A kind of azaspirofluorene compound and organic electroluminescent element containing the same

Abstract

The present invention relates to the field of organic electroluminescence technology, and more specifically, to an azaspirofluorene compound, an organic element material, an organic electroluminescent element, and a display or lighting device. An azaspirofluorene compound has a structure as shown in Formula 1 below: #imgabs0# Formula 1 The azaspirofluorene compound provided by the present invention has a lower driving voltage and a longer service life, and is suitable for preparing high-performance organic electroluminescent elements.

Description

Technical Field

[0001] The present invention relates to the technical field of organic electroluminescence, and more specifically to an azaspirofluorene compound, a material for an organic element, an organic electroluminescent element, and a display or lighting device. Background Art

[0002] Organic electroluminescent elements (OLEDs) are self-luminous display devices based on organic electroluminescent materials. Compared with existing liquid crystal display devices, they have the advantages of not requiring a backlight source and being thin. They are a technology suitable for flexible device devices (flexible light-emitting display devices) and can be used to manufacture new display products as well as new lighting products. They have broad application prospects.

[0003] An organic electroluminescent element includes an anode, a cathode, and an organic functional layer located between the anode and the cathode. The organic functional layer is composed of a multilayer structure composed of various different substances, such as a hole injection layer, a hole transport layer, a second hole transport layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an N-type charge generation layer, a P-type charge generation layer, a hole transport layer, a second hole transport layer, a light-emitting layer, a hole blocking layer, an electron transport layer, a second electrode layer, etc., which can make the carriers of holes and electrons recombine in the light-emitting layer, and the carrier recombination generates excitons, which transition from an excited state to a ground state to generate light.

[0004] Current research into improving the performance of organic electroluminescent devices includes reducing the device's driving voltage, increasing its luminous efficiency, and extending its lifespan. The properties of the organic compound components contained in each layer significantly influence the device's driving voltage, luminous efficiency, and lifespan. Therefore, the use of specific organic materials with excellent performance is considered crucial in organic electroluminescent devices.

[0005] Furthermore, a charge generation layer is required to increase the efficiency of the current generated in the light-emitting layer and facilitate charge distribution between two or more stacks (or light-emitting units) in a tandem OLED. This, depending on the material used for the N-type charge generation layer, affects the driving voltage and lifetime of the entire device.

[0006] Therefore, it is necessary to continuously research and innovate organic electroluminescent functional materials to produce higher performance organic electroluminescent functional materials, and then produce organic electroluminescent elements with excellent performance. Summary of the Invention

[0007] The technical problem to be solved by the present invention is to further develop an azaspirofluorene compound that can be used as an organic electroluminescent material, thereby improving the performance of the organic electroluminescent element.

[0008] The technical solutions of the present invention are as follows:

[0009] In a first aspect, the present invention provides an azaspirofluorene compound, wherein the structure of the azaspirofluorene compound is preferably as shown in Formula 1 below:

[0010]

[0011] Formula 1

[0012] in,

[0013] Ar1 is preferably hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted C6-C 60 aryl, substituted or unsubstituted C3-C 60 The heteroaryl group is preferably hydrogen, deuterium, halogen, substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted C6-C 60 aryl, substituted or unsubstituted C3-C 60 The heteroaryl group is more preferably hydrogen, deuterium, halogen, substituted or unsubstituted C6-C 60 aryl, substituted or unsubstituted C3-C 60 Heteroaryl, most preferably hydrogen, substituted or unsubstituted C6-C 60 aryl, substituted or unsubstituted C3-C 60 heteroaryl;

[0014] L is preferably a substituted or unsubstituted C6-C 60 arylene, substituted or unsubstituted C3-C 60 Heteroarylene, C1-C 10 Alkenylene, C1-C 10 substituted or unsubstituted fluorenyl, substituted or unsubstituted heterofluorenyl; preferably substituted or unsubstituted C6-C 60 arylene, substituted or unsubstituted C3-C 60 Heteroarylene, C1-C 10 substituted or unsubstituted fluorenyl, substituted or unsubstituted heterofluorenyl; most preferably substituted or unsubstituted C6-C 60 arylene, substituted or unsubstituted C3-C 60 and is not a substituted or unsubstituted fluorenyl group or a substituted or unsubstituted heterofluorenyl group;

[0015] Ar2 is preferably represented by the following formula a, formula b, formula c or formula d:

[0016]

[0017] Formula a Formula b

[0018]

[0019] Formula c Formula d

[0020] “ " represents the connection position of the Ar2 group and the L group;

[0021] R1 and R2 are each independently preferably hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted C6-C 60 aryl, substituted or unsubstituted C3-C 60 The heteroaryl group is preferably hydrogen, deuterium, halogen, substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted C6-C 60 aryl, substituted or unsubstituted C3-C 60 The heteroaryl group is more preferably hydrogen, deuterium, halogen, substituted or unsubstituted C6-C 60 aryl, substituted or unsubstituted C3-C 60 Heteroaryl, most preferably hydrogen, substituted or unsubstituted C6-C 60 aryl, substituted or unsubstituted C3-C 60 heteroaryl;

[0022] R3, R4, R5, R6 are the same as or different from each other, and are each independently preferably hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C 10 The alkyl group is preferably hydrogen, deuterium, halogen, substituted or unsubstituted C1-C 10 More preferably, hydrogen, halogen, substituted or unsubstituted C1-C 10 Especially preferably hydrogen, substituted or unsubstituted C1-C 10 Most preferably, hydrogen;

[0023] a is preferably an integer from 0 to 4, more preferably an integer from 0 to 3, more preferably 0, 1, 2, particularly preferably 0, 1, and most preferably 0; when a is 2 or greater, multiple R3 are the same or different from each other;

[0024] b is preferably an integer of 0 to 4, more preferably an integer of 0 to 3, more preferably 0, 1, 2, particularly preferably 0, 1, and most preferably 0; when b is 2 or greater, multiple R4 are the same or different from each other;

[0025] c is preferably an integer from 0 to 2, more preferably 0, 1, and most preferably 0; when c is 2 or greater, multiple R5 are the same or different from each other;

[0026] d is preferably an integer from 0 to 2, more preferably 0, 1, and most preferably 0; when d is 2 or greater, multiple R6 are the same as or different from each other;

[0027] The substituents in the "substituted or unsubstituted" are preferably each independently selected from deuterium, halogen, cyano, C1-C 10 Alkyl, C1-C 10 Alkoxy, amino, C3-C 10 Cycloalkyl, C3-C 10 Cycloalkoxy, C6-C 60 Aryl, C6-C 60 Aryloxy, C3-C 60 One or a combination of heteroaryl groups;

[0028] The heteroatoms in the heteroaryl group and the heteroarylene group are preferably selected from one or more of N, O, S, Si, P, and B;

[0029] Preferably, the above compound may not contain or contain at least one substituent selected from deuterium, fluoro group, and cyano group; more preferably, the above compound may not contain or contain at least one substituent selected from deuterium and fluoro group; more preferably, the above compound may not contain or contain at least one deuterium.

[0030] According to the above-mentioned azaspirofluorene compound, the structure of the azaspirofluorene compound is preferably as shown in the following formula 1':

[0031]

[0032] Formula 1'

[0033] Wherein, L, Ar1, and Ar2 are as defined above;

[0034] Preferably, the above compound may not contain or contain at least one substituent selected from deuterium, fluoro group, and cyano group; more preferably, the above compound may not contain or contain at least one substituent selected from deuterium and fluoro group; more preferably, the above compound may not contain or contain at least one deuterium.

[0035] According to the above-mentioned azaspirofluorene compound, the structure of the azaspirofluorene compound is preferably as shown in the following formula 1a, formula 1b, formula 1c, and formula 1d:

[0036]

[0037] Formula 1a Formula 1b

[0038]

[0039] Formula 1c Formula 1d

[0040] Wherein, Ar1, L, R1, and R2 are as defined above;

[0041] Preferably, the above compound may not contain or contain at least one substituent selected from deuterium, fluoro group, and cyano group; more preferably, the above compound may not contain or contain at least one substituent selected from deuterium and fluoro group; more preferably, the above compound may not contain or contain at least one deuterium.

[0042] According to the above-mentioned azaspirofluorene compound, wherein,

[0043] The Ar1 is preferably hydrogen, substituted or unsubstituted C6-C 60 aryl, substituted or unsubstituted C3-C 60 The heteroaryl group is preferably hydrogen, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted pyrrolyl, substituted or unsubstituted imidazolyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted triazinyl, preferably hydrogen, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted a substituted dibenzothienyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted pyridyl group, or a substituted or unsubstituted triazinyl group, more preferably a hydrogen atom, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted dibenzothienyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted pyridyl group, particularly preferably a hydrogen atom, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted pyridyl group, most preferably a hydrogen atom, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted pyridyl group;

[0044] The L is preferably a substituted or unsubstituted C6-C 60 arylene, substituted or unsubstituted C3-C 60and L is not a substituted or unsubstituted fluorenyl group or a substituted or unsubstituted heterofluorenyl group, more preferably a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted anthrylene group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted pyrrolylene group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzothiophenylene group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted triazinyl group, more preferably a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted dibenzothiophenylene group, a substituted or unsubstituted substituted or unsubstituted dibenzofuranylene, substituted or unsubstituted pyridylene, substituted or unsubstituted triazinylene, more preferably substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted dibenzothiophenylene, substituted or unsubstituted dibenzofuranylene, substituted or unsubstituted pyridylene, particularly preferably substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted dibenzothiophenylene, substituted or unsubstituted dibenzofuranylene, substituted or unsubstituted pyridylene, most preferably substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted dibenzothiophenylene, substituted or unsubstituted dibenzofuranylene, substituted or unsubstituted pyridylene;

[0045] Said R1 and R2 are preferably independently hydrogen, substituted or unsubstituted C6-C 60 aryl, substituted or unsubstituted C3-C 60The heteroaryl group is preferably hydrogen, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted pyrrolyl, substituted or unsubstituted imidazolyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted triazinyl, preferably hydrogen, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted a substituted dibenzothienyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted pyridyl group, or a substituted or unsubstituted triazinyl group, more preferably a hydrogen atom, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted dibenzothienyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted pyridyl group, particularly preferably a hydrogen atom, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted pyridyl group, most preferably a hydrogen atom, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted pyridyl group;

[0046] In the case of "substituted or unsubstituted", the substituent is as defined above.

