阅读说明：本技术 螺环类化合物及其制备方法、发光辅助材料和有机电致发光器件 (Spiro compound, preparation method thereof, light-emitting auxiliary material and organic electroluminescent device ) 是由 汪康 马晓宇 张雪 黄悦 徐佳楠 于 2021-07-21 设计创作，主要内容包括：本发明涉及有机电致发光材料技术领域,具体而言,涉及螺环类化合物及其制备方法、发光辅助材料和有机电致发光器件。螺环类化合物结构式如下所示：其中,X和Y分别独立地选自O、S、CR-(5)R-(6)和NR-(7)中的任意一种；W和V分别独立地选自连接键、O、S、CR-(5)R-(6)和NR-(7)中的任意一种,且W和V不能同时为连接键；m、n和p分别独立地为0-2之间的任意整数,且m、n和p三者不同时为0；L-(1)-L-(3)分别独立地选自连接键或取代或未取代的亚芳基；该螺环类化合物可以作为发光辅助材料,继而有利于改善制备得到的有机电致发光器件的发光效率、驱动电压和使用寿命等。(The invention relates to the technical field of organic electroluminescent materials, in particular to a spiro compound, a preparation method thereof, a luminescent auxiliary material and an organic electroluminescent device. The structural formula of the spiro compound is shown as follows: wherein X and Y are each independently selected from O, S, CR 5 R 6 And NR 7 Any one of the above; w and V are each independently selected from the group consisting of a bond, O, S, CR 5 R 6 And NR 7 And W and V cannot be simultaneously a connecting bond; m, n and p are respectively and independently any integer between 0 and 2, and m, n and p are not 0 at the same time; l is 1 ‑L 3 Each independently selected from a linkage or a substituted or unsubstituted arylene; the spiro compound can be used as a luminescent auxiliary material, and is further beneficial to improving the luminous efficiency, the driving voltage, the service life and the like of the prepared organic electroluminescent device.)

1. The spiro compound is characterized by having a structural formula as follows:

wherein X and Y are each independently selected from O, S, CR₅R₆And NR₇Any one of the above;

w and V are each independently selected from the group consisting of a bond, O, S, CR₅R₆And NR₇And W and V cannot be simultaneously a connecting bond;

m, n and p are respectively and independently any integer between 0 and 2, and m, n and p are not 0 at the same time;

L₁-L₃each independently selected from a linkage or a substituted or unsubstituted arylene;

Ar₁-Ar₆each independently selected from any one of substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, and substituted or unsubstituted fused ring group;

R₁-R₄each independently selected from any one of hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted alkyl and substituted or unsubstituted heteroaryl;

R₅-R₇each independently selected from any one of hydrogen, deuterium, halogen, cyano, nitro, carboxyl, sulfonic acid group, phosphoric acid group, boryl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl.

2. The spiro-compound according to claim 1, wherein said spiro-compound is selected from any one of the compounds represented by the following structural formula:

3. the spiro compound according to claim 1, wherein W and V are each independently selected from any one of the groups represented by the following structural formulae:

preferably, L₁-L₃Each independently selected from a linking bond or a substituted or unsubstituted C6-C20 arylene;

preferably, L₁-L₃Each independently selected from any one of the groups shown in the following structural formula:

4. the spirocyclic compound of claim 1, wherein Ar is Ar₁-Ar₆Each independently selected from the group consisting of substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted 3-to 30-membered heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-to 30-membered heteroaryl, and substituted or unsubstituted C10-C30 fused ring, wherein the heteroatoms in the heterocycloalkyl and heteroaryl are each independently selected from at least one of N, O, S, Si, P, and Se;

preferably, Ar₁-Ar₆Each independently selected from any one of the groups shown in the following structural formula:

5. the spirocyclic compound of claim 1, wherein R is₁-R₄Each independently selected from hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C30 alkyl, and substituted or unsubstituted 3-to 30-membered heteroAny one of aryl, wherein the heteroatom in the heteroaryl is selected from at least one of N, O, S, Si, P and Se;

preferably, R₁-R₄Each independently selected from any one of hydrogen, substituted or unsubstituted C1-C15 alkyl and substituted or unsubstituted 3-20 membered heteroaryl, wherein the heteroatoms in the heteroaryl are selected from at least one of N, O, S, Si, P and Se;

preferably, R₅-R₇Each independently selected from any one of hydrogen, deuterium, halogen, cyano, nitro, carboxyl, sulfonic acid group, phosphoric acid group, boryl, substituted or unsubstituted C1-C25 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted 3-to 20-membered heteroalkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted 3-to 30-membered heteroaryl, wherein the heteroatoms in the heterocycloalkyl and heteroaryl are each independently selected from at least one of N, O, S, Si, P, and Se;

preferably, R₅-R₇Each independently selected from any one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted 3-to 15-membered heteroalkyl, substituted or unsubstituted C6-C20 aryl, and substituted or unsubstituted 3-to 20-membered heteroaryl, wherein the heteroatoms in the heterocycloalkyl and heteroaryl are each independently selected from at least one of N, O, S, Si, P, and Se.

