Aza-spirofluorene compound and organic electroluminescent element containing aza-spirofluorene compound

Abstract

The invention relates to the technical field of organic electroluminescence, in particular to an aza-spirofluorene compound, a material for an organic element, an organic electroluminescence element and a display or lighting device. The invention relates to an aza-spirofluorene compound, the structure of the aza-spirofluorene compound is as shown in the following formula 1: # imgabs0 # formula 1, and the aza-spirofluorene compound provided by the invention has lower driving voltage and longer service life, and is suitable for preparing a high-performance organic electroluminescent element.

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] An organic electroluminescent element (OLED) is a self-luminous display device based on an organic electroluminescent material. Compared with existing liquid crystal display devices, it has the advantages of not requiring a backlight source and being thin, and is a technology suitable for flexible device devices (flexible light-emitting display devices). It can be used to manufacture new display products and new lighting products, and has a very broad application prospect.

[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 multi-layer structure formed by various different substances. For example, 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 cause carriers of holes and electrons to recombine in the light-emitting layer. The carriers recombine to generate excitons, and these excitons transition from the excited state to the ground state to generate light.

[0004] Currently, research on improving the performance of organic electroluminescent elements includes: reducing the driving voltage of the device, improving the luminous efficiency of the device, and increasing the service life of the element. The characteristics of the organic compound components contained in each layer have a great influence on the driving voltage, luminous efficiency, and life of the element. Therefore, in organic electroluminescent elements, it is considered important to use specific organic materials with excellent performance.

[0005] In addition, a charge generation layer is required to increase the efficiency of the current generated in the light-emitting layer and promote the charge distribution between two or more stacked bodies (or light-emitting units) in a tandem OLED. This depends on the material used for the N-type charge generation layer and affects the driving voltage and service life of the entire device.

[0006] Therefore, it is necessary to continuously research and innovate organic electroluminescent functional materials to manufacture higher-performance organic electroluminescent functional materials, and then manufacture 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 to improve the performance of organic electroluminescent elements.

[0008] The technical solution of the present invention is as follows:

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

[0010] Wherein,

[0011] Ar1 is preferably hydrogen, deuterium, halogen, cyano, a substituted or unsubstituted C1-C 10 alkyl group, a substituted or unsubstituted C6-C 60 aryl group, a substituted or unsubstituted C3-C 60 heteroaryl group, more preferably hydrogen, deuterium, halogen, a substituted or unsubstituted C1-C 10 alkyl group, a substituted or unsubstituted C6-C 60 aryl group, a substituted or unsubstituted C3-C 60 heteroaryl group, even more preferably hydrogen, deuterium, halogen, a substituted or unsubstituted C6-C 60 aryl group, a substituted or unsubstituted C3-C 60 heteroaryl group, most preferably hydrogen, a substituted or unsubstituted C6-C 60 aryl group, a substituted or unsubstituted C3-C 60 heteroaryl group;

[0012] L is preferably a substituted or unsubstituted C6-C 60 arylene group, a substituted or unsubstituted C3-C 60 heteroarylene group, a C1-C 10 alkenylene group, a C1-C 10 alkynylene group, and is not a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted hetero-fluorenyl group; more preferably a substituted or unsubstituted C6-C 60 arylene group, a substituted or unsubstituted C3-C 60 heteroarylene group, a C1-C 10 alkynylene group, and is not a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted hetero-fluorenyl group; most preferably a substituted or unsubstituted C6-C 60 arylene group, a substituted or unsubstituted C3-C 60 heteroarylene group and is not a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted hetero-fluorenyl group;

[0013] Ar2 is preferably shown as Formula a, Formula b, Formula c or Formula d below: Formula a Formula b Formula c Formula d

[0014] “ ” indicates the connection position of the Ar2 group and the L group;

[0015] 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 heteroaryl, more preferably hydrogen, deuterium, halogen, substituted or unsubstituted C1-C 10 alkyl, substituted or unsubstituted C6-C 60 aryl, substituted or unsubstituted C3-C 60 heteroaryl, even 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;

[0016] R3, R4, R5, R6 are the same as or different from each other, and each independently is preferably hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C 10 alkyl, more preferably hydrogen, deuterium, halogen, substituted or unsubstituted C1-C 10 alkyl; even more preferably hydrogen, halogen, substituted or unsubstituted C1-C 10 alkyl; particularly preferably hydrogen, substituted or unsubstituted C1-C 10 alkyl; most preferably hydrogen;

[0017] a is preferably an integer from 0 to 4, more preferably an integer from 0 to 3, even more preferably 0, 1, 2, particularly preferably 0, 1, and most preferably 0; when a is 2 or greater, the multiple R3s are the same as or different from each other;

[0018] b is preferably an integer from 0 to 4, more preferably an integer from 0 to 3, even more preferably 0, 1, 2, particularly preferably 0, 1, and most preferably 0; when b is 2 or greater, the multiple R4s are the same as or different from each other;

[0019] c is preferably an integer from 0 to 2, more preferably 0, 1, and most preferably 0; when c is 2 or greater, the multiple R5s are the same as or different from each other;

[0020] d is preferably an integer from 0 to 2, more preferably 0, 1, and most preferably 0; when d is 2 or greater, the multiple R6s are the same as or different from each other;

[0021] When the substituents in the "substituted or unsubstituted" are substituted, the substituents 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 heteroaryl, or a combination thereof;

[0022] The heteroatoms in the heteroaryl and heteroarylene are preferably selected from one or more of N, O, S, Si, P, B;

[0023] Preferably, the above compound may not contain or contain at least one substituent selected from deuterium, fluorine group, cyano group; More preferably, the above compound may not contain or contain at least one substituent selected from deuterium, fluorine group; Even more preferably, the above compound may not contain or contain at least one deuterium.

[0024] According to the above azaspirofluorene compounds, the structure of the azaspirofluorene compounds is preferably shown as the following formula 1': Formula 1'

[0025] Wherein, the definitions of L, Ar1, and Ar2 are the same as above;

[0026] Preferably, the above compound may not contain or contain at least one substituent selected from deuterium, fluorine group, cyano group; More preferably, the above compound may not contain or contain at least one substituent selected from deuterium, fluorine group; Even more preferably, the above compound may not contain or contain at least one deuterium.

[0027] According to the above azaspirofluorene compounds, the structure of the azaspirofluorene compounds is preferably shown as the following formula 1a, formula 1b, formula 1c, formula 1d: Formula 1a Formula 1b Formula 1c Formula 1d

[0028] Wherein, the definitions of Ar1, L, R1, and R2 are the same as above;

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

[0030] According to the above azaspirofluorene compounds, wherein,

[0031] Ar1 is preferably hydrogen, a substituted or unsubstituted C6-C 60 aryl group, a substituted or unsubstituted C3-C 60 heteroaryl group, more preferably hydrogen, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted triazinyl group, more preferably hydrogen, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted triazinyl group, still more preferably hydrogen, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted pyridyl group, particularly preferably hydrogen, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted pyridyl group, most preferably hydrogen, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted pyridyl group;

[0032] L is preferably a substituted or unsubstituted C6-C 60 arylene group, a substituted or unsubstituted C3-C 60is a heteroarylene and L is not a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted hetero-fluorenyl group, more preferably a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted anthrylene group, a substituted or unsubstituted phenanthrylene group, a substituted or unsubstituted pyrrolylene group, a substituted or unsubstituted imidazolylene group, a substituted or unsubstituted carbazolylene group, a substituted or unsubstituted dibenzothiophenylene group, a substituted or unsubstituted dibenzofuranylene group, a substituted or unsubstituted pyridinylene group, a substituted or unsubstituted pyrimidinylene group, a substituted or unsubstituted triazinylene group, 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 dibenzofuranylene group, a substituted or unsubstituted pyridinylene group, a substituted or unsubstituted triazinylene 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 dibenzofuranylene group, a substituted or unsubstituted pyridinylene group, particularly 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 dibenzofuranylene group, a substituted or unsubstituted pyridinylene group, most preferably a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted dibenzothiophenylene group, a substituted or unsubstituted dibenzofuranylene group, a substituted or unsubstituted pyridinylene group;

[0033] Said R1 and R2 are each independently preferably hydrogen, a substituted or unsubstituted C6-C 60 aryl group, a substituted or unsubstituted C3-C 60The heteroaryl group, more preferably hydrogen, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyrrolyl, substituted or unsubstituted imidazolyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted triazinyl, more preferably hydrogen, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted pyridyl, substituted or unsubstituted triazinyl, even more preferably hydrogen, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted pyridyl, particularly preferably hydrogen, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridyl, most preferably hydrogen, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridyl;

[0034] Among them, when "substituted or unsubstituted" is substituted, the definition of the substituent is the same as above.