[0047] According to the above-mentioned azaspirofluorene compound, wherein,

[0048] Ar1 is preferably hydrogen, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridyl, more preferably hydrogen, substituted or unsubstituted phenyl, substituted or unsubstituted pyridyl, more preferably hydrogen, unsubstituted phenyl, deuterium-substituted phenyl, fluorine-substituted phenyl, unsubstituted pyridyl, most preferably hydrogen, unsubstituted phenyl;

[0049] The L is preferably a substituted or unsubstituted phenylene, a substituted or unsubstituted biphenylene, a substituted or unsubstituted dibenzothienylene, a substituted or unsubstituted dibenzofuranylene, or a substituted or unsubstituted pyridylene; more preferably, it is an unsubstituted phenylene, a deuterium-substituted phenylene, a fluorine-substituted phenylene, an unsubstituted biphenylene, a deuterium-substituted biphenylene, a fluorine-substituted biphenylene, an unsubstituted dibenzothienylene, an unsubstituted dibenzofuranylene, or an unsubstituted pyridylene; most preferably, it is an unsubstituted phenylene, a fluorine-substituted phenylene, an unsubstituted biphenylene, an unsubstituted dibenzothienylene, an unsubstituted dibenzofuranylene, or an unsubstituted pyridylene;

[0050] Said R1 is preferably hydrogen, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridyl, more preferably hydrogen, substituted or unsubstituted phenyl, substituted or unsubstituted pyridyl, more preferably hydrogen, substituted or unsubstituted benzene, particularly preferably hydrogen, unsubstituted phenyl, deuterium-substituted phenyl, fluorine-substituted phenyl, particularly preferably hydrogen, unsubstituted benzene, most preferably hydrogen;

[0051] Said R2 is preferably hydrogen, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridyl, more preferably hydrogen, unsubstituted phenyl, deuterium-substituted phenyl, fluorine-substituted phenyl, unsubstituted naphthyl, deuterium-substituted naphthyl, fluorine-substituted naphthyl, unsubstituted pyridyl, more preferably hydrogen, unsubstituted phenyl, deuterium-substituted phenyl, fluorine-substituted phenyl, unsubstituted naphthyl, unsubstituted pyridyl, most preferably hydrogen, unsubstituted phenyl, unsubstituted naphthyl, unsubstituted pyridyl;

[0052] In the case of "substituted or unsubstituted", the substituent is as defined above.

[0053] According to the above-mentioned azaspirofluorene compound, wherein L in the structure of the azaspirofluorene compound is preferably a substituted or unsubstituted group as follows:

[0054] , preferably substituted or unsubstituted following groups:

[0055] , more preferably the following substituted or unsubstituted groups:

[0056] , more preferably the following substituted or unsubstituted groups: , more preferably the following substituted or unsubstituted groups: , most preferably substituted or unsubstituted following groups: ;

[0057] Wherein, the substituents in "substituted or unsubstituted" are as defined above;

[0058] Preferably, the structure of the azaspirofluorene compound is selected from one or more of the above formulas 1, 1', 1a, 1b, 1c, and 1d; more preferably, the structure of the azaspirofluorene compound is selected from one or more of the above formulas 1', 1a, 1b, 1c, and 1d; more preferably, the structure of the azaspirofluorene compound is selected from one or more of the above formulas 1a, 1b, 1c, and 1d; more preferably, the structure of the azaspirofluorene compound is selected from one or more of the above formulas 1b, 1c, and 1d; more preferably, the structure of the azaspirofluorene compound is selected from one or more of the above formulas 1b and 1d; more preferably, the structure of the azaspirofluorene compound is selected from the above formula 1b or 1d; most preferably, the structure of the azaspirofluorene compound is selected from the above formula 1b;

[0059] Preferably, the above group is unsubstituted or substituted with one or more substituents selected from deuterium, fluoro, and cyano; more preferably, the above group is unsubstituted or substituted with one or more substituents selected from deuterium and fluoro; more preferably, the above group is unsubstituted or substituted with one or more deuterium; more preferably, the above group is unsubstituted or substituted with one or more deuterium; most preferably, the above group is unsubstituted.

[0060] According to the above-mentioned azaspirofluorene compound, wherein Ar1 in the structure of the azaspirofluorene compound is preferably hydrogen, or a substituted or unsubstituted group as follows:

[0061] , preferably hydrogen, or a substituted or unsubstituted group: , more preferably hydrogen, 、 , more preferably hydrogen, , most preferably hydrogen;

[0062] Wherein, the substituents in "substituted or unsubstituted" are as defined above;

[0063] Preferably, the structure of the azaspirofluorene compound is selected from one or more of the above formulas 1, 1', 1a, 1b, 1c, and 1d; more preferably, the structure of the azaspirofluorene compound is selected from one or more of the above formulas 1', 1a, 1b, 1c, and 1d; more preferably, the structure of the azaspirofluorene compound is selected from one or more of the above formulas 1a, 1b, 1c, and 1d; more preferably, the structure of the azaspirofluorene compound is selected from one or more of the above formulas 1b, 1c, and 1d; more preferably, the structure of the azaspirofluorene compound is selected from one or more of the above formulas 1b and 1d; more preferably, the structure of the azaspirofluorene compound is selected from the above formula 1b or 1d; most preferably, the structure of the azaspirofluorene compound is selected from the above formula 1b;

[0064] Preferably, the above group is unsubstituted or substituted with one or more substituents selected from deuterium, fluoro, and cyano; more preferably, the above group is unsubstituted or substituted with one or more substituents selected from deuterium and fluoro; more preferably, the above group is unsubstituted or substituted with one or more deuterium; more preferably, the above group is unsubstituted or substituted with one or more deuterium; most preferably, the above group is unsubstituted.

[0065] According to the above-mentioned azaspirofluorene compound, wherein R1 in the structure of the azaspirofluorene compound is preferably hydrogen, or a substituted or unsubstituted group as follows:

[0066] , preferably hydrogen, or a substituted or unsubstituted group: , more preferably hydrogen, 、 , more preferably hydrogen, , most preferably hydrogen;

[0067] Wherein, the substituents in "substituted or unsubstituted" are as defined above;

[0068] Preferably, the structure of the azaspirofluorene compound is selected from one or more of the above formulas 1, 1', 1a, 1b, 1c, and 1d; more preferably, the structure of the azaspirofluorene compound is selected from one or more of the above formulas 1', 1a, 1b, 1c, and 1d; more preferably, the structure of the azaspirofluorene compound is selected from one or more of the above formulas 1a, 1b, 1c, and 1d; more preferably, the structure of the azaspirofluorene compound is selected from one or more of the above formulas 1b, 1c, and 1d; more preferably, the structure of the azaspirofluorene compound is selected from one or more of the above formulas 1b and 1d; more preferably, the structure of the azaspirofluorene compound is selected from the above formula 1b or 1d; most preferably, the structure of the azaspirofluorene compound is selected from the above formula 1b;

[0069] Preferably, the above group is unsubstituted or substituted with one or more substituents selected from deuterium, fluoro, and cyano; more preferably, the above group is unsubstituted or substituted with one or more substituents selected from deuterium and fluoro; more preferably, the above group is unsubstituted or substituted with one or more deuterium; more preferably, the above group is unsubstituted or substituted with one or more deuterium; most preferably, the above group is unsubstituted.

[0070] According to the above-mentioned azaspirofluorene compound, wherein R2 in the structure of the azaspirofluorene compound is preferably hydrogen, or a substituted or unsubstituted group as follows:

[0071] , preferably substituted or unsubstituted following groups: , more preferably hydrogen, 、 , more preferably hydrogen, , most preferably hydrogen;

[0072] Wherein, the substituents in "substituted or unsubstituted" are as defined above;

[0073] Preferably, the structure of the azaspirofluorene compound is selected from one or more of the above formulas 1, 1', 1a, 1b, 1c, and 1d; more preferably, the structure of the azaspirofluorene compound is selected from one or more of the above formulas 1', 1a, 1b, 1c, and 1d; more preferably, the structure of the azaspirofluorene compound is selected from one or more of the above formulas 1a, 1b, 1c, and 1d; more preferably, the structure of the azaspirofluorene compound is selected from one or more of the above formulas 1b, 1c, and 1d; more preferably, the structure of the azaspirofluorene compound is selected from one or more of the above formulas 1b and 1d; more preferably, the structure of the azaspirofluorene compound is selected from the above formula 1b or 1d; most preferably, the structure of the azaspirofluorene compound is selected from the above formula 1b;

[0074] Preferably, the above group is unsubstituted or substituted with one or more substituents selected from deuterium, fluoro, and cyano; more preferably, the above group is unsubstituted or substituted with one or more substituents selected from deuterium and fluoro; more preferably, the above group is unsubstituted or substituted with one or more deuterium; more preferably, the above group is unsubstituted or substituted with one or more deuterium; most preferably, the above group is unsubstituted.

