阅读说明：本技术 稠环化合物及制备方法和应用及共主体材料、发光组合物、发光器件、照明设备和显示设备 (Condensed ring compound, preparation method and application thereof, co-host material, light-emitting composition, light-emitting device, lighting device and display device ) 是由 夏清华 李洪泊 于飞玲 杭晓春 于 2020-03-16 设计创作，主要内容包括：本发明公开了具有式1或式2所示结构的稠环化合物及其制备方法和应用、含有该稠环化合物的共主体材料和发光组合物、含有所述稠环化合物的发光器件以及含有所述发光器件的照明设备和显示设备。本发明的稠环化合物具有提高的电子传输性能,采用该稠环化合物的发光器件显示出提高的量子效率,能更好地实现载流子的传输平衡,并且该稠环化合物具有较好的溶解性和稳定性,采用简单的器件结构就可以制备高效率的红光器件,可以用作白光照明或者OLEDs显示设备。(The invention discloses a condensed ring compound with a structure shown in formula 1 or formula 2, a preparation method and application thereof, a co-host material and a luminescent composition containing the condensed ring compound, a luminescent device containing the condensed ring compound, and an illumination device and a display device containing the luminescent device. The condensed ring compound of the present invention has improved electron transport properties, and a light emitting device using the condensed ring compound exhibits improved quantum efficiency, can better achieve transport balance of carriers, and has better electron transport propertiesThe solubility and stability of the organic electroluminescent device are improved, and the high-efficiency red light device can be prepared by adopting a simple device structure and can be used as white light illumination or OLED display equipment.)

1. A fused ring compound having a structure represented by formula 1 or a structure represented by formula 2:

in formula 1, Ar₁、Ar₂、Ar₃And Ar₄The same or different, each independently is aryl or substituted aryl;

in formula 2, Ar₁₁、Ar₂₂、Ar₃₃And Ar₄₄The same or different, each independently is an aryl group or a substituted aryl group.

2. The fused ring compound according to claim 1, wherein, in formula 1, Ar₁、Ar₂、Ar₃And Ar₄Are each aryl, preferably phenyl; in formula 2, Ar₁₁、Ar₂₂、Ar₃₃And Ar₄₄Are each aryl, preferably phenyl; or

In formula 1, Ar₁And Ar₄Is aryl, preferably phenyl, Ar₂And Ar₃Is alkylaryl, preferably C₁-C₅An alkyl-substituted aryl group, an aryl group substituted with an alkyl group,more preferably an alkylphenyl group, and still more preferably C₁-C₅Alkyl-substituted phenyl, more preferably o-tolyl, m-tolyl or p-tolyl, particularly preferably m-tolyl; in formula 2, Ar₁₁And Ar₄₄Is aryl, preferably phenyl, Ar₂₂And Ar₃₃Is alkylaryl, preferably C₁-C₅Alkyl-substituted aryl, more preferably alkylphenyl, and still more preferably C₁-C₅The alkyl-substituted phenyl group is more preferably an o-tolyl group, an m-tolyl group or a p-tolyl group, and particularly preferably an m-tolyl group.

3. The fused ring compound according to claim 1, wherein the fused ring compound is a compound represented by formula 2, wherein Ar is Ar in formula 2₁₁、Ar₂₂And Ar₃₃Identical or different, are each independently alkyl-substituted aryl, preferably C₁-C₅Alkyl-substituted aryl, more preferably alkylphenyl, and still more preferably C₁-C₅Alkyl-substituted phenyl, more preferably o-tolyl, m-tolyl or p-tolyl, particularly preferably m-tolyl; ar (Ar)₄₄Aryl, preferably phenyl.

4. The fused ring compound according to claim 1, wherein the fused ring compound is a compound represented by formula 2, wherein Ar is Ar in formula 2₁₁、Ar₂₂、Ar₃₃And Ar₄₄Identical or different, are each independently alkyl-substituted aryl, preferably C₁-C₅Alkyl-substituted aryl, more preferably alkylphenyl, and still more preferably C₁-C₅The alkyl-substituted phenyl group is more preferably an o-tolyl group, an m-tolyl group or a p-tolyl group, and particularly preferably an m-tolyl group.

5. The fused ring compound according to claim 1, wherein the fused ring compound is one or more selected from the group consisting of compounds 1 to 15:

6. a method of preparing a fused ring compound, the method comprising:

s1, under the condition of nucleophilic addition reaction, contacting aryl ketone with phenyl quinoline to obtain an intermediate product;

s2, carrying out cyclization reaction on the intermediate product to obtain the condensed ring compound, wherein the condensed ring compound has a structure shown in a formula 1 or a structure shown in a formula 2,

the aryl ketone has a structure represented by formula 3 or a structure represented by formula 4,

the phenylquinoline has a structure shown in a formula 5,

in formula 5, X₁Is a halogen atom, and is a halogen atom,

the intermediate product has a structure represented by formula 6 or a structure represented by formula 7,

in formula 1, formula 3 and formula 6, Ar₁、Ar₂、Ar₃And Ar₄The same or different, each independently is aryl or substituted aryl;

in formula 2, formula 4 and formula 7, Ar₁₁、Ar₂₂、Ar₃₃And Ar₄₄The same or different, each independently is an aryl group or a substituted aryl group.

7. The method of claim 6, wherein in step S1, the molar ratio of aryl ketone to phenyl quinoline is 1: 0.8-1.2, the temperature of the contact of the aryl ketone with the phenyl quinoline is from-50 ℃ to-85 ℃, the duration of the contact is from 1 to 4 hours, the contact is carried out in the presence of an alkyl lithium, the molar ratio of the alkyl lithium to the aryl ketone is from 1 to 1.3: preferably, the alkyl lithium is butyl lithium.

8. A method of preparing a fused ring compound, the method comprising:

s1', under the condition of nucleophilic addition reaction, contacting the quinoline derivative with halogenated aromatic hydrocarbon to obtain an intermediate product;

s2', carrying out cyclization reaction on the intermediate product to obtain the condensed ring compound, wherein the condensed ring compound has a structure shown in a formula 2,

the quinoline derivative has a structure shown in a formula 11,

the halogenated aromatic hydrocarbon has a structure shown in formula 12,

in formula 12, X₂Is a halogen atom, and is a halogen atom,

the intermediate product has a structure represented by formula 13,

in formula 2, formula 12 and formula 13, Ar₁₁、Ar₂₂、Ar₃₃And Ar₄₄The same or different, each independently is an aryl group or a substituted aryl group.

9. The process of claim 8, wherein in step S1', the molar ratio of quinoline derivative to halogenated aromatic hydrocarbon is 1: 0.8-1.2, the contact temperature of the quinoline derivative with the halogenated aromatic hydrocarbon is-50 ℃ to-85 ℃, the duration of the contact is 1-4 hours, the contact is carried out in the presence of alkyl lithium, and the molar ratio of the alkyl lithium to the quinoline derivative is 1-1.3: preferably, the alkyl lithium is butyl lithium.

10. The process according to claim 6 or 8, wherein in steps S2 and S2', the cyclization reaction is carried out at a temperature of 40-70 ℃, the duration of the cyclization reaction is 5-6 hours, the cyclization reaction is carried out in the presence of a catalyst, the catalyst is an organic acid and/or an inorganic acid, preferably one or more selected from the group consisting of trifluoromethanesulfonic acid, polyphosphoric acid, trifluoroacetic acid, hydrochloric acid and acetic acid, and the molar ratio of the catalyst to the intermediate product is preferably 80-300: 1.

11. use of the fused ring compound according to any one of claims 1 to 5 or the fused ring compound produced by the method according to any one of claims 6 to 10 as an organic photoelectric material.

12. The use according to claim 11, wherein the fused ring compound is used as a host material or an electron transport material for an organic light emitting device.

13. Use of a fused ring compound according to any one of claims 1 to 5 or a fused ring compound prepared by a process according to any one of claims 6 to 10 in a lighting device or a display device.

14. A co-host material comprising an electron-transporting material and a hole-transporting material, wherein the electron-transporting material is a fused ring compound according to any one of claims 1 to 5 or a fused ring compound prepared by a process according to any one of claims 6 to 10.

15. A co-host material according to claim 14, wherein the hole transport material is one or more of [ N, N ' -bis (1-naphthyl) -N, N ' -diphenyl ] - (1,1 ' -biphenyl) -4,4 ' -diamine, 1, 3-bis (9H-carbazol-9-yl) benzene, 4 ', 4 ″ -tris (carbazol-9-yl) triphenylamine, 4 ', 4 ″ -tris [ phenyl (m-tolyl) amino ] triphenylamine, and 4,4 ' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline ].

16. A co-host material according to claim 14 or 15, wherein the mass ratio of the electron-transporting material to the hole-transporting material is from 1-3.5: 1, preferably 1 to 1.5: 1, more preferably 1-1.2: 1.

17. a light-emitting composition comprising a light-emitting material and the condensed ring compound according to any one of claims 1 to 5 or the condensed ring compound produced by the method according to any one of claims 6 to 10.

18. The composition of claim 17, wherein the composition further comprises a hole transport material;

preferably, the mass ratio of the light-emitting material, the condensed ring compound, and the hole-transporting material is 1: 2-7: 2-7, preferably 1: 3-6: 3-6, more preferably 1: 4-5: 4-5.

19. A composition according to claim 17, wherein the composition comprises a co-host material as claimed in any one of claims 14 to 16.

20. The composition of any one of claims 17-19, wherein the luminescent material is one or more of a red phosphorescent material, a green phosphorescent material, and a yellow phosphorescent material;

preferably, the luminescent material is one or more than two of a red iridium complex phosphorescent material, a green iridium complex phosphorescent material and a yellow iridium complex phosphorescent material;

more preferably, the light-emitting material is one or two or more of bis [2- (3, 5-dimethylphenyl) isoquinolyl ] (2, 8-dimethyl-4, 6-nonadianionic group) iridium, bis (2-phenylpyridine) iridium acetylacetonate, tris (1-phenyl-isoquinoline) iridium, bis (1-phenyl-isoquinoline) (acetylacetonate) iridium, and tris (2-phenylpyridine) iridium.

21. A light-emitting device comprising a cathode layer, an anode layer and at least one light-emitting layer disposed between said cathode layer and said anode layer, wherein said light-emitting layer comprises a fused ring compound according to any one of claims 1 to 5 or a fused ring compound prepared by a method according to any one of claims 6 to 10.

22. The light-emitting device according to claim 21, wherein the light-emitting layer contains the co-host material according to any one of claims 14 to 16.

23. The light-emitting device according to claim 21, wherein the light-emitting layer is formed from the composition of any one of claims 17 to 20.

24. The light-emitting device according to any one of claims 21 to 23, further comprising a hole transport layer and/or an electron transport layer, the hole transport layer being disposed between the anode layer and the light-emitting layer, the electron transport layer being disposed between the cathode layer and the light-emitting layer;

preferably, the hole transport layer contains one or more of polyethylene dioxythiophene, polystyrene sulfonate, [ N, N ' -bis (1-naphthyl) -N, N ' -diphenyl ] - (1,1 ' -biphenyl) -4,4 ' -diamine, [ N, N ' -diphenyl-N, N ' -bis (3-methylphenyl) ] - (1,1 ' -biphenyl) -4,4 ' -diamine, and 4,4 ' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline ];

preferably, the electron transport layer contains one or more of 2,4, 6-tris [3- (diphenylphosphinyloxy) phenyl ] -1,3, 5-triazole, 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene, 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthroline, and 4, 7-diphenyl-1, 10-phenanthroline;

preferably, the hole transport layer and the electron transport layer are the same or different in thickness, each independently from 30 to 50nm, preferably from 35 to 45nm, more preferably from 40 to 45 nm.

