阅读说明：本技术 一种螺苯并蒽芴类化合物、有机电致发光器件及显示面板 (Spirobenzanthracene fluorene compound, organic electroluminescent device and display panel ) 是由 韩建厅 于 2021-06-30 设计创作，主要内容包括：本发明公开了一种螺苯并蒽芴类化合物,有机电致发光器件和显示面板。该螺苯并蒽芴类化合物结构如通式(1)所示。本发明提供的螺苯并蒽芴类化合物具有较高的玻璃化温度和分子热稳定性,应用于有机电致发光器件后,可有效提升有机电致发光器件的光电性能以及寿命。(The invention discloses a spirobenzanthracene fluorene compound, an organic electroluminescent device and a display panel. The structure of the spirobenzanthracene fluorene compound is shown as a general formula (1). The spirobenzanthracene fluorene compound provided by the invention has higher glass transition temperature and molecular thermal stability, and can effectively improve the photoelectric property and the service life of an organic electroluminescent device after being applied to the organic electroluminescent device.)

1. A spirobenzanthracene fluorene compound is characterized in that: has a structure represented by the following general formula (1):

wherein X is selected from-O-, -S-, -C (R)₇)(R₈) -or-N (R)₉)-；

Z is C-R;

each occurrence of R is independently selected from cyano, halogen, C_1-10Alkyl, substituted or unsubstituted C_6-30Aryl, or substituted or unsubstituted C_2-30A heteroaryl group;

R₀、R₁、R₂、R₃、R₄each independently selected from a hydrogen atom, a structure represented by the general formula (2) or the general formula (3), and R₀、R₁、R₂、R₃、R₄At least one of the compounds is selected from the structures shown in the general formula (2) or the general formula (3);

in the general formula (2), X₁Selected from single bond, -O-, -S-, -C (R)₁₀)(R₁₁) -or-N (R)₁₂)-；

i is 0 or 1;

Z₁selected from N, C or C-R₁₃Z is the same as₁Each occurrence is the same or different;

Ar₁selected from single bond, substituted or unsubstituted C_6-30Arylene or substituted or unsubstituted C_2-30A heteroarylene group;

in the general formula (3), Z₂、Z₃、Z₄Is N or CH, and Z₂、Z₃、Z₄At least one of which is N;

Ar₂is a single bond, substituted or unsubstituted C_6-30Arylene radicals, or substituted or unsubstitutedSubstituted C_2-30A heteroarylene group;

R₅、R₆、R₉、R₁₂each independently selected from substituted or unsubstituted C_6-30Aryl or substituted or unsubstituted C_2-30A heteroaryl group;

R₇、R₈、R₁₀、R₁₁、R₁₃each independently selected from hydrogen atom, C_1-10Alkyl, substituted or unsubstituted C_6-30Aryl of (2), or substituted or unsubstituted C_2-30A heteroaryl group;

the substituents of the above-mentioned substitutable groups are independently selected from cyano, halogen, C_1-10Alkyl radical, C_6-30Aryl radical, C_2-30One or more heteroaryl groups; the heteroatoms in the heteroaryl and heteroarylene groups are independently selected from oxygen, sulfur or nitrogen atoms.

2. The spirobenzanthracene fluorene compound according to claim 1, wherein in the general formula (2), at least one Z is₁Is N.

3. The spirobenzanthracene fluorene compound according to claim 1, wherein C is_6-30The aryl is phenyl, naphthyl, anthryl, phenanthryl, pyrenyl, biphenylyl, terphenylyl, dimethylfluorenyl or diphenylfluorenyl;

said C is_2-30Heteroaryl is pyridyl, naphthyridinyl, dibenzofuranyl, dibenzothienyl, carbazolyl or azacarbazolyl;

said C is_1-10Alkyl is methyl, ethyl, propyl, isopropyl or tert-butyl.

4. The spirobenzanthracene fluorene compound according to claim 1, wherein Ar is₁、Ar₂Each independently selected from the group consisting of a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted biphenylene, substituted or unsubstituted terphenylene, substituted or unsubstituted pyridylene, and mixtures thereofA substituted or unsubstituted furanylene group, a substituted or unsubstituted naphthyridine group, a substituted or unsubstituted dibenzofuranylene group, a substituted or unsubstituted dibenzothiophenylene group, a substituted or unsubstituted dimethylfluorenyl group, or a substituted or unsubstituted carbazolyl group.