6. The spirocyclic compound of any one of claims 1-5, wherein said spirocyclic compound is selected from any one of the compounds represented by the following structural formula:

7. a process for the preparation of a spirocyclic compound according to any one of claims 1 to 6, wherein said spirocyclic compound is synthesized by reference to the following synthetic route:

，

wherein Hal₁-Hal₃Selected from halogens;

preferably, the preparation conditions of intermediate 1 include: the molar ratio of the compound A to the compound B is 1:1-1.2, the reaction temperature is 80-100 ℃, and the reaction time is 4-6 hours;

the preparation conditions of the intermediate 2 comprise: the molar ratio of the intermediate 1 to the compound C is 1:1-1:1.2, the reaction temperature is 80-100 ℃, and the reaction time is 4-6 hours;

the preparation conditions of the intermediate 3 comprise: the molar ratio of the compound D to the compound E is 1:1-1:1.2, the reaction temperature is 80-100 ℃, and the reaction time is 4-6 hours;

the preparation conditions of the intermediate 4 comprise: the molar ratio of the intermediate 3 to the intermediate 2 is 1:1-1:1.2, the reaction temperature is 20-30 ℃, and the reaction time is 8-12 hours;

the preparation conditions of the spiro compound comprise: the reaction temperature is 120-150 ℃, and the reaction time is 5-15 minutes.

8. A luminescent auxiliary material comprising the spiro compound according to any one of claims 1 to 6 or the spiro compound produced by the method for producing the spiro compound according to claim 7.

9. A composite functional layer comprising a luminescence auxiliary layer, the luminescence auxiliary layer being obtained by a spiro-compound according to any one of claims 1 to 6 or a spiro-compound obtained by the method for producing a spiro-compound according to claim 7 or a luminescence auxiliary material according to claim 8,

preferably, the light-emitting diode further comprises a light-emitting layer and a hole transport layer, wherein the light-emitting auxiliary layer is arranged between the light-emitting layer and the hole transport layer.

10. An organic electroluminescent device, characterized in that it comprises a composite functional layer according to claim 9.

Technical Field

The invention relates to the technical field of organic electroluminescent materials, in particular to a spiro compound, a preparation method thereof, a luminescent auxiliary material and an organic electroluminescent device.

Background

In general, the organic light emitting phenomenon refers to a phenomenon of converting electric energy into light energy using an organic substance. An organic light emitting device manufactured by using the organic light emitting phenomenon has advantages of a wide viewing angle, an excellent contrast, a fast response time, luminance, driving voltage, and response speed characteristics, and the like, and thus, a great deal of research is being conducted.

Many improvements have been made to make organic light emitting devices practical. For example, an anode, a hole injection layer, a hole transport layer, a hole blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode are provided on a substrate, and further various roles of the laminated structure are distributed, thereby realizing high efficiency and high durability of the organic light emitting device. In an organic light emitting device, charges injected from two electrodes are recombined in a light emitting layer to obtain light emission, and in this case, it is important how to efficiently transfer charges of a hole layer and an electron layer to the light emitting layer, and the device is required to have excellent carrier balance. Also, the light emitting efficiency is improved by enhancing a hole injecting property and an electron blocking property of blocking electrons injected from the cathode to increase a recombination probability of holes and electrons, and by confining excitons generated in the light emitting layer. Therefore, the role of the luminescence assisting material is so important. However, until now, the development of stable and efficient light-emitting auxiliary materials for organic light-emitting device elements has not been fully developed, and the industrialization of the technology still faces many key problems, so that the development of new materials is a problem to be solved by those skilled in the art.

In view of this, the invention is particularly proposed.

Disclosure of Invention

The invention aims to provide a spiro compound, a preparation method thereof, a luminescent auxiliary material and an organic electroluminescent device. The embodiment of the invention provides a novel spiro-compound which can be used as a luminescence auxiliary material, and is further beneficial to improving the luminescence efficiency, the driving voltage, the service life and the like of the prepared organic electroluminescent device.

The invention is realized by the following steps:

in a first aspect, the present invention provides a spiro compound, which has a structural formula as follows:

wherein X and Y are each independently selected from O, S, CR₅R₆And NR₇Any one of the above;

w and V are each independently selected from the group consisting of a bond, O, S, CR₅R₆And NR₇And W and V cannot be simultaneously a connecting bond;

m, n and p are respectively and independently any integer between 0 and 2, and m, n and p are not 0 at the same time;

L₁-L₃each independently selected from a linkage or a substituted or unsubstituted arylene;

Ar₁-Ar₆each independently selected from any one of substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, and substituted or unsubstituted fused ring group;

R₁-R₄each independently selected from any one of hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted alkyl and substituted or unsubstituted heteroaryl;

R₅-R₇each independently selected from any one of hydrogen, deuterium, halogen, cyano, nitro, carboxyl, sulfonic acid group, phosphoric acid group, boryl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl.

In a second aspect, the present invention provides a method for producing a spiro compound according to any one of the above embodiments, wherein the spiro compound is synthesized by referring to the following synthetic route:

wherein Hal₁-Hal₃Selected from halogens.

In a third aspect, the present invention provides a luminescent auxiliary material, which includes the spiro compound according to any one of the foregoing embodiments or the spiro compound prepared by the method for preparing the spiro compound according to the foregoing embodiments.

In a fourth aspect, the present invention provides a composite functional layer, which includes a luminescence auxiliary layer, wherein the luminescence auxiliary layer is prepared from the spiro-cyclic compound according to any one of the foregoing embodiments or the spiro-cyclic compound prepared by the method for preparing the spiro-cyclic compound according to the foregoing embodiments or the luminescence auxiliary material according to the foregoing embodiments.

In a fifth aspect, the present invention provides an organic electroluminescent device comprising the composite functional layer according to the previous embodiments.

