rotary evaporator to obtain 3.0g of compound 1-40 (32%) with HPLC purity of over 99% as a yellow solid.

The melting point of the compounds 1-40 is 202.82 ℃ and the glass transition temperature is 107.65 ℃.

1H NMR(CDCl₃,δ)：7.77-7.43(m,1H)；7.68-7.62(m,3H)；7.62-7.58(m,3H)；7.55-7.47(m,5H)； 7.46-7.23(m,20H)；7.20-7.16(m,1H)。

Synthesis example 11

A mixture of 4- (3' -bromophenyl) dibenzofuran (2.7g), bis (4-biphenyl) amino (3.1g), bis (dibenzylideneacetone) palladium (0) (0.14g), sodium tert-butoxide (1.6g), xylene (40ml) and tributylphosphine (0.13g) was refluxed under a nitrogen atmosphere, and the reaction was monitored by thin layer chromatography. After completion of the reaction, the reaction mixture was quenched with water (30mL) and extracted with ethyl acetate (50mL), the organic layer was extracted with water (3 × 30mL) and dried over anhydrous sodium sulfate. The collected ethyl acetate layer was further purified by celite column chromatography. The ethyl acetate layer was then evaporated to dryness under vacuum using a rotary evaporator, the residue was further precipitated by addition of 200mL of methanol, filtered and dried under vacuum. 3g of compounds 1-43 (63%) are obtained in a yellow solid with an HPLC purity of more than 99%.

The melting point of compounds 1-43 is 177 ℃ and the glass transition temperature is 86.8 ℃.

1H NMR(CDCl₃,δ)：7.97-7.94(d,1H)；7.92-7.88(m,1H)；7.77-7.74(t,1H)；7.64-7.54(m,10H)； 7.51-7.30(m,15H)；7.30-7.26(m,1H)。

Synthesis example 12

A mixture of 4- (3' -bromophenyl) dibenzo [ b, d ] thiophene (2.6g), N1- (naphthalen-1-yl) -N4, N4-diphenylphenyl-1, 4-diamine (3.55g), bis (dibenzylideneacetone) palladium (0) (0.15g), sodium t-butoxide (1.7g), toluene (50mL), tributylphosphine (0.14g) was refluxed under a nitrogen atmosphere, and the reaction was monitored by thin layer chromatography. After completion of the reaction, the reaction mixture was quenched with water (30mL) and extracted with ethyl acetate (50mL), the organic layer was extracted with water (3 × 30mL) and dried over anhydrous sodium sulfate. The collected ethyl acetate layer was further purified by celite column chromatography. The ethyl acetate layer was then evaporated to dryness under vacuum using a rotary evaporator, the residue was further precipitated by addition of 200mL of methanol, filtered and dried under vacuum. 2g of compounds 1-51 (40%) are obtained in a yellow solid with an HPLC purity of more than 99%.

The melting point of the compounds 1-51 is 167.01 ℃ and the glass transition temperature is 99.93 ℃.

1H NMR(CDCl₃,δ)：8.14-8.06(m,7H)；7.93-7.90(d,3H)；7.71-7.73(m,1H)；7.68-7.62(t,2H)； 7.62-7.58(m,2H)；7.55-7.47(m,4H)；7.46-7.67(m,3H)；7.52-7.39(m,19H)。

A triazine derivative of formula (II):

in one embodiment, the A₁Represents a substituted or unsubstituted C6-C20 arylene group, examples of which include, but are not limited to, phenylene, naphthylene, anthrylene, biphenylene, phenanthrylene, fluorenylene, and the like.

In another embodiment, the A₁Represents a substituted or unsubstituted C3-20 heteroarylene group containing at least one heteroatom selected from the group consisting of N, O, and S, examples of which include, but are not limited to, pyridylene, pyrazinylene, pyrimidinyl, pyridazinylene, indolyl, indazolylene, carbazolyl, thiazolyl, thiophenylene, furanylene, and the like.

In one embodiment, Y of the triazine derivative of formula (II) may be bonded to A₁At any one of the positions.

In one embodiment, A of the triazine derivative of formula (II)₁Are all the same, Y is all the same and is bonded to A₁The same applies to the position of (2).