[0035] According to the above-mentioned azaspirofluorene compounds, among them,

[0036] The said 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, even more preferably hydrogen, unsubstituted phenyl, deuterium-substituted phenyl, fluorine-substituted phenyl, unsubstituted pyridyl, most preferably hydrogen, unsubstituted phenyl;

[0037] The said L is preferably substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted dibenzothienylene, substituted or unsubstituted dibenzofuranylene, substituted or unsubstituted pyridylene, more preferably unsubstituted phenylene, deuterium-substituted phenylene, fluorine-substituted phenylene, unsubstituted biphenylene, deuterium-substituted biphenylene, fluorine-substituted biphenylene, unsubstituted dibenzothienylene, unsubstituted dibenzofuranylene, unsubstituted pyridylene, most preferably unsubstituted phenylene, fluorine-substituted phenylene, unsubstituted biphenylene, unsubstituted dibenzothienylene, unsubstituted dibenzofuranylene, unsubstituted pyridylene;

[0038] R1 is preferably hydrogen, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted pyridyl group; more preferably hydrogen, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted pyridyl group; still more preferably hydrogen, a substituted or unsubstituted benzene ring; particularly preferably hydrogen, an unsubstituted phenyl group, a deuterium-substituted phenyl group, or a fluorine-substituted phenyl group; especially preferably hydrogen, an unsubstituted benzene ring; and most preferably hydrogen.

[0039] R2 is preferably hydrogen, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted pyridyl group; more preferably hydrogen, an unsubstituted phenyl group, a deuterium-substituted phenyl group, a fluorine-substituted phenyl group, an unsubstituted naphthyl group, a deuterium-substituted naphthyl group, a fluorine-substituted naphthyl group, or an unsubstituted pyridyl group; still more preferably hydrogen, an unsubstituted phenyl group, a deuterium-substituted phenyl group, a fluorine-substituted phenyl group, an unsubstituted naphthyl group, or an unsubstituted pyridyl group; and most preferably hydrogen, an unsubstituted phenyl group, an unsubstituted naphthyl group, or an unsubstituted pyridyl group.

[0040] Among them, when "substituted or unsubstituted" is substituted, the definition of the substituent is the same as above.

[0041] According to the above-mentioned azaspirofluorene compounds, in which L in the structure of the azaspirofluorene compounds is preferably a substituted or unsubstituted group selected from the following: , more preferably a substituted or unsubstituted group selected from the following: , more preferably a substituted or unsubstituted group selected from the following: , more preferably a substituted or unsubstituted group selected from the following: , more preferably a substituted or unsubstituted group selected from the following: , most preferably a substituted or unsubstituted group selected from the following: ;

[0042] Among them, the definition of the substituent when substituting in "substituted or unsubstituted" is the same as above;

[0043] 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; Even more preferably, the structure of the azaspirofluorene compound is selected from one or more of the above formulas 1a, 1b, 1c, and 1d; Even more preferably, the structure of the azaspirofluorene compound is selected from one or more of the above formulas 1b, 1c, and 1d; Even more preferably, the structure of the azaspirofluorene compound is selected from one or more of the above formulas 1b and 1d; Even 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;

[0044] Preferably, the above group is unsubstituted or substituted with one or more substituents selected from deuterium, fluorine group, and cyano group; More preferably, the above group is unsubstituted or substituted with one or more substituents selected from deuterium and fluorine group; Even more preferably, the above group is unsubstituted or substituted with one or more deuteriums; Even more preferably, the above group is unsubstituted or substituted with one or more deuteriums; Most preferably, the above group is unsubstituted.

[0045] According to the above azaspirofluorene compound, among them, Ar1 in the structure of the azaspirofluorene compound is preferably hydrogen, a substituted or unsubstituted group selected from the following: , more preferably hydrogen, a substituted or unsubstituted group selected from the following: , even more preferably hydrogen, , , even more preferably hydrogen, , most preferably hydrogen;

[0046] Among them, the definition of the substituent when substituting in "substituted or unsubstituted" is the same as above;

[0047] 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; Even more preferably, the structure of the azaspirofluorene compound is selected from one or more of the above formulas 1a, 1b, 1c, and 1d; Even more preferably, the structure of the azaspirofluorene compound is selected from one or more of the above formulas 1b, 1c, and 1d; Even more preferably, the structure of the azaspirofluorene compound is selected from one or more of the above formulas 1b and 1d; Even 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;

[0048] Preferably, the above groups are unsubstituted or substituted with one or more substituents selected from deuterium, fluorine group, and cyano group; More preferably, the above groups are unsubstituted or substituted with one or more substituents selected from deuterium and fluorine group; Even more preferably, the above groups are unsubstituted or substituted with one or more deuteriums; Even more preferably, the above groups are unsubstituted or substituted with one or more deuteriums; Most preferably, the above groups are unsubstituted.

[0049] According to the above azaspirofluorene compound, wherein R1 in the structure of the azaspirofluorene compound is preferably hydrogen, a substituted or unsubstituted group as follows: , more preferably hydrogen, a substituted or unsubstituted group as follows: , even more preferably hydrogen, , , even more preferably hydrogen, , most preferably hydrogen;

[0050] Wherein, the definition of the substituent when "substituted or unsubstituted" is substituted is the same as above;

[0051] 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; even more preferably, the structure of the azaspirofluorene compound is selected from one or more of the above formulas 1a, 1b, 1c, and 1d; even more preferably, the structure of the azaspirofluorene compound is selected from one or more of the above formulas 1b, 1c, and 1d; even more preferably, the structure of the azaspirofluorene compound is selected from one or more of the above formulas 1b and 1d; even 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;

[0052] Preferably, the above group is unsubstituted or substituted by one or more substituents selected from deuterium, fluorine group, and cyano group; more preferably, the above group is unsubstituted or substituted by one or more substituents selected from deuterium and fluorine group; even more preferably, the above group is unsubstituted or substituted by one or more deuteriums; even more preferably, the above group is unsubstituted or substituted by one or more deuteriums; most preferably, the above group is unsubstituted.

[0053] According to the above azaspirofluorene compound, wherein R2 in the structure of the azaspirofluorene compound is preferably hydrogen, a substituted or unsubstituted following group: , more preferably a substituted or unsubstituted following group: , even more preferably hydrogen, , , even more preferably hydrogen, , most preferably hydrogen;

[0054] Wherein, the definition of the substituent when "substituted or unsubstituted" is substituted is the same as above;

[0055] 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; Even more preferably, the structure of the azaspirofluorene compound is selected from one or more of the above formulas 1a, 1b, 1c, and 1d; Even more preferably, the structure of the azaspirofluorene compound is selected from one or more of the above formulas 1b, 1c, and 1d; Even more preferably, the structure of the azaspirofluorene compound is selected from one or more of the above formulas 1b and 1d; Even 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;

[0056] Preferably, the above group is unsubstituted or substituted with one or more substituents selected from deuterium, fluorine group, and cyano group; More preferably, the above group is unsubstituted or substituted with one or more substituents selected from deuterium and fluorine group; Even more preferably, the above group is unsubstituted or substituted with one or more deuteriums; Even more preferably, the above group is unsubstituted or substituted with one or more deuteriums; Most preferably, the above group is unsubstituted.

[0057] According to the above azaspirofluorene compound, preferably, when Ar2 is Formula b, Ar1 is hydrogen or When, if L is , then R2 is not hydrogen, .

[0058] According to the above azaspirofluorene compound, preferably, when Ar2 is Formula b, Ar1 is hydrogen or When, if L is , then R2 is not hydrogen.

[0059] According to the above azaspirofluorene compound, preferably, when Ar2 is Formula b, Ar1 is hydrogen or When, if L is , then R2 is not hydrogen.

[0060] According to the above azaspirofluorene compound, preferably, when the structure of the azaspirofluorene compound is as shown in the above formula 1b, Ar1 is hydrogen or When, if L is Then R2 is not hydrogen, .

[0061] According to the above azaspirofluorene compound, preferably, when the structure of the azaspirofluorene compound is as shown in the above formula 1b, Ar1 is hydrogen or When, if L is Then R2 is not hydrogen.

[0062] According to the above-mentioned azaspirofluorene compounds, preferably, when the structure of the azaspirofluorene compound is as shown in Formula 1b above and Ar1 is hydrogen or When, if L is Then R2 is not hydrogen.