[0075] According to the above-mentioned azaspirofluorene compounds, preferably, when Ar2 is Formula b, Ar1 is hydrogen or When L is , then R2 is not hydrogen, .

[0076] According to the above-mentioned azaspirofluorene compounds, preferably, when Ar2 is Formula b, Ar1 is hydrogen or When L is , then R2 is not hydrogen.

[0077] According to the above-mentioned azaspirofluorene compounds, preferably, when Ar2 is Formula b, Ar1 is hydrogen or When L is , then R2 is not hydrogen.

[0078] According to the above-mentioned azaspirofluorene compound, preferably, when the structure of the azaspirofluorene compound is as shown in the above formula 1b, Ar1 is hydrogen or When L is Then R2 is not hydrogen, .

[0079] According to the above-mentioned azaspirofluorene compound, preferably, when the structure of the azaspirofluorene compound is as shown in the above formula 1b, Ar1 is hydrogen or When L is Then R2 is not hydrogen.

[0080] According to the above-mentioned azaspirofluorene compound, preferably, when the structure of the azaspirofluorene compound is as shown in the above formula 1b, Ar1 is hydrogen or When L is Then R2 is not hydrogen.

[0081] According to the above-mentioned azaspirofluorene compounds, preferably, when Ar2 is In formula c, if Ar1 is , then L is not .

[0082] According to the above-mentioned azaspirofluorene compound, preferably, when the structure of the azaspirofluorene compound is as shown in the above formula 1c, if Ar1 is , then L is not .

[0083] According to the above-mentioned azaspirofluorene compounds, preferably, when Ar2 is When formula a and Ar1 are hydrogen, if L is , then R1 is not hydrogen.

[0084] According to the above-mentioned azaspirofluorene compounds, preferably, when Ar2 is Formula a, Ar1 is When L is , then R1 is not hydrogen, .

[0085] According to the above-mentioned azaspirofluorene compounds, preferably, when Ar2 is Formula a, Ar1 is When L is , then R1 is not hydrogen.

[0086] According to the above-mentioned azaspirofluorene compounds, preferably, when Ar2 is When formula a and Ar1 are hydrogen, if L is 、 or , then R1 is not hydrogen.

[0087] According to the above-mentioned azaspirofluorene compounds, preferably, when Ar2 is When formula a and Ar1 are hydrogen, if L is , then R1 is not hydrogen, 、 .

[0088] According to the above-mentioned azaspirofluorene compounds, preferably, when Ar2 is Formula a, Ar1 is When L is , then R1 is not hydrogen, .

[0089] According to the above-mentioned azaspirofluorene compounds, preferably, when Ar2 is Formula a, Ar1 is When L is , then R1 is not hydrogen.

[0090] According to the above-mentioned azaspirofluorene compounds, preferably, when Ar2 is Formula a, Ar1 is When L is , then R1 is not hydrogen.

[0091] According to the above-mentioned azaspirofluorene compounds, preferably, when Ar2 is When formula a and Ar1 are hydrogen, if L is , then R1 is not hydrogen, 、 .

[0092] According to the above-mentioned azaspirofluorene compounds, preferably, when Ar2 is Formula a, Ar1 is When L is , then R1 is not hydrogen, .

[0093] According to the above-mentioned azaspirofluorene compounds, preferably, when Ar2 is When formula a and Ar1 are hydrogen, if L is , then R1 is not .

[0094] According to the above-mentioned azaspirofluorene compound, preferably, when the structure of the azaspirofluorene compound is as shown in the above formula 1a and Ar1 is hydrogen, if L is , then R1 is not hydrogen.

[0095] According to the above-mentioned azaspirofluorene compound, preferably, when the structure of the azaspirofluorene compound is as shown in the above formula 1a, Ar1 is When L is , then R1 is not hydrogen, .

[0096] According to the above-mentioned azaspirofluorene compound, preferably, when the structure of the azaspirofluorene compound is as shown in the above formula 1a, Ar1 is When L is , then R1 is not hydrogen.

[0097] According to the above-mentioned azaspirofluorene compound, preferably, when the structure of the azaspirofluorene compound is as shown in the above formula 1a and Ar1 is hydrogen, if L is 、 or , then R1 is not hydrogen.

[0098] According to the above-mentioned azaspirofluorene compound, preferably, when the structure of the azaspirofluorene compound is as shown in the above formula 1a and Ar1 is hydrogen, if L is , then R1 is not hydrogen, 、 .

[0099] According to the above-mentioned azaspirofluorene compound, preferably, when the structure of the azaspirofluorene compound is as shown in the above formula 1a, Ar1 is When L is , then R1 is not hydrogen, .

[0100] According to the above-mentioned azaspirofluorene compound, preferably, when the structure of the azaspirofluorene compound is as shown in the above formula 1a, Ar1 is When L is , then R1 is not hydrogen.

[0101] According to the above-mentioned azaspirofluorene compound, preferably, when the structure of the azaspirofluorene compound is as shown in the above formula 1a, Ar1 is When L is , then R1 is not hydrogen.

[0102] According to the above-mentioned azaspirofluorene compound, preferably, when the structure of the azaspirofluorene compound is as shown in the above formula 1a and Ar1 is hydrogen, if L is , then R1 is not hydrogen, 、 .

[0103] According to the above-mentioned azaspirofluorene compound, preferably, when the structure of the azaspirofluorene compound is as shown in the above formula 1a, Ar1 is When L is , then R1 is not hydrogen, .

[0104] According to the above-mentioned azaspirofluorene compound, preferably, when the structure of the azaspirofluorene compound is as shown in the above formula 1a and Ar1 is hydrogen, if L is , then R1 is not .

[0105] According to the above-mentioned azaspirofluorene compound, preferably, when the structure of the azaspirofluorene compound is as shown in the above formula 1a, if Ar1 is , then L is not .

[0106] According to the above-mentioned azaspirofluorene compound, the halogen is preferably F, Br, Cl, or I;

[0107] And / or, the C1-C 10 The alkyl group is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, neopentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, isooctyl, nonyl, 2-ethylhexyl;

[0108] And / or, the C6-C 60 The aryl group is preferably phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, naphthyl, phenanthrenyl, fluorenyl, indenyl, pyrenyl, perylenyl, fluoranthenyl, triphenylenyl, triphenylene, chrysyl, spirobifluorenyl, benzopyrenyl, benzochrysyl;

[0109] And / or, the C6-C 60 The arylene group is preferably a phenylene group, a biphenylene group, a terphenylene group, a naphthylene group, an anthrylene group, a tetraphenylene group, a phenanthrenyl group, a fluorenyl group, an indenyl group, a pyrenyl group, a perylene group, a fluoranthenyl group, a triphenylene group, a chrysene group, a spirobifluorenyl group, a benzopyrenyl group, or a benzochrysene group;

[0110] And / or, the C3-C 60 The heteroaryl group of is preferably thienyl, furyl, pyrrolyl, thiazolyl, oxazolyl, imidazolyl, pyrazolyl, triazolyl, benzothienyl, benzofuranyl, indolyl, isoindolyl, benzothiazolyl, benzoxazolyl, benzimidazolyl, benzotriazolyl, purinyl, carbazolyl, dibenzothienyl, dibenzofuranyl, pyridyl, pyrimidinyl, triazinyl, phenazinyl, quinolyl, isoquinolyl, naphthyridinyl, acridinyl, phenanthrolinyl, carbolinyl;

[0111] And / or, the C3-C 60 The heteroarylene group is preferably a thienylene, a furylene, a pyrrolylene, a thiazolylene, an oxazolylene, an imidazolylene, a pyrazolylene, a triazolylene, a benzothienylene, a benzofuranylene, an indolylene, an isoindolylene, a benzothiazolylene, a benzoxazolylene, a benzimidazolylene, a benzotriazolylene, a purinylene, a carbazolylene, a dibenzothienylene, a dibenzofuranylene, a pyridylene, a pyrimidylene, a triazinylene, a phenazinylene, a quinolylene, an isoquinolylene, a naphthyridinylene, an acridinylene, a phenanthrolinylene, or a carbolylene group;

[0112] And / or, the C1-C 10 The alkenylene group is preferably vinylene, 1-propenylene, allylene, 1-butenylene, 2-butenylene, 1-pentenylene, 1-hexenylene, isopropenylene, isobutenylene;

[0113] And / or, the C1-C 10 The alkynylene group is preferably ethynylene, propargylene or butynylene.

[0114] According to the above-mentioned azaspirofluorene compounds, the halogen is preferably F, Br, Cl, I, more preferably F, Br, Cl, more preferably F, Cl, and most preferably F.