25. The light emitting device of any one of claims 21-24, wherein the anode layer comprises indium tin oxide, the cathode layer comprises a LiF layer and an Al layer, the LiF layer being between the light emitting layer and the Al layer;

preferably, the anode layer has a thickness of 120-180nm, the light-emitting layer has a thickness of 30-50nm, preferably 35-45nm, more preferably 40-45nm, the LiF layer in the cathode layer has a thickness of 0.5-2nm, and the Al layer has a thickness of 80-150 nm.

26. A lighting device comprising the light emitting device of any one of claims 21-25.

27. A display device comprising the light-emitting device according to any one of claims 21 to 25.

Technical Field

The invention relates to a condensed ring compound, a preparation method and application thereof, a co-host material and a luminescent composition containing the condensed ring compound, a luminescent device containing the condensed ring compound, and a lighting device and a display device containing the luminescent device.

Background

Organic Light Emitting Diodes (OLEDs) have many advantages as self-light emitting devices, such as ultra-wide viewing angles, high contrast ratios, fast response, excellent brightness, and low turn-on voltages. At the same time, these advantages make flexible multi-color flat panel displays possible.

OLEDs emit photons by recombination of holes injected from the anode and electrons injected from the cathode in the light emitting layer. The light-emitting layer is usually formed by uniformly distributing a dopant (also referred to as an emitter) in a host material having a large band gap.

The problem of unbalanced carrier transport is common in the OLEDs. For example, the mobility of electrons in the electron transport layer is as low as 1-2 orders of magnitude lower than the mobility of holes in the hole transport layer. The imbalance of electron/hole transport results in increased turn-on voltage and reduced lifetime of phosphorescent OLEDs. Therefore, materials having high electron transport properties are still a hot spot of research.

Disclosure of Invention

The invention aims to solve the problem of unbalanced carrier transmission of an organic light-emitting diode and provide an electron transmission material with high electron transmission performance.

According to a first aspect of the present invention, there is provided a fused ring compound having a structure represented by formula 1 or a structure represented by formula 2:

in formula 1, Ar₁、Ar₂、Ar₃And Ar₄The same or different, each independently is aryl or substituted aryl;

in formula 2, Ar₁₁、Ar₂₂、Ar₃₃And Ar₄₄The same or different, each independently is an aryl group or a substituted aryl group.

According to a second aspect of the present invention, there is provided a process for the preparation of a fused ring compound, which comprises:

s1, under the condition of nucleophilic addition reaction, contacting aryl ketone with phenyl quinoline to obtain an intermediate product;

s2, carrying out cyclization reaction on the intermediate product to obtain the condensed ring compound, wherein the condensed ring compound has a structure shown in a formula 1 or a structure shown in a formula 2,

the aryl ketone has a structure represented by formula 3 or a structure represented by formula 4,

the phenylquinoline has a structure shown in a formula 5,

in formula 5, X₁Is a halogen atom, and is a halogen atom,

the intermediate product has a structure represented by formula 6 or a structure represented by formula 7,

in formula 1, formula 3 and formula 6, Ar₁、Ar₂、Ar₃And Ar₄The same or different, each independently is aryl or substituted aryl;

in formula 2, formula 4 and formula 7, Ar₁₁、Ar₂₂、Ar₃₃And Ar₄₄The same or different, each independently is an aryl group or a substituted aryl group.

According to a third aspect of the invention. The present invention provides a method for producing a fused ring compound, which comprises:

s1', under the condition of nucleophilic addition reaction, contacting the quinoline derivative with halogenated aromatic hydrocarbon to obtain an intermediate product;

s2', carrying out cyclization reaction on the intermediate product to obtain the condensed ring compound, wherein the condensed ring compound has a structure shown in a formula 2,

the quinoline derivative has a structure shown in a formula 11,

the halogenated aromatic hydrocarbon has a structure shown in formula 12,

in formula 12, X₂Is a halogen atom, and is a halogen atom,

the intermediate product has a structure represented by formula 13,

in formula 2, formula 12 and formula 13, Ar₁₁、Ar₂₂、Ar₃₃And Ar₄₄The same or different, each independently is an aryl group or a substituted aryl group.

According to a fourth aspect of the present invention, there is provided use of the fused ring compound according to the first aspect described above or the fused ring compound produced by the method according to the second or third aspect described above as an organic photoelectric material.

According to a fifth aspect of the present invention, there is provided the use of a fused ring compound as described in the first aspect above or a fused ring compound produced by a process as described in the second or third aspect above in a lighting device or display device.

According to a sixth aspect of the present invention, there is provided a co-host material comprising an electron-transporting material and a hole-transporting material, wherein the electron-transporting material is a fused ring compound according to the first aspect of the present invention or a fused ring compound prepared by a method according to the second or third aspect of the present invention.

According to a seventh aspect of the present invention, there is provided a light-emitting composition comprising a light-emitting material and a fused ring compound according to the first aspect of the present invention or a fused ring compound produced by a method according to the second or third aspect of the present invention.

According to an eighth aspect of the present invention, there is provided a light-emitting device comprising a cathode layer, an anode layer and at least one organic layer disposed between the cathode layer and the anode layer, wherein the light-emitting layer contains the condensed ring compound according to the first aspect of the present invention or the condensed ring compound produced by the method according to the second aspect or the third aspect of the present invention.

According to a ninth aspect of the present invention, there is provided a lighting device comprising the light emitting device according to the eighth aspect of the present invention.

According to a tenth aspect of the present invention, there is provided a display apparatus comprising the light emitting device according to the eighth aspect of the present invention.

The condensed ring compound according to the present invention has improved electron transport properties, and a light emitting device using the condensed ring compound exhibits improved quantum efficiency, enabling better balance of transport of carriers.

The fused ring compounds according to the present invention also have the following advantages:

(1) the composite material has better solubility and stability, and has advantages in the preparation of displays by a wet method;

(2) the red light device with high efficiency can be prepared by adopting a simple device structure, and thus, the red light device can be used as white light illumination or OLED display equipment.

Drawings

FIG. 1 shows the hydrogen nuclear magnetic resonance of Compound 5: (¹H NMR) spectrum.

FIG. 2 is a mass spectrum of Compound 5.

Figure 3 is a photoluminescence spectrum of compound 5.

FIG. 4 is a cyclic voltammogram of Compound 5.

FIG. 5 shows the hydrogen nuclear magnetic resonance of Compound 4: (¹H NMR) spectrum.

FIG. 6 is a mass spectrum of Compound 4.

FIG. 7 is a photoluminescence spectrum of Compound 4.

Fig. 8 is a schematic cross-sectional structure of a device in which a compound 5 and NPB are co-host doped with 10 wt% of a red phosphorescent material ir (mpiq) divm and fabricated into an OLEDs device.

FIG. 9 is a photoluminescence spectrum of compound 5, NPB and a thin film blend of compound 5 and NPB.

FIG. 10 is a diagram showing the electroluminescence spectrum of a thin film formed by doping a compound 5 and NPB co-host with 10 wt% of a red phosphorescent material Ir (mpiq) divm.

FIG. 11 is an electroluminescence spectrum of a device prepared by doping 10 wt% of a red phosphorescent material Ir (mpiq) divm into a co-host of compound 5 and NPB.

Fig. 12 is a current density-voltage diagram of light emitting devices made from compound 5 and comparative compound 1, respectively, co-host doped with NPB with 10 wt% of red phosphorescent light emitting material ir (mpiq) divm.

Fig. 13 is a graph of luminance vs. voltage for light emitting devices made with compound 5 and comparative compound 1, respectively, co-host doped with 10 wt% red phosphorescent light emitting material ir (mpiq) divm.

Fig. 14 is a graph of current efficiency for light emitting devices made from compound 5 and comparative compound 1, respectively, co-host doped with NPB with 10 wt% of red phosphorescent light emitting material ir (mpiq) divm.

Fig. 15 is a graph of the power efficiency of light emitting devices made from compound 5 and comparative compound 1, respectively, co-host doped with NPB with 10 wt% of red phosphorescent light emitting material ir (mpiq) divm.

FIG. 16 is a graph of the external quantum efficiency of a light emitting device made by co-host doping of compound 5 with NPB with 10 wt% of a red phosphorescent light emitting material Ir (mpiq) divm.

Fig. 17 is a photoluminescence spectrum of compound 4 doped with 5 wt% phosphorescent material.

Detailed Description

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

According to a first aspect of the present invention, there is provided a fused ring compound having a structure represented by formula 1 or a structure represented by formula 2:

in formula 1, Ar₁、Ar₂、Ar₃And Ar₄The same or different, each independently is aryl or substituted aryl;

in formula 2, Ar₁₁、Ar₂₂、Ar₃₃And Ar₄₄The same or different, each independently is an aryl group or a substituted aryl group.

In the present invention, the aryl group means an aryl group in which none of the hydrogens on the aromatic ring in the aryl group is substituted with a substituent, and may be C₆-C₁₈Aryl of (2), for example phenyl. In the present invention, a substituted aryl group means an aryl group in which at least one hydrogen on at least one aromatic ring in the aryl group is substituted with a substituent.

Preferably, Ar₁、Ar₂、Ar₃、Ar₄、Ar₁₁、Ar₂₂、Ar₃₃And Ar₄₄The same or different, each independently is an aryl group or an alkyl-substituted aryl group. More preferably, Ar₁、Ar₂、Ar₃、Ar₄、Ar₁₁、Ar₂₂、Ar₃₃And Ar₄₄Identical or different, each independently is aryl or C₁-C₅Alkyl-substituted aryl. In the present invention, C₁-C₅The alkyl group comprising C₁-C₅Straight chain alkyl of (2) and C₃-C₅Specific examples thereof may include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 2-methylbutyl, 3-methylbutyl and 2, 2-dimethylpropyl. Further preferably, Ar₁、Ar₂、Ar₃、Ar₄、Ar₁₁、Ar₂₂、Ar₃₃And Ar₄₄Identical or different, each independently is phenyl or C₁-C₅Alkyl substitutedA phenyl group. Even more preferably, Ar₁、Ar₂、Ar₃、Ar₄、Ar₁₁、Ar₂₂、Ar₃₃And Ar₄₄The same or different, each independently is phenyl, o-tolyl, m-tolyl, or p-tolyl.

In a preferred embodiment, the fused ring compound has a structure represented by formula 1 or a structure represented by formula 2, wherein in formula 1, Ar₁、Ar₂、Ar₃And Ar₄Are each aryl, preferably phenyl; in formula 2, Ar₁₁、Ar₂₂、Ar₃₃And Ar₄₄Are each aryl, preferably phenyl. The light-emitting device including the condensed ring compound of the preferred embodiment has higher quantum efficiency.