[0063] According to the above-mentioned azaspirofluorene compounds, preferably, when Ar2 is Formula c, if Ar1 is , then L is not .

[0064] According to the above-mentioned azaspirofluorene compounds, preferably, when the structure of the azaspirofluorene compound is as shown in Formula 1c above, if Ar1 is , then L is not .

[0065] According to the above-mentioned azaspirofluorene compounds, preferably, when Ar2 is Formula a and Ar1 is hydrogen, if L is , then R1 is not hydrogen.

[0066] According to the above-mentioned azaspirofluorene compounds, preferably, when Ar2 is Formula a and Ar1 is , if L is , then R1 is not hydrogen, .

[0067] According to the above-mentioned azaspirofluorene compounds, preferably, when Ar2 is Formula a and Ar1 is , if L is , then R1 is not hydrogen.

[0068] According to the above-mentioned azaspirofluorene compounds, preferably, when Ar2 is Formula a and Ar1 is hydrogen, if L is , or , then R1 is not hydrogen.

[0069] According to the above-mentioned azaspirofluorene compounds, preferably, when Ar2 is Formula a and Ar1 is hydrogen, if L is , then R1 is not hydrogen, , .

[0070] According to the above-mentioned azaspirofluorene compounds, preferably, when Ar2 is Formula a and Ar1 is , if L is , then R1 is not hydrogen, 。

[0071] According to the above-mentioned azaspirofluorene compounds, preferably, when Ar2 is Formula a and Ar1 is When L is , then R1 is not hydrogen.

[0072] According to the above-mentioned azaspirofluorene compounds, preferably, when Ar2 is Formula a and Ar1 is When L is , then R1 is not hydrogen.

[0073] According to the above-mentioned azaspirofluorene compounds, preferably, when Ar2 is Formula a and Ar1 is hydrogen, when L is , then R1 is not hydrogen, , 。

[0074] According to the above-mentioned azaspirofluorene compounds, preferably, when Ar2 is Formula a and Ar1 is When L is , then R1 is not hydrogen, 。

[0075] According to the above-mentioned azaspirofluorene compounds, preferably, when Ar2 is Formula a and Ar1 is hydrogen, when L is , then R1 is not 。

[0076] According to the above-mentioned azaspirofluorene compounds, preferably, when the structure of the azaspirofluorene compound is as shown in the above formula 1a and Ar1 is hydrogen, when L is , then R1 is not hydrogen.

[0077] According to the above-mentioned azaspirofluorene compounds, preferably, when the structure of the azaspirofluorene compound is as shown in the above formula 1a and Ar1 is When L is , then R1 is not hydrogen, 。

[0078] According to the above-mentioned azaspirofluorene compounds, preferably, when the structure of the azaspirofluorene compound is as shown in the above formula 1a and Ar1 is When L is , then R1 is not hydrogen.

[0079] According to the above-mentioned azaspirofluorene compounds, preferably, when the structure of the azaspirofluorene compound is as shown in the above formula 1a and Ar1 is hydrogen, when L is , or then R1 is not hydrogen.

[0080] According to the above-mentioned azaspirofluorene compounds, preferably, when the structure of the azaspirofluorene compound is as shown in Formula 1a above and Ar1 is hydrogen, if L is then R1 is not hydrogen, , .

[0081] According to the above-mentioned azaspirofluorene compounds, preferably, when the structure of the azaspirofluorene compound is as shown in Formula 1a above and Ar1 is if L is then R1 is not hydrogen, .

[0082] According to the above-mentioned azaspirofluorene compounds, preferably, when the structure of the azaspirofluorene compound is as shown in Formula 1a above and Ar1 is if L is then R1 is not hydrogen.

[0083] According to the above-mentioned azaspirofluorene compounds, preferably, when the structure of the azaspirofluorene compound is as shown in Formula 1a above and Ar1 is if L is then R1 is not hydrogen.

[0084] According to the above-mentioned azaspirofluorene compounds, preferably, when the structure of the azaspirofluorene compound is as shown in Formula 1a above and Ar1 is hydrogen, if L is then R1 is not hydrogen, , .

[0085] According to the above-mentioned azaspirofluorene compounds, preferably, when the structure of the azaspirofluorene compound is as shown in Formula 1a above and Ar1 is if L is then R1 is not hydrogen, .

[0086] According to the above-mentioned azaspirofluorene compounds, preferably, when the structure of the azaspirofluorene compound is as shown in Formula 1a above and Ar1 is hydrogen, if L is then R1 is not .

[0087] According to the above-mentioned azaspirofluorene compounds, preferably, when the structure of the azaspirofluorene compound is as shown in Formula 1a above, if Ar1 is then L is not .

[0088] According to the above-mentioned azaspirofluorene compounds, the halogen is preferably F, Br, Cl, I;

[0089] and / or, the C1-C 10 alkyl 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;

[0090] and / or, the C6-C 60 aryl is preferably phenyl, biphenyl, terphenyl, naphthyl, anthryl, tetraphenyl, phenanthryl, fluorenyl, indenyl, pyrenyl, perylenyl, fluoranthenyl, benzophenanthryl, triphenylenyl, chrysenyl, spirobifluorenyl, benzopyrenyl, benzochrysenyl;

[0091] and / or, the C6-C 60 arylene is preferably phenylene, biphenylene, terphenylene, naphthylene, anthrylene, tetraphenylene, phenanthrylene, fluorenylene, indenylene, pyrenylene, perylenylene, fluoranthenylene, benzophenanthrylene, triphenylenylene, chrysenylene, spirobifluorenylene, benzopyrenylene, benzochrysenylene;

[0092] and / or, the C3-C 60 heteroaryl is preferably thienyl, furyl, pyrrolyl, thiazolyl, oxazolyl, imidazolyl, pyrazolyl, triazolyl, benzothienyl, benzofuryl, indolyl, isoindolyl, benzothiazolyl, benzoxazolyl, benzimidazolyl, benzotriazolyl, purinyl, carbazolyl, dibenzothienyl, dibenzofuryl, pyridyl, pyrimidinyl, triazinyl, phenazinyl, quinolinyl, isoquinolinyl, naphthyridinyl, acridinyl, phenanthrolinyl, carbolinyl;

[0093] and / or, the C3-C 60 heteroarylene is preferably thienylene, furylene, pyrrolylene, thiazolylene, oxazolylene, imidazolylene, pyrazolylene, triazolylene, benzothienylene, benzofurylene, indolylene, isoindolylene, benzothiazolylene, benzoxazolylene, benzimidazolylene, benzotriazolylene, purinylene, carbazolylene, dibenzothienylene, dibenzofurylene, pyridinylene, pyrimidinylene, triazinylene, phenazinylene, quinolinylene, isoquinolinylene, naphthyridinylene, acridinylene, phenanthrolinylene, carbolinylene;

[0094] and / or, the C1-C 10 alkenylene is preferably vinylidene, 1-propenylene, allylidene, 1-butenylene, 2-butenylene, 1-pentenylene, 1-hexenylene, isopropenylidene, isobutenylidene;

[0095] and / or, the C1-C 10 The alkynylene group is preferably ethynylene, propynylene, butynylene.

[0096] According to the above-mentioned azaspirofluorene compounds, the halogen is preferably F, Br, Cl, I, more preferably F, Br, Cl, still more preferably F, Cl, and most preferably F.

[0097] According to the above-mentioned azaspirofluorene compounds, 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-heptane, more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, neopentyl, isopentyl, n-hexyl, still more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, particularly preferably methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-pentyl, particularly preferably methyl, ethyl, n-propyl, isopropyl, tert-butyl, especially preferably methyl, ethyl, tert-butyl, especially preferably methyl, ethyl, and most preferably methyl.

[0098] According to the above-mentioned azaspirofluorene compounds, the C6-C 60 The aryl group is preferably phenyl, biphenyl, terphenyl, naphthyl, anthryl, tetraphenyl, phenanthryl, fluorenyl, indenyl, pyrenyl, perylenyl, fluoranthenyl, benzo[a]phenanthryl, triphenylenyl, chrysenyl, spirobifluorenyl, benzo[a]pyrenyl, benzo[a]chrysenyl, more preferably phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, fluoranthenyl, triphenylenyl, perylenyl, pyrenyl, benzo[a]pyrenyl, chrysenyl, benzo[a]chrysenyl, still more preferably phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, particularly preferably biphenyl, phenyl, naphthyl, and most preferably phenyl.