[0115] According to the above-mentioned azaspirofluorene compound, the C1-C 10 The alkyl group is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, neopentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, isooctyl, nonyl, 2-ethylhexyl, more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, neopentyl, isopentyl, n-hexyl, n-octyl, n-heptyl, more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, neopentyl, isopentyl, n-hexyl, n-octyl, n-heptyl, more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl Butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, neopentyl, isopentyl, n-hexyl, more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, especially preferably methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-pentyl, especially preferably methyl, ethyl, n-propyl, isopropyl, tert-butyl, particularly preferably methyl, ethyl, tert-butyl, particularly preferably methyl, ethyl, and tert-butyl, most preferably methyl.

[0116] According to the above-mentioned azaspirofluorene compound, the C6-C 60 The aryl group is preferably phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, naphthacene, phenanthrenyl, fluorenyl, indenyl, pyrenyl, peryl, fluoranthenyl, triphenylene, chrysyl, spirobifluorenyl, benzopyrenyl, benzochrysyl, more preferably phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, fluoranthenyl, triphenylene, perylene, pyrenyl, benzopyrenyl, chrysyl, benzochrysyl, more preferably phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, especially preferably biphenyl, phenyl, naphthyl, and most preferably phenyl.

[0117] According to the above-mentioned azaspirofluorene compound, the C6-C 60The arylene group is preferably a phenylene group, a biphenylene group, a terphenylene group, a naphthylene group, an anthrylene group, a tetraphenylene group, a phenanthrenyl group, a fluorenyl group, an indenyl group, a pyrenyl group, a perylene group, a fluoranthenyl group, a triphenylene group, a chrysyl group, a spirobifluorenyl group, a benzopyrenyl group, and a benzochrysyl group; more preferably a phenylene group, a biphenylene group, a terphenylene group, a naphthylene group, an anthrylene group, a phenanthrenyl group, a fluoranthenyl group, a triphenylene group, a perylene group, a pyrenyl group, a benzopyrenyl group, and a chrysyl group; more preferably a phenylene group, a biphenylene group, a terphenylene group, a naphthylene group, an anthrylene group, a phenanthrenyl group; especially preferably a biphenylene group, a phenylene group, and a naphthylene group; most preferably a phenylene group.

[0118] According to the above-mentioned azaspirofluorene compound, the C3-C 60 The heteroaryl group is preferably thienyl, furyl, pyrrolyl, thiazolyl, oxazolyl, imidazolyl, pyrazolyl, triazolyl, benzothienyl, benzofuranyl, indolyl, isoindolyl, benzothiazolyl, benzoxazolyl, benzimidazolyl, benzotriazolyl, purinyl, carbazolyl, dibenzothienyl, dibenzofuranyl, pyridyl, pyrimidinyl, triazinyl, phenazinyl, quinolyl, isoquinolyl, naphthyridinyl, acridinyl, phenanthrolinyl, carbolinyl, more preferably thienyl, furyl, pyrrolyl, imidazolyl, pyrrolyl, oxazolyl, benzothiophenyl, benzofuranyl, benzimidazolyl, carbazolyl, dibenzothiophenyl, dibenzofuranyl, pyridyl, pyrimidinyl, triazinyl, phenazinyl, quinolyl, isoquinolyl, phenanthroline, more preferably pyrrolyl, imidazolyl, carbazolyl, dibenzothiophenyl, dibenzofuranyl, pyridyl, pyrimidinyl, triazinyl, especially preferably dibenzothiophenyl, dibenzofuranyl, pyridyl, triazinyl, particularly preferably dibenzothiophenyl, dibenzofuranyl, pyridyl, most preferably pyridyl.

[0119] According to the above-mentioned azaspirofluorene compound, the C3-C 60The heteroarylene group is preferably a thienylene group, a furylene group, a pyrrolylene group, a thiazolylene group, an oxazolylene group, an imidazolylene group, a pyrazolylene group, a triazolylene group, a benzothienylene group, a benzofuranylene group, an indolylene group, an isoindolylene group, a benzothiazolylene group, a benzoxazolylene group, a benzoimidazolylene group, a benzotriazolylene group, a purinylene group, a carbazolylene group, a dibenzothienylene group, a dibenzofuranylene group, a pyridylene group, a pyrimidylene group, a triazinylene group, a phenazinylene group, a quinolylene group, an isoquinolylene group, a naphthyridinylene group, an acridinylene group, a phenanthrolinylene group, a carbolylene group, more preferably a thienylene group, a furylene group, a pyrrolylene group, an imidazolylene group, a The present invention relates to a benzophenone group comprising: a benzothiophene group, a benzofuran group, a benzoimidazolyl group, a carbazolyl group, a dibenzothiophene group, a dibenzofuran group, a pyridyl group, a pyrimidyl group, a triazinyl group, a phenazinyl group, a quinolyl group, an isoquinolyl group, a phenanthroline group, more preferably a pyrrolyl group, an imidazolyl group, a carbazolyl group, a dibenzothiophene group, a dibenzofuran group, a pyridyl group, a pyrimidyl group, a triazinyl group, especially preferably a dibenzothiophene group, a dibenzofuran group, a pyridyl group, a triazinyl group, particularly preferably a dibenzothiophene group, a dibenzofuran group, a pyridyl group, and most preferably a pyridyl group.

[0120] According to the above-mentioned azaspirofluorene compound, the C1-C 10 The alkenylene group is preferably vinylene, 1-propenylene, allylene, 1-butenylene, 2-butenylene, 1-pentenylene, 1-hexenylene, isopropenylene, isobutenylene, more preferably vinylene, 1-propenylene, allylene, 1-butenylene, 2-butenylene, isopropenylene, isobutenylene, more preferably vinylene, 1-propenylene, allylene, isopropenylene, and most preferably vinylene.

[0121] According to the above-mentioned azaspirofluorene compound, the C1-C 10The alkynylene group is preferably ethynylene, propargylene or butynylene, more preferably ethynylene or propargylene, and most preferably ethynylene. According to the above-mentioned azaspirofluorene compounds, the definition of the substituent when substituted in the "substituted or unsubstituted" is preferably independently selected from the combination of one or more of deuterium, fluoro, cyano, methyl, ethyl, tert-butyl, cyclohexyl, phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, pyrene, fluoranthenyl, quinolyl, triphenylene, chrysyl, dibenzofuranyl, dibenzothiophenyl, and pyridyl; more preferably selected from the combination of one or more of deuterium, fluoro, cyano, methyl, ethyl, tert-butyl, phenyl, biphenyl, terphenyl, quinolyl, naphthyl, anthracenyl, phenanthrenyl, dibenzofuranyl, dibenzothiophenyl, and pyridyl; more preferably selected from the combination of one or more of deuterium, fluoro, cyano, methyl, ethyl, tert-butyl, phenyl, biphenyl, terphenyl, quinolyl, naphthyl , dibenzofuranyl, dibenzothienyl, pyridyl combination of one or more; particularly preferably selected from the combination of one or more of deuterium, fluoro, cyano, methyl, phenyl, biphenyl, naphthyl, dibenzofuranyl, dibenzothienyl, pyridyl; particularly preferably selected from the combination of one or more of deuterium, fluoro, phenyl, biphenyl, naphthyl, pyridyl; particularly preferably selected from the combination of one or more of deuterium, fluoro, phenyl, naphthyl, pyridyl; particularly preferably selected from the combination of one or more of deuterium, fluoro, phenyl, pyridyl; particularly preferably selected from the combination of one or more of deuterium, fluoro, phenyl; particularly preferably selected from the combination of one or more of deuterium, phenyl, most preferably selected from the combination of one or more of deuterium.

[0122] According to the above-mentioned azaspirofluorene compound, the azaspirofluorene compound is preferably selected from the structure shown below:

[0123]

[0124] 1-1 1-2 1-3

[0125]

[0126] 1-4 1-5 1-6

[0127]

[0128] 1-7 1-8 1-9

[0129]

[0130] 1-10 1-11 1-12

[0131]

[0132] 1-13 1-14 1-15

[0133]

[0134] 1-16 1-17 1-18

[0135]

[0136] 1-19 1-20 1-21

[0137]

[0138] 1-22 1-23 1-24

[0139]

[0140] 1-25 1-26 1-27

[0141]

[0142] 1-28 1-29 1-30

[0143]

[0144] 1-31 1-32 1-33

[0145]

[0146] 1-34 1-35 1-36

[0147]

[0148] 1-37 1-38 1-39

[0149]

[0150] 1-40 1-41 1-42

[0151]

[0152] 1-43 1-44 1-45

[0153]

[0154] 1-46 1-47 1-48

[0155]

[0156] 1-49 1-50 1-51

[0157]

[0158] 1-52 1-53 1-54

[0159]

[0160] 1-55 1-56 1-57.

[0161] In a second aspect, the present invention provides a material for an organic device, which may include the above-mentioned azaspirofluorene compound.

[0162] The above-mentioned material for an organic element is preferably a charge generation layer material, more preferably an N-type charge generation layer material.

[0163] In a third aspect, the present invention provides an organic electroluminescent element, which may comprise the above-mentioned azaspirofluorene compound or the above-mentioned organic element material.

[0164] According to the above organic electroluminescent element, the organic electroluminescent element may include a cathode, an anode

[0165] and an organic functional layer located between the anode and the cathode, at least one of the organic functional layers comprising the above-mentioned azaspirofluorene compound or the above-mentioned organic component material; preferably, the organic functional layer comprises an N-type charge generation layer, and the N-type charge generation layer comprises an azaspirofluorene compound having the general structure shown in Formula 1 above.