In another preferred embodiment, the fused ring compound has a structure represented by formula 1 or a structure represented by formula 2, wherein in formula 1, Ar₁And Ar₄Is aryl, preferably phenyl, Ar₂And Ar₃Is alkylaryl, preferably C₁-C₅Alkyl-substituted aryl, more preferably alkylphenyl, and still more preferably C₁-C₅Alkyl-substituted phenyl, more preferably o-tolyl, m-tolyl or p-tolyl, particularly preferably m-tolyl; in formula 2, Ar₁₁And Ar₄₄Is aryl, preferably phenyl, Ar₂₂And Ar₃₃Is alkylaryl, preferably C₁-C₅Alkyl-substituted aryl, more preferably alkylphenyl, and still more preferably C₁-C₅The alkyl-substituted phenyl group is more preferably an o-tolyl group, an m-tolyl group or a p-tolyl group, and particularly preferably an m-tolyl group. The light-emitting device containing the fused ring compound according to the preferred embodiment shows higher quantum efficiency.

In still another preferred embodiment, the fused ring compound is a compound represented by formula 2, wherein Ar in formula 2₁₁、Ar₂₂And Ar₃₃Identical or different (preferably identical), each independently is an alkyl-substituted aryl radical, preferably C₁-C₅Alkyl-substituted aryl, more preferablyIs alkylphenyl, more preferably C₁-C₅Alkyl-substituted phenyl, more preferably o-tolyl, m-tolyl or p-tolyl, particularly preferably m-tolyl; ar (Ar)₄₄Aryl, preferably phenyl. The light-emitting device containing the condensed-cyclic compound according to this embodiment has higher quantum efficiency.

In another preferred embodiment, the fused ring compound is a compound represented by formula 2, wherein Ar is Ar in formula 2₁₁、Ar₂₂、Ar₃₃And Ar₄₄Identical or different (preferably identical), each independently is an alkyl-substituted aryl radical, preferably C₁-C₅Alkyl-substituted aryl, more preferably alkylphenyl, and still more preferably C₁-C₅The alkyl-substituted phenyl group is more preferably an o-tolyl group, an m-tolyl group or a p-tolyl group, and particularly preferably an m-tolyl group. The light-emitting device containing the condensed-cyclic compound according to this embodiment can achieve a better balance between the starting voltage and the quantum efficiency.

According to the fused ring compound of the present invention, the fused ring compound is preferably one or two or more selected from the group consisting of compounds 1 to 15:

the condensed ring compound is preferably compound 1, compound 2, compound 4, compound 5, or compound 8 from the viewpoint of further improving the quantum efficiency of the light-emitting device. More preferably, the condensed ring compounds are compounds 1 and 4, and the light emitting device containing compounds 1 and 4 has not only higher quantum efficiency but also lower starting voltage.

According to a second aspect of the present invention, there is provided a process for the preparation of a fused ring compound, which comprises:

s1, under the condition of nucleophilic addition reaction, contacting aryl ketone with phenyl quinoline to obtain an intermediate product;

s2, carrying out cyclization reaction on the intermediate product to obtain the condensed ring compound, wherein the condensed ring compound has a structure shown in a formula 1 or a structure shown in a formula 2,

in formulae 1 and 2, Ar₁、Ar₂、Ar₃、Ar₄、Ar₁₁、Ar₂₂、Ar₃₃And Ar₄₄The definitions of (a) and (b) have been described in detail above and are not described in detail herein.

According to the method of the second aspect of the present invention, the aryl ketone has a structure represented by formula 3 or a structure represented by formula 4,

ar in formula 3₁、Ar₂、Ar₃And Ar₄Is as defined for the corresponding group in formula 1, Ar in formula 4₁₁、Ar₂₂、Ar₃₃And Ar₄₄The definitions of (a) are the same as those of the corresponding groups in formula 2 and are not described in detail herein.

According to the method of the second aspect of the present invention, the phenylquinoline has a structure represented by formula 5,

in formula 5, X₁Is a halogen atom, preferably a bromine atom or an iodine atom.

According to the method of the second aspect of the present invention, the intermediate product has a structure represented by formula 6 or a structure represented by formula 7,

ar in formula 6₁、Ar₂、Ar₃And Ar₄Is as defined for the corresponding group in formula 1, Ar in formula 7₁₁、Ar₂₂、Ar₃₃And Ar₄₄The definitions of (a) are the same as those of the corresponding groups in formula 2 and are not described in detail herein.

In step S1, the molar ratio of aryl ketone to phenyl quinoline may be 1: 0.8 to 1.2, preferably 1: 0.85-1.1, more preferably 1: 0.9-1.05. The contact temperature of the aryl ketone and the phenyl quinoline may be from-50 ℃ to-85 ℃, preferably from-56 ℃ to-80 ℃, more preferably from-68 ℃ to-78 ℃. The duration of the contact may be from 1 to 4 hours, preferably from 1 to 2 hours.

In step S1, the contacting is performed in the presence of an alkyl lithium, and the molar ratio of the alkyl lithium to the aryl ketone may be 1 to 1.3: 1, preferably 1.05 to 1.25: 1. the alkyllithium is preferably butyllithium, more preferably one or two or more of n-butyllithium, isobutyllithium and tert-butyllithium, and still more preferably n-butyllithium.

According to the method of the second aspect of the present invention, after the contacting of step S1 is completed, the method further includes adding a quenching agent to the mixture obtained by the contacting, thereby terminating the reaction. The quenching agent can be one or more than two of ammonium salt, water, sodium salt and alcohol. The alcohol may be C₁-C₅One or more of the alcohols of (a), preferably one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol and tert-butanol. The ammonium and sodium salts are preferably provided in the form of aqueous solutions. Preferably, the quencher is an ammonium salt, more preferably ammonium chloride. The molar ratio of the quencher to the phenylquinoline can be from 10 to 60: 1, preferably 20 to 50: 1, more preferably 30 to 40: 1.

according to the method of the second aspect of the present invention, the mixture containing the intermediate product obtained by the contacting in step S1 may be separated and purified by a conventional method to obtain the intermediate product. In one embodiment, the mixture containing the intermediate product may be subjected to column chromatography to yield the intermediate product. The column chromatography separation can adopt a mixed solvent of petroleum ether and ethyl acetate as an eluent, and the volume ratio of the petroleum ether to the ethyl acetate can be 8-12: for example, petroleum ether (60 to 90 ℃): ethyl acetate 10: 1 (volume ratio) as eluent.

According to the process of the second aspect of the present invention, the aryl ketone is commercially available or can be synthesized by a method comprising the steps of: contacting a ketone compound represented by formula 8 with an aniline compound under coupling reaction conditions, wherein the aniline compound is a compound represented by formula 9 or a compound represented by formula 10,

ar in formula 9₁、Ar₂、Ar₃And Ar₄Is as defined for the corresponding group in formula 1, Ar in formula 10₁₁、Ar₂₂、Ar₃₃And Ar₄₄The definitions of (a) are the same as those of the corresponding groups in formula 2 and are not described in detail herein.

The ketone compound and the aniline compound may be reacted in the presence of a transition metal catalyst system comprising a palladium catalyst and a ligand. The palladium catalyst may be tris (dibenzylideneacetone) dipalladium (Pd)₂(dba)₃) Palladium acetate and tetrakis (triphenylphosphine) palladium, and the ligand may be 1, 1' -bis (diphenylphosphino) ferrocene (DPPF), triarylphosphine (for example: triphenylphosphine), trialkylphosphines (for example: tributylphosphine, preferably tri-tert-butylphosphine), 1 '-binaphthyl-2, 2' -Bisdiphenylphosphine (BINAP) and 2-dicyclohexylphosphine-2 ', 6' -dimethoxy-biphenyl (S-Phos). The dosage of the catalyst system is based on the catalytic function,wherein, in the catalyst system, the amount of the ligand can be selected according to the amount of the palladium catalyst, and generally, the molar ratio of the ligand to the palladium catalyst can be 1-2: 1, the palladium catalyst is calculated by palladium element.

The ketone compound and the aniline compound may be contacted at 100-110 deg.C, and the duration of the contact may be 18-24 hours.

The ketone compound and the aniline compound are preferably carried out in the presence of at least one base, which is preferably a sodium alkoxide, more preferably sodium tert-butoxide. The molar ratio of the base to the ketone compound may be 2 to 3: 1, preferably 2.2 to 2.6: 1.

the mixture obtained by contacting the ketone compound and the aniline compound can be separated and purified by a conventional method to obtain the aryl ketone. In one embodiment, the mixture resulting from the contacting may be subjected to column chromatography to provide the aryl ketone. The eluent used for the column chromatography separation can be one or more than two of Petroleum Ether (PE), Ethyl Acetate (EA) and dichloromethane, preferably a mixed solution of petroleum ether and ethyl acetate, wherein the volume ratio of the petroleum ether to the ethyl acetate is preferably 50-100: 1.

the ketone compound is commercially available, or can be synthesized by a method comprising the steps of: the method comprises the steps of firstly contacting 1, 3-dibromobenzene with alkyl lithium in at least one solvent, secondly contacting a mixture obtained by the contact with 3-bromobenzaldehyde, and finally carrying out oxidation reaction on the mixture obtained by the second contact. The alkyl lithium is preferably butyl lithium, more preferably n-butyl lithium. The molar ratio of the alkyl lithium to the 1, 3-dibromobenzene may be from 1 to 1.2: 1, preferably 1.02 to 1.1: 1. the molar ratio of the 3-bromobenzaldehyde to the 1, 3-dibromobenzene may be from 0.8 to 1.2: 1, preferably 0.9 to 1.1: 1. the solvent may be one or more of ether (preferably diethyl ether), tetrahydrofuran, cyclohexane and n-hexane. Preferably, the solvent is diethyl ether. The first contacting may be carried out at a temperature of-50 ℃ to-85 ℃, preferably at a temperature of-56 ℃ to-80 ℃, more preferably at a temperature of-68 ℃ to-78 ℃. The duration of the first contact may be from 0.1 to 1.5 hours, preferably from 0.2 to 1 hour. The second contacting may be carried out at ambient temperature, preferably at a temperature of from 10 to 30 c, more preferably at a temperature of from 15 to 25 c, and the contact time of the second contacting may be from 1.5 to 3 hours. The 3-bromobenzaldehyde is preferably added to the mixture obtained in the first contact at the first contact temperature. One or more of pyridinium dichromate, potassium permanganate and hydrogen peroxide can be used as an oxidizing agent in the oxidation reaction. The oxidation reaction may be carried out at ambient temperature, preferably at a temperature of from 10 to 30 c, more preferably at a temperature of from 15 to 25 c. The duration of the oxidation reaction may be 3-5 hours. The oxidizing agent is mixed with the product obtained by the second contacting, preferably at a temperature of-4 ℃ to 4 ℃.

According to the production method of the second aspect of the present invention, in step S2, the cyclization reaction may be carried out at a temperature of 40 to 70 ℃, preferably at a temperature of 50 to 60 ℃. The duration of the cyclization reaction may be 5-6 hours.