[0099] According to the above-mentioned azaspirofluorene compounds, the C6-C 60The arylene group is preferably a phenylene group, a biphenylene group, a terphenylenyl group, a naphthylene group, an anthrylene group, a tetracenylene group, a phenanthrylene group, a fluorene group, an indenyl group, a pyrenyl group, a perylenyl group, a fluoranthenyl group, a benzo[a]phenanthrenyl group, a triphenylene group, a chrysenyl group, a spirobifluorene group, a benzo[a]pyrenyl group, a benzo[a]chrysenyl group, more preferably a phenylene group, a biphenylene group, a terphenylenyl group, a naphthylene group, an anthrylene group, a phenanthrylene group, a fluoranthenyl group, a triphenylene group, a perylenyl group, a pyrenyl group, a benzo[a]pyrenyl group, a chrysenyl group, a benzo[a]chrysenyl group, still more preferably a phenylene group, a biphenylene group, a terphenylenyl group, a naphthylene group, an anthrylene group, a phenanthrylene group, particularly preferably a biphenylene group, a phenylene group, a naphthylene group, and most preferably a phenylene group.

[0100] According to the above-mentioned azaspirofluorene compounds, the C3-C 60 The heteroaryl group is preferably a thienyl group, a furyl group, a pyrrolyl group, a thiazolyl group, an oxazolyl group, an imidazolyl group, a pyrazolyl group, a triazolyl group, a benzothienyl group, a benzofuryl group, an indolyl group, an isoindolyl group, a benzothiazolyl group, a benzoxazolyl group, a benzimidazolyl group, a benzotriazolyl group, a purinyl group, a carbazolyl group, a dibenzothienyl group, a dibenzofuryl group, a pyridyl group, a pyrimidinyl group, a triazinyl group, a phenazinyl group, a quinolinyl group, an isoquinolinyl group, a naphthyridinyl group, an acridinyl group, a phenanthrolinyl group, a carbolinyl group, more preferably a thienyl group, a furyl group, a pyrrolyl group, an imidazolyl group, a pyrazolyl group, a benzothienyl group, a benzofuryl group, a benzimidazolyl group, a carbazolyl group, a dibenzothienyl group, a dibenzofuryl group, a pyridyl group, a pyrimidinyl group, a triazinyl group, a phenazinyl group, a quinolinyl group, an isoquinolinyl group, a phenanthroline, still more preferably a pyrrolyl group, an imidazolyl group, a carbazolyl group, a dibenzothienyl group, a dibenzofuryl group, a pyridyl group, a pyrimidinyl group, a triazinyl group, particularly preferably a dibenzothienyl group, a dibenzofuryl group, a pyridyl group, a triazinyl group, especially preferably a dibenzothienyl group, a dibenzofuryl group, a pyridyl group, and most preferably a pyridyl group.

[0101] According to the above-mentioned azaspirofluorene compounds, the C3-C 60The heteroarylene is preferably thienylene, furylene, pyrrolylene, thiazolylene, oxazolylene, imidazolylene, pyrazolylene, triazolylene, benzothienylene, benzofurylene, indolylene, isoindolylene, benzothiazolylene, benzoxazolylene, benzimidazolylene, benzotriazolylene, purinylene, carbazolylene, dibenzothienylene, dibenzofurylene, pyridinylene, pyrimidinylene, triazinylene, phenazinylene, quinolinylene, isoquinolinylene, naphthyridinylene, acridinylene, phenanthrolinylene, carbolinylene, more preferably thienylene, furylene, pyrrolylene, imidazolylene, pyrazolylene, benzothienylene, benzofurylene, benzimidazolylene, carbazolylene, dibenzothienylene, dibenzofurylene, pyridinylene, pyrimidinylene, triazinylene, phenazinylene, quinolinylene, isoquinolinylene, phenanthroline, still more preferably pyrrolylene, imidazolylene, carbazolylene, dibenzothienylene, dibenzofurylene, pyridinylene, pyrimidinylene, triazinylene, particularly preferably dibenzothienylene, dibenzofurylene, pyridinylene, triazinylene, especially preferably dibenzothienylene, dibenzofurylene, pyridinylene, and most preferably pyridinylene.

[0102] According to the above azaspirofluorene compounds, the C1-C 10 The alkenylene is preferably vinylidene, 1-propenylene, allylidene, 1-butenylene, 2-butenylene, 1-pentenylene, 1-hexenylene, isopropenylidene, isobutenylidene, more preferably vinylidene, 1-propenylene, allylidene, 1-butenylene, 2-butenylene, isopropenylidene, isobutenylidene, still more preferably vinylidene, 1-propenylene, allylidene, isopropenylidene, and most preferably vinylidene.

[0103] According to the above azaspirofluorene compounds, the C1-C 10The alkynylene group is preferably ethynylene, propynylene, butynylene, more preferably ethynylene, propynylene, and most preferably ethynylene. According to the above-mentioned azaspirofluorene compounds, wherein the definition of the substituent when substituted in the "substituted or unsubstituted" is preferably independently selected from one or more combinations of deuterium, fluorine group, cyano group, methyl group, ethyl group, tert-butyl group, cyclohexyl group, phenyl group, biphenyl group, terphenyl group, naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, fluoranthenyl group, quinolinyl group, triphenylene group, chrysenyl group, dibenzofuranyl group, dibenzothiophenyl group, pyridyl group; more preferably selected from one or more combinations of deuterium, fluorine group, cyano group, methyl group, ethyl group, tert-butyl group, phenyl group, biphenyl group, terphenyl group, quinolinyl group, naphthyl group, anthracenyl group, phenanthryl group, dibenzofuranyl group, dibenzothiophenyl group, pyridyl group; still more preferably selected from one or more combinations of deuterium, fluorine group, cyano group, methyl group, tert-butyl group, phenyl group, quinolinyl group, biphenyl group, naphthyl group, dibenzofuranyl group, dibenzothiophenyl group, pyridyl group; particularly preferably selected from one or more combinations of deuterium, fluorine group, cyano group, methyl group, phenyl group, biphenyl group, naphthyl group, dibenzofuranyl group, dibenzothiophenyl group, pyridyl group; especially preferably selected from one or more combinations of deuterium, fluorine group, phenyl group, biphenyl group, naphthyl group, pyridyl group; especially preferably selected from one or more combinations of deuterium, fluorine group, phenyl group, naphthyl group, pyridyl group; especially preferably selected from one or more combinations of deuterium, fluorine group, phenyl group, pyridyl group; especially preferably selected from one or more combinations of deuterium, fluorine group, phenyl group; especially preferably selected from one or more combinations of deuterium, phenyl group; most preferably selected from one or more combinations of deuterium.

[0104] According to the above-mentioned azaspirofluorene compounds, the azaspirofluorene compounds are preferably selected from the structures shown below: 1-1 1-2 1-3 1-4 1-5 1-6 1-7 1-8 1-9 1-10 1-11 1-12 1-13 1-14 1-15 1-16 1-17 1-18 1-19 1-20 1-21 1-22 1-23 1-24 1-25 1-26 1-27 1-28 1-29 1-30 1-31 1-32 1-33 1-34 1-35 1-36 1-37 1-38 1-39 1-40 1-41 1-42 1-43 1-44 1-45 1-46 1-47 1-48 1-49 1-50 1-51 1-52 1-53 1-54 1-55 1-56 1-57.

[0105] In a second aspect, the present invention provides a material for an organic element, which may include the above-mentioned azaspirofluorene compounds.

[0106] According to the above-mentioned material for an organic element, it is preferably a charge generation layer material, and more preferably an N-type charge generation layer material.

[0107] In a third aspect, the present invention provides an organic electroluminescent element, which may include the above-mentioned azaspirofluorene compounds or the above-mentioned material for an organic element.

[0108] According to the above-mentioned organic electroluminescent element, the organic electroluminescent element may include a cathode and an anode

[0109] and an organic functional layer located between the anode and the cathode, at least one layer of the organic functional layer containing the above-mentioned azaspirofluorene compounds or the above-mentioned materials for organic elements; preferably, the organic functional layer contains an N-type charge generation layer, and the N-type charge generation layer contains the azaspirofluorene compounds having the general formula structure shown in the above formula 1.

[0110] According to the above-mentioned organic electroluminescent element, the organic electroluminescent element may include an anode, a cathode, a hole injection layer, 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 located between the anode and the cathode. 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 contains the azaspirofluorene compounds having the general formula structure shown in the above formula 1.

[0111] In a fourth aspect, the present invention provides a display or lighting device, which may contain the above-mentioned azaspirofluorene compounds or the above-mentioned materials for organic elements or the above-mentioned organic electroluminescent elements; preferably, the device further includes a control unit for driving the above-mentioned display device.