In one embodiment, the A₁Are both biphenylene or phenylene.

In another embodiment, A of the triazine derivative of formula (II)₁When all are phenylene, and Y is bonded to A with respect to the triazine ring₁The neutral position.

Preferred embodiments of the triazine derivatives of formula (II) are selected from Table 2, but are not limited thereto.

TABLE 2

Synthetic procedures for triazine derivatives of formula (II) are disclosed in Taiwan patent No. I501959, which is also incorporated herein by reference in its entirety.

In the organic light emitting device capable of generating a light emitting exciplex of the present invention, the thickness of the light emitting layer is 200 to 300 angstroms; wherein the light-emitting layer can be composed of the heterocyclic compound of formula (I) and the triazine derivative of formula (II) alone, or the heterocyclic compound of formula (I) and the triazine derivative of formula (II) can be used as light-emitting hosts and combined with other guest light-emitting bodies.

In one embodiment, the light-emitting layer of the organic light-emitting device capable of generating light-emitting exciplex of the present invention further comprises a guest light-emitting body.

In one embodiment, the guest emitters of the organic light emitting device capable of generating an exciplex are phosphorescent dopants, and the heterocyclic compound of formula (I) and the triazine derivative of formula (II) are used as light emitting host materials, so that the energy of singlet state and triplet state is completely transferred to the phosphorescent dopants, and the charge injection barrier is greatly reduced.

In the organic light emitting device capable of generating the light emitting exciplex of the present invention, the content of the phosphorescent dopant in the light emitting layer is 1 wt% to 5 wt%, which is less than the doping addition amount in the prior art, and is more favorable for reducing the preparation cost. Wherein the content of the phosphorescent dopant in the light-emitting layer is preferably 1 wt% to 3 wt%.

In one embodiment, the light-emitting layer of the organic light-emitting device capable of generating light-emitting exciplex of the present invention emits red light.

In another embodiment, the phosphorescent dopant comprises an organometallic complex of at least one metal selected from the group consisting of ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum, and gold.

In yet another embodiment, the phosphorescent dopant (PER) is tris [ 1-phenylisoquinoline-C2, N]Iridium (III))(Ir(piq)₃) The structure of the compound is shown as the following formula (3-1):

in the organic light emitting device capable of generating light emitting exciplex of the present invention, in addition to the light emitting layer, at least one hole auxiliary layer formed between the anode and the light emitting layer is further included. The material of the hole auxiliary layer can be selected from common materials, and the common material for the hole auxiliary layer includes at least one selected from the group consisting of triazole derivatives, oxadiazole derivatives, imidazole derivatives, phenylenediamine derivatives, star-like polyamine derivatives, spiro-linked molecule derivatives, and arylamine derivatives.

In one embodiment, the hole-assist layer excludes the heterocyclic compound of formula (I), and the light-emitting layer provided by the technical means of the present invention can be used to optimize and enhance the performance of the light-emitting device.

In the organic light emitting device capable of generating light emitting exciplex of the present invention, at least one electron assist layer formed between the light emitting layer and the cathode may be further included. The material of the electron-assist layer can be selected from common materials, and the common materials for the electron-injection layer include alkali metal halides or alkali metal chelates containing nitrogen and oxygen, such as: LiF, 8-quinonolato lithium (Liq); conventional electron transport layer materials include one selected from the group consisting of organic alkali/alkaline earth metal complexes, oxides, halides, carbonates and alkali/alkaline earth metal phosphates containing at least one metal selected from lithium and cesium.

In one embodiment, the electron-assist layer excludes the use of the triazine derivative of formula (II), and the light-emitting layer provided by the technical means of the present invention can be used to optimize and enhance the performance of the light-emitting device.

The hole auxiliary layer can be a hole injection layer, a hole transmission layer or an electron blocking layer; similarly, the electron-assist layer can also be an electron injection layer, an electron transport layer or a hole blocking layer.

The structure of the organic light emitting device of the present invention will be described with reference to the drawings.

Fig. 1 is a schematic cross-sectional view of an embodiment of an organic light emitting device 100 according to the present invention, which includes a substrate 110, an anode 120, a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, an electron transport layer 160, an electron injection layer 170, and a cathode 180. The organic light emitting device 100 may be fabricated by sequentially depositing the above layers.