5. The spirobenzanthracene fluorene compound according to claim 1, wherein R is₅、R₆、R₉、R₁₂Each independently selected from any one of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted pyridyl, substituted or unsubstituted biphenylyl, substituted or unsubstituted terphenylyl, substituted or unsubstituted dimethylfluorenyl, substituted or unsubstituted diphenylfluorenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, and substituted or unsubstituted azacarbazolyl.

6. The spirobenzanthracene fluorene compound according to claim 1, wherein R is₇、R₈、R₁₀、R₁₁、R₁₃Each independently selected from any one of a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted naphthyridinyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted biphenylyl group, a substituted or unsubstituted terphenylyl group, a substituted or unsubstituted dimethylfluorenyl group, a substituted or unsubstituted diphenylfluorenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, and a substituted or unsubstituted azacarbazolyl group.

7. A spirobenzanthracene fluorene compound according to any one of claims 1 to 6, wherein the substituent of the substitutable group is selected from one or more of a fluorine atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a phenyl group, a naphthyl group, a naphthyridinyl group, a biphenylyl group, a terphenyl group, a furyl group, a dibenzofuryl group, a carbazolyl group or a pyridyl group.

8. A spirobenzanthracene fluorene compound according to any one of claims 1 to 7, which is a compound having one of the following structures:

9. an organic electroluminescent device comprising an anode, a cathode and at least one organic functional layer disposed in a stacked arrangement, the at least one organic functional layer being located between the cathode and the anode, at least one of the at least one organic functional layer comprising a spirobenzanthracene fluorene compound according to any one of claims 1 to 8;

preferably, the organic functional layer is selected from a light emitting layer, a hole blocking layer or an electron transport layer.

10. A display panel comprising the organic electroluminescent device according to claim 9.

Technical Field

The invention relates to a spirobenzanthracene fluorene compound, an organic electroluminescent device and a display panel, and belongs to the technical field of organic electroluminescence.

Background

Currently, an Organic Light-Emitting Diode (OLED) display technology has been applied in the fields of smart phones, tablet computers, and the like, and is further expanded to large-size application fields such as televisions, but compared with actual product application requirements, the performance of the OLED device, such as Light-Emitting efficiency and service life, needs to be further improved. Aiming at the industrial application requirements of the current OLED device and the photoelectric characteristic requirements of the OLED device, the comprehensive characteristics of high efficiency, long service life and low voltage of the device can be realized only by selecting a more suitable OLED functional material or material combination with higher performance.

Disclosure of Invention

Aiming at the problems in the prior art, the invention provides a spirobenzanthracene fluorene compound which has higher glass transition temperature and molecular thermal stability, and can effectively improve the photoelectric property and the service life of an organic electroluminescent device after being applied to the organic electroluminescent device.

In order to achieve the purpose, the invention adopts the following technical scheme:

the invention provides a spirobenzanthracene fluorene compound which has a structure shown in a general formula (1):

wherein X is selected from-O-, -S-, -C (R)₇)(R₈) -or-N (R)₉)-；

Z is C-R;

each occurrence of R is independently selected from cyano, halogen, C_1-10Alkyl, substituted or unsubstituted C_6-30Aryl, or substituted or unsubstituted C_2-30A heteroaryl group;

R₀、R₁、R₂、R₃、R₄each independently selected from a hydrogen atom, a structure represented by the general formula (2) or the general formula (3), and R₀、R₁、R₂、R₃、R₄At least one of the compounds is selected from the structures shown in the general formula (2) or the general formula (3);

in the general formula (2), X₁Selected from single bond, -O-, -S-, -C (R)₁₀)(R₁₁) -or-N (R)₁₂)-；

i is 0 or 1;

Z₁selected from N, C or C-R₁₃Z is the same as₁Each occurrence is the same or different;

Ar₁selected from single bond, substituted or unsubstituted C_6-30Arylene or substituted or unsubstituted C_2-30A heteroarylene group;

in the general formula (3), Z₂、Z₃、Z₄Is N or CH, and Z₂、Z₃、Z₄At least one of which is N;

Ar₂is a single bond, substituted or unsubstituted C_6-30Arylene, or substituted or unsubstituted C_2-30A heteroarylene group;

R₅、R₆、R₉、R₁₂each independently selected from substituted or unsubstituted C_6-30Aryl or substituted or unsubstituted C_2-30A heteroaryl group;

R₇、R₈、R₁₀、R₁₁、R₁₃each independently selected from hydrogen atom, C_1-10Alkyl, substituted or unsubstituted C_6-30Aryl of (2), or substituted or unsubstituted C_2-30A heteroaryl group;

the substituents of the above-mentioned substitutable groups are independently selected from cyano, halogen, C_1-10Alkyl radical, C_6-30Aryl radical, C_2-30One or more heteroaryl groups; the heteroatoms in the heteroaryl and heteroarylene groups are independently selected from oxygen, sulfur or nitrogen atoms.