[0112] In the present invention, the term "C1-C 10 alkyl" refers to a monovalent substituent derived from a straight-chain or branched-chain saturated hydrocarbon having 1 to 10 carbon atoms, and examples thereof include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, and hexyl.

[0113] In the present invention, the term "C6-C 60 aryl" 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 may have a form in which two or more of these rings are simply side-bonded to each other or fused to each other. Examples of such an aryl include, but are not limited to, phenyl, biphenyl, naphthyl, phenanthryl, anthryl, pyrenyl, triphenylenyl, fluoranthenyl, dimethyl 9,9-dimethylfluorene, 9,9-diphenylfluorene, spirobifluorene, etc.

[0114] In the present invention, the term "C1-C 10 alkenylene" refers to a divalent substituent formed by removing two hydrogen atoms from an olefin molecule having 1 to 10 carbon atoms, and examples thereof include, but are not limited to, vinylene, 1-propenylene, etc.

[0115] In the present invention, the term "C1-C 10 alkynylene" refers to a divalent substituent formed by removing two hydrogen atoms from an alkyne molecule having 1 to 10 carbon atoms, and examples thereof include, but are not limited to, ethynylene, propargylene, etc.

[0116] In the present invention, the term "C3-C 60 heteroaryl" refers to a monovalent substituent derived from a monocyclic or polycyclic aromatic hydrocarbon having 3 to 60 carbon atoms. In this connection, at least one carbon atom, preferably 1 - 3 carbon atoms in the ring are replaced by a heteroatom such as N, O, S, P, B or Si. In addition, such heteroaryl can have a form in which two or more of the rings are simply linked to each other side by side or fused to each other or fused to an aryl group. Examples of such heteroaryl include pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, indolizinyl, indolyl, indolopyridyl, purinyl, phenanthrolinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, thiazolyl, imidazolyl, oxazolyl, furyl, thienyl, benzofuranyl, benzothienyl, benzothiazolyl, benzimidazolyl, benzoxazolyl, carbazolyl, dibenzofuranyl, dibenzothienyl, etc., but the present invention is not limited thereto.

[0117] In the present invention, the term "arylene" refers to a divalent aryl group derived by removing one hydrogen atom from "aryl", for example, phenyl becomes phenylene by removing one hydrogen atom, and naphthyl becomes naphthylene by removing one hydrogen atom.

[0118] In the present invention, the term "halogen" may include fluorine, chlorine, bromine or iodine.

[0119] In the present invention, the term "C3-C 60 heteroarylene" refers to a divalent monocyclic aromatic group and / or divalent polycyclic aromatic group derived from a compound having 3 to 60 carbon atoms and containing at least one aromatic ring, wherein at least one aromatic ring contains one or more heteroatoms independently selected from O, S and N. Each ring of the heteroarylene 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 less than four and each ring contains at least one carbon atom.

[0120] In the present invention, " " represents a connecting bond.

[0121] In the present invention, the term "substituted or unsubstituted" means that a hydrogen atom in a compound is replaced by a non-hydrogen group or not replaced by a non-hydrogen group. The number of substituents is not limited as long as it can be obtained by a chemical reaction. 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, as long as not otherwise described in this specification, includes any of the following groups, but is not limited thereto, ," " represents the substitution position. "Unsubstituted" means that a hydrogen atom is retained, and in this case, the hydrogen atom includes protium, deuterium and tritium.

[0122] In the present invention, when there are two or more substituents, the two or more substituents may be the same or different.

[0123] In the present invention, terms such as 1, 2, 1a, 1b, 1c, 1d, a, b, c, d, etc. are used. The above terms are only used to distinguish the constituent elements and do not limit the nature or order of the constituent elements corresponding to the terms.

[0124] Generally speaking, compared with the prior art, the above technical solutions conceived by the present invention can achieve the following beneficial effects:

[0125] 1. The azaspirofluorene compounds described in the present invention have an azaspirofluorene structure, which can effectively improve the electron transport ability of the material, and the evaporation film-forming effect is better, which is beneficial to reducing the device voltage and improving the device life;

[0126] 2. The organic electroluminescent device prepared by using the compound with a specific parent nucleus structure in the present invention as the N-type charge generation layer material has a lower driving voltage;

[0127] 3. The organic electroluminescent device prepared by using the compound with a specific parent nucleus structure in the present invention as the N-type charge generation layer material has a longer service life. Description of the Drawings

[0128] Figure 1 It is a schematic structural diagram of the organic electroluminescent device described in Application Example 1; wherein: Figure 1 Each mark in represents: 1, the first electrode layer, 2, the hole injection layer, 3, the hole transport layer, 4, the second hole transport layer, 5, the light-emitting layer, 6, the hole blocking layer, 7, the electron transport layer, 8, the N-type charge generation layer, 9, the P-type charge generation layer, 10, the hole transport layer, 11, the second hole transport layer, 12, the light-emitting layer, 13, the hole blocking layer, 14, the electron transport layer, 15, the second electrode layer, 100, the first light-emitting unit, 200, the second light-emitting unit.

[0129] Figure 2 It is the mass spectrum (LC-MS) of Compound 1-2 prepared in Synthesis Example 1 in the Compound Preparation Example.

[0130] Figure 3 It is the nuclear magnetic resonance (1H NMR) spectrum of Compound 1-2 prepared in Synthesis Example 1 in the Compound Preparation Example.

[0131] Figure 4 It is the mass spectrum (LC-MS) of Compound 1-3 prepared in Synthesis Example 2 in the Compound Preparation Example.

[0132] Figure 5It is the nuclear magnetic resonance (1H NMR) spectrum of Compound 1-3 prepared in Synthesis Example 2 in the compound preparation examples.

[0133] Figure 6 It is the mass spectrum (LC-MS) of Compound 1-5 prepared in Synthesis Example 3 in the compound preparation examples.

[0134] Figure 7 It is the nuclear magnetic resonance (1H NMR) spectrum of Compound 1-5 prepared in Synthesis Example 3 in the compound preparation examples. Detailed implementation manners

[0135] Exemplary embodiments will now be described in detail, the examples of which are illustrated in the accompanying drawings, where the same reference numerals always refer to the same elements. In this regard, the present exemplary embodiments may have different forms and should not be construed as limited to the description set forth herein. Therefore, the exemplary embodiments are described below only by reference to the accompanying drawings for purposes of illustration. As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items. The expression "at least one layer (type) of" modifies the entire list of elements when before or after the list of elements and does not modify the individual elements of the list.

[0136] It will be further understood that the terms "comprises" or "comprising", when used in this specification, indicate the presence of the stated features, regions, wholes, steps, operations, elements, and / or components, but do not preclude the presence or addition of one or more other features, regions, wholes, steps, operations, elements, components, and / or their groups.

[0137] Unless otherwise defined, the meanings of all terms (including technical and scientific terms) used herein are the same as those 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 a commonly used dictionary, should be interpreted as having a meaning consistent with their meaning in the relevant art and the context of this disclosure, and will not be interpreted in an idealized or overly formal sense unless clearly so defined herein.

[0138] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and not to limit the protection scope of the present invention. In addition, it should be understood that after reading the content disclosed in the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the protection scope defined by the present invention.

[0139] In the present invention, unless otherwise specified, all parts and percentages are by weight, and the equipment and raw materials used can be obtained from the market or are commonly used in the art. The methods in the following examples are conventional methods in the art unless otherwise specified.

[0140] Unless otherwise specified, the experimental methods used in the following examples are all conventional methods; the starting materials, reaction raw materials, reagents, materials, etc. used in the following examples can be obtained from commercial sources unless otherwise specified.

[0141] Compound Preparation Example

[0142] LC-MS brand: Waters, model: SQ Detector 2

[0143] NMR brand: Bruker, model: AVANCE NEO 400

[0144] Those skilled in the art can synthesize the compounds of the present invention by referring to the synthesis of the following compounds and well-known synthesis methods.

[0145] Synthesis Example 1: Preparation of Compound 1-2

[0146] Step 1: Synthesis of Intermediate 1-2-1:

[0147] Under a nitrogen atmosphere, magnesium (1.1 g, 45 mmol) and iodine (50 mg, 19.7 mmol) were added to a four-necked flask, and then tetrahydrofuran (50 mL) was added. Subsequently, it was heated and stirred for 20 minutes. Then a tetrahydrofuran solution of 100 mL of 2-bromobiphenyl (10 g, 42.9 mmol) was slowly added dropwise to the four-necked flask. The reaction was stopped until the magnesium completely disappeared. At 25 °C, the mixed solution obtained in the above flask was added to a tetrahydrofuran solution of 100 mL of 2-bromo-4,5-diazafluorene-9-one (10 g, 38.6 mmol). After stirring at 25 °C for 12 hours, it was quenched with 50 ml of water. Purification was carried out by silica gel chromatography (developing solvent: dichloromethane:tetrahydrofuran = 100:1) to obtain Intermediate 1-2-1 as a pale yellow solid (7 g, yield 43.7%).