According to the method of the second aspect of the present invention, in step S2, the cyclization reaction is a Friedel-Crafts cyclization reaction. The cyclization reaction is carried out in the presence of a catalyst, wherein the catalyst can be an organic acid and/or an inorganic acid, preferably one or more selected from trifluoromethanesulfonic acid, polyphosphoric acid, trifluoroacetic acid, hydrochloric acid and acetic acid, and is preferably trifluoromethanesulfonic acid. The molar ratio of the catalyst to the intermediate product is preferably from 80 to 300: 1, more preferably 100-: 1, more preferably 140-: 1.

the mixture obtained by the cyclization reaction can be separated and purified by a conventional method to obtain a fused ring compound according to the present invention. In one embodiment, the mixture resulting from the cyclization reaction may be subjected to column chromatography to provide the fused ring compound. The eluent used for the column chromatography separation can be one or more than two of petroleum ether, ethyl acetate and dichloromethane, preferably a mixed solution of petroleum ether and ethyl acetate, and the volume ratio of the petroleum ether to the ethyl acetate is preferably 50-100: 1.

according to a third aspect of the present invention, there is provided a process for producing a fused ring compound, the process comprising:

s1', under the condition of nucleophilic addition reaction, contacting the quinoline derivative with halogenated aromatic hydrocarbon to obtain an intermediate product;

s2', carrying out cyclization reaction on the intermediate product to obtain the condensed ring compound, wherein the condensed ring compound has a structure shown in a formula 2,

the quinoline derivative has a structure shown in a formula 11,

the halogenated aromatic hydrocarbon has a structure shown in formula 12,

in formula 12, X₂Is a halogen atom, preferably a bromine atom or an iodine atom,

the intermediate product has a structure represented by formula 13,

ar in formula 12 and formula 13₁₁、Ar₂₂、Ar₃₃And Ar₄₄The definitions of (a) are the same as those of the corresponding groups in formula 2 and are not described in detail herein.

The reaction mechanism of the method according to the third aspect of the present invention is the same as that of the method according to the second aspect of the present invention, and therefore, the reaction conditions of step S1 'and step S2' of the method according to the third aspect of the present invention may be performed with reference to the reaction conditions described in the foregoing step S1 and step S2, for example: in step S1', the molar ratio of quinoline derivative to halogenated aromatic hydrocarbon is 1: 0.8-1.2, the contact temperature of the quinoline derivative with the halogenated aromatic hydrocarbon is-50 ℃ to-85 ℃, the duration of the contact is 1-4 hours, the contact is carried out in the presence of alkyl lithium, and the molar ratio of the alkyl lithium to the quinoline derivative is 1-1.3: preferably, the alkyl lithium is butyl lithium. The compounds represented by formula 11 and formula 12 according to the method of the third aspect of the present invention are commercially available or can be synthesized by conventional methods, and will not be described in detail herein.

According to a fourth aspect of the present invention, there is provided use of the fused ring compound according to the first aspect described above or the fused ring compound produced by the method according to the second or third aspect described above as an organic photoelectric material.

The fused ring compound according to the present invention has improved electron transport properties and is suitable as a host material and/or an electron transport material for an organic light-emitting device, for example, as a host material or an electron transport material for a light-emitting layer of an organic light-emitting device.

According to a fourth aspect of the present invention there is provided the use of a fused ring compound according to the first aspect of the present invention or a fused ring compound prepared by a process according to the second or third aspects of the present invention in a lighting device or display device. The illumination device may be a white light illumination device and the display device may be an OLEDs display device.

According to a fifth aspect of the present invention, there is provided a co-host material comprising an electron-transporting material and a hole-transporting material, wherein the electron-transporting material is a fused ring compound according to the first aspect of the present invention or a fused ring compound prepared by a method according to the second or third aspect of the present invention.

The hole transport material may be one or more of [ N, N ' -bis (1-naphthyl) -N, N ' -diphenyl ] - (1,1 ' -biphenyl) -4,4 ' -diamine (NPB), 1, 3-bis (9H-carbazol-9-yl) benzene, 4 ', 4 ″ -tris (carbazol-9-yl) triphenylamine, 4 ', 4 ″ -tris [ phenyl (m-tolyl) amino ] triphenylamine, and 4,4 ' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline ].

The mass ratio of the electron transport material to the hole transport material may be 1 to 3.5: 1, preferably 1 to 1.5: 1.

in a preferred embodiment, the hole transporting material is N, N '- [ di (1-naphthyl) -N, N' -diphenyl ] - (1,1 '-biphenyl) -4, 4' -diamine and the electron transporting material is a fused ring compound according to the first aspect of the present invention or a fused ring compound prepared by a method according to the second or third aspect of the present invention. According to this preferred embodiment, the mass ratio of the electron transport material to the hole transport material may be 1 to 3.5: 1, preferably 1 to 1.5: 1, more preferably 1-1.2: 1.

according to a sixth aspect of the present invention, there is provided a light-emitting composition comprising a light-emitting material and a fused ring compound according to the first aspect of the present invention or a fused ring compound produced by a method according to the second or third aspect of the present invention.

According to the light-emitting composition of the present invention, the light-emitting composition further contains a hole-transporting material. The mass ratio of the light-emitting material, the condensed ring compound, and the hole-transporting material may be 1: 2-7: 2-7, preferably 1: 3-6: 3-6, more preferably 1: 4-5: 4-5, particularly preferably 1: 4.5: 4.5.

in a preferred embodiment, the luminescent composition preferably comprises a co-host material, preferably the co-host material according to the fifth aspect of the present invention.

According to the light-emitting composition of the present invention, the light-emitting material may be one or more of a red phosphorescent material, a green phosphorescent material and a yellow phosphorescent material, and preferably one or more of a red iridium complex phosphorescent material, a green iridium complex phosphorescent material and a yellow iridium complex phosphorescent material. According to the light-emitting composition of the present invention, the light-emitting material is more preferably bis [2- (3, 5-dimethylphenyl) isoquinolinyl](2, 8-dimethyl-4, 6-nonanedianionic group) Iridium (Ir (mpiq)₂divm)、Bis (2-phenylpyridine) iridium acetylacetonate (Ir (ppy)₂acac), tris (1-phenyl-isoquinoline) iridium (Ir (piq)₃) Bis (1-phenyl-isoquinoline) (acetylacetonato) iridium (Ir (piq)₂(acac)) and tris (2-phenylpyridine) iridium (Ir (ppy)₃) One or more than two of them.

According to a seventh aspect of the present invention, there is provided a light-emitting device comprising a cathode layer, an anode layer and at least one light-emitting layer disposed between the cathode layer and the anode layer, wherein the light-emitting layer contains the condensed ring compound according to the first aspect of the present invention or the condensed ring compound prepared by the method according to the second aspect of the present invention.

According to the light-emitting device of the present invention, in a preferred embodiment, the light-emitting layer contains the co-host material according to the fifth aspect of the present invention. In a more preferred embodiment, the light-emitting layer contains the light-emitting composition according to the sixth aspect of the present invention. According to the light-emitting device of the present invention, the thickness of the light-emitting layer may be 30 to 50nm, preferably 35 to 45nm, and more preferably 40 to 45 nm.

The light-emitting device according to the present invention preferably further comprises a hole transport layer and/or an electron transport layer, the hole transport layer being disposed between the anode layer and the light-emitting layer, the electron transport layer being disposed between the cathode layer and the light-emitting layer.

The hole transport layer contains a hole transport material. Preferably, the hole transport layer contains one or more of polyethylene dioxythiophene (PEDOT), polystyrene sulfonate (PSS), and [ N, N ' -bis (1-naphthyl) -N, N ' -diphenyl ] - (1,1 ' -biphenyl) -4,4 ' -diamine, [ N, N ' -diphenyl-N, N ' -bis (3-methylphenyl) ] - (1,1 ' -biphenyl) -4,4 ' -diamine, and 4,4 ' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline ]. More preferably, the hole transport layer contains polyethylene dioxythiophene and polystyrene sulfonate. Mixtures of the polyethylene dioxythiophene and the polystyrene sulfonate are commercially available. The thickness of the hole transport layer may be 30 to 50nm, preferably 35 to 45nm, and more preferably 40 to 45 nm.

The electron transport layer contains an electron transport material, and preferably contains one or more of 2,4, 6-tris [3- (diphenylphosphinyloxy) phenyl ] -1,3, 5-triazole (PO-T2T), 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene, 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthroline, and 4, 7-diphenyl-1, 10-phenanthroline. The thickness of the electron transport layer may be 30 to 50nm, preferably 35 to 45nm, and more preferably 40 to 45 nm.

The thicknesses of the hole transport layer and the electron transport layer may be the same or different.

The number of layers of the hole transport layer and the electron transport layer can be selected according to specific use requirements, and each layer can be one or more than two. For example, more than two hole transport layers may be provided to better achieve charge transport balance; more than two electron transport layers can also be arranged to better achieve charge transport balance.

According to the light emitting device of the present invention, the light emitting device may further include an electron blocking layer and/or a hole blocking layer. The electron blocking layer is disposed between the hole transport layer and the light emitting layer, and the hole transport blocking layer is disposed between the light emitting layer and the electron transport layer.

According to the light emitting device of the present invention, the anode layer may contain Indium Tin Oxide (ITO). The cathode layer comprises a LiF layer and an Al layer, and the LiF layer is positioned between the light emitting layer and the Al layer. The thickness of the anode layer may be 120-180nm, preferably 130-170nm, more preferably 140-160 nm. The thickness of the LiF layer in the cathode layer may be 0.5-2nm, preferably 0.8-1.2 nm. The thickness of the Al layer may be 80-150nm, preferably 90-120 nm.

According to an eighth aspect of the present invention, there is provided a lighting device comprising the light emitting device according to the seventh aspect of the present invention. The lighting device may be a white light lighting device.

According to a ninth aspect of the present invention, there is provided a display device comprising the light emitting device according to the seventh aspect of the present invention. The display device may be an OLEDs display device.

The present invention will be described in detail with reference to the following preparation examples and examples, but the scope of the present invention is not limited thereto.

In the following preparation examples and comparative preparation examples, NMR spectroscopy was performed on CDCl₃Or DMSO-d⁶In solution, recording by Varian liquid NMR¹H NMR (hydrogen nuclear magnetic resonance) spectrum. Chemical shifts are based on residual protonated solvent. If deuterated chloroform (CDCl) is used₃) As the solvent, tetramethylsilane (δ ═ 0.00ppm) was used as an internal reference, and the recording was made¹H NMR spectrum. If deuterated dimethyl sulfoxide (DMSO-d) is used⁶) As solvent, residual H is used₂O (δ ═ 3.33ppm) was recorded as the internal reference¹H NMR spectrum. The following abbreviations (or combinations thereof) are used for the explanation¹Diversity of H NMR: s is singlet, d is singlet, t is triplet, q is tetrad, p is quintet, m is multiline, br is broad.

In the following preparations and comparative preparations, mass spectrometry was carried out on a Bruker Autoflex type II mass spectrometer available from Bruker corporation, germany; UV-Vis spectroscopy was performed on a DRX-400 model UV spectrometer, available from Bruker, Germany; photoluminescence analysis was performed on a fluorescence spectrometer model F-4600, available from hitachi, japan; cyclic voltammetry analysis was performed on a CHI600D electrochemical workstation purchased from chenhua, shanghai.

Preparation examples 1 to 8 were used to prepare the fused ring compounds according to the present invention.