[0166] According to the above-mentioned organic electroluminescent element, the organic electroluminescent element may include an anode, a cathode, a hole injection layer located between the anode and the cathode, a hole transport layer, a light-emitting layer, a hole blocking layer, an electron transport layer, a charge generation layer, a hole transport layer, a second hole transport layer, a light-emitting layer, a hole blocking layer, and an electron transport layer. Preferably, the charge generation layer includes an N-type charge generation layer and a P-type charge generation layer, and the N-type charge generation layer includes an azaspirofluorene compound having the general structure shown in Formula 1 above.

[0167] In a fourth aspect, the present invention provides a display or lighting device, which may include the above-mentioned azaspirofluorene compound or the above-mentioned organic element material or the above-mentioned organic electroluminescent element; preferably, the device also includes a control unit, which is used to drive the above-mentioned display device.

[0168] In the present invention, the term "C1-C 10 The term "alkyl" refers to a monovalent substituent derived from a straight or branched chain saturated hydrocarbon having 1 to 10 carbon atoms, examples of which include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, and hexyl.

[0169] In the present invention, the term "C6-C 60The term "aryl group" refers to a monovalent substituent derived from an aromatic hydrocarbon having a single ring or a combination of two or more rings and having 6 to 60 carbon atoms. Further, such an aryl group may have a form in which two or more rings are simply pendant to each other or fused to each other. Examples of such an aryl group include, but are not limited to, phenyl, biphenyl, naphthyl, phenanthrenyl, anthracenyl, pyrenyl, triphenylene, fluoranthenyl, dimethyl 9,9-dimethylfluorene, 9,9-diphenylfluorene, spirobifluorenyl, and the like.

[0170] In the present invention, the term "C1-C 10 The term "alkenylene" refers to a divalent substituent formed by removing two hydrogen atoms from an olefin molecule having 1 to 10 carbon atoms, examples of which include but are not limited to vinylene, 1-propenylene, and the like.

[0171] In the present invention, the term "C1-C 10 The term "alkynylene" refers to a divalent substituent formed by removing two hydrogen atoms from an alkyne molecule having 1 to 10 carbon atoms, examples of which include but are not limited to ethynylene, propargylene, and the like.

[0172] In the present invention, the term "C3-C 60 The term "heteroaryl" refers to a monovalent substituent derived from a monocyclic or polycyclic heterocyclic aromatic hydrocarbon having 3 to 60 carbon atoms. In this connection, at least one carbon, preferably 1 to 3 carbons, in the ring is substituted by a heteroatom such as N, O, S, P, B or Si. In addition, such a heteroaryl group may have a form in which two or more rings are simply pendant to each other or fused to each other or to an aryl group. Examples of such heteroaryl groups include pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, indolizinyl, indolyl, indolopyridinyl, purinyl, phenanthrolinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, thiazolyl, imidazolyl, oxazolyl, furyl, thienyl, benzofuranyl, benzothienyl, benzothiazolyl, benzimidazolyl, benzoxazolyl, carbazolyl, dibenzofuranyl, dibenzothienyl and the like, but the present invention is not limited thereto.

[0173] In the present invention, the term "arylene group" refers to a divalent aromatic group derived from an "aryl group" by removing a hydrogen atom. For example, a phenyl group is converted to a phenylene group by removing a hydrogen atom, and a naphthyl group is converted to a naphthylene group by removing a hydrogen atom.

[0174] In the present invention, the term "halogen" may include fluorine, chlorine, bromine or iodine.

[0175] In the present invention, the term "C3-C 60The term "heteroarylene" refers to a divalent monocyclic aromatic group and / or a divalent polycyclic aromatic group derived from at least one aromatic ring having 3 to 60 carbon atoms, wherein the at least one aromatic ring contains one or more heteroatoms independently selected from O, S and N. Each ring of the heteroarylene group may contain one or two O atoms, one or two S atoms, and / or one to four N atoms, provided that the total number of heteroatoms in each ring is four or less and each ring contains at least one carbon atom.

[0176] In the present invention, “ ” indicates a connecting key.

[0177] In the present invention, the term "substituted or unsubstituted" means that the hydrogen atoms in the compound are replaced by non-hydrogen groups or are not replaced by non-hydrogen groups. The number of substituents is not limited, as long as they can be obtained through chemical reactions. It is not limited to a specific position, as long as the hydrogen at that position can be replaced by a substituent. For example, carbazolyl includes any of the following groups, but is not limited thereto, unless otherwise specified in this specification:

[0178] , " " indicates the position of substitution. "Unsubstituted" means that a hydrogen atom remains, which in this case includes protium, deuterium, and tritium.

[0179] In the present invention, when two or more substituents are present, the two or more substituents may be the same or different.

[0180] In the present invention, terms such as 1, 2, 1a, 1b, 1c, 1d, a, b, c, d, etc. are used only to distinguish components and do not limit the nature or order of the components to which the terms correspond.

[0181] In general, the above technical solutions conceived by the present invention can achieve the following beneficial effects compared with the prior art:

[0182] 1. The azaspirofluorene compound of the present invention has an azaspirofluorene structure, which can effectively improve the electron transport ability of the material and has better evaporation film-forming effect, which is beneficial to reducing device voltage and improving device life;

[0183] 2. The organic electroluminescent element prepared by using the compound with the specific core structure of the present invention as the N-type charge generation layer material has a lower driving voltage;

[0184] 3. The organic electroluminescent element prepared by using the compound having the specific mother core structure of the present invention as the material of the N-type charge generation layer has a longer service life. BRIEF DESCRIPTION OF THE DRAWINGS

[0185] Figure 1 Schematic diagram of the structure of the organic electroluminescent element described in Application Example 1; wherein: Figure 1 The marks in the figure represent: 1. first electrode layer, 2. hole injection layer, 3. hole transport layer, 4. second hole transport layer, 5. light-emitting layer, 6. hole blocking layer, 7. electron transport layer, 8. N-type charge generation layer, 9. P-type charge generation layer, 10. hole transport layer, 11. second hole transport layer, 12. light-emitting layer, 13. hole blocking layer, 14. electron transport layer, 15. second electrode layer, 100. first light-emitting unit, 200. second light-emitting unit.

[0186] Figure 2 This is a mass spectrum (LC-MS) of compound 1-2 prepared in Synthesis Example 1 in Compound Preparation Examples.

[0187] Figure 3 This is the nuclear magnetic resonance (1H NMR) spectrum of compound 1-2 prepared in Synthesis Example 1 in Compound Preparation Example.

[0188] Figure 4 It is the mass spectrum (LC-MS) of compound 1-3 prepared in Synthesis Example 2 in Compound Preparation Example.

[0189] Figure 5 This is the nuclear magnetic resonance (1H NMR) spectrum of compound 1-3 prepared in Synthesis Example 2 in Compound Preparation Example.

[0190] Figure 6 It is the mass spectrum (LC-MS) of compound 1-5 prepared in Synthesis Example 3 in Compound Preparation Example.

[0191] Figure 7 This is the nuclear magnetic resonance (1H NMR) spectrum of compound 1-5 prepared in Synthesis Example 3 in Compound Preparation Example. DETAILED DESCRIPTION

[0192] Exemplary embodiments will now be described in detail, examples of which are illustrated in the accompanying drawings, wherein the same reference numerals refer to the same elements throughout. In this regard, the present exemplary embodiments may have different forms and should not be construed as being limited to the description set forth herein. Therefore, exemplary embodiments are described below only with reference to the accompanying drawings to illustrate aspects. As used herein, the term "and / or" includes any and all combinations of one or more of the relevant enumerated items. Expressions such as "at least one layer (kind) of" modify the entire list of elements when preceding or following a list of elements and do not modify the individual elements of the list.

[0193] It will be further understood that the terms “comprise” or “comprising” when used in this specification indicate the presence of stated features, regions, integers, steps, operations, elements, and / or components, but do not preclude the presence or addition of one or more additional features, regions, integers, steps, operations, elements, components, and / or combinations thereof.

[0194] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this general inventive concept belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning consistent with their meaning in the context of the relevant art and the present disclosure, and will not be interpreted in an idealized or overly formal sense unless clearly so defined herein.

[0195] The present invention will be further described below in conjunction with specific examples. It should be understood that these examples are intended only to illustrate the present invention and are not intended to limit the scope of protection of the present invention. In addition, it should be understood that after reading the disclosure of the present invention, those skilled in the art may make various changes or modifications to the present invention, and these equivalent forms also fall within the scope of protection defined by the present invention.

[0196] In the present invention, unless otherwise specified, all parts and percentages are by weight, and the equipment and raw materials used are commercially available or commonly used in the art. The methods in the following examples are all conventional methods in the art unless otherwise specified.

[0197] Unless otherwise specified, the experimental methods used in the following examples are conventional methods; the starting materials, reaction raw materials, reagents, materials, etc. used in the following examples are all commercially available unless otherwise specified.

[0198] Compound Preparation Examples

[0199] LC-MS Brand: Waters, Model: SQ Detector 2

[0200] NMR brand: Bruker, model: AVANCE NEO 400

[0201] Those skilled in the art can synthesize the compounds of the present invention by referring to the synthesis of the following compounds and known synthesis methods.