[0148] LC-MS (APCI): 415.29 (M+H + ). Calcd for C 23 H 15 BrN2O 414.03.

[0149] Step 2: Synthesis of Intermediate 1-2-2:

[0150] 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 added and stirred until dissolved. 4 mL of concentrated sulfuric acid was added. Under nitrogen protection, the mixture was heated to 120 °C and refluxed for 8 h. The reaction solution was cooled to 25 °C and poured into a 100 ml beaker of ice water and stirred. The resulting Intermediate 1-2-2 as a pale yellow solid was obtained by filtration (6 g, yield 90%).

[0151] LC-MS (APCI): 397.33 (M+H + ). Calcd for C 23 H3BrN2 396.02.

[0152] Step 3: Synthesis of Compound 1-2

[0153] 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 bis(triphenylphosphine)palladium(II) dichloride (0.2 g, 0.3 mmol) were added to a four-necked reaction flask. Then 120 ml of tetrahydrofuran and 40 ml of water were added. The temperature was raised to 75 °C for reaction. After the reaction was completed, the reaction solution was poured into a beaker containing 200 ml of ethanol, stirred and cooled to 25 °C. The resulting Compound 1-2 as a pale yellow solid was obtained by filtration (8 g, yield 82%).

[0154] LC-MS (APCI): 649.57 (M+H + ). Calcd for C 47 H 28 N4 648.23; The corresponding mass spectrum is shown in the attached specification Figure 2 .

[0155] 1 1H NMR (400 MHz, Methylene Chloride-d2) δ 9.29 (t, J = 1.8 Hz, 1H), 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); The corresponding NMR spectrum is shown in the attached specificationFigure 3 .

[0156] Synthesis Example 2: Synthesis of Compound 1-3 (wherein, Bpin represents a pinacol borate group)

[0157] 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 bis(triphenylphosphine)palladium(II) dichloride (0.2 g, 0.3 mmol) were added to a four-necked reaction flask. Then, 120 ml of tetrahydrofuran and 40 ml of water were added, and the reaction solution was heated to 75 °C and reacted for 5 hours. After the reaction was completed, the temperature of the reaction solution was cooled to 25 °C, and the reaction solution was poured into a beaker containing 200 ml of ethanol. The mixture was stirred for 30 minutes, and the crude product was obtained by filtration. The crude product was purified by column chromatography (mobile phase: dichloromethane) to obtain Compound 1-3 (7 g, yield 72%) as a pale yellow solid.

[0158] LC-MS (APCI): 649.39 [M+H] + . Calcd for C 47 H 28 N4648.23; The corresponding mass spectrum is shown in the attached specification Figure 4 .

[0159] 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). The corresponding NMR spectrum is shown in the attached specification Figure 5 .

[0160] Synthesis Example 3: Synthesis of Compound 1-5 (wherein, Bpin represents a pinacol borate group)

[0161] 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 bis(triphenylphosphine)palladium(II) dichloride (0.2 g, 0.3 mmol) were added to a four-necked reaction flask, followed by the addition of 120 ml of tetrahydrofuran and 40 ml of water; the temperature was raised to 75 °C for reaction. After the reaction was completed, the temperature of the reaction solution was lowered to 25 °C. The reaction solution was extracted with dichloromethane and separated, and the organic phase was dried over anhydrous sodium sulfate and then rotary evaporated to dryness. The crude product was purified by column chromatography (mobile phase: dichloromethane) to obtain compound 1-5 (5.9 g, yield 68%) as a pale yellow solid.

[0162] LC-MS (APCI): 573.37 [M+H] + .Calcd for: C 41 H 24 N4572.20; see the corresponding mass spectrum in the attached specification Figure 6 。

[0163] 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). See the corresponding NMR spectrum in the attached specification Figure 7 。

[0164] Synthesis Example 4: Synthesis of Compound 1-10

[0165] (1) Synthesis of Intermediate 1-10-1

[0166] Under a nitrogen atmosphere, intermediate 1-2-2 (10.00 g, 25.25 mmol), m-chlorophenylboronic acid (3.10 g, 27.78 mmol), tetrakis(triphenylphosphine)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. Then, 90 ml of tetrahydrofuran and 30 ml of water were added. The temperature was raised to 70 °C and the reaction was carried out for 6 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 the organic phase was concentrated to obtain a crude product. The crude product was purified by silica gel chromatography (mobile phase: dichloromethane:tetrahydrofuran = volume ratio 50:1) to obtain intermediate 1-10-1 (8.1 g, yield 74.9%) as a white solid.

[0167] (2) Synthesis of intermediate 1-10-2

[0168] Under a nitrogen atmosphere, intermediate 1-10-1 (8.00 g, 18.65 mmol), bis(pinacolato)diboron (5.21 g, 20.52 mmol), 1,1'-bis(diphenylphosphino)ferrocene palladium(II) dichloride (0.27 g, 0.37 mmol), and potassium acetate (3.66 g, 37.30 mmol) were added to a 500 ml four-necked reaction flask. Then, 100 ml of anhydrous 1,4-dioxane was added. The temperature was raised to 110 °C and the reaction was carried out for 8 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 the organic phase was 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.

[0169] (3) Synthesis of compound 1-10

[0170] Under a nitrogen atmosphere, intermediate 1-10-2 (4.0 g, 7.68 mmol), intermediate 1-10-3 (2.57 g, 7.68 mmol), tetrakis(triphenylphosphine)palladium (0.44 g, 0.38 mmol), and potassium carbonate (2.12 g, 15.37 mmol) were added to a 500 ml four-necked reaction flask. Then, 60 ml of tetrahydrofuran and 20 ml of water were added. The temperature was raised to 70 °C and the reaction was carried out for 12 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 separated and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, and the organic phase was concentrated to obtain a crude product. The crude product was purified by silica gel chromatography (mobile phase: dichloromethane:tetrahydrofuran = 20:1 by volume). Thus, compound 1-10 (3.0 g, yield 60.3%) was obtained as a white solid.

[0171] LC-MS (APCI): 649.44[M+H] + . Calcd for: C 47 H 28 N4 648.23.

[0172] Synthesis Example 5: Synthesis of Compound 1-17

[0173] (1) Synthesis of Intermediate 1-17-1

[0174] 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), tetrakis(triphenylphosphine)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. Then, 90 ml of tetrahydrofuran and 30 ml of water were added. The temperature was raised to 70 °C and the reaction was carried out for 6 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 with dichloromethane and dried over anhydrous sodium sulfate. The organic phase was concentrated to obtain a crude product, and the crude product was purified by silica gel chromatography (mobile phase: dichloromethane:tetrahydrofuran = 40:1 by volume). Thus, intermediate 1-17-1 (6.0 g, yield 51.2%) was obtained as a white solid.

[0175] LC-MS (APCI): 292.38[M+H] + . Calcd for: C 17 H 10 ClN3 291.05.

[0176] (2) Synthesis of Compound 1-17

[0177] Under a nitrogen atmosphere, intermediate 1-10-2 (4.0 g, 7.68 mmol), intermediate 1-17-1 (2.24 g, 7.68 mmol), tetrakis(triphenylphosphine)palladium (0.44 g, 0.38 mmol), and potassium carbonate (2.12 g, 15.37 mmol) were added to a 500 ml four-necked reaction flask. Then, 90 ml of tetrahydrofuran and 30 ml of water were added, and the reaction mixture was heated to 70 °C and reacted for 8 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 the organic phase was concentrated to obtain a crude product. The crude product was purified by silica gel chromatography (mobile phase: dichloromethane:tetrahydrofuran = volume ratio 20:1) to obtain intermediate 1-17 (3.2 g, yield 64.2%) as a white solid.

[0178] LC-MS (APCI): 650.38[M+H] + . Calcd for: C 46 H 27 N5 649.22.