Alternatively, in the general formula (2), at least one Z₁Is N.

Optionally, the C_6-30The aryl is phenyl, naphthyl, anthryl, phenanthryl, pyrenyl, biphenylyl, terphenylyl, dimethylfluorenyl or diphenylfluorenyl;

said C is_2-30Heteroaryl is pyridyl, naphthyridinyl, dibenzofuranyl, dibenzothienyl, carbazolyl or azacarbazolyl;

said C is_1-10Alkyl is methyl, ethyl, propyl, isopropyl or tert-butyl.

Optionally, the Ar is₁、Ar₂Each independently selected from the group consisting of a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted furylene group, a substituted or unsubstituted naphthyrylene group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenylene group, a substituted or unsubstituted dimethylfluorenylene group, and a substituted or unsubstituted naphthylene groupAny of the substituted carbazolyl groups.

Alternatively, the R is₅、R₆、R₉、R₁₂Each independently selected from any one of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted pyridyl, substituted or unsubstituted biphenylyl, substituted or unsubstituted terphenylyl, substituted or unsubstituted dimethylfluorenyl, substituted or unsubstituted diphenylfluorenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, and substituted or unsubstituted azacarbazolyl.

Alternatively, the R is₇、R₈、R₁₀、R₁₁、R₁₃Each independently selected from any one of a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted naphthyridinyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted biphenylyl group, a substituted or unsubstituted terphenylyl group, a substituted or unsubstituted dimethylfluorenyl group, a substituted or unsubstituted diphenylfluorenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, and a substituted or unsubstituted azacarbazolyl group.

Optionally, the substituent of the substitutable group is selected from one or more of a fluorine atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a phenyl group, a naphthyl group, a naphthyridinyl group, a biphenyl group, a terphenyl group, a furyl group, a dibenzofuryl group, a carbazolyl group or a pyridyl group.

Optionally, the spirobenzanthracene fluorene compound is selected from compounds shown as formula (1) to formula (224).

The invention provides an organic electroluminescent device, which comprises an anode, a cathode and at least one organic functional layer, wherein the anode, the cathode and the at least one organic functional layer are stacked, the at least one organic functional layer is positioned between the cathode and the anode, and at least one layer of the at least one organic functional layer comprises the spirobenzanthracene fluorene compound.

Preferably, the organic functional layer is selected from a light emitting layer, a hole blocking layer or an electron transport layer.

The present invention provides a display panel comprising an organic electroluminescent device as described in any one of the above.

Compared with the prior art, the invention has the beneficial technical effects that:

(1) the compound provided by the invention takes spirobenzanthracene fluorene as a core, and the structure has the advantages of strong rigidity, large steric hindrance and difficult rotation; the spirobenzanthracene fluorene compound is connected with a heteroanthrone or triazine branched chain, so that the asymmetry of molecules is increased, the crystallinity and the planarity of the molecules can be reduced, the molecules are prevented from moving on a plane, and the three-dimensional structure of the spirobenzanthracene fluorene compound is more stable.

(2) After the substituted group of heteroanthrone or triazine is further added on the parent nucleus of the spirobenzanthracene fluorene compound, the glass transition temperature (Tg) of the material is increased, the active C-H bond is passivated, the stability of the material is improved, and the molecular weight of the material is increased simultaneously by adding the substituted group; in the practical application process, the evaporation temperature of the spirobenzanthracene fluorene compound is reduced compared with that of the existing material, so that the temperature interval between the processing temperature and the decomposition temperature of the material is widened, and the use and processing window of the material is improved.