[0202] Synthesis Example 1: Preparation of Compound 1-2

[0203] Step 1: Synthesis of intermediate 1-2-1:

[0204]

[0205] Under a nitrogen atmosphere, magnesium (1.1 g, 45 mmol) and iodine (50 mg, 19.7 mmol) were added to a four-necked flask, followed by tetrahydrofuran (50 mL). The mixture was heated and stirred for 20 minutes. A solution of 2-bromobiphenyl (10 g, 42.9 mmol) in tetrahydrofuran (100 mL) was then slowly added dropwise to the flask. The reaction was stopped until the magnesium completely disappeared. The resulting mixture was added to a solution of 2-bromo-4,5-diazafluoren-9-one (10 g, 38.6 mmol) in tetrahydrofuran (100 mL) at 25°C. After stirring at 25°C for 12 hours, the mixture was quenched with 50 mL of water. Purification by silica gel chromatography (developing solvent: dichloromethane:tetrahydrofuran = 100:1) afforded intermediate 1-2-1 as a pale yellow solid (7 g, 43.7% yield).

[0206] LC-MS (APCI): 415.29 (M+H + ).Calcd for C 23 H 15 BrN2O 414.03.

[0207] Step 2: Synthesis of intermediate 1-2-2:

[0208]

[0209] Intermediate 1-2-1 (7 g, 16.8 mmol) was added to a 250 mL three-necked flask. 100 mL of glacial acetic acid was stirred and dissolved. 4 mL of concentrated sulfuric acid was added under nitrogen, heated to 120°C, and refluxed for 8 hours. The reaction solution was cooled to 25°C, poured into a 100 mL beaker of ice water, stirred, and filtered to obtain Intermediate 1-2-2 (6 g, 90% yield) as a pale yellow solid.

[0210] LC-MS (APCI): 397.33 (M+H + ).Calcd for C 23 H3BrN2396.02.

[0211] Step 3: Synthesis of compound 1-2

[0212]

[0213] Under a nitrogen atmosphere, intermediate 1-2-2 (6 g, 15.1 mmol), intermediate 1-2-3 (6.9 g, 15.1 mmol), potassium carbonate (4.2 g, 30.2 mmol), and bistriphenylphosphine palladium dichloride (0.2 g, 0.3 mmol) were added to a four-necked reaction flask. 120 ml of tetrahydrofuran and 40 ml of water were then added. The temperature was raised to 75°C for reaction. After completion of the reaction, the reaction solution was poured into a beaker containing 200 ml of ethanol, stirred, cooled to 25°C, and filtered to afford compound 1-2 (8 g, 82% yield) as a pale yellow solid.

[0214] LC-MS (APCI): 649.57 (M+H + ).Calcd for C 47 H 28 N4648.23; see the appendix of the manual for the corresponding mass spectrum Figure 2 .

[0215] 1 H NMR (400 MHz, Methylene Chloride-d2) δ 9.29 (t, J = 1.8 Hz, 1H),

[0216] 8.75 (dd, J = 4.3, 2.1 Hz, 1H),8.56 (dt, J = 7.8, 1.3 Hz, 1H),8.51 –8.30 (m, 6H),8.18 (d, J = 8.4 Hz, 1H),8.01 – 7.75 (m, 6H),7.52 –7.09 (m,10H),6.84 (dt, J = 7.6, 0.9 Hz, 2H); see the appendix of the manual for the corresponding NMR spectrum. Figure 3 .

[0217] Synthesis Example 2: Synthesis of Compound 1-3

[0218]

[0219] (Wherein, Bpin represents a pinacol boronate group)

[0220] Under a nitrogen atmosphere, intermediate 1-2-2 (6 g, 15.1 mmol), 2-phenyl-9-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-1,10-phenanthroline (6.9 g, 15.1 mmol), potassium carbonate (4.2 g, 30.2 mmol), and bistriphenylphosphine palladium dichloride (0.2 g, 0.3 mmol) were added to a four-necked reaction flask. 120 ml of tetrahydrofuran and 40 ml of water were then added. The reaction solution was heated to 75°C and reacted for 5 hours. After the reaction, the temperature of the reaction solution was lowered to 25°C and poured into a beaker containing 200 ml of ethanol. The mixture was stirred for 30 minutes and filtered to obtain the crude product. The crude product was purified by column chromatography (mobile phase: dichloromethane) to obtain compound 1-3 (7 g, 72% yield) as a pale yellow solid.

[0221] LC-MS (APCI): 649.39 [M+H] + Calcd for C 47 H 28 N4648.23; see the appendix of the manual for the corresponding mass spectrum Figure 4 .

[0222] 1 H NMR (400 MHz, Methylene Chloride-d2) δ 8.79 (dd, J = 4.6, 1.7 Hz,1H), 8.71 – 8.58 (m, 2H), 8.55 – 8.33 (m, 6H), 8.25 (dd, J = 29.5, 8.4 Hz,2H), 7.99 – 7.75 (m, 5H), 7.64 (dd, J = 8.4, 7.0 Hz, 2H), 7.58 – 7.50 (m,1H), 7.45 (td, J = 7.5, 1.1 Hz, 2H), 7.29 – 7.06 (m, 5H), 6.81 (dt, J = 7.6,0.9 Hz, 2H). For the corresponding NMR spectrum, see the appendix of the manual. Figure 5 .

[0223] Synthesis Example 3: Synthesis of Compound 1-5

[0224]

[0225] (Wherein, Bpin represents a pinacol boronate group)

[0226] Under a nitrogen atmosphere, intermediate 1-2-2 (6 g, 15.1 mmol), 2-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-phenyl]-1,10-phenanthroline (5.8 g, 15.1 mmol), potassium carbonate (4.2 g, 30.2 mmol), and bistriphenylphosphine palladium dichloride (0.2 g, 0.3 mmol) were added to a four-necked reaction flask. 120 ml of tetrahydrofuran and 40 ml of water were then added. The reaction was heated to 75°C. After completion of the reaction, the temperature of the reaction solution was lowered to 25°C. The reaction solution was extracted with dichloromethane, separated, and the organic phase was dried over anhydrous sodium sulfate and spin-dried to dryness. The crude product was purified by column chromatography (mobile phase: dichloromethane) to obtain compound 1-5 (5.9 g, 68% yield) as a pale yellow solid.

[0227] LC-MS (APCI): 573.37 [M+H] + .Calcd for: C 41 H 24 N4572.20; see the appendix of the manual for the corresponding mass spectrum Figure 6 .

[0228] 1 H NMR (400 MHz, Methylene Chloride-d2) δ 9.26 – 9.24 (m, 1H), 9.11 –9.10 (m, 1H), 8.82 – 8.81 (m, 1H), 8.48 – 8.44 (m, 2H), 8.36 – 8.31 (m, 3H),7.98 – 7.96 (d, J = 8 Hz, 2H), 7.94 – 7.87 (m, 2H), 7.86 – 7.84 (d, J = 8 Hz,1H), 7.80 – 7.76 (t, 1H), 7.72 – 7.69 (m, 1H), 7.51 – 7.47 (t, 2H), 7.30 –7.28 (d, J = 8 Hz, 1H), 7.24 – 7.17 (m, 4H), 6.87 – 6.85 (d, J = 8 Hz, 2H). The corresponding NMR spectrum is shown in the appendix of the manual. Figure 7 .

[0229] Synthesis Example 4: Synthesis of Compound 1-10

[0230] (1) Synthesis of intermediate 1-10-1

[0231]

[0232] Under a nitrogen atmosphere, intermediate 1-2-2 (10.00 g, 25.25 mmol), m-chlorophenylboronic acid (3.10 g, 27.78 mmol), tetrakistriphenylphosphine palladium (1.46 g, 1.26 mmol), and potassium carbonate (6.97 g, 50.50 mmol) were added to a 500 ml four-necked reaction flask. 90 ml of tetrahydrofuran and 30 ml of water were then added. The mixture was heated to 70°C for 6 h. After completion of the reaction, the reaction solution was cooled to 25°C, 100 ml of water was added, and the mixture was extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate and concentrated to obtain the crude product. The crude product was purified by silica gel chromatography (mobile phase: dichloromethane:tetrahydrofuran = 50:1, volume ratio) to obtain intermediate 1-10-1 (8.1 g, 74.9% yield) as a white solid.

[0233] (2) Synthesis of intermediate 1-10-2

[0234]

[0235] Under nitrogen atmosphere, intermediate 1-10-1 (8.00 g, 18.65 mmol), bis-pinacol borate (5.21 g, 20.52 mmol), 1,1'-bis(diphenylphosphino)ferrocenepalladium(II) chloride (0.27 g, 0.37 mmol), potassium acetate (3.66 g, 37.30 mmol) were added to a 500 ml four-necked reaction flask, and then 100 ml of anhydrous 1,4-dioxane was added and the reaction was heated to 110 °C for 8 min. h. After the reaction was completed, the reaction solution was cooled to 25°C, 100 ml of water was added, and the reaction solution was extracted and separated with dichloromethane. The organic phase was dried over anhydrous sodium sulfate and concentrated to obtain a crude product. The crude product was purified by silica gel chromatography (mobile phase: dichloromethane:tetrahydrofuran = volume ratio 30:1) to obtain intermediate 1-10-2 (7.8 g, yield 80.4%) as an off-white solid.