[0179] Synthesis Example 6: Synthesis of Compound 1-21

[0180] 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 added to a 250 mL four-necked flask. 45 mL of tetrahydrofuran and 15 mL of water were added, and the reaction solution was heated to 70 °C, and then the reaction was continued under stirring at this temperature for 6 h. After the reaction was completed, the temperature of the reaction solution was lowered to 25 °C, and a solid precipitated. The solid was filtered. The crude product was purified by silica gel chromatography (mobile phase: dichloromethane:tetrahydrofuran = volume ratio 20:1) to obtain compound 1-21 (4.5 g, yield 48.5%) as a white solid.

[0181] LC-MS (APCI): 663.45[M+H] + . Calcd for: C 47 H 26 N4O 662.21.

[0182] Synthesis Example 7: Synthesis of Compound 1-50

[0183] (1) Synthesis of Intermediate 1-50-2

[0184] Under nitrogen protection, Intermediate 1-50-1 (15.5 g, 30.9 mmol), bis(pinacolato)diboron (10.3 g, 40.56 mmol), potassium acetate (7.3 g, 74.4 mmol), 1,1'-bis(diphenylphosphino)ferrocene dichloropalladium (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. Then, 200 mL of anhydrous dioxane was added, and the temperature was raised to 110 °C and reacted for 6 hours. After the reaction was completed, the reaction temperature was lowered to 25 °C. 200 mL of water was added to the reaction solution, and it was extracted and separated with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, and the organic phase was concentrated to obtain a crude product. The crude product was purified by silica gel chromatography (mobile phase: dichloromethane:tetrahydrofuran = 80:1 by volume) to obtain Intermediate 1-50-2 as a solid (10.3 g, yield 61.1%).

[0185] (2)Synthesis of Compound 1-50

[0186] Under nitrogen protection, Intermediate 1-2-2 (4.04 g, 12.1 mmol), Intermediate 1-50-2 (6.6, 12.1 mmol), potassium carbonate (3.3 g, 23.8 mmol), and 1,1'-bis(diphenylphosphino)ferrocene dichloropalladium (0.17 g, 0.24 mmol) were added to a four-necked reaction flask. Then, 60 mL of toluene, 20 mL of ethanol, and 20 mL of water were added, and the reaction solution was heated to 90 °C and reacted for 6 hours. After the reaction was completed, the reaction solution temperature was lowered to 25 °C. 100 mL of water was added, and it was extracted and separated with dichloromethane. The organic phase was dried over anhydrous sodium sulfate, and the organic phase was concentrated to obtain a crude product. The crude product was purified by silica gel chromatography (mobile phase: dichloromethane:tetrahydrofuran = 15:1 by volume) to obtain Compound 1-50 as a pale yellow solid (5.3 g, yield 59.1%).

[0187] LC-MS (APCI): 739.43[M+H] + . Calcd for: C 53 H 30 N4O 738.24.

[0188] The following application examples further illustrate the application of the azaspirofluorene compounds described in the present invention in the preparation of organic electroluminescent devices.

[0189] Application Example 1

[0190] This embodiment provides an organic electroluminescent element, as Figure 1 shown, including 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 sequentially stacked. Among them, 100 is the first light-emitting unit and 200 is the second light-emitting unit.

[0191] The specific device structure is as follows: ITO / HT1:PD(3%)(10nm) / HT1(60nm) / HT2(5nm) / ADN:BD(3%)(20nm) / HB(5nm) / ET-Liq(50%) (10nm) / REF-1:Li(2%)(10nm) / HT1:PD(10%)(10nm) / HT1(60nm) / HT2(5nm) / ADN:BD(3%)(20nm) / HB(5nm) / ET-Liq(50%) (20nm) / Mg:Ag 1:9(100nm).

[0192] Device fabrication process:

[0193] The bottom-emitting glass substrate used in this embodiment is purchased from Guangdong Xinyi Display Technology Co., Ltd., and ITO is used as the anode. First, the bottom-emitting glass substrate is sequentially cleaned with ITO cleaning agent, deionized water, and isopropyl alcohol, and then the bottom-emitting glass substrate is baked at 180 degrees Celsius for 30 minutes to dry it.

[0194] Then the bottom-emitting glass substrate is placed in the evaporation chamber, and the vacuum degree is about 10 -8In the case of the support, each organic layer was sequentially deposited on the ITO anode by thermal vacuum evaporation at a rate of 0.2 - 2 Å / second. Among them, PD (3%) was incorporated into HT1 to form a thickness of 10 nm as the hole injection layer. HT1 was formed to a thickness of 60 nm as the hole transport layer, and a layer of 5 nm of HT2 material was evaporated thereon as the second hole transport layer. Then, a blue light-emitting layer with a thickness of 20 nm was formed by evaporating anthracene host ADN (9,10-bis(2-naphthyl)anthracene) doped with 3% of BD. A 5 nm thick HB was evaporated thereon as the hole blocking material. ET doped with 50% Liq was formed to a thickness of 10 nm as the electron transport layer. 2% of Li was doped in REF-1 to form an N-type charge generation layer 8 with a thickness of 10 nm. 10% of PD was doped in HT1 to form a P-type charge generation layer with a thickness of 10 nm. HT1 was formed to a thickness of 60 nm as the hole transport layer, and a layer of 5 nm of HT2 material was evaporated thereon as the second hole transport layer. Then, a blue light-emitting layer with a thickness of 20 nm was formed by evaporating anthracene host ADN (9,10-bis(2-naphthyl)anthracene) doped with 3% of BD. A 5 nm thick HB was evaporated thereon as the hole blocking material. ET doped with 50% Liq was formed to a thickness of 20 nm as the electron transport layer. Mg:Ag (1:9) was formed to a thickness of 100 nm as the cathode. In the same layer of this device embodiment, different materials were co-evaporated and existed in the layer in a certain volume ratio. For example, 50% of Liq was in a volume ratio of ET 50% and Liq 50%. The materials of the present invention were used after sublimation purification, HPLC: 99.9%.

[0195] Finally, the device was transferred back to the glove box and encapsulated with a glass cover and a moisture absorbent to complete the device, denoted as organic electroluminescent element 1 (comparative example).

[0196] The specific structures of the compounds involved are as follows: PD HT1 HT2 AND BD ET HB

[0197] Structure of Comparative Example 1 (REF-1):

[0198] Structure of Comparative Example 2 (REF-2):

[0199] Structure of Comparative Example 3 (REF-3):

[0200] Structure of Comparative Example 4 (REF-4):

[0201] Device Example

[0202] Compound 1-2 obtained in Synthesis Example 1 of the present invention was used to replace the REF-1 material to prepare the N-type charge generation layer 8, and the organic electroluminescent element 2 was fabricated in the same manner.

[0203] Compound 1-3 obtained in Synthesis Example 2 of the present invention was used to replace the REF-1 material to prepare the N-type charge generation layer 8, and the organic electroluminescent element 3 was fabricated in the same manner.

[0204] Compound 1-5 obtained in Synthesis Example 3 of the present invention was used to replace the REF-1 material to prepare the N-type charge generation layer 8, and the organic electroluminescent element 4 was fabricated in the same manner.

[0205] Compound 1-10 obtained in Synthesis Example 4 of the present invention was used to replace the REF-1 material to prepare the N-type charge generation layer 8, and the organic electroluminescent element 5 was fabricated in the same manner.

[0206] Compound 1-17 obtained in Synthesis Example 5 of the present invention was used to replace the REF-1 material to prepare the N-type charge generation layer 8, and the organic electroluminescent element 6 was fabricated in the same manner.

[0207] Compound 1-21 obtained in Synthesis Example 6 of the present invention was used to replace the REF-1 material to prepare the N-type charge generation layer 8, and the organic electroluminescent element 7 was fabricated in the same manner.

[0208] Compound 1-50 obtained in Synthesis Example 7 of the present invention was used to replace the REF-1 material to prepare the N-type charge generation layer 8, and the organic electroluminescent element 8 was fabricated in the same manner.

[0209] REF-2 was used to replace the REF-1 material to prepare the N-type charge generation layer 8, and the organic electroluminescent element 9 was fabricated in the same manner.

[0210] REF-3 was used to replace the REF-1 material to prepare the N-type charge generation layer 8, and the organic electroluminescent element 10 was fabricated in the same manner.

[0211] REF-4 was used to replace the REF-1 material to prepare the N-type charge generation layer 8, and the organic electroluminescent element 11 was fabricated in the same manner.

[0212] Evaluation of Organic Electroluminescent Elements

[0213] Lifetime test method: Apply a voltage to the obtained organic electroluminescent device so that the current density reaches 30 mA / cm 2 , and measure the time (LT95 (unit: hours)) until the luminance becomes 95% of the initial luminance.

[0214] The driving voltage is tested at a current density of 15 mA / cm 2 .