The invention has the following beneficial effects: the spiro-compound provided by the embodiment of the invention has spiro-group or triarylamine functional group, when the compound is used as a luminescent auxiliary material, the compound can greatly improve the hole transmission efficiency and the electron blocking capability, and the charge balance of holes and electrons in a luminescent layer is increased, so that the luminescence is well formed in the luminescent layer instead of the surface of a hole transport layer, thereby judging the maximization efficiency and the service life. Meanwhile, the spiro compound introduces structures such as benzo-hexahydric heterocycles and the like, reduces the symmetry of molecules, increases conformational isomers of the molecules, has a rigid planar structure, is not easy to crystallize and aggregate among the molecules, improves the yield of organic light-emitting elements, and has the characteristics of improving the light-emitting efficiency, the driving voltage, the service life and the like in an organic light-emitting device.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

The embodiment of the invention provides a spiro compound, which has the following structural formula:

wherein X and Y are each independently selected from O, S, CR₅R₆And NR₇Any one of the above;

w and V are each independently selected from the group consisting of a bond, O, S, CR₅R₆And NR₇And W and V cannot be simultaneously a connecting bond;

m, n and p are respectively and independently any integer between 0 and 2, and m, n and p are not 0 at the same time;

L₁-L₃each independently selected from a linkage or a substituted or unsubstituted arylene;

Ar₁-Ar₆each independently selected from any one of substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, and substituted or unsubstituted fused ring group;

R₁-R₄each independently selected from any one of hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted alkyl and substituted or unsubstituted heteroaryl;

R₅-R₇each independently selected from any one of hydrogen, deuterium, halogen, cyano, nitro, carboxyl, sulfonic acid group, phosphoric acid group, boryl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl.

When the compound is used as a light-emitting auxiliary material, the hole transmission efficiency and the electron blocking capability can be improved to a great extent, and the charge balance of holes and electrons in a light-emitting layer is increased, so that the light-emitting layer does not emit light well in the light-emitting layer instead of the surface of a hole transport layer, and the maximization efficiency and the service life are judged. Meanwhile, the spiro compound introduces structures such as benzo-hexahydric heterocycles and the like, reduces the symmetry of molecules, increases conformational isomers of the molecules, has a rigid planar structure, is not easy to crystallize and aggregate among the molecules, improves the yield of organic light-emitting elements, and has the characteristics of improving the light-emitting efficiency, the driving voltage, the service life and the like in an organic light-emitting device.

In the above structural formula, the position of the functional group, that is, R is not clearly shown₁-R₄、L₁-L₃W and V do not indicate their position on the corresponding benzene ring, which means that R is₁-R₄、L₁-L₃W and V may be in any position corresponding to the phenyl ring.

Further, the spiro compound is selected from any one of the compounds shown in the following structural formula:

further, W and V are each independently selected from any one of the groups represented by the following structural formulae:

further, L₁-L₃Each independently selected from a linking bond or a substituted or unsubstituted C6-C20 arylene; preferably, L₁-L₃Each independently selected from any one of the groups shown in the following structural formula:

further, Ar₁-Ar₆Each independently selected from the group consisting of substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted 3-to 30-membered heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-to 30-membered heteroaryl, and substituted or unsubstituted C10-C30 fused ring, wherein the heteroatoms in the heterocycloalkyl and heteroaryl are each independently selected from at least one of N, O, S, Si, P, and Se; preferably any one of the groups represented by the structural formula:

in the above formula, the position indicated by a letter represents a position where it is bonded to another group or a mother nucleus.

Further, R₁-R₄Each independently selected from any one of hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C30 alkyl (or substituted or unsubstituted C1-C15 alkyl), and substituted or unsubstituted 3-to 30-membered heteroaryl (or substituted or unsubstituted 3-to 20-membered heteroaryl), wherein the heteroatom in the heteroaryl is selected from at least one of N, O, S, Si, P, and Se.

Further, R₅-R₇Each independently selected from any one of hydrogen, deuterium, halogen, cyano, nitro, carboxyl, sulfonic acid group, phosphoric acid group, boryl, substituted or unsubstituted C1-C25 alkyl (or substituted or unsubstituted C1-C20 alkyl), substituted or unsubstituted C3-C20 cycloalkyl (or substituted or unsubstituted C3-C15 cycloalkyl), substituted or unsubstituted 3-to 20-membered heteroalkyl (or substituted or unsubstituted 3-to 15-membered heteroalkyl), substituted or unsubstituted C6-C30 aryl (or substituted or unsubstituted C6-C20 aryl), and substituted or unsubstituted 3-to 30-membered heteroaryl (or substituted or unsubstituted 3-to 20-membered heteroaryl), wherein the heteroatoms in the heterocycloalkyl and heteroaryl groups are each independently selected from at least one of N, O, S, Si, P and Se.

Note that (1) the above "substituted or unsubstituted" means that one, two or more of H linked to C of the corresponding group are substituted with at least one of the following substituents: deuterium, halogen, nitrile group, hydroxyl group, carbonyl group; an ester group, a silyl group, a boryl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted heterocyclylamino group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclyl group, or a substituent linked by two or more of the substituents shown above, or no substituent. For example, "a substituent in which two or more substituents are linked" may include a biphenyl group. In other words, biphenyl can be an aryl group, or can be interpreted as a substituent with two phenyl groups attached.

(2) The C value in the above-mentioned groups such as C6-C20 arylene, C3-C20 cycloalkyl, C3-C15 cycloalkyl, C6-C20 aryl, C6-C30 aryl, C1-C25 alkyl, C1-C20 alkyl and C1-C30 alkyl indicates the number of carbons in the corresponding group.