Preparation example 1

Preparation example 1 for the preparation of Compound 5 (m-TPA-DPIQ):

(1) synthesis of bis (3-bromophenyl) methanol

To a 150mL Schlenk tube were added 1, 3-dibromobenzene (3.54g, 15mmol, ex Adamas) and diethyl ether (Et)₂O) (50mL), the solution was cooled to-78 deg.C, stirred for 15 minutes and n-butyllithium (1.6M, 10mL) was added. After stirring for 1.5 hours, the mixture was added to dissolve in Et₂3-Bromobenzaldehyde (2.5g, 13.5mmol, from Adamas) in O (10mL) and the mixture was allowed to warm to room temperature (25 ℃ C., same below) and stirred for an additional 2 h. Aqueous ammonium chloride (2M, 20mL) was added for quenching. The mixture was extracted with dichloromethane, the organic phases were combined and washed with anhydrous Na₂SO₄After drying, the solvent was removed by rotary evaporator to obtain the product, which was used in the next reaction.

(2) Synthesis of bis (3-bromophenyl) ketone

The product from step (1) was added to dry Dichloromethane (DCM) (75mL), dissolved with stirring at room temperature, cooled to 0 deg.C, Pyridinium Dichromate (PDC) (12.4g, 32.96mmol) was added slowly and the reaction mixture stirred at room temperature for 3 hours. At the end of the reaction, H is added₂O and Ethyl Acetate (EA) (H)₂O: the mass ratio of EA is 1: 1) extracting, mixing the organic phase with anhydrous Na₂SO₄After drying, the solvent was removed by rotary evaporator to give the crude product. The crude product was purified by column chromatography (silica gel column, eluent PE: EA ═ 50: 1, volume ratio) to afford white powder as product in 72% yield.

(3) Synthesis of bis (3- (phenyl (m-tolyl) amino) phenyl) methanone

To a 100mL Schlenk flask was added bis (3-bromophenyl) methanone (1.35g, 3.75mmol), 3-methyl-N-phenylaniline (1.5g, 8.25mmol, ex Adamas), tri-tert-butylphosphine (30mg, 0.15mmol)mmol)、Pd₂(dba)₃(137mg, 0.15mmol), sodium tert-butoxide (828mg, 8.625mmol) and toluene (20mL), the reaction was heated to 110 ℃ under nitrogen and stirred for 24 h. Cooling to room temperature, adding H₂Extracting with O and EA, combining the organic phases, and adding anhydrous Na₂SO₄After drying, the solvent was removed by rotary evaporator to give the crude product. The crude product was purified by column chromatography (silica gel column, eluent PE: EA ═ 100: 1, volume ratio) to afford the product as a light yellow solid in 88% yield.

(4) Synthesis of bis (3- (phenyl (m-tolyl) amino) phenyl) (2- (quinolin-2-yl) phenyl) methanol

To a 50mL Schlenk tube was added 2- (2-bromophenyl) quinoline (270mg, 0.5mmol, from Adamas) and Et₂O (10 mL). The solution was cooled to-78 deg.C, stirred for 15 minutes and then n-butyllithium (1.6M, 0.38mL) was added. After stirring for 1.5 hours, the mixture was added to dissolve in Et₂Bis (3- (phenyl (m-tolyl) amino) phenyl) methanone (158mg, 0.55mmol) in O (10mL) and the mixture was warmed to room temperature and stirred for an additional 2 h. Aqueous ammonium chloride (2M, 10mL) was added for quenching. The mixture was extracted with dichloromethane, the organic phases were combined and washed with anhydrous Na₂SO₄After drying, the solvent was removed by rotary evaporator to obtain a crude product. The crude product was purified by column chromatography (silica gel column, eluent PE: EA ═ 10: 1, volume ratio) to afford the product as a light yellow solid in 80% yield.

(5) Synthesis of Compound 5

To a 10mL stopcock were added bis (3- (phenyl (m-tolyl) amino) phenyl) (2- (quinolin-2-yl) phenyl) methanol (120mg, 0.16mmol) and CF₃SO₃H (2.5mL), reactionThe system was heated to 50 ℃ under nitrogen and stirred for 5 hours. Cooling to room temperature, adding sodium bicarbonate aqueous solution for neutralization, and adding H₂Extracting with O and EA, mixing the organic phases, and adding anhydrous Na₂SO₄After drying, the solvent was removed by rotary evaporator to give the crude product. The crude product was purified by column chromatography (silica gel column, eluent PE: EA ═ 50: 1, volume ratio) to afford the desired product (i.e., compound 5) as a pale yellow solid in 25% yield.

Wherein, FIG. 1 shows the preparation of Compound 5¹H NMR spectrum, wherein each peak is assigned as follows:

¹H NMR(300MHz,DMSO-d₆)δ7.33(s,1H),7.28(t,2H),7.10(d,J＝8.1Hz,1H),6.96(t,J＝7.6Hz,1H),6.80(t,1H),6.72-6.66(m,2H),6.53(d,J＝7.5Hz,1H),6.45(t,J＝8.0Hz,4H),6.35-6.31(m,J＝7.8,5.4Hz,4H),6.20(t,2H),6.11(d,J＝8.0Hz,4H),6.05–6.03(m,4H),5.96–5.90(m,8H),1.37(s,6H)。

fig. 2 is a mass spectrum of the prepared compound 5. Fig. 1 and 2 confirm that the target product obtained is compound 5.

Fig. 3 is a photoluminescence spectrum of the prepared compound 5, and fig. 4 is a Cyclic Voltammetry (CV) graph of the prepared compound 5, illustrating the redox ability of the compound and whether the compound has a reversible cycle characteristic. As can be seen from fig. 4, compound 5 exhibited very stable, reversible reduction behavior. From the initial reduction potential of the cyclic voltammogram of FIG. 4, the HOMO and LUMO levels of the molecule (based on ferrocene) were estimated to be-5.30 eV and-2.47 eV, respectively.

Preparation example 2

Preparation example 2 for preparation of Compound 4(m-TPA-SFIQ)

(1) Synthesis of 2, 7-bis (phenyl (m-tolyl) amino) -9H-fluorenone

To a 100mL Schlenk tube was added 2, 7-dibromo-9-fluorenone (1g, 3mmol from Adamas), 3-methyl-N-phenylaniline (1.2g, 6.6mmol from Adamas), Pd₂(dba)₃(100mg, 0.12mmol), tri-tert-butylphosphine (24mg, 0.12mmol), sodium tert-butoxide (663mg, 6.9mmol) and toluene (20mL), the reaction was heated to 110 ℃ under nitrogen and stirred for 24 hours. Cooling to room temperature, adding H₂Extracting with O and EA, combining the organic phases, and adding anhydrous Na₂SO₄After drying, the solvent was removed by rotary evaporator to obtain the crude product. The crude product was purified by column chromatography (silica gel column, eluent PE: EA 50: 1 by volume) to give a violet solid as product in 92.6% yield.

(2) Synthesis of 2, 7-bis (phenyl (m-tolyl) amino) -9- (2- (quinolin-2-yl) phenyl) -9H-fluoren-9-ol

To a 50mL Schlenk tube was added 2- (2-bromophenyl) quinoline (316mg, 1.1mmol) and Et₂O (10 mL). The solution was cooled to-78 deg.C, stirred for 15 minutes and then n-butyllithium (1.6M, 0.76mL) was added. After stirring for 1.5 hours, the mixture was added to dissolve in Et₂2, 7-bis (phenyl (m-tolyl) amino) -9H-fluorenone (542mg, 1mmol) in O (10mL) the mixture was warmed to room temperature and stirred for an additional 2H. Aqueous ammonium chloride (2M, 15mL) was added for quenching. The mixture was extracted with dichloromethane, the organic phases were combined and washed with anhydrous Na₂SO₄After drying, the solvent was removed by rotary evaporator to obtain the crude product. The crude product was purified by column chromatography (silica gel column, eluent PE: EA ═ 10: 1, volume ratio) to afford the product as a light yellow solid in 46.7% yield.

(3) Synthesis of Compound 4

To a 10mL stopcock were added 2, 7-bis (phenyl (m-tolyl) amino) -9- (2- (quinolin-2-yl) phenyl) -9H-fluoren-9-ol (101mg, 0.13mmol) and CF₃SO₃H (2mL), the reaction was heated to 50 ℃ under nitrogen and stirred for 5 hours. Cooling to room temperature, adding sodium bicarbonate aqueous solution for neutralization, and adding H₂Extracting with O and EA, combining the organic phases, and adding anhydrous Na₂SO₄After drying, the solvent was removed by rotary evaporator to give the crude product. The crude product was purified by column chromatography (silica gel column, eluent PE: EA 50: 1 by volume) to afford the desired product (i.e., compound 4) as a pale yellow solid in 22.4% yield.

Wherein FIG. 5 is a drawing of Compound 4 prepared¹H NMR spectrum, wherein each peak is assigned as follows:

¹H NMR(300MHz,CDCl₃)δ8.20(s,2H),7.69(d,J＝10.5Hz,5H),7.46(d,J＝7.9Hz,2H),7.39(d,J＝2.6Hz,2H),7.19–7.06(m,5H),7.01(s,2H),6.97(d,J＝6.9Hz,7H),6.71(s,5H),6.52(s,2H),5.39(d,1H),2.04(s,6H)。

fig. 6 is a mass spectrum of the prepared compound 4. Fig. 5 and 6 confirm that the target product obtained is compound 4. FIG. 7 is a photoluminescence spectrum of the prepared Compound 4.

Preparation example 3

Preparation 3 for the preparation of compound 1:

(1) synthesis of 2, 7-bis (diphenylamino) -9H-fluorenone

To a 100mL Schlenk tube were added 2, 7-dibromo-9-fluorenone (1g, 3mmol, ex Adamas), diphenylamine (1.1g, 6.6mmol, ex Adamas),Pd₂(dba)₃(100mg, 0.12mmol), tri-tert-butylphosphine (24mg, 0.12mmol), sodium tert-butoxide (663mg, 6.9mmol) and toluene (20mL), the reaction was heated to 110 ℃ under nitrogen and stirred for 24 hours. Cooling to room temperature, adding H₂Extracting with O and EA, combining the organic phases, and adding anhydrous Na₂SO₄After drying, the solvent was removed by rotary evaporator to give the crude product. The crude product was purified by column chromatography (silica gel column, eluent PE: EA ═ 50: 1, volume ratio) to give a violet solid as product in 90.2% yield.

(2) Synthesis of 2, 7-bis (diphenylamino) -9- (2- (quinolin-2-yl) phenyl) -9H-fluoren-9-ol

To a 50mL Schlenk tube was added 2- (2-bromophenyl) quinoline (316mg, 1.1mmol) and Et₂O (10 mL). The solution was cooled to-78 deg.C, stirred for 15 minutes and then n-butyllithium (1.6M, 0.76mL) was added. After stirring for 1.5 hours, 2, 7-bis (diphenylamino) -9H-fluorenone (515mg, 1mmol) dissolved in diethyl ether (10mL) was added and the mixture was allowed to warm to room temperature and stirred for an additional 2 hours. Aqueous ammonium chloride (2M, 15mL) was added for quenching. The mixture was extracted with dichloromethane, the organic phases were combined and washed with anhydrous Na₂SO₄After drying, the solvent was removed by rotary evaporator to give the crude product. The crude product was purified by column chromatography (silica gel column, eluent PE: EA ═ 10: 1, volume ratio) to afford the product as a white solid in 48.3% yield.