[0215] The test results are shown in Table 1:

[0216] As can be seen from Table 1, compared with organic electroluminescent devices 1, 9, 10, and 11, the organic electroluminescent devices 2-8 prepared from the azaspirofluorene compounds of the present application have lower driving voltages and longer service lives. Therefore, the compounds of the present invention are suitable for preparing high-performance organic electroluminescent devices.

[0217] It is easy for those skilled in the art to understand that the above are only preferred embodiments of the present invention and are not used to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principle of the present invention should be included within the protection scope of the present invention.

Claims

1. A nitrogen-containing spirofluorene compound, characterized in that, The structure of the azaspirofluorene compound is shown in Formula 1 below: Formula 1 Wherein, Ar1 is hydrogen, deuterium, a halogen, a cyano group, a substituted or unsubstituted C1-C 10 alkyl group, a substituted or unsubstituted C6-C 60 aryl group, a substituted or unsubstituted C3-C 60 heteroaryl group; L is a substituted or unsubstituted C6-C 60 arylene, a substituted or unsubstituted C3-C 60 heteroarylene, a C1-C 10 alkenylene, a C1-C 10 alkynylene, and L is not a substituted or unsubstituted fluorenyl group or a substituted or unsubstituted hetero-fluorenyl group; Ar2 is shown in Formula a, Formula b, Formula c or Formula d below: Formula a Formula b Formula c Formula d " " indicates the connection position of the Ar2 group and the L group; R1 and R2 are each independently hydrogen, deuterium, halogen, cyano, a substituted or unsubstituted C1-C 10 alkyl group, a substituted or unsubstituted C6-C 60 aryl group, a substituted or unsubstituted C3-C 60 heteroaryl group; R3, R4, R5, and R6 are the same as or different from one another and each independently is hydrogen, deuterium, a halogen, a cyano group, a substituted or unsubstituted C1-C 10 alkyl group; a is an integer from 0 to 4; when a is 2 or greater, multiple R3s are the same as or different from each other; b is an integer from 0 to 4; when b is 2 or greater, multiple R4s are the same as or different from each other; c is an integer from 0 to 2; when c is 2 or greater, multiple R5s are the same as or different from each other; d is an integer from 0 to 2; when d is 2 or greater, multiple R6s are the same as or different from each other; When the "substituted or unsubstituted" is substituted, the substituents 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 heteroaryl, or a combination thereof; The heteroatoms in the heteroaryl and heteroarylene are selected from one or more of N, O, S, Si, P, B; The above compound does not contain or contains at least one substituent selected from deuterium, fluorine group, and cyano group.

2. The azaspirofluorene compound according to claim 1, wherein The structure of the azaspirofluorene compound is shown in Formula 1' below: Formula 1' Wherein, the definitions of L, Ar1, and Ar2 are the same as above; The above compound does not contain or contains at least one substituent selected from deuterium, fluorine group, and cyano group.

3. The azaspirofluorene compound according to any one of claims 1-2, characterized in that, The structure of the azaspirofluorene compound is shown in Formula 1a, Formula 1b, Formula 1c, and Formula 1d below: Formula 1a Formula 1b Formula 1c Formula 1d Wherein, the definitions of Ar1, L, R1, and R2 are the same as above; The above compound does not contain or contains at least one substituent selected from deuterium, fluorine group, and cyano group.

4. The azaspirofluorene compound according to any one of claims 1-3, characterized in that Ar1 is hydrogen, a substituted or unsubstituted C6-C 60 aryl group, or a substituted or unsubstituted C3-C 60 heteroaryl group; The L is a substituted or unsubstituted C6-C 60 arylene, a substituted or unsubstituted C3-C 60 heteroarylene, and L is not a substituted or unsubstituted fluorenyl group or a substituted or unsubstituted hetero-fluorenyl group; R1 and R2 are each independently hydrogen, a substituted or unsubstituted C6-C 60 aryl, or a substituted or unsubstituted C3-C 60 heteroaryl; Wherein, the definition of the substituent when "substituted or unsubstituted" is substituted is the same as above.

5. The azaspirofluorene compound according to any one of claims 1-3, characterized in that The Ar1 is hydrogen, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted pyridyl group; The L is a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted dibenzothiophene group, a substituted or unsubstituted dibenzofuran group, or a substituted or unsubstituted pyridine group; The R1 is hydrogen, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted pyridyl group; The R2 is hydrogen, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted pyridyl group; Wherein, the definition of the substituent when "substituted or unsubstituted" is substituted is the same as above.

6. The azaspirofluorene compound according to any one of claims 1-3, characterized in that, L in the structure of the azaspirofluorene compound is a substituted or unsubstituted group as follows: ； And / or, Ar1 in the structure of the azaspirofluorene compound is hydrogen, a substituted or unsubstituted group selected from the following: ; And / or, R1 in the structure of the azaspirofluorene compound is hydrogen, a substituted or unsubstituted group selected from the following: ; And / or, R2 in the structure of the azaspirofluorene compound is preferably hydrogen, a substituted or unsubstituted group selected from the following: ; Wherein, the definition of the substituent when "substituted or unsubstituted" is substituted is the same as above; The above groups are unsubstituted or substituted by one or more substituents selected from deuterium, fluorine group, and cyano group.

7. The azaspirofluorene compound according to any one of claims 1-3, characterized in that, The halogen is F, Br, Cl, I; and / or, the C1-C 10 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 aryl is phenyl, biphenyl, terphenyl, naphthyl, anthryl, tetracenyl, phenanthryl, fluorenyl, indenyl, pyrenyl, perylenyl, fluoranthenyl, benzophenanthryl, triphenylenyl, chrysenyl, spirobifluorenyl, benzopyrenyl, benzochrysenyl; and / or, the C6-C 60 arylene is phenyl, biphenylene, terphenyl, naphthylene, anthrylene, tetracenylene, phenanthrylene, fluorenylene, indenylene, pyrenylene, perylenylene, fluoranthenylene, benzo[a]phenanthrylene, triphenylene, chrysenylene, spirobifluorenylene, benzo[a]pyrenylene, benzo[e]pyrenylene; and / or, the C3-C 60 heteroaryl is thiophenyl, furyl, pyrrolyl, thiazolyl, oxazolyl, imidazolyl, pyrazolyl, triazolyl, benzothiophenyl, benzofuryl, indolyl, isoindolyl, benzothiazolyl, benzoxazolyl, benzimidazolyl, benzotriazolyl, purinyl, carbazolyl, dibenzothiophenyl, dibenzofuryl, pyridyl, pyrimidinyl, triazinyl, phenazinyl, quinolinyl, isoquinolinyl, naphthyridinyl, acridinyl, phenanthrolinyl, carbolinyl; and / or, the C3-C 60 heteroarylene is thienylene, furylene, pyrrolylene, thiazolylene, oxazolylene, imidazolylene, pyrazolylene, triazolylene, benzothienylene, benzofurylene, indolylene, isoindolylene, benzothiazolylene, benzoxazolylene, benzimidazolylene, benzotriazolylene, purinylene, carbazolylene, dibenzothienylene, dibenzofurylene, pyridinylene, pyrimidinylene, triazinylene, phenazinylene, quinolinylene, isoquinolinylene, naphthyridinylene, acridinylene, phenanthrolinylene, carbolinylene; and / or, the C1-C 10 alkenylene is vinylidene, 1-propenylene, allylidene, 1-butenylene, 2-butenylene, 1-pentenylene, 1-hexenylene, isopropenylidene, isobutenylene; and / or, the C1-C 10 alkynylene group is ethynylene, propynylene, butynylene.

8. The azaspirofluorene compound according to claim 1, wherein The azaspirofluorene compound is selected from the structures shown below: 1-1 1-2 1-3 1-4 1-5 1-6 1-7 1-8 1-9 1-10 1-11 1-12 1-13 1-14 1-15 1-16 1-17 1-18 1-19 1-20 1-21 1-22 1-23 1-24 1-25 1-26 1-27 1-28 1-29 1-30 1-31 1-32 1-33 1-34 1-35 1-36 1-37 1-38 1-39 1-40 1-41 1-42 1-43 1-44 1-45 1-46 1-47 1-48 1-49 1-50 1-51 1-52 1-53 1-54 1-55 1-56 1-57。 9. An organic electroluminescent element, comprising a first electrode, a second electrode, and an organic layer between the first electrode and the second electrode, the organic layer including a light-emitting layer, characterized in that, The organic layer has one or more, and at least one organic layer contains the azaspirofluorene compound according to any one of claims 1-8.

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

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

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