[0236] (3) Synthesis of compounds 1-10

[0237]

[0238] Under a nitrogen atmosphere, intermediate 1-10-2 (4.0 g, 7.68 mmol), intermediate 1-10-3 (2.57 g, 7.68 mmol), tetrakistriphenylphosphine palladium (0.44 g, 0.38 mmol), and potassium carbonate (2.12 g, 15.37 mol) were added to a 500 ml four-necked reaction flask. 60 ml of tetrahydrofuran and 20 ml of water were then added. The temperature was raised to 70°C and the reaction was allowed to proceed for 12 h. After completion of the reaction, the reaction solution was cooled to 25°C and 100 ml of water was added. The reaction solution was separated and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate and concentrated to obtain a crude product. The crude product was purified by silica gel chromatography (mobile phase: dichloromethane:tetrahydrofuran = 20:1 by volume). Compound 1-10 (3.0 g, 60.3% yield) was obtained as a white solid.

[0239] LC-MS (APCI): 649.44[M+H] + . Calcd for: C 47 H 28 N4 648.23.

[0240] Synthesis Example 5: Synthesis of Compound 1-17

[0241] (1) Synthesis of intermediate 1-17-1

[0242]

[0243] Under a nitrogen atmosphere, 2,9-dichloro-1,10-phenanthroline (10.00 g, 40.32 mmol), 3-pyridineboronic acid (4.96 g, 40.32 mmol), tetrakistriphenylphosphine palladium (2.33 g, 2.02 mmol), and potassium carbonate (11.13 g, 80.65 mmol) were added to a 500 ml four-necked reaction flask. 90 ml of tetrahydrofuran and 30 ml of water were then added. The mixture was heated to 70°C for 6 h. After completion of the reaction, the reaction solution was cooled to 25°C and 100 ml of water was added. The solution was extracted with dichloromethane and dried over anhydrous sodium sulfate. The organic phase was concentrated to obtain a crude product, which was then purified by silica gel chromatography (mobile phase: dichloromethane:tetrahydrofuran = 40:1 by volume). Intermediate 1-17-1 (6.0 g, 51.2% yield) was obtained as a white solid.

[0244] LC-MS (APCI): 292.38[M+H] + . Calcd for: C 17 H 10 ClN3 291.05.

[0245] (2) Synthesis of Compounds 1-17

[0246]

[0247] Under a nitrogen atmosphere, intermediate 1-10-2 (4.0 g, 7.68 mmol), intermediate 1-17-1 (2.24 g, 7.68 mmol), tetrakistriphenylphosphine palladium (0.44 g, 0.38 mmol), and potassium carbonate (2.12 g, 15.37 mol) were added to a 500 ml four-necked reaction flask. 90 ml of tetrahydrofuran and 30 ml of water were then added. The mixture was heated to 70°C for 8 h. After completion of the reaction, the reaction solution was cooled to 25°C, 100 ml of water was added, and the mixture was extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate and concentrated to obtain the crude product. The crude product was purified by silica gel chromatography (mobile phase: dichloromethane:tetrahydrofuran = 20:1, volume ratio) to obtain intermediate 1-17 (3.2 g, 64.2% yield) as a white solid.

[0248] LC-MS (APCI): 650.38[M+H] + . Calcd for: C 46 H 27 N5 649.22.

[0249] Synthesis Example 6: Synthesis of Compound 1-21

[0250]

[0251] Under a nitrogen atmosphere, intermediate 1-2-2 (5.5 g, 14 mmol), intermediate 1-21-1 (6.9 g, 14.6 mmol), Pd(PPh3)2Cl2 (0.2 g, 0.3 mmol), and K2CO3 (4.0 g, 28.9 mmol) were placed in a 250 mL four-necked flask. 45 mL of tetrahydrofuran and 15 mL of water were added. The reaction solution was heated to 70°C and then stirred at this temperature for 6 hours. After the reaction was complete, the reaction solution was cooled to 25°C. A solid precipitated and was filtered. The crude product was purified by silica gel chromatography (mobile phase: dichloromethane:tetrahydrofuran = 20:1 by volume) to obtain compound 1-21 (4.5 g, 48.5% yield) as a white solid.

[0252] LC-MS (APCI): 663.45[M+H] + . Calcd for: C 47 H 26 N4O 662.21.

[0253] Synthesis Example 7: Synthesis of Compound 1-50

[0254] (1) Synthesis of intermediate 1-50-2

[0255]

[0256] Under nitrogen, intermediate 1-50-1 (15.5 g, 30.9 mmol), bis(pinacol borate) (10.3 g, 40.56 mmol), potassium acetate (7.3 g, 74.4 mmol), 1,1'-bis(diphenylphosphino)ferrocenepalladium dichloride (0.54 g, 0.74 mmol), and 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (0.61 g, 1.5 mmol) were added to a four-necked reaction flask. 200 mL of anhydrous dioxane was then added, and the mixture was heated to 110°C for 6 hours. After completion of the reaction, the temperature was lowered to 25°C, 200 mL of water was added to the reaction solution, and the mixture was extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate and concentrated to obtain the crude product. The crude product was purified by silica gel chromatography (mobile phase: dichloromethane:tetrahydrofuran = volume ratio 80:1) to obtain intermediate 1-50-2 as a solid (10.3 g, yield 61.1%).

[0257] (2) Synthesis of Compound 1-50

[0258]

[0259] Under nitrogen, intermediate 1-2-2 (4.04 g, 12.1 mmol), intermediate 1-50-2 (6.6 g, 12.1 mmol), potassium carbonate (3.3 g, 23.8 mmol), and 1,1'-bis(diphenylphosphino)ferrocenepalladium dichloride (0.17 g, 0.24 mmol) were added to a four-necked reaction flask. 60 mL of toluene, 20 mL of ethanol, and 20 mL of water were then added. The reaction solution was heated to 90°C for 6 hours. After completion of the reaction, the temperature was lowered to 25°C, 100 mL of water was added, and the mixture was extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate and concentrated to obtain the crude product. The crude product was purified by silica gel chromatography (mobile phase: dichloromethane:tetrahydrofuran = 15:1 by volume) to obtain compound 1-50 (5.3 g, 59.1% yield) as a pale yellow solid.

[0260] LC-MS (APCI): 739.43[M+H] + . Calcd for: C 53 H 30 N4O 738.24.

[0261] The following application examples further illustrate the application of the azaspirofluorene compounds of the present invention in the preparation of organic electroluminescent devices.

[0262] Application Example 1

[0263] This embodiment provides an organic electroluminescent element, such as Figure 1 As shown, it includes a first electrode layer 1, a hole injection layer 2, a hole transport layer 3, a second hole transport layer 4, a light-emitting layer 5, a hole blocking layer 6, an electron transport layer 7, an N-type charge generation layer 8, a P-type charge generation layer 9, a hole transport layer 10, a second hole transport layer 11, a light-emitting layer 12, a hole blocking layer 13, an electron transport layer 14, and a second electrode layer 15, which are stacked in sequence, wherein 100 is a first light-emitting unit and 200 is a second light-emitting unit.

[0264] The specific device structure is:

[0265] / HT2(5nm) / ADN:BD(3%)(20nm) / HB(5nm) / ET-Liq(50%) (20nm) / Mg:Ag 1:9(100nm).

[0266] Device preparation process:

[0267] The bottom-emitting glass substrate used in this example was purchased from Guangdong Truly Display Technology Co., Ltd., and ITO was used as the anode. First, the bottom-emitting glass substrate was cleaned using an ITO cleaner, deionized water, and isopropyl alcohol, in that order. The bottom-emitting glass substrate was then baked at 180 degrees Celsius for 30 minutes to dry it.

[0268] Then put the bottom luminescent glass substrate into the evaporation chamber and -8Under the condition of support, each organic layer is deposited on the ITO anode in sequence by thermal vacuum evaporation at a rate of 0.2-2 angstroms / second. Among them, PD (3%) is doped into HT1 to form a thickness of 10nm as a hole injection layer. HT1 is formed to a thickness of 60nm as a hole transport layer, and a 5nm layer of HT2 material is evaporated thereon as a second hole transport layer. Then, anthracene main body ADN (9,10-di(2-naphthyl)anthracene) is doped with 3% BD to form a 20nm thick blue light-emitting layer, on which 5nm HB is evaporated as a hole blocking material. ET is doped with 50% Liq to form a thickness of 10nm as an electron transport layer. 2% Li is doped in REF-1 to form a 10nm thick N-type charge generation layer 8. 10% PD is doped in HT1. A 10nm thick P-type charge generation layer was formed. HT1 was deposited to a 60nm thickness as a hole transport layer, and a 5nm layer of HT2 was evaporated on top as a second hole transport layer. A 20nm thick blue light-emitting layer was formed by evaporating an anthracene host, ADN (9,10-di(2-naphthyl)anthracene), doped with 3% BD. 5nm of HB was evaporated on top as a hole-blocking material. ET was doped with 50% Liq to a 20nm thickness as an electron transport layer. Mg:Ag (1:9) was deposited to a thickness of 100nm as the cathode. In this device embodiment, different materials were co-evaporated in the same layer, with a specific volume ratio within the layer. For example, 50% Liq resulted in a volume ratio of 50% ET to 50% Liq. The material of this invention was purified by sublimation before use, with an HPLC purity of 99.9%.