(3) The arylene group having C6-C20 mentioned above may be selected from biphenylyl groups bonded at different positions, naphthyl groups bonded at different positions, and phenyl groups bonded at different positions as defined above, and may be selected from terphenyls bonded at different positions, phenanthrene-bonded at different positions, and the like. The alkyl group may be a cycloalkyl group such as a cyclopropane group, a cyclohexane group, or a cyclobutane group, the heterocycloalkyl group may be an oxirane group, a thiirane group, a tetrahydrofuran group, or a cyclic ethylimino group, the aryl group may be a phenyl group, a biphenyl group, a terphenyl group, or a naphthyl group, the heteroaryl group may be a heteroaryl group such as a pyridine, a pyrimidine, an imidazole, a piperazine, or a benzindole, the condensed ring group may be a naphthalene, an anthracene, a phenanthrene, an indole, or a quinoline, and the alkyl group may be an alkyl group such as a methyl group, an ethyl group, an isopropyl group, an isobutyl group, or a tert-butyl group.

The spiro compound is selected from any one of the compounds shown in the following structural formula:

the numerical numbers below the above-mentioned structural formulae correspond to the numbers of the compounds described in the following examples, that is, the specific structures of the compounds described in the following examples are determined by: and corresponding to the serial number in the structural formula according to the serial number, and determining the corresponding structural formula according to the serial number.

The embodiment of the invention also provides a preparation method of the spiro-compound, and the spiro-compound is synthesized by referring to the following synthetic route:

wherein Hal₁-Hal₃Selected from halogens, such as any one of fluorine, chlorine, bromine and iodine.

Specifically, intermediate 1 was prepared: under the protection of protective gas (such as nitrogen), dissolving a compound A (1.0eq) and a compound B (1.0-1.2eq) in an organic solution (such as toluene), adding a catalyst (such as tris (dibenzylideneacetone) dipalladium)) (0.005-0.01 eq), a ligand (such as tri-tert-butylphosphine) (0.05-0.10 eq) and a strong base (such as sodium tert-butoxide) (2.0-3.0 eq), uniformly stirring, heating to 80-100 ℃, refluxing for 4-6 hours, keeping an organic phase after the solution is cooled to room temperature, and extracting an aqueous phase (such as extraction by ethyl acetate); after combining the organic phases, drying (e.g., using anhydrous magnesium sulfate) and removal of the solvent is used to obtain a solid organic. And (3) completely dissolving the solid organic matter (for example, using a small amount of dichloromethane), slowly dripping the dissolved solid organic matter into petroleum ether solution, uniformly stirring, precipitating, filtering to obtain a solid, leaching, drying (for example, leaching with absolute ethyl alcohol and petroleum ether in sequence), and preparing the intermediate 1.

Preparation of intermediate 2: under the protection of protective gas (such as nitrogen), dissolving the intermediate 1(1.0eq) and the compound C (1.0-1.2eq) in an organic solution (such as toluene), adding a catalyst (such as tris (dibenzylideneacetone) dipalladium)) (0.005-0.01 eq), a ligand (such as tri-tert-butylphosphine) (0.05-0.10 eq) and a strong base (such as sodium tert-butoxide) (2.0-3.0 eq), uniformly stirring, heating to 80-100 ℃, refluxing for 4-6 hours, keeping an organic phase after the solution is cooled to room temperature, and extracting an aqueous phase (such as extraction by ethyl acetate); after combining the organic phases, drying is carried out (for example using anhydrous magnesium sulfate) and the solvent is removed to give a solid organic. Then dissolving the solid obtained by drying (for example, dissolving in a methanol solution), heating and stirring for 3-5 hours, then carrying out suction filtration on the solution while the solution is hot to obtain a solid, then leaching (for example, petroleum ether), and drying to prepare an intermediate 2;

preparation of intermediate 3: under the protection of protective gas (such as nitrogen), dissolving a compound D (1.0eq) and a compound E (1.0-1.2eq) in an organic solution (such as toluene), adding a catalyst (such as tris (dibenzylideneacetone) dipalladium)) (0.005-0.01 eq), a ligand (such as tri-tert-butylphosphine) (0.05-0.10 eq) and a strong base (such as sodium tert-butoxide) (2.0-3.0 eq), uniformly stirring, heating to 80-100 ℃, refluxing for 4-6 hours, keeping an organic phase after the solution is cooled to room temperature, and extracting an aqueous phase (such as extraction by ethyl acetate); after combining the organic phases, drying (e.g., using anhydrous magnesium sulfate) and removal of the solvent is used to obtain a solid organic. Then dissolving the solid obtained by drying (for example, dissolving in a methanol solution), heating and stirring for 3-5 hours, then carrying out suction filtration on the solution while the solution is hot to obtain a solid, then leaching (for example, petroleum ether), and drying to prepare an intermediate 3;

preparation of intermediate 4: under the protection of protective gas (such as nitrogen), adding the intermediate 3(1.0eq) into a three-neck flask, adding an organic solution (such as anhydrous tetrahydrofuran), then cooling the reaction system to-78 ℃, dropwise adding n-BuLi (1.0-1.5 eq), and stirring at-78 ℃ (2-3 h). Dissolving the intermediate 2(1-1.2eq) in an organic solution (such as tetrahydrofuran), then dropwise adding the solution into the reaction system, heating to room temperature after the dropwise adding is finished, and stirring for 10 hours. Then, the reaction was quenched by adding a saturated ammonium chloride solution, the reaction solution was extracted 3 times with ethyl acetate, and the organic phases were combined and successively washed with water, washed with saturated brine, and dried (with anhydrous magnesium sulfate, for example). Adding the dried solid into an alcohol solution (such as ethanol), heating to 60-80 ℃, stirring for 3-5 hours, carrying out suction filtration on the solution while the solution is hot to obtain a solid, leaching (such as petroleum ether), and drying to prepare an intermediate 4;

preparation of the final product: adding the intermediate 4(1.0eq) into a three-neck flask, adding an organic solution (such as glacial acetic acid), heating to 120-. After cooling to room temperature, the reaction is terminated by adding a sodium bicarbonate solution, the phases are separated, the aqueous phase is extracted three times (for example, with dichloromethane), the organic phase is collected, dried (for example, with anhydrous magnesium sulfate), the solvent is removed, and the residue is purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V dichloromethane: V petroleum ether ═ 10:4) to obtain the desired spiro compound.