(3) When the spirobenzanthracene fluorene compound is used as a luminescent layer material of an organic electroluminescent device, especially as a main body material, the distribution of electrons and holes in the luminescent layer is more balanced, and under the appropriate HOMO energy level, the hole injection and transmission performance is improved. When the material is used as a light-emitting functional layer material of an OLED light-emitting device, the exciton utilization rate and the high fluorescence radiation efficiency can be effectively improved, the device efficiency roll-off under the high current density is reduced, the device driving voltage is reduced, the current efficiency of the device is improved, and the service life of the device is prolonged. When the spirobenzanthracene fluorene compound is used as a hole blocking layer material or an electron transport layer material of an OLED, the appropriate LUMO energy level can effectively realize electron transport, the recombination efficiency of excitons in a light-emitting layer is improved, the energy loss is reduced, and the energy of a main material of the light-emitting layer is fully transferred to a doping material, so that the light-emitting efficiency of a light-emitting device is improved.

(4) When the spirobenzanthracene fluorene compound is applied to an OLED device, high film stability can be kept through device structure optimization, the photoelectric property of the OLED device and the service life of the OLED device can be effectively improved, and the spirobenzanthracene fluorene compound has good application effect and industrialization prospect.

Drawings

Fig. 1 is a schematic structural view of an organic electroluminescent device according to the present invention.

Reference numerals:

1. transparent substrate layer, 2, ITO anode layer, 3, hole injection layer, 4, hole transport layer, 5, electron blocking layer, 6, luminescent layer, 7, hole blocking layer, 8, electron transport layer, 9, electron injection layer, 10, cathode layer.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The first aspect of the invention provides a spirobenzanthracene fluorene compound, which has a structure shown in the following general formula (1):

wherein X is selected from-O-, -S-, -C (R)₇)(R₈) -or-N (R)₉)-；

Z is C-R;

each occurrence of R is independently selected from cyano, halogen, C_1-10Alkyl, substituted or unsubstituted C_6-30Aryl, or substituted or unsubstituted C_2-30Heteroaromatic compoundsA group;

R₀、R₁、R₂、R₃、R₄each independently selected from a hydrogen atom, a structure represented by the general formula (2) or the general formula (3), and R₀、R₁、R₂、R₃、R₄At least one of the compounds is selected from the structures shown in the general formula (2) or the general formula (3);

in the general formula (2), X₁Selected from single bond, -O-, -S-, -C (R)₁₀)(R₁₁) -or-N (R)₁₂)-；

i is 0 or 1;

Z₁selected from N, C or C-R₁₃Z is the same as₁Each occurrence is the same or different;

Ar₁selected from single bond, substituted or unsubstituted C_6-30Arylene or substituted or unsubstituted C_2-30A heteroarylene group;

in the general formula (3), Z₂、Z₃、Z₄Is N or CH, and Z₂、Z₃、Z₄At least one of which is N;

Ar₂is a single bond, substituted or unsubstituted C_6-30Arylene, or substituted or unsubstituted C_2-30A heteroarylene group;

R₅、R₆、R₉、R₁₂each independently selected from substituted or unsubstituted C_6-30Aryl or substituted or unsubstituted C_2-30A heteroaryl group;

R₇、R₈、R₁₀、R₁₁、R₁₃each independently selected from hydrogen atom, C_1-10Alkyl, substituted or unsubstituted C_6-30Aryl of (2), or substituted or unsubstituted C_2-30A heteroaryl group;

the substituents of the above-mentioned substitutable groups are independently selected from cyano, halogen, C_1-10Alkyl radical, C_6-30Aryl radical, C_2-30Heteroaromatic compoundsOne or more of the groups; the heteroatoms in the heteroaryl and heteroarylene groups are independently selected from oxygen, sulfur or nitrogen atoms.

In an alternative embodiment, in formula (2), at least one Z₁Is N.

In an alternative embodiment, preferably C is as described above_6-30The aryl group is phenyl, naphthyl, anthryl, phenanthryl, pyrenyl, biphenylyl, terphenylyl, dimethylfluorenyl or diphenylfluorenyl.

Preferably, C is as defined above_2-30Heteroaryl is pyridyl, naphthyridinyl, dibenzofuranyl, dibenzothienyl, carbazolyl or azacarbazolyl.

Preferably, C is as defined above_1-10Alkyl is methyl, ethyl, propyl, isopropyl or tert-butyl.

In an alternative embodiment, Ar₁、Ar₂Each independently selected from any one of a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted furylene group, a substituted or unsubstituted naphthyrylene group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenylene group, a substituted or unsubstituted dimethylfluorenylene group, and a substituted or unsubstituted carbazolyl group.