FIG. 2 is a schematic cross-sectional view of another embodiment of an organic light emitting device of the present invention. The organic light emitting device 200 includes a substrate 210, an anode 220, a hole injection layer 230, a hole transport layer 240, an electron blocking layer 245, a light emitting layer 250, an electron transport layer 260, an electron injection layer 270, and a cathode 280, and differs from fig. 1 in that the electron blocking layer 245 is disposed between the hole transport layer 240 and the light emitting layer 250.

FIG. 3 is a schematic cross-sectional view of another embodiment of an organic light emitting device of the present invention. The organic light emitting device 300 includes a substrate 310, an anode 320, a hole injection layer 330, a hole transport layer 340, a light emitting layer 350, a hole blocking layer 355, an electron transport layer 360, an electron injection layer 370, and a cathode 380, and is different from fig. 1 in that the hole blocking layer 355 is disposed between the light emitting layer 350 and the electron transport layer 360.

The organic light emitting device of the structure shown in the above figures can be fabricated in reverse, in which one or more layers can be added or removed as desired.

The anode is a metal or conductive compound with high work function, and common materials can be selected from transparent metal oxides such as: ITO, IZO, SnO₂ZnO, or a substrate such as poly-Si, a-Si, etc., U.S. Pat. No. 5844363, the entire contents of which are incorporated herein by reference, discloses a flexible transparent substrate incorporating an anode.

The cathode is a metal or conductive compound with low work function, and can be selected from commonly used materials including Au, Al, In, Mg, Ca or similar metals, alloys, etc., and the cathodes exemplified In us patent nos. 5703436 and 5707745, which are incorporated herein In their entirety, have a thin metal layer, such as: magnesium/silver (Mg: Ag), and a transparent conductive Layer (ITO Layer) deposited by sputtering covering the metal thin Layer.

In addition, at least one of the electrodes is transparent or semitransparent to facilitate the transmission of the emitted light.

Structures and materials not specifically described may also be used in the present invention, such as organic light emitting devices including polymer materials (PLEDs) as disclosed in U.S. Pat. No. 5247190, which is incorporated herein by reference in its entirety. As exemplified in U.S. patent No. 20030230980, an n-type doped electron transport layer is formed by mixing an electron transport material having a molar ratio of 1: doping of lithium in BPhen, the entire contents of which are incorporated herein by reference. The application and principles of each barrier layer disclosed in U.S. patent nos. 6097147 and 20030230980 are incorporated herein by reference in their entirety. The implant layer and the protection layer described in the same patent 20040174116 are incorporated by reference in their entirety.

Unless otherwise specified, any of the layers in the various embodiments may be deposited using any suitable method. For organic layers, preferred methods include thermal evaporation and jet printing as disclosed in U.S. Pat. Nos. 6013982 and 6087196, the entire contents of which are incorporated herein by reference; the organic vapor deposition (OVPD) method disclosed in U.S. patent No. 6337102, which is incorporated herein by reference in its entirety; U.S. Pat. No. 10/233470 discloses an Organic Vapor Jet Printing (OVJP) method, the entire contents of which are incorporated herein by reference. Other suitable methods include spin coating and solution-based processes. The solution-based process is preferably carried out in a nitrogen or inert gas environment. For other layers, preferred methods include thermal evaporation. Preferred patterning methods include processes such as cold welding by masked deposition as disclosed in U.S. patent nos. 6294398 and 6468819, and processes that integrate jet printing or organic vapor jet printing deposition with patterning, the entire contents of which are incorporated herein by reference. Of course, other methods may be used. The materials used for deposition may be tailored to the deposition process for which they are used.

The organic light emitting device of the present invention can be applied to a single component, and the structure thereof is an array configuration or an array of components having a cathode and an anode in X-Y coordinates. Compared with the conventional component, the invention can obviously improve the service life and the driving stability of the organic light-emitting device.

The following examples are provided to illustrate the various features and effects of the present invention. The detailed description is to be construed as merely illustrative of the invention and not limitative of the invention to the particular embodiments shown.