The embodiment of the invention also provides a luminescent auxiliary material which comprises the spiro compound or the spiro compound prepared by the preparation method of the spiro compound.

The embodiment of the invention also provides a composite functional layer, which comprises a luminescence auxiliary layer, a luminescent layer and a hole transport layer, wherein the luminescence auxiliary layer is prepared from the spiro compound or the spiro compound prepared by the preparation method of the spiro compound, and the luminescent layer and the hole transport layer are arranged between the luminescent layer and the hole transport layer.

The embodiment of the invention also provides an organic electroluminescent device which comprises a first electrode, a second electrode and at least one organic layer arranged between the first electrode and the second electrode. The organic layer may be a single layer or a multi-layer structure, for example, the organic layer may be a composite functional layer according to an embodiment of the present invention. Specifically, the organic electroluminescent device has a structure including a hole injection layer, a hole transport layer, a light emission auxiliary layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like as organic material layers. It is to be noted that the structure of the organic electroluminescent device is not limited thereto, and a smaller number of organic material layers or a larger number of organic material layers may be included.

The material forming the anode is generally preferably a material having a large work function, which in turn allows holes to be smoothly injected into the organic material layer. Materials that can be used in the present disclosure as anodes include, but are not limited to: metals, e.g. vanadium, chromium, copper, zinc and gold, or alloys thereof(ii) a Metal oxides such as zinc oxide, Indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); combinations of metals and oxides, e.g. ZnO: Al or SnO₂Sb; conductive polymers, e.g. poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene](PEDOT), polypyrrole and polyaniline.

The hole injection material forming the hole injection layer is a material that advantageously receives holes from the anode at low voltages, and the Highest Occupied Molecular Orbital (HOMO) of the hole injection material is preferably between the work function of the anode material and the HOMO of the surrounding organic material layer. The hole injection material includes metalloporphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, perylene-based organic material, anthraquinone, and polyaniline-and polythiophene-based conductive polymer, etc., but is not limited thereto, and may further include another compound capable of p-doping.

The hole transport material forming the hole transport layer is a material capable of receiving holes from the anode or the hole injection layer and transporting the holes to the light emitting layer, and a material having high hole mobility is suitable. Specific examples thereof include arylamine-based organic materials, conductive polymers, block copolymers having both conjugated portions and non-conjugated portions, and the like, but are not limited thereto.

The light emitting layer may emit red, green or blue light, and may be formed of a phosphorescent material or a fluorescent material. The light-emitting material forming the light-emitting layer is a material capable of emitting light in the visible light region by receiving holes and electrons from the hole-transport layer and the electron-transport layer, respectively, and combining the holes and the electrons, and is preferably a material having favorable quantum efficiency for fluorescence or phosphorescence. Specific examples thereof include: 8-hydroxyquinoline aluminum complex (Alq 3); a carbazole-based compound; a di-polystyrene based compound; BAlq; 10-hydroxybenzoquinoline-metal compounds; benzocarbazole-, benzothiazole-, and benzimidazole-based compounds; polymers based on poly (p-phenylene vinylene) (PPV); a spiro compound; a polyfluorene; rubrene, and the like, but is not limited thereto.

The host material of the light-emitting layer includes a condensed aromatic ring derivative, a heterocyclic ring-containing compound, and the like. Specifically, the fused aromatic ring derivative includes an anthracene derivative, a pyrene derivative, a naphthalene derivative, a pentacene derivative, a phenanthrene compound, a fluoranthene compound, and the like, and the heterocycle-containing compound includes a carbazole derivative, a dibenzofuran derivative, a ladder-type furan compound, a pyrimidine derivative, and the like, however, the material is not limited thereto.

The electron transport layer may function to facilitate electron transport. The electron transport material forming the electron transport layer is a material that favorably receives electrons from the cathode and transports the electrons to the light emitting layer, and a material having high electron mobility is suitable. Specific examples thereof include: al complexes of 8-hydroxyquinoline; a complex comprising Alq 3; an organic radical compound; a hydroxyflavone-metal complex; and the like, but are not limited thereto. The thickness of the electron transport layer may be 1nm to 50 nm. The electron transport layer having a thickness of 1nm or more has an advantage of preventing the electron transport property from being degraded, and the electron transport layer having a thickness of 50nm or less has an advantage of preventing the driving voltage for enhancing electron transfer from being increased due to the electron transport layer being too thick.

The electron injection layer may function to promote electron injection. The electron injection material forming the electron injection layer is preferably a compound of: it has an ability to transport electrons, has an electron injection effect from a cathode, has an excellent electron injection effect on a light emitting layer or a light emitting material, prevents excitons generated in the light emitting layer from migrating to a hole injection layer, and, in addition, has an excellent thin film forming ability. Specific examples thereof include fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenylidene methane, anthrone, and the like and derivatives thereof, metal complexes, nitrogen-containing 5-membered ring derivatives, and the like, but are not limited thereto.