In an alternative embodiment, R₅、R₆、R₉、R₁₂Each independently selected from any one of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted pyridyl, substituted or unsubstituted biphenylyl, substituted or unsubstituted terphenylyl, substituted or unsubstituted dimethylfluorenyl, substituted or unsubstituted diphenylfluorenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, and substituted or unsubstituted azacarbazolyl.

In an alternative embodiment, R₇、R₈、R₁₀、R₁₁、R₁₃Each independently selected from any one of a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted naphthyridinyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted biphenylyl group, a substituted or unsubstituted terphenylyl group, a substituted or unsubstituted dimethylfluorenyl group, a substituted or unsubstituted diphenylfluorenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, and a substituted or unsubstituted azacarbazolyl group.

In an alternative embodiment, the substituent of the substitutable group is selected from one or more of a fluorine atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a phenyl group, a naphthyl group, a naphthyridinyl group, a biphenylyl group, a terphenyl group, a furyl group, a dibenzofuryl group, a carbazolyl group or a pyridyl group.

In an alternative embodiment, in particular, the spirobenzanthracene fluorene-based compound is a compound having one of the following structures:

a second aspect of the present invention provides an organic electroluminescent device comprising an anode, a cathode and at least one organic functional layer, which are stacked, wherein the at least one organic functional layer is located between the cathode and the anode, and at least one of the at least one organic functional layer comprises a spirobenzanthracene fluorene compound as described in any one of the above.

Preferably, in an alternative embodiment, the organic functional layer is selected from a light emitting layer, a hole blocking layer or an electron transport layer.

A third aspect of the invention provides a display panel comprising the above organic electroluminescent device.

The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention.

Preparation of intermediate A

Preparation process of intermediate a 1:

under nitrogen atmosphere, in a 250ml three-necked flask, 5mmol of C1 as a starting material and 5mmol of D1 as a starting material were added and dissolved in 50ml of tetrahydrofuran, and 15mmol of potassium carbonate and 0.25mmol of Pd (PPh) were added₃)₄The reaction mixture was heated to 70 ℃ and refluxed for 25 hours until the reaction was complete, cooled naturally to room temperature, then treated with triflic acid followed by demethylation with a water-pyridine mixture (5: 1). Extraction with ether, collection of the organic layer, drying over anhydrous magnesium sulfate, rotary evaporation to remove the solvent, and purification of the resulting material through a silica gel column afforded the desired product, intermediate E1.

Adding 0.5mmol of raw material F1 and 20mL of dry tetrahydrofuran into a 500mL three-necked bottle, cooling to-78 ℃ under the protection of nitrogen, slowly dropwise adding 4mL of butyl lithium n-hexane solution (2.5M), keeping the temperature at-78 ℃ for reaction for 30 minutes after the addition is finished, slowly dropwise adding 0.5mmol of intermediate E1, slowly heating to 25 ℃ for reaction for two hours, and stopping the reaction; adding ammonium chloride aqueous solution for hydrolysis, drying the organic layer sodium sulfate, and concentrating to dryness; then 20mL of dichloromethane is added for dissolution, 2g of methane sulfonic acid is slowly dripped into the mixture at 0 ℃ under nitrogen, the mixture is heated to 25 ℃ after the addition for reaction for 1 hour, water is added for separating liquid, an organic layer is concentrated and then is separated by silica gel column chromatography, petroleum ether is used for elution, and the eluent is concentrated to obtain a target product intermediate A1, wherein the yield is 72.3%.

The preparation of intermediate a2 to intermediate a11 is similar to the preparation of intermediate a1, involving the starting materials and the reaction equations shown in table 1:

TABLE 1

Preparation example 1 Synthesis of Compound (2)

Weighing 9.55mol of intermediate A1 and 7.25mol of raw material B1 in a 250mL three-necked bottle, and dissolving the intermediate A1 and the raw material B1 in a mixed solution of toluene, water and ethanol in a volume ratio of 3:1: 1; then 0.021mol Pd (OAc) is added₂、7.53mmol Cs₂CO₃And 14.85mmol Xphos; and (3) carrying out microwave reaction for 5 hours at 120 ℃ under the protection of nitrogen, sampling a sample, completely reacting, and naturally cooling. After the reaction, the organic layer was extracted with dichloromethane and anhydrous MgSO₄Drying, separating and purifying with silica gel column (petroleum ether: ethyl acetate 3:1 as eluent)To the compound (2).