(3) Synthesis of Compound 1

To a 10mL stopcock was added 2, 7-bis (diphenylamino) -9- (2- (quinolin-2-yl) phenyl) -9H-fluoren-9-ol (108mg, 0.15mmol) and CF₃SO₃H (2mL), the reaction was heated to 5 deg.C under nitrogenStirred at 0 ℃ for 5 hours. Cooling to room temperature, adding sodium bicarbonate aqueous solution for neutralization, and adding H₂Extracting with O and EA, combining the organic phases, and adding anhydrous Na₂SO₄After drying, the solvent was removed by rotary evaporator to give the crude product. The crude product was purified by column chromatography (silica gel column, eluent PE: EA ═ 50: 1, volume ratio) to afford the desired product (i.e., compound 1) as a pale yellow solid in 25% yield. The molecular weight of the product was determined to be M701 by mass spectrometry, and the product was identified as a target product.

Preparation example 4

Preparation 4 for the preparation of compound 2:

(1) synthesis of bis (3- (diphenylamino) phenyl) methanone

To a 100mL Schlenk flask was added bis (3-bromophenyl) methanone (1.35g, 3.75mmol), diphenylamine (1.4g, 8.25mmol, ex Adamas), tri-tert-butylphosphine (30mg, 0.15mmol), Pd₂(dba)₃(137mg, 0.15mmol), sodium tert-butoxide (828mg, 8.625mmol) and toluene (20mL), the reaction was heated to 110 ℃ under nitrogen and stirred for 24 h. Cooling to room temperature, adding H₂Extracting with O and EA, mixing the organic phases, and adding anhydrous Na₂SO₄After drying, the solvent was removed by rotary evaporator to give the crude product. The crude product was purified by column chromatography (silica gel column, eluent PE: EA ═ 100: 1, volume ratio) to afford the product as a yellow solid in 90% yield.

(2) Synthesis of bis (3- (diphenylamino) phenyl) (2- (quinolin-2-yl) phenyl) methanol

To a 50mL Schlenk tube was added 2- (2-bromophenyl) quinoline (270mg, 0.5mmol, from Adamas) and Et₂O (10 mL). The solution was cooled to-78 deg.C, stirred for 15 minutes and then n-butyllithium (1.6M, 0.38mL) was added. After stirring for 1.5 hours, the mixture was added to dissolve in Et₂Bis (3- (diphenylamino) phenyl) methanone (285mg, 0.55mmol) in O (10mL) and the mixture was warmed to room temperature and stirred for an additional 2 h. Aqueous ammonium chloride (2M, 10mL) was added for quenching. The mixture was extracted with dichloromethane, the organic phases were combined and washed with anhydrous Na₂SO₄After drying, the solvent was removed by rotary evaporator to obtain the crude product. The crude product was purified by column chromatography (silica gel column, eluent PE: EA ═ 10: 1, volume ratio) to afford the product as a white solid in 83% yield.

(3) Synthesis of Compound 2

To a 10mL stopcock was added bis (3- (diphenylamino) phenyl) (2- (quinolin-2-yl) phenyl) methanol (116mg, 0.16mmol) and CF₃SO₃H (2.5mL), the reaction was heated to 50 ℃ under nitrogen and stirred for 5 hours. Cooling to room temperature, adding sodium bicarbonate aqueous solution for neutralization, and adding H₂Extracting with O and EA, combining the organic phases, and adding anhydrous Na₂SO₄After drying, the solvent was removed by rotary evaporator to give the crude product. The crude product was purified by column chromatography (silica gel column, eluent PE: EA ═ 50: 1, volume ratio) to afford the desired product (i.e., compound 5) as a pale yellow solid in 23% yield. The molecular weight of the product was determined to be M703 by mass spectrometry, which was the target product.

Preparation example 5

Preparation 5 for compound 7:

(1) synthesis of 2-bromo-7- (phenyl (m-tolyl) amino) -9H-fluorenone

To a 100mL Schlenk tube was added 2, 7-dibromo-9-fluorenone (1g, 3mmol, ex Adamas), 3-methyl-N-phenylaniline (367mg, 2mmol, ex Adamas), Pd₂(dba)₃(192mg, 0.1mmol), tri-tert-butylphosphine (10mg, 0.1mmol), sodium tert-butoxide (576mg, 6mmol) and toluene (20mL), and the reaction was heated to 110 ℃ under nitrogen and stirred for 24 hours. Cooling to room temperature, adding H₂Extracting with O and EA, combining the organic phases, and adding anhydrous Na₂SO₄After drying, the solvent was removed by rotary evaporator to give the crude product. The crude product was purified by column chromatography (silica gel column, eluent PE: EA ═ 50: 1, volume ratio) to afford a rose red solid as product in 84% yield.

(2) Synthesis of 2- (di-m-tolylamino) -7- (phenyl (m-tolyl) amino) -9H-fluorenone

To a 100mL Schlenk tube was added 2-bromo-7- (phenyl (m-tolyl) amino) -9H-fluorenone (1.3g, 3mmol, ex Adamas), di-m-toluidine (709mg, 3.6mmol, ex Adamas), Pd₂(dba)₃(100mg, 0.12mmol), tri-tert-butylphosphine (24mg, 0.12mmol), sodium tert-butoxide (663mg, 6.9mmol) and toluene (20mL), the reaction was heated to 110 ℃ under nitrogen and stirred for 24 hours. Cooling to room temperature, adding H₂Extracting with O and EA, combining the organic phases, and adding anhydrous Na₂SO₄After drying, the solvent was removed by rotary evaporator to give the crude product. The crude product was purified by column chromatography (silica gel column, eluent PE: EA 50: 1 by volume) to give a violet solid as product in 92.6% yield.

(3)2- (di-m-tolylamino) -7- (phenyl (m-tolyl) amino-9- (2- (quinolin-2-yl) phenyl) - Synthesis of 9H-fluoren-9-ol

To a 50mL Schlenk tube was added 2- (2-bromophenyl) quinoline (270mg, 0.5mmol, from Adamas) and Et₂O (10 mL). The solution was cooled to-78 deg.C, stirred for 15 minutes and then n-butyllithium (1.6M, 0.38mL) was added. After stirring for 1.5 hours, the mixture was added to dissolve in Et₂2- (di-m-tolylamino) -7- (phenyl (m-tolyl) amino) -9H-fluorenone (306mg, 0.55mmol) in O (10mL) and the mixture was allowed to warm to room temperature and stirred for an additional 2H. Aqueous ammonium chloride (2M, 10mL) was added for quenching. The mixture was extracted with dichloromethane, the organic phases combined and anhydrous Na₂SO₄After drying, the solvent was removed by rotary evaporator to obtain the crude product. The crude product was purified by column chromatography (silica gel column, eluent PE: EA ═ 10: 1, volume ratio) to afford the product as a white solid in 73% yield.

(4) Synthesis of Compound 7

To a 10mL stopcock were added 2- (di-m-tolylamino) -7- (phenyl (m-tolyl) amino-9- (2- (quinolin-2-yl) phenyl) -9H-fluoren-9-ol (122mg, 0.2mmol) and CF₃SO₃H (2.5mL), the reaction was heated to 50 ℃ under nitrogen and stirred for 5 hours. Cooling to room temperature, adding sodium bicarbonate aqueous solution for neutralization, and adding H₂Extracting with O and EA, combining the organic phases, and adding anhydrous Na₂SO₄After drying, the solvent was removed by rotary evaporator to give the crude product. The crude product was purified by column chromatography (silica gel column, eluent PE: EA ═ 50: 1, volume ratio) to afford the desired product (i.e., compound 7) as a pale yellow solid in 30% yield. Determination by Mass SpectrometryThe molecular weight of the product is M743, which is the target product.

Preparation example 6

Preparation 6 for the preparation of compound 8:

(1) synthesis of (3- (phenyl (m-tolyl) amino) phenyl) (m-tolyl) methanone

To a 100mL Schlenk flask was added bis (3-bromophenyl) methanone (1.35g, 3.75mmol), 3-methyl-N-phenylaniline (458g, 2.5mmol, ex Adamas), tri-tert-butylphosphine (30mg, 0.15mmol), Pd₂(dba)₃(137mg, 0.15mmol), sodium tert-butoxide (720mg, 7.5mmol) and toluene (20mL), the reaction was heated to 110 ℃ under nitrogen and stirred for 24 h. Cooling to room temperature, adding H₂Extracting with O and EA, mixing the organic phases, and adding anhydrous Na₂SO₄After drying, the solvent was removed by rotary evaporator to give the crude product. The crude product was purified by column chromatography (silica gel column, eluent PE: EA ═ 100: 1, volume ratio) to afford the product as a light yellow solid in 76% yield.

(2) Synthesis of (3- (di-m-tolylamino) phenyl) (3- (phenyl (m-tolyl) amino) phenyl) methanone

To a 100mL Schlenk tube was added (3- (phenyl (m-tolyl) amino) phenyl) (m-tolyl) methanone (1.13g, 3mmol, ex Adamas), di-toluidine (709mg, 3.6mmol, ex Adamas), Pd₂(dba)₃(100mg, 0.12mmol), tri-tert-butylphosphine (24mg, 0.12mmol), sodium tert-butoxide (663mg, 6.9mmol) and toluene (20mL)) The reaction system was heated to 110 ℃ under nitrogen and stirred for 24 hours. Cooling to room temperature, adding H₂Extracting with O and EA, mixing the organic phases, and adding anhydrous Na₂SO₄After drying, the solvent was removed by rotary evaporator to give the crude product. The crude product was purified by column chromatography (silica gel column, eluent PE: EA ═ 50: 1, volume ratio) to afford the product as a yellow solid in 95% yield.

(3) (3- (di-m-tolylamino) phenyl) (3- (phenyl (m-tolyl) amino) phenyl) (2- (quinoline-2-) Phenyl) methanol synthesis

To a 50mL Schlenk tube was added 2- (2-bromophenyl) quinoline (270mg, 0.5mmol, from Adamas) and Et₂O (10 mL). The solution was cooled to-78 deg.C, stirred for 15 minutes and then n-butyllithium (1.6M, 0.38mL) was added. After stirring for 1.5 hours, the mixture was added to dissolve in Et₂(3- (di-m-tolylamino) phenyl) (3- (phenyl (m-tolyl) amino) phenyl) methanone (307mg, 0.55mmol) in O (10mL), the mixture was warmed to room temperature and stirred for an additional 2 hours. Aqueous ammonium chloride (2M, 10mL) was added for quenching. The mixture was extracted with dichloromethane, the organic phases were combined and washed with anhydrous Na₂SO₄After drying, the solvent was removed by rotary evaporator to obtain the crude product. The crude product was purified by column chromatography (silica gel column, eluent PE: EA ═ 10: 1, volume ratio) to afford the product as a white solid in 75% yield.