[0269] Finally, the device was transferred back to the glove box and encapsulated with a glass cover and a moisture absorbent to complete the device, which was recorded as organic electroluminescent element 1 (comparative example).

[0270] The specific structures of the compounds involved are as follows:

[0271]

[0272] PD HT1 HT2

[0273]

[0274] AND BD ET

[0275]

[0276] HB

[0277] Comparative Example 1 (REF-1) Structure:

[0278]

[0279] Comparative Example 2 (REF-2) Structure:

[0280]

[0281] Comparative Example 3 (REF-3) Structure:

[0282]

[0283] Comparative Example 4 (REF-4) Structure:

[0284]

[0285] Device Examples

[0286] The N-type charge generation layer 8 was prepared by using the compound 1-2 prepared in Synthesis Example 1 of the present invention instead of the REF-1 material, and the organic electroluminescent element 2 was prepared by the same method.

[0287] The N-type charge generation layer 8 was prepared by using the compound 1-3 prepared in Synthesis Example 2 of the present invention instead of the REF-1 material, and the organic electroluminescent element 3 was prepared by the same method.

[0288] The N-type charge generation layer 8 was prepared by using the compound 1-5 prepared in Synthesis Example 3 of the present invention instead of the REF-1 material, and the organic electroluminescent element 4 was prepared by the same method.

[0289] The N-type charge generation layer 8 was prepared by using the compound 1-10 prepared in Synthesis Example 4 of the present invention instead of the REF-1 material, and the organic electroluminescent element 5 was prepared by the same method.

[0290] The N-type charge generation layer 8 was prepared by using the compound 1-17 prepared in Synthesis Example 5 of the present invention instead of the REF-1 material, and the organic electroluminescent element 6 was prepared by the same method.

[0291] The N-type charge generation layer 8 was prepared by using the compound 1-21 obtained in Synthesis Example 6 of the present invention instead of the REF-1 material, and the organic electroluminescent element 7 was prepared by the same method.

[0292] The N-type charge generation layer 8 was prepared by using the compound 1-50 prepared in Synthesis Example 7 of the present invention instead of the REF-1 material, and the organic electroluminescent element 8 was prepared by the same method.

[0293] The N-type charge generation layer 8 was prepared by using REF-2 instead of REF-1 material, and the organic electroluminescent element 9 was prepared by the same method.

[0294] The N-type charge generation layer 8 was prepared by using REF-3 instead of REF-1 material, and the organic electroluminescent element 10 was prepared by the same method.

[0295] The N-type charge generation layer 8 was prepared by using REF-4 instead of REF-1 material, and the organic electroluminescent element 11 was prepared by the same method.

[0296] Organic electroluminescent device evaluation

[0297] Life test method: Apply voltage to the obtained organic electroluminescent element so that the current density reaches 30 mA / cm 2 The time until the brightness reaches 95% of the initial brightness (LT95 (unit: hours)) was measured.

[0298] The driving voltage is at a current density of 15 mA / cm 2 Next test.

[0299] The test results are shown in Table 1:

[0300]

[0301] As can be seen from Table 1, the organic electroluminescent elements 2-8 prepared from the azaspirofluorene compounds of the present application have lower driving voltages and longer service lives than the organic electroluminescent elements 1, 9, 10 and 11. Therefore, the compounds of the present invention are suitable for preparing high-performance organic electroluminescent elements.

[0302] It will be easily understood by those skilled in the art that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. An azaspirofluorene compound, characterized in that The structure of the azaspirofluorene compound is shown in Formula 1 below: in, Ar1 is hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted C6-C 60 aryl, substituted or unsubstituted C3-C 60 heteroaryl; L is a substituted or unsubstituted C6-C 60 arylene, substituted or unsubstituted C3-C 60 and L is not a substituted or unsubstituted fluorenyl group or a substituted or unsubstituted heterofluorenyl group; The C3-C 60 The heteroarylene group is thienylene, furylene, pyrrolylene, thiazolylene, oxazolylene, imidazolylene, pyrazolylene, triazolylene, benzothienylene, benzofuranylene, indolylene, isoindolylene, benzothiazolylene, benzoxazolylene, benzimidazolylene, benzotriazolylene, purinylene, carbazolylene, dibenzothienylene, dibenzofuranylene, pyridylene, pyrimidylene, triazinylene, phenazinylene, quinolylene, isoquinolylene, naphthyridinylene, acridinylene, phenanthrolinylene, carbolylene; Ar2 is represented by the following formula a, formula b, formula c or formula d: Indicates the connection position of the Ar2 group and the L group; R1 and R2 are independently hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted C6-C 60 aryl, substituted or unsubstituted C3-C 60 heteroaryl; R3, R4, R5, and R6 are the same or different from each other and are each independently hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C 10 Alkyl; a is an integer from 0 to 4; when a is 2 or greater, multiple R3 are the same as or different from each other; b is an integer from 0 to 4; when b is 2 or greater, multiple R4 are the same as or different from each other; c is an integer from 0 to 2; when c is 2 or greater, multiple R5 are the same as or different from each other; d is an integer from 0 to 2; when d is 2 or greater, multiple R6 are the same as or different from each other; The substituents in the "substituted or unsubstituted" are each independently selected from deuterium, halogen, cyano, C1-C 10 Alkyl, C1-C 10 Alkoxy, amino, C3-C 10 Cycloalkyl, C3-C 10 Cycloalkoxy, C6-C 60 Aryl, C6-C 60 Aryloxy, C3-C 60 One or a combination of heteroaryl groups; The heteroatoms in the heteroaryl group are selected from one or more of N, O, S, Si, P, and B.

2. The azaspirofluorene compound according to claim 1, characterized in that The structure of the azaspirofluorene compound is shown in the following formula 1': Wherein, L, Ar1, and Ar2 are as defined above.

3. The azaspirofluorene compound according to any one of claims 1 to 2, characterized in that The structures of the azaspirofluorene compounds are shown in the following formulas 1a, 1b, 1c, and 1d: Wherein, Ar1, L, R1, and R2 are as defined above.

4. The azaspirofluorene compound according to any one of claims 1 to 2, characterized in that Ar1 is hydrogen, substituted or unsubstituted C6-C 60 aryl, substituted or unsubstituted C3-C 60 heteroaryl; The L is a substituted or unsubstituted C6-C 60 arylene, substituted or unsubstituted C3-C 60 and L is not a substituted or unsubstituted fluorenyl group or a substituted or unsubstituted heterofluorenyl group; R1 and R2 are independently hydrogen, substituted or unsubstituted C6-C 60 aryl, substituted or unsubstituted C3-C 60 heteroaryl; In the phrase "substituted or unsubstituted", the substituents when substituted are as defined above.

5. The azaspirofluorene compound according to any one of claims 1 to 2, characterized in that Ar1 is hydrogen, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridyl; The L is a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted dibenzothienylene group, a substituted or unsubstituted dibenzofuranylene group, or a substituted or unsubstituted pyridylene group; R1 is hydrogen, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridyl; R2 is hydrogen, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridyl; In the phrase "substituted or unsubstituted", the substituents when substituted are as defined above.

6. The azaspirofluorene compound according to any one of claims 1 to 2, characterized in that: The halogen is F, Br, Cl, or I; And / or, the C1-C 10 The alkyl group is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, neopentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, isooctyl, nonyl, 2-ethylhexyl; And / or, the C6-C 60 The aryl group is phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, naphthyl, phenanthrenyl, fluorenyl, indenyl, pyrenyl, perylenyl, fluoranthenyl, triphenylenyl, triphenylene, benzopyrenyl, spirobifluorenyl, benzo base; And / or, the C6-C 60 The arylene group is phenylene, biphenylene, terphenylene, naphthylene, anthracene, tetraphenylene, phenanthrenyl, fluorenylene, indenylene, pyrenylene, perylene, fluoranthenylene, triphenylene, triphenylene, pyrenylene, terphenylene, pyrenylene, fluorenylene, pyren ... yl, spirobifluorenyl, benzopyrenyl, benzopyrenyl base; And / or, the C3-C 60 The heteroaryl group is thienyl, furyl, pyrrolyl, thiazolyl, oxazolyl, imidazolyl, pyrazolyl, triazolyl, benzothienyl, benzofuranyl, indolyl, isoindolyl, benzothiazolyl, benzoxazolyl, benzimidazolyl, benzotriazolyl, purinyl, carbazolyl, dibenzothienyl, dibenzofuranyl, pyridyl, pyrimidinyl, triazinyl, phenazinyl, quinolyl, isoquinolyl, naphthyridinyl, acridinyl, phenanthrolinyl, or carbolinyl.

7. The azaspirofluorene compound according to claim 1, characterized in that The azaspirofluorene compound is selected from the structure shown below:

8. An organic electroluminescent element comprising a first electrode, a second electrode, and an organic layer between the first electrode and the second electrode, wherein the organic layer comprises a light-emitting layer, characterized in that: The organic layer has one or more organic layers, and at least one organic layer comprises the azaspirofluorene compound according to any one of claims 1 to 7.

9. The organic electroluminescent element according to claim 8, wherein: The organic layer includes at least two light-emitting units, an N-type charge generation layer is included between the two light-emitting units, and the N-type charge generation layer includes the azaspirofluorene compound according to any one of claims 1 to 7.

10. An electronic device comprising: One or more of a display, a monitor, and a lighting device, comprising the organic electroluminescent element according to claim 8 or 9.

Images