Preparation example 2 Synthesis of Compound (16)

Compound (16) was prepared in the same manner as in preparation example 1, except that starting material B2 was used in place of starting material B1.

Preparation example 3 Synthesis of Compound (38)

Compound (38) was prepared in the same manner as in preparation example 1, except that intermediate a2 was used instead of intermediate a1, and starting material B3 was used instead of starting material B1.

Preparation example 4 Compound (Synthesis of 41)

Compound (41) was prepared by the same method as in preparation example 1, except that intermediate A3 was used instead of intermediate a1, and starting material B4 was used instead of starting material B1.

Preparation example 5 Synthesis of Compound (56)

Compound (56) was prepared in the same manner as in preparation example 1, except that intermediate a4 was used instead of intermediate a1, and starting material B5 was used instead of starting material B1.

Preparation example 6 Synthesis of Compound (66)

Compound (66) was prepared in the same manner as in preparation example 1, except that intermediate a5 was used instead of intermediate a1, and starting material B6 was used instead of starting material B1.

Preparation example 7 Synthesis of Compound (72)

Compound (72) was prepared in the same manner as in preparation example 1, except that intermediate a6 was used instead of intermediate a1, and starting material B7 was used instead of starting material B1.

Preparation example 8 Synthesis of Compound (94)

Compound (94) was prepared by the same method as in preparation example 1, except that intermediate a7 was used instead of intermediate a1, and starting material B8 was used instead of starting material B1.

Preparation example 9 Synthesis of Compound (100)

Compound (100) was prepared in the same manner as in preparation example 1, except that intermediate A8 was used instead of intermediate a1, and starting material B9 was used instead of starting material B1.

Preparation example 10 Synthesis of Compound (110)

Compound (110) was prepared in the same manner as in preparation example 1, except that intermediate a9 was used instead of intermediate a1, and starting material B10 was used instead of starting material B1.

Preparation example 11 Synthesis of Compound (119)

Compound (119) was prepared in the same manner as in preparation example 1, except that intermediate a10 was used instead of intermediate a1, and starting material B11 was used instead of starting material B1.

Preparation example 12 Synthesis of Compound (122)

Compound (122) was prepared by the same method as in preparation example 1, except that intermediate a11 was used instead of intermediate a1, and starting material B12 was used instead of starting material B1.

Preparation example 13 Synthesis of Compound (131)

Compound (131) was prepared by the same method as in preparation example 1, except that intermediate a12 was used instead of intermediate a1, and starting material B13 was used instead of starting material B1.

Preparation example 14 Synthesis of Compound (141)

Compound (141) was prepared by the same method as in preparation example 1, except that intermediate a13 was used instead of intermediate a1, and starting material B14 was used instead of starting material B1.

Preparation example 15 Synthesis of Compound (160)

Compound (160) was prepared in the same manner as in preparation example 1, except that intermediate a14 was used instead of intermediate a1, and starting material B15 was used instead of starting material B1.

Preparation example 16 Synthesis of Compound (176)

Compound (176) was prepared by the same method as in preparation example 1, except that intermediate a15 was used instead of intermediate a1, and starting material B16 was used instead of starting material B1.

Synthesis of Compound (180) of preparation example 17

Compound (180) was prepared by the same method as in preparation example 1, except that intermediate a16 was used instead of intermediate a1 and intermediate B17 was used instead of starting material B1.

Synthesis of Compound (181) of preparation example 18

Compound (181) was prepared in the same manner as in preparation example 1, except that intermediate a17 was used instead of intermediate a1, and starting material B18 was used instead of starting material B1.

The structural characterization of the compound obtained in the above preparation example is shown in table 2:

TABLE 2

The spirobenzanthracene fluorene compound provided by the invention has high glass transition temperature (Tg) and triplet state energy level (T1), and appropriate HOMO and LUMO energy levels, can be used in an organic electroluminescent device, and can be particularly used as a light-emitting layer material or a hole blocking layer material or an electron transport layer material. The compounds prepared in the above examples of the present invention were tested for thermal properties, T1 energy level, and HOMO energy level, respectively, and the results are shown in table 3.