(4) Synthesis of Compound 8

To a 10mL stopcock were added (3- (di-m-tolylamino) phenyl) (3- (phenyl (m-tolyl) amino) phenyl) (2- (quinolin-2-yl) phenyl) methanol (150mg, 0.2mmol) and CF₃SO₃H (2.5mL), reactionThe system was heated to 50 ℃ under nitrogen and stirred for 5 hours. Cooling to room temperature, adding sodium bicarbonate aqueous solution for neutralization, and adding H₂Extracting with O and EA, mixing the organic phases, and adding anhydrous Na₂SO₄After drying, the solvent was removed by rotary evaporator to give the crude product. The crude product was purified by column chromatography (silica gel column, eluent PE: EA 50: 1 by volume) to afford the desired product (i.e., compound 8) as a pale yellow solid in 40% yield. The molecular weight of the product was determined to be M745 by mass spectrometry, and the product was the target product.

Preparation example 7

Preparation 7 for the preparation of compound 13:

(1) synthesis of 2, 7-bis (di-m-toluylamino) -9-fluorenone

To a 100mL Schlenk tube was added 2, 7-dibromo-9-fluorenone (1g, 3mmol, ex Adamas), di-m-toluidine (1.3g, 6.6mmol, ex Adamas), Pd₂(dba)₃(100mg, 0.12mmol), tri-tert-butylphosphine (24mg, 0.12mmol), sodium tert-butoxide (663mg, 6.9mmol) and toluene (20mL), the reaction was heated to 110 ℃ under nitrogen and stirred for 24 hours. Cooling to room temperature, adding H₂Extracting with O and EA, combining the organic phases, and adding anhydrous Na₂SO₄After drying, the solvent was removed by rotary evaporator to give the crude product. The crude product was purified by column chromatography (silica gel column, eluent PE: EA ═ 50: 1, volume ratio) to give a violet solid as product in 90% yield.

(2) Synthesis of 2, 7-bis (di-m-toluylamino) -9- (2- (quinolin-2-yl) phenyl) -9H-fluoren-9-ol

To a 50mL Schlenk tube was added 2- (2-bromophenyl) quinoline (270mg, 0.5mmol, from Adamas) and Et₂O (10 mL). The solution was cooled to-78 deg.C, stirred for 15 minutes and then n-butyllithium (1.6M, 0.38mL) was added. After stirring for 1.5 hours, the mixture was added to dissolve in Et₂2, 7-bis (di-m-toluidino) -9-fluorenone (313mg, 0.55mmol) in O (10mL) and the mixture was warmed to room temperature and stirred for an additional 2 h. Aqueous ammonium chloride (2M, 10mL) was added for quenching. The mixture was extracted with dichloromethane, the organic phases combined and anhydrous Na₂SO₄After drying, the solvent was removed by rotary evaporator to obtain the crude product. The crude product was purified by column chromatography (silica gel column, eluent PE: EA ═ 10: 1, volume ratio) to afford the product as a white solid in 78% yield.

(3) Synthesis of Compound 13

To a 10mL stopcock were added 2, 7-bis (di-m-toluidino) -9- (2- (quinolin-2-yl) phenyl) -9H-fluoren-9-ol (124mg, 0.16mmol) and CF₃SO₃H (2.5mL), the reaction was heated to 50 ℃ under nitrogen and stirred for 5 hours. Cooling to room temperature, adding sodium bicarbonate aqueous solution for neutralization, and adding H₂Extracting with O and EA, mixing the organic phases, and adding anhydrous Na₂SO₄After drying, the solvent was removed by rotary evaporator to give the crude product. The crude product was purified by column chromatography (silica gel column, eluent PE: EA 50: 1 by volume) to afford the desired product (i.e., compound 13) as a pale yellow solid in 28% yield. The molecular weight of the product was determined to be M757 by mass spectrometry, and the product was the target product.

Preparation example 8

Preparation 8 for compound 14:

(1) synthesis of bis (3- (di-m-tolylamino) phenyl) methanone

A100 mL Schlenk flask was charged with bis (3-bromophenyl) methanone (1.35g, 3.75mmol), di-m-toluidine (1.6g, 8.25mmol, ex Adamas), tri-tert-butylphosphine (30mg, 0.15mmol), Pd₂(dba)₃(137mg, 0.15mmol), sodium tert-butoxide (828mg, 8.625mmol) and toluene (20mL), the reaction was heated to 110 ℃ under nitrogen and stirred for 24 h. Cooling to room temperature, adding H₂Extracting with O and EA, combining the organic phases, and adding anhydrous Na₂SO₄After drying, the solvent was removed by rotary evaporator to give the crude product. The crude product was purified by column chromatography (silica gel column, eluent PE: EA ═ 100: 1, volume ratio) to afford the product as a light yellow solid in 79% yield.

(2) Synthesis of bis (3- (di-m-tolylamino) phenyl) (2- (quinolin-2-yl) phenyl) methanol

To a 50mL Schlenk tube was added 2- (2-bromophenyl) quinoline (270mg, 0.5mmol, from Adamas) and Et₂O (10 mL). The solution was cooled to-78 deg.C, stirred for 15 minutes and then n-butyllithium (1.6M, 0.38mL) was added. After stirring for 1.5 hours, the mixture was added to dissolve in Et₂Bis (3- (di-m-tolylamino) phenyl) methanone (315mg, 0.55mmol) in O (10mL) and the mixture was warmed to room temperature and stirred for an additional 2 h. Aqueous ammonium chloride (2M, 10mL) was added for quenching. The mixture was extracted with dichloromethane, the organic phases combined and anhydrous Na₂SO₄After drying, the solvent was removed by rotary evaporator to obtain the crude product. The crude product was purified by column chromatography (silica gel column, eluent PE: EA ═ 10: 1, volume ratio),an off-white solid was obtained as product in 68% yield.

(3) Synthesis of Compound 14

To a 10mL stopcock were added bis (3- (di-m-tolylamino) phenyl) (2- (quinolin-2-yl) phenyl) methanol (124mg, 0.16mmol) and CF₃SO₃H (2.5mL), the reaction was heated to 50 ℃ under nitrogen and stirred for 5 hours. Cooling to room temperature, adding sodium bicarbonate aqueous solution for neutralization, and adding H₂Extracting with O and EA, mixing the organic phases, and adding anhydrous Na₂SO₄After drying, the solvent was removed by rotary evaporator to give the crude product. The crude product was purified by column chromatography (silica gel column, eluent PE: EA ═ 50: 1, volume ratio) to afford the desired product (i.e., compound 14) as a yellow solid in 36% yield. The molecular weight of the product was determined to be M759 by mass spectrometry, and the product was the target product.

Preparation of comparative example 1

Preparation of comparative example 1 for the preparation of comparative compound 1:

(1) synthesis of diphenyl (2- (quinolin-2-yl) phenyl) methanol

To a 50mL Schlenk tube was added 2- (2-bromophenyl) quinoline (270mg, 0.5mmol, from Adamas) and Et₂O (10 mL). The solution was cooled to-78 deg.C, stirred for 15 minutes and then n-butyllithium (1.6M, 0.38mL) was added. After stirring for 1.5 hours, the mixture was added to dissolve in Et₂Benzophenone (100mg, 0.55mmol, from Adamas) in O (10mL) and the mixture was warmed to room temperature and stirred for 2 h.Aqueous ammonium chloride (2M, 10mL) was added for quenching. The mixture was extracted with dichloromethane, the organic phases were combined and washed with anhydrous Na₂SO₄After drying, the solvent was removed by rotary evaporator to obtain the crude product. The crude product was purified by column chromatography (silica gel column, eluent PE: EA ═ 10: 1, volume ratio) to afford the product as a light yellow solid in 73% yield.

(2) Synthesis of comparative Compound 1

To a 10mL stopcock was added diphenyl (2- (quinolin-2-yl) phenyl) methanol (77mg, 0.2mmol) and CF₃SO₃H (2.5mL), the reaction was heated to 50 ℃ under nitrogen and stirred for 5 hours. Cooling to room temperature, adding sodium bicarbonate aqueous solution for neutralization, and adding H₂Extracting with O and EA, combining the organic phases, and adding anhydrous Na₂SO₄After drying, the solvent was removed by rotary evaporator to give the crude product. The crude product was purified by column chromatography (silica gel column, eluent PE: EA 50: 1, vol) to afford the desired product (i.e., comparative compound 1) as a pale yellow solid in 40% yield. The molecular weight of the product was determined to be M369 by mass spectrometry, and the product was identified as a target product.

Preparation of comparative example 2

Preparation of comparative example 2 for the preparation of comparative compound 2:

(1) bis (3- (phenyl (m-tolyl) amino) phenyl) [ (1, 1' -biphenyl) -2-yl]Methanol synthesis

To a 50mL Schlenk tube was added 2-bromo-1, 1' -bi-bromoBenzene (116mg, 0.5mmol, from Adamas) and Et₂O (10 mL). The solution was cooled to-78 deg.C, stirred for 15 minutes and then n-butyllithium (1.6M, 0.38mL) was added. After stirring for 1.5 hours, the mixture was added to dissolve in Et₂Bis (3- (phenyl (m-tolyl) amino) phenyl) methanone (158mg, 0.55mmol) in O (10mL) and the mixture was warmed to room temperature and stirred for an additional 2 h. Aqueous ammonium chloride (2M, 10mL) was added for quenching. The mixture was extracted with dichloromethane, the organic phases were combined and washed with anhydrous Na₂SO₄After drying, the solvent was removed by rotary evaporator to obtain the crude product. The crude product was purified by column chromatography (silica gel column, eluent PE: EA ═ 10: 1, volume ratio) to afford the product as a light yellow solid in 70% yield.

(2) Synthesis of comparative Compound 2

To a 10mL sealed tube was added bis (3- (phenyl (m-tolyl) amino) phenyl) [ (1, 1' -biphenyl) -2-yl]Methanol (140mg, 0.2mmol) and CF₃SO₃H (2.5mL), the reaction was heated to 50 ℃ under nitrogen and stirred for 5 hours. Cooling to room temperature, adding sodium bicarbonate aqueous solution for neutralization, and adding H₂Extracting with O and EA, combining the organic phases, and adding anhydrous Na₂SO₄After drying, the solvent was removed by rotary evaporator to give the crude product. The crude product was purified by column chromatography (silica gel column, eluent PE: EA 50: 1, vol) to afford the desired product (i.e., comparative compound 2) as a pale yellow solid in 30% yield. The molecular weight of the product is determined to be 680 by mass spectrometry, and the product is the target product.

Preparation of comparative example 3

Preparation of comparative example 3 for the preparation of comparative compound 3:

(1) synthesis of 9- ([ (1, 1' -biphenyl) -2-yl ] -2, 7-bis (phenyl (m-tolyl) amino) -9H-fluoren-9-ol

To a 50mL Schlenk tube were added 2-bromo-1, 1' -biphenyl (116mg, 0.5mmol, ex Adamas) and Et₂O (10 mL). The solution was cooled to-78 deg.C, stirred for 15 minutes and then n-butyllithium (1.6M, 0.38mL) was added. After stirring for 1.5 hours, the mixture was added to dissolve in Et₂2, 7-bis (phenyl (m-tolyl) amino) -9H-fluorenone (158mg, 0.55mmol) in O (10mL), the mixture was warmed to room temperature and stirred for an additional 2H. Aqueous ammonium chloride (2M, 10mL) was added for quenching. The mixture was extracted with dichloromethane, the organic phases were combined and washed with anhydrous Na₂SO₄After drying, the solvent was removed by rotary evaporator to obtain the crude product. The crude product was purified by column chromatography (silica gel column, eluent PE: EA ═ 10: 1, volume ratio) to afford the product as a light yellow solid in 80% yield.