As the cathode material, a material having a small work function is generally preferred so that electrons are smoothly injected into the organic material layer. Specific examples of the cathode material include: metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; multilayer structure materialFor example LiF/Al or LiO₂Al; and the like, but are not limited thereto.

The organic electroluminescent device provided by the invention can be applied to Organic Light Emitting Devices (OLEDs), Organic Solar Cells (OSCs), electronic paper (e-paper), Organic Photoreceptors (OPC) or Organic Thin Film Transistors (OTFTs).

The features and properties of the present invention are described in further detail below with reference to examples.

Example 1

The embodiment of the invention provides a spiro compound (number: compound-6), which comprises the following synthetic steps:

step 1: under the protection of nitrogen, dissolving a compound D-6(20.00mmol) and a compound E-6(20.00mmol) in 140.00ml of toluene solution, adding tris (dibenzylideneacetone) dipalladium (0.20mmol), tri-tert-butylphosphine (1.00mmol) and sodium tert-butoxide (40.00mmol), uniformly stirring, heating to 90 ℃, refluxing for 5 hours, cooling the solution to room temperature, retaining an organic phase, and extracting an aqueous phase by using ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. The solid obtained by drying was then dissolved in a methanol solution and stirred at elevated temperature for 5 hours, and then the solution was suction-filtered while still hot to obtain a solid, which was then rinsed with petroleum ether and dried to prepare intermediate 3(9.83g, yield: 86.43%). The synthesis route of step 1 is as follows:

step 2: under the protection of nitrogen, the intermediate 3(15.83mmol) is added into a three-neck flask, 90.00ml of anhydrous tetrahydrofuran is added, then the reaction system is cooled to-78 ℃, n-BuLi (15.00ml) is added dropwise, and the mixture is stirred for 2 hours at-78 ℃. The compound A-6(19.00mmol) is dissolved in 60.00ml tetrahydrofuran solution, then is dripped into the reaction system, and after the dripping is finished, the temperature is raised to the room temperature and the stirring is carried out for 10 h. Then, a saturated ammonium chloride solution was added to quench the reaction, the reaction solution was extracted 3 times with ethyl acetate, and the organic phases were combined and successively washed with water and saturated brine, followed by drying over anhydrous magnesium sulfate. The dried solid was then added to an ethanol solution and warmed to 80 ℃ and stirred for 5 hours, and then the solution was suction filtered while hot to give a solid, which was then rinsed with petroleum ether and dried to give intermediate 4(10.50g, yield: 82.11%). The synthesis route of step 2 is as follows:

and step 3: adding intermediate 4(12.38mmol) into a three-neck flask, adding 62.00ml of glacial acetic acid, heating to 120 ℃, dropwise adding 1.20ml of concentrated sulfuric acid, and stirring for 5 min. After cooling to room temperature, 12.00ml of sodium hydrogencarbonate solution was added to terminate the reaction, the aqueous phase was separated, extracted three times with dichloromethane, the organic phase was collected, dried over anhydrous magnesium sulfate was added, the solvent was removed by a rotary evaporator, and the remaining substance was purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V dichloromethane: V petroleum ether ═ 10:4) to obtain compound-6 (7.86g, yield: 80.33%, Mw: 790.04). The synthesis route of step 3 is as follows:

compound-6 was characterized with the following data:

HPLC purity: is more than 99 percent.

Mass spectrometry test: a theoretical value of 790.06; the test value was 790.04.

Elemental analysis: the calculated values are: c, 85.14; h, 4.98; n, 1.77; and S, 8.12.

The test values are: c, 85.15; h, 4.97; n, 1.76; and S, 8.13.

Example 2

The embodiment of the invention provides a spiro compound (number: compound-31), which comprises the following synthetic steps:

step 1: under the protection of nitrogen, dissolving a compound A-31(20.00mmol) and a compound C-31(20.00mmol) in 150.00ml of toluene solution, adding tris (dibenzylideneacetone) dipalladium (0.20mmol), tri-tert-butylphosphine (1.00mmol) and sodium tert-butoxide (40.00mmol), uniformly stirring, heating to 90 ℃, refluxing for 5 hours, cooling the solution to room temperature, retaining an organic phase, and extracting an aqueous phase by using ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. The solid obtained by drying was then dissolved in a methanol solution and stirred at elevated temperature for 5 hours, and then the solution was suction-filtered while it was hot to obtain a solid, which was then rinsed with petroleum ether and dried to prepare intermediate 2(11.40g, yield: 86.40%). The synthesis route of step 1 is specifically as follows:

step 2: under the protection of nitrogen, compound D-31(13.89mmol) was added into a three-necked flask, 30.00ml of anhydrous tetrahydrofuran was added, and then the reaction system was cooled to-78 ℃, n-BuLi (13.00ml) was added dropwise, and stirred at-78 ℃ for 2 hours. The intermediate 2(16.67mmol) was dissolved in 110.00ml of tetrahydrofuran solution, and then added dropwise to the above reaction system, after completion of the addition, the temperature was raised to room temperature, and stirred for 10 hours. Then, a saturated ammonium chloride solution was added to quench the reaction, the reaction solution was extracted 3 times with ethyl acetate, and the organic phases were combined and successively washed with water and saturated brine, followed by drying over anhydrous magnesium sulfate. The dried solid was then added to an ethanol solution and warmed to 80 ℃ and stirred for 5 hours, and the solution was then suction filtered while hot to give a solid which was then rinsed with petroleum ether and dried to afford intermediate 4(9.46g, yield: 82.04%). The synthesis route of step 2 is specifically as follows:

and step 3: adding intermediate 4(10.84mmol) into a three-neck flask, adding 50.00ml glacial acetic acid, heating to 120 deg.C, adding 1.10ml concentrated sulfuric acid dropwise, and stirring for 5 min. After cooling to room temperature, 10.00ml of sodium bicarbonate solution was added to terminate the reaction, the reaction solution was separated, the aqueous phase was extracted three times with dichloromethane, the organic phase was collected, dried over anhydrous magnesium sulfate, the solvent was removed by a rotary evaporator, and the remaining substance was purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V dichloromethane: V petroleum ether ═ 10:4) to obtain compound-31 (7.07g, yield: 80.36%, Mw: 811.93). The synthesis route of step 3 is specifically as follows:

characterization data for compound-31 are as follows: HPLC purity: is more than 99 percent.