TABLE 3

Wherein: the triplet energy level T1 was measured by Fluorolog-3 series fluorescence spectrometer from Horiba under the conditions of 2 x 10^-5A toluene solution of mol/L; the glass transition temperature Tg is determined by differential scanning calorimetry (DSC, DSC204F1 DSC, Germany Chi corporation), the heating rate is 10 ℃/min; the highest occupied molecular orbital HOMO energy level is tested by an ionization energy testing system (IPS-3), and the test is in an atmospheric environment; eg was measured by a two-beam uv-vis spectrophotometer (model: TU-1901), LUMO ═ HOMO + Eg.

The data in the table show that the compound of the present invention has high glass transition temperature, and can improve the phase stability of the material film, further improve the device lifetime. Meanwhile, the material has proper HOMO and LUMO energy levels. The organic electroluminescent material can solve the problem of carrier injection, reduce the driving voltage of the device, and is suitable to be used as a luminescent layer material or a hole blocking layer material or an electron transport layer material. Therefore, after the spirobenzanthracene fluorene compound is applied to an OLED device, the luminous efficiency of the device can be effectively improved, and the service life of the device can be effectively prolonged.

The effect of the spirobenzanthracene fluorene compound of the present invention as a light-emitting layer or an electron-transporting layer or a hole-blocking layer in a device will be described in detail below by device examples 1 to 18 and device comparative example 1. Compared with the device embodiment 1, the device embodiments 2 to 18 and the device comparative example 1 have the same manufacturing process, adopt the same substrate material and electrode material, and keep the film thickness of the electrode material consistent, except that the material of the luminescent layer or the material of the hole blocking layer or the material of the electron transport layer in the device is changed; the composition of each layer in each device is shown in table 4, and the performance test results of each device are shown in table 5.

Device example 1

As shown in FIG. 1, the transparent substrate layer 1 is a transparent PI film, and the ITO anode layer 2 (having a film thickness of 150nm) is washed, i.e., washed with a cleaning agent (Semiclean M-L20), washed with pure water, dried, and then washed with ultraviolet rays and ozone to remove organic residues on the surface of the transparent ITO layer. On the ITO anode layer 2 after the above washing, HT-1 and P-1 having a film thickness of 10nm were deposited as the hole injection layer 3 by a vacuum deposition apparatus, and the mass ratio of HT-1 to P-1 was 97: 3. Then, HT-1 was evaporated to a thickness of 60nm as the hole transport layer 4. EB-1 was then evaporated to a thickness of 40nm as an electron blocking layer 5. After the evaporation of the electron blocking material is finished, a light emitting layer 6 of the OLED light emitting device is manufactured, and the structure of the light emitting layer 6 comprises that the compound 2 and the GH-2 used in the OLED light emitting layer 6 are used as main body materials, the GD-1 is used as a doping material, the mass ratio of the compound 2 to the GH-2 to the GD-1 is 47:47:6, and the thickness of the light emitting layer is 40 nm. After the light-emitting layer 6, HB-1 was continuously vacuum-deposited to a film thickness of 5nm, and this layer was a hole-blocking layer 7. After the hole-blocking layer 7, ET-1 and Liq were continuously vacuum-evaporated at a mass ratio of ET-1 to Liq of 1:1 and a film thickness of 35nm, and this layer was an electron-transporting layer 8. On the electron transport layer 8, a LiF layer having a film thickness of 1nm was formed by a vacuum evaporation apparatus, and this layer was an electron injection layer 9. On the electron injection layer 9, a vacuum deposition apparatus was used to produce an Mg: the Ag electrode layer is used as a cathode layer 10, and the mass ratio of Mg to Ag is 1: 9. The molecular structural formula of the related material is shown as follows:

TABLE 4

TABLE 5

Wherein the voltage, current efficiency and color coordinate are measured at a current density of 10mA/cm²Tested under conditions using an IVL (current-voltage-brightness) test system (frastd scientific instruments ltd, su); the life test system is an EAS-62C type OLED device life tester of Japan System research company; LT95 refers to the time it takes for the device luminance to decay to 95% at 10000 nits.

From the results in table 5, it can be seen that the spirobenzanthracene fluorene compound provided by the present invention can be used as a light emitting layer host material, an electron transport layer material or a hole blocking layer material when applied to an organic electroluminescent device. Device examples 1-18 gave greater improvements in both efficiency and lifetime than the device using known OLED materials, particularly greater improvements in lifetime degradation of the device, compared to device comparative example 1.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.