(2) Synthesis of comparative Compound 3

To a 10mL sealed tube was added 9- ([ (1, 1' -biphenyl) -2-yl)]-2, 7-bis (phenyl (m-tolyl) amino) -9H-fluoren-9-ol (139mg, 0.2mmol) and CF₃SO₃H (2.5mL), the reaction was heated to 50 ℃ under nitrogen and stirred for 5 hours. Cooling to room temperature, adding sodium bicarbonate aqueous solution for neutralization, and adding H₂Extracting with O and EA, combining the organic phases, and adding anhydrous Na₂SO₄After drying, the solvent was removed by rotary evaporator to give the crude product. The crude product was purified by column chromatography (silica gel column, eluent PE: EA 50: 1 by volume) to afford the desired product (i.e., comparative compound 3) as a pale yellow solid in 28% yield. The molecular weight of the product was determined to be M678 by mass spectrometry, and the product was identified as the target product.

Table 1 lists the spectra and energy level data for the compounds prepared in the preparation examples and the preparation comparative examples.

TABLE 1

Absλ_abs: an ultraviolet visible spectrum absorption peak;

PLλ_maxsolution: emission peak in solution, dichloromethane solution at room temperature (1X 10)^-5M) is measured;

film: emission peaks in the film, measured in the film at room temperature;

E_S1: singlet lowest excited state energy from dichloromethane solution (1X 10) at room temperature^-5Calculating the initial position of the emission peak in M);

E_T1: triplet minimum excited State energy, 2-methyltetrahydrofuran solution at 77K (1.4X 10)^-3M) calculating the initial position of the phosphorescence spectrum;

HOMO and LUMO: in N, N-Dimethylformamide (DMF) (4.1X 10)^-3M) is calculated by CV test;

eg: the energy level difference was calculated from HOMO ═ LUMO-Eg.

Test example 1

Test example 1 condensed ring compounds prepared in preparation examples and comparative preparation examples were respectively prepared into light emitting devices by a solution method and subjected to performance tests.

Fig. 8 is a schematic sectional view of the fabricated light emitting device for explaining a device structure of the fabricated light emitting device. As shown in fig. 8, the device structure for preparing the light emitting device includes: the device comprises an anode layer, a hole transport layer, a luminescent layer (EML layer), an electron transport layer and a metal cathode layer, and has the following specific structure: ITO (150 nm)/PEDOT: PSS (from Sai An Bao Lai Te photoelectric technology Co., Ltd., model PLT302191T) (40 nm)/NPB: condensed ring compound: ir (mpiq)₂divm(45: 45: 10 mass ratio) (40nm)/PO-T2T (45nm)/LiF (1nm)/Al (100nm), wherein the condensed-cyclic compounds prepared in the preparation examples and the preparation comparative examples were used, respectively, and the cathode layer included a LiF layer and an Al layer.

1. Photoluminescence and electroluminescence spectroscopy

(1) Photoluminescence spectrum research is carried out on the fused ring compound, the NPB and the blended film of the fused ring compound and the NPB, and the photoluminescence spectrum research is used for explaining whether the fused ring compound and the NPB interact to generate an exciplex. The experimental results demonstrated that the fused ring compounds prepared in preparation examples 1 to 8 did not interact with NPB and did not produce exciplex.

Fig. 9 shows photoluminescence spectra of compound 5, NPB, and a blend film of compound 5 and NPB. The peak value of the pure film compound 5 is 441nm, the peak value of the emission peak of the pure film NPB is 435nm, the peak value of the emission peak of the compound 5 and the NPB blended film is 444nm, the spectral shift after blending is very small, no new peak is generated, and the half-peak width is widened, which indicates that the compound 5 and the NPB do not interact to generate an exciplex.

(2) Doping the Red phosphorescent Material Ir (mpiq) with a fused Ring Compound and NPB Co-host Material₂divm (CAS number: 2250322-71-3), and photoluminescence spectrum analysis of the obtained film revealed that photoluminescence of the film using the fused ring compound prepared in preparation examples 1 to 8 was completely derived from a red phosphorescent material Ir (mpiq)₂divm。

Wherein, FIG. 10 shows the compound 5 and NPB co-host doped red phosphorescent material Ir (mpiq)₂Thin film electroluminescence spectrum after divm. As can be seen from FIG. 10, the emission peak position and the red phosphorescent material Ir (mpiq)₂The emission peak positions of divm are consistent, which indicates that the luminescence of the film comes from the red phosphorescent material Ir (mpiq)₂divm。

(3) Doping the Red phosphorescent Material Ir (mpiq) with a fused Ring Compound and NPB Co-host Material₂The divm is used as a light emitting layer of the light emitting device to make the light emitting device. The results of measuring the electroluminescence spectra of the luminescent devices show that the electroluminescence of the luminescent devices adopting the fused ring compounds prepared in preparation examples 1 to 8 is completely from red phosphorescent luminescent materialsMaterial Ir (mpiq)₂divm。

Wherein, FIG. 11 shows that the compound 5 and NPB co-host doped red phosphorescent material Ir (mpiq)₂divm and the electroluminescence spectrum of the device is made. As can be seen from FIG. 11, the position of the emission peak is not substantially changed, indicating that the emission of the device is entirely from the red phosphorescent material Ir (mpiq)₂divm。

2. Light emitting device performance testing

(1) Current density-voltage test

And carrying out current density-voltage test on the prepared light-emitting device by adopting a photoelectric test system. Test results show that a light-emitting device using the fused ring compound of the present invention can perform charge transport well. FIG. 12 shows that the compounds 5 (1-8 shown in the figure) and the comparative compounds 1 (1-3 shown in the figure) respectively have the NPB co-host doped red phosphorescent light emitting material Ir (mpiq)₂divm makes the current density-voltage diagram of the device. As can be seen from fig. 12, the light emitting device prepared by the compound 5 and NPB co-host doped red phosphorescent light emitting material can perform charge transport well.

(2) Luminance-voltage test

And performing brightness-voltage test on the prepared light-emitting device by adopting a photoelectric test system. Test results show that the light-emitting device using the condensed ring compound of the present invention has a low turn-on voltage, so that power consumption can be reduced and device efficiency can be improved. FIG. 13 shows that compounds 5 (1-8 shown in the figure) and comparative compounds 1 (1-3 shown in the figure) are doped with 10 wt% of red phosphorescent light-emitting material Ir (mpiq) respectively with NPB co-host₂Luminance vs. voltage diagram for light emitting devices made of divm. As can be seen from fig. 13, the turn-on voltage of the light emitting device prepared by the compound 5 and the NPB co-host doped red phosphorescent light emitting material is 3.01V, which can reduce power consumption and improve device efficiency.

(3) Current efficiency testing

And testing the current efficiency of the prepared light-emitting device by adopting a photoelectric testing system. Test results show that the light-emitting device using the condensed ring compound of the present invention has high current efficiency. FIG. 14 shows the co-host doping 1 of compound 5 (1-8 shown in the figure) and comparative compound 1 (1-3 shown in the figure) with NPB, respectively0 wt% of Red phosphorescent light-emitting Material Ir (mpiq)₂divm makes a current efficiency map of the light emitting device. As can be seen from FIG. 14, the peak value of the current efficiency of the light-emitting device prepared by the compound 5 and NPB co-host doped red phosphorescent light-emitting material can reach 13.6 cd.A^-1At 1000cd · m^-2Can reach 11.2 cd.A^-1。

(4) Power efficiency analysis

And testing the power efficiency of the prepared light-emitting device by adopting a photoelectric testing system. Test results show that the light-emitting device using the condensed ring compound of the present invention has high power efficiency. FIG. 15 shows that compounds 5 (1-8 shown in the figure) and comparative compounds 1 (1-3 shown in the figure) are doped with 10 wt% of red phosphorescent light-emitting material Ir (mpiq) respectively with NPB co-host₂divm makes a power efficiency map of the light emitting device. As can be seen from FIG. 15, the peak of the power efficiency of the light-emitting device prepared by the compound 5 and the NPB co-host doped red phosphorescent material can reach 10.3 lm.W^-1At 1000cd · m^-2Can reach 4.2 lm.W^-1。

(5) Quantum efficiency testing

And testing the quantum efficiency of the prepared light-emitting device by adopting a photoelectric testing system. Test results show that the luminescent device adopting the fused ring compound has high external quantum efficiency and lower efficiency roll-off. FIG. 16 shows the co-host doping of 10 wt% of the red phosphorescent material Ir (mpiq) with NPB for compound 5₂divm makes an external quantum efficiency map of the light emitting device. As can be seen from FIG. 16, the peak value of the external quantum efficiency of the luminescent device prepared by the compound 5 and NPB co-host doped red phosphorescent luminescent material can reach 23.3 percent, and is 1000cd/m²Still has 19.2 percent of external quantum efficiency under the luminosity of (A), and has lower efficiency roll-off. The high quantum efficiency indicates that the device using compound 5 as the host material has a good carrier balance in the light emitting layer.

Table 2 shows performance data of the light emitting devices prepared using preparation examples 1 to 8 and comparative examples 1 to 3, respectively.

As shown in Table 2, the electroluminescent wavelength of the light-emitting device containing the condensed ring compound according to the present invention is mainly composed of red phosphorescent light-emitting materialsMaterial Ir (mpiq)₂divm itself photoluminescence. The EL spectrum of the light emitting device containing fused ring compounds 4, 5 and 2 was stable in deep red emission, with a peak at 635nm, and with the commission internationale de l' eclairage CIE coordinates (0.70, 0.30), indicating that it can cover all the visible color gamut and reach a potential saturation of 103%.

As shown in table 2, the light-emitting devices containing the condensed ring compound according to the present invention showed higher quantum efficiency, and particularly, the light-emitting devices containing the condensed ring compounds 1, 2,4, 5 and 8 showed higher quantum efficiency.

TABLE 2

Test example 2

The compounds prepared in preparation examples 1 to 8 were doped with 5 wt% of a phosphorescent material and subjected to photoluminescence spectroscopy, wherein Ir (ppy)₂acac (CAS number: 337526-85-9; 890306-54-4) is a green phosphorescent light-emitting material, Ir (phq)₂acac (CAS number: 337526-95-1; 1173886-71-9) is a red phosphorescent light-emitting material. The test results showed that the compounds prepared in preparation examples 1 to 8 can be applied to hosts of phosphorescent materials for red/green/yellow light.

Fig. 17 is a photoluminescence spectrum of compound 4 doped with 5 wt% phosphorescent material. The emission spectrum shown in fig. 17 is a distinct emission characteristic spectrum of the phosphorescent material, and shows that the excited state energy of the compound 4 can be well transferred from the host material to the phosphorescent dopant material.

The above experimental results confirm that the fused ring compound according to the present invention has the following advantages:

(1) the solubility and the stability are excellent, and the preparation method can be used for preparing wet display devices;

(2) experimental data show that the fused ring compound can be used as a host material or a co-host material for red phosphorescence, green phosphorescence and yellow phosphorescence;

(3) the fused ring compound according to the present invention can produce a high-efficiency red light device with a simple device structure, and thus can be used as a white light illumination or an OLEDs display device.

The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.