Mass spectrometry test: a theoretical value of 811.94; the test value was 811.93.

Elemental analysis: the calculated values are: c, 85.80; h, 4.59; n, 1.73; and O, 7.88.

The test values are: c, 85.81; h, 4.58; n, 1.74; and O, 7.87.

Example 3

The embodiment of the invention provides a spiro compound (number: compound-57), which comprises the following synthetic steps:

step 1: under the protection of nitrogen, dissolving a compound A-57(20.00mmol) and a compound C-57(20.00mmol) in 140.00ml of toluene solution, adding tris (dibenzylideneacetone) dipalladium (0.20mmol), tri-tert-butylphosphine (1.00mmol) and sodium tert-butoxide (40.00mmol), uniformly stirring, heating to 90 ℃, refluxing for 5 hours, cooling the solution to room temperature, retaining an organic phase, and extracting an aqueous phase with ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. The solid obtained by drying was then dissolved in a methanol solution and stirred at elevated temperature for 5 hours, and then the solution was suction-filtered while it was hot to obtain a solid, which was then rinsed with petroleum ether and dried to prepare intermediate 2(11.15g, yield: 86.44%). The synthesis route of step 1 is specifically as follows:

step 2: under the protection of nitrogen, compound D-57(14.22mmol) was added to a three-necked flask, 40.00ml of anhydrous tetrahydrofuran was added, and then the reaction system was cooled to-78 ℃, n-BuLi (1.40ml) was added dropwise, and stirred at-78 ℃ for 2 h. The intermediate 2(17.06mmol) was dissolved in 110.00ml of tetrahydrofuran solution, and then added dropwise to the above reaction system, after completion of the dropwise addition, the temperature was raised to room temperature, and the mixture was stirred for 10 hours. Then, a saturated ammonium chloride solution was added to quench the reaction, the reaction solution was extracted 3 times with ethyl acetate, and the organic phases were combined and successively washed with water and saturated brine, followed by drying over anhydrous magnesium sulfate. The dried solid was then added to an ethanol solution and warmed to 80 ℃ and stirred for 5 hours, and the solution was then suction filtered while hot to give a solid which was then rinsed with petroleum ether and dried to afford intermediate 4(9.82g, yield: 82.08%). The synthesis route of step 2 is specifically as follows:

and step 3: adding intermediate 4(10.93mmol) into a three-neck flask, adding 50.00ml glacial acetic acid, heating to 120 deg.C, adding 1.10ml concentrated sulfuric acid dropwise, and stirring for 5 min. After cooling to room temperature, a sodium hydrogencarbonate solution was added to terminate the reaction, the liquid was separated, the aqueous phase was extracted three times with dichloromethane, the organic phase was collected, dried over anhydrous magnesium sulfate was added, the solvent was removed by a rotary evaporator, and the remaining substance was purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V dichloromethane: V petroleum ether ═ 10:4) to obtain compound-57 (7.24g, yield: 80.39%, Mw: 823.05). The synthesis route of step 3 is specifically as follows:

characterization data for compound-57 are as follows:

HPLC purity: is more than 99 percent.

Mass spectrometry test: a theoretical value of 823.05; the test value was 823.05.

Elemental analysis: the calculated values are: c, 89.02; h, 5.63; n, 3.40; o, 1.94.

The test values are: c, 89.03; h, 5.62; n, 3.41; o, 1.93.

Example 4

The embodiment of the invention provides a spiro compound (number: compound-88), which comprises the following synthetic steps:

step 1: under the protection of nitrogen, dissolving a compound A-88(20.00mmol) and a compound B-88(20.00mmol) in 160.00ml of toluene solution, adding tris (dibenzylideneacetone) dipalladium (0.20mmol), tri-tert-butylphosphine (1.00mmol) and sodium tert-butoxide (40.00mmol), uniformly stirring, heating to 90 ℃, refluxing for 5 hours, after the solution is cooled to room temperature, retaining an organic phase, and then extracting an aqueous phase with ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. And (2) completely dissolving the solid organic matter by using a small amount of dichloromethane, slowly dropwise adding the dissolved organic matter into a petroleum ether solution, uniformly stirring, precipitating, performing suction filtration to obtain a solid, sequentially leaching by using absolute ethyl alcohol and petroleum ether, and drying to obtain an intermediate 1(12.45g, yield: 86.11%). The synthesis route of step 1 is specifically as follows:

step 2: under the protection of nitrogen, compound D-88(13.83mmol) was added into a three-necked flask, 30.00ml of anhydrous tetrahydrofuran was added, and then the reaction system was cooled to-78 ℃, n-BuLi (1.40ml) was added dropwise, and stirred at-78 ℃ for 2 h. The intermediate 1(16.60mmol) was dissolved in 120.00ml of tetrahydrofuran solution, and then added dropwise to the above reaction system, after completion of the dropwise addition, the temperature was raised to room temperature, and stirred for 10 hours. Then, a saturated ammonium chloride solution was added to quench the reaction, the reaction solution was extracted 3 times with ethyl acetate, and the organic phases were combined and successively washed with water and saturated brine, followed by drying over anhydrous magnesium sulfate. The dried solid was then added to an ethanol solution, and heated to 80 ℃ and stirred for 5 hours, followed by suction filtration of the solution while it was hot to give a solid, which was then rinsed with petroleum ether and dried to give intermediate 4(10.13g, yield: 82.06%). The synthesis route of step 2 is specifically as follows:

and step 3: adding intermediate 4(11.20mmol) into a three-neck flask, adding 50.00ml glacial acetic acid, heating to 120 deg.C, adding 1.10ml concentrated sulfuric acid dropwise, and stirring for 5 min. After cooling to room temperature, 11.00ml of sodium bicarbonate solution was added to terminate the reaction, the reaction solution was separated, the aqueous phase was extracted three times with dichloromethane, the organic phase was collected, dried over anhydrous magnesium sulfate, the solvent was removed by a rotary evaporator, and the remaining substance was purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V dichloromethane: V petroleum ether ═ 10:4) to obtain compound-88 (7.88g, yield: 80.43%, Mw: 875.08). The synthesis route of step 3 is specifically as follows:

characterization data for compound-88 is as follows:

HPLC purity: is more than 99 percent.

Mass spectrometry test: a theoretical value of 875.09; the test value was 875.08.

Elemental analysis: the calculated values are: c, 78.23; h, 3.92; n, 3.20; o, 3.66; and S, 10.99.

The test values are: c, 78.24; h, 3.93; n, 3.21; o, 3.65; s, 10.97.

The general structural formula is chemical formula 1 described in the summary of the invention, and the synthetic routes and principles of other compounds are the same as those of the above-mentioned examples, so the whole list is not exhaustive.

The compounds synthesized in the examples of the present invention were tested for their glass transition temperature (tg) using TMA4000, the results of which are shown in the following table:

as can be seen from the above table, the spiro-compound provided by the embodiment of the invention has better thermal stability.

Organic electroluminescent device example 1

The embodiment provides a method for manufacturing an organic electroluminescent device, which includes the steps of:

the method comprises the following steps of putting an ITO (indium tin oxide) -Ag-ITO (indium tin oxide) glass substrate with the coating thickness of 150nm into distilled water for cleaning for 2 times, ultrasonically cleaning for 30 minutes, repeatedly cleaning for 2 times by using the distilled water, ultrasonically cleaning for 10 minutes, after the cleaning by using the distilled water is finished, ultrasonically cleaning solvents such as isopropanol, acetone, methanol and the like in sequence, drying, transferring the substrates into a plasma cleaning machine, cleaning for 5 minutes, and conveying the substrates into an evaporation machine.

Firstly, evaporating a hole injection layer material HAT-CN on an ITO (indium tin oxide) -Ag-ITO (indium tin oxide) anode layer in a vacuum evaporation mode, wherein the thickness of the hole injection layer material HAT-CN is 10 nm; vacuum evaporating TCTA of 15nm as a hole transport layer on the hole injection layer; vacuum evaporating 95nm of the compound-6 provided in example 1 above on the hole transport layer to form a light-emitting auxiliary layer; then, vacuum evaporation is carried out on the light-emitting auxiliary layer to form a main material CBP with the thickness of 40nm and a doping material Ir (PPy)2(acac) which are used as light-emitting layers, wherein the weight ratio of the main material to the doping material is 96: 4; then, BCP and Liq with the thickness of 35nm are subjected to vacuum evaporation on the light-emitting layer to form an electron transport layer, wherein the weight ratio of the BCP to the Liq is 60: 40; vacuum evaporating Yb with the thickness of 1nm on the electron transport layer to form an electron injection layer; finally, performing vacuum evaporation on the electron injection layer to form magnesium and silver as cathodes, wherein the weight ratio of the magnesium to the silver is 1:9, and the evaporation thickness is 18 nm; IDX002 with the thickness of 70nm is vacuum evaporated on the cathode to be used as a light extraction layer, and then the organic electroluminescent device can be obtained.

By referring to the method provided in device example 1 above, compounds 1, 10, 15, 21, 25, 28, 31, 35, 44, 50, 52, 55, 57, 65, 70, 79, 84, 88, and 93 were selected instead of compound-6 above, respectively, and evaporation of a light-emitting auxiliary layer was performed to prepare corresponding organic electroluminescent devices, which are denoted as device examples 2 to 20, respectively.

Organic electroluminescent device comparative example 1:

this comparative example provides an organic electroluminescent device, which was prepared by a method different from that of the above-mentioned organic electroluminescent device example 1 only in that the organic electroluminescent device was subjected to evaporation using the existing comparative compound a instead of the light-emitting auxiliary material (compound-6) in the above-mentioned device example 1. Wherein the chemical structural formula of comparative compound a is:

the driving voltages, the light emitting efficiencies, and the lifetimes of the organic electroluminescent devices obtained in the above organic electroluminescent device examples 1 to 100 and the organic electroluminescent device comparative example 1 were characterized at a luminance of 15000(nits), and the test results are as follows:

according to the above table, the organic electroluminescent device prepared by using the spiro compound provided by the present invention as a luminescent auxiliary material has a significantly reduced driving voltage, and significantly improved luminous efficiency and lifetime, compared to the conventional organic electroluminescent device provided in comparative example 1.

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.