A spiro compound and its application

Abstract

The present invention relates to the field of organic electroluminescent materials, and particularly to a spiro compound and its application. The chemical structure of the spiro compound of the present invention has excellent carrier transport properties and stability, simple molecular synthesis, and can be applied to hole transport layer materials of various colors by connecting different substituents, which can improve the luminous efficiency and lifespan of the device and reduce the production cost of the device.

Description

Technical Field

[0001] The present invention relates to the field of organic electroluminescent materials, and particularly to a spiro compound and its application. Background Art

[0002] Organic Light-Emitting Diodes (OLEDs) are a type of self-luminous electronic component, first reported by the Chinese-American scientist C.W. Tang (Appl. Phys. Lett. 51, 913 (1987)). OLED displays have advantages such as a wide viewing angle, high contrast ratio, fast response speed, and low driving voltage, and are widely used in various electronic products. Since OLED devices emit light under a forward bias, relying on the conduction and recombination of carriers between organic layers, the development of organic materials with excellent performance is the research focus in the OLED field.

[0003] Currently, a widely used OLED device structure is as follows: anode / hole injection layer (HIL) / hole transport layer (HTL) / emitting layer (EML, host material for light emission: guest material for light emission) / electron transport layer (ETL) / electron injection layer (EIL) / cathode. In the emitting layer, introducing a host material for light emission is beneficial to reducing the concentration quenching effect and improving the light emission efficiency of the OLED device. The introduction of other functional layers (such as HIL, HTL, ETL, EIL, etc.) can reduce the injection barrier of carriers, increase the carrier migration rate, and is beneficial to reducing the turn-on voltage and power consumption of the OLED device.

[0004] In recent years, as the usage proportion of OLED displays in the consumer electronics field has increased year by year, the industry has put forward higher requirements for OLED displays, that is, while driving with low power, the light emission efficiency and lifespan are not lower than those of other conventional displays. In terms of OLED organic materials, they should have good carrier (hole or electron) transport rates and appropriate frontier orbital energy levels to ensure effective injection and transport of carriers between layers. In addition, research has shown that the phase change of the organic thin film is an important factor affecting the lifespan of OLED devices. For example, for some OLED devices, the Joule heat generated during their operation will cause defects such as crystallization or pinholes in the thin film, leading to the accelerated aging of the device. Therefore, film-forming property and thermal stability are also key concerns in the development of organic materials. Currently, there is still a large room for improvement in the performance of existing materials. Therefore, the present invention provides a series of spiro-based compounds and their application in OLED devices, showing excellent device performance. Summary of the Invention

[0005] In view of the above-mentioned disadvantages of the prior art, the purpose of the present invention is to provide a spiro compound and its application in an organic electroluminescent device to solve the problems in the prior art.

[0006] To achieve the above object and other related objects, on the one hand, the present invention provides a spiro compound, and the chemical structure of the spiro compound is shown in formula (1):

[0007]

[0008] In formula (1), A is selected from O, S or NR0; wherein, R0 is selected from substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted C2-30 heteroaryl;

[0009] The rings G1 and G2, the same or different, are each independently selected from substituted or unsubstituted C6-C18 aromatic rings, or substituted or unsubstituted C3-C18 heteroaromatic rings;

[0010] The rings G3 and G4, the same or different, are each independently selected from the groups shown in formula (2) to formula (4), or a benzene ring, and are not benzene rings at the same time;

[0011]

[0012] In formula (2) to formula (4), Z are the same or different, and are each independently selected from CR A R B 、NR C 、O or S; wherein, any two adjacent * carbons represent the common connection sites with the five-membered ring in formula (1);

[0013] The R A 、R B are the same or different, and are each independently selected from hydrogen, deuterium, deuterated or non-deuterated methyl; the R C is selected from substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C1-C8 heteroalkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C3-C12 heterocycloalkyl, substituted or unsubstituted C6-C12 aryl, substituted or unsubstituted C2-C12 heteroaryl;

[0014] Formula (1) satisfies the condition: at least one of G3 and G4 is selected from one of formula (2) to formula (4);

[0015] Both G3 and G4 satisfy the condition: when the heteroatom NR CWhen the number of N, S or O is more than 1, there is at least one CR spacer between any two heteroatoms NRc, S or O. A R B ;

[0016] R1, R2, R3 and R4 are each independently selected from deuterium, fluorine, chlorine, bromine, cyano, isocyano, trifluoromethyl, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C1-C30 alkylthio, substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C2-C40 heteroaryl, substituted or unsubstituted C1-C40 keto, substituted or unsubstituted C2-C40 alkoxycarbonyl, substituted or unsubstituted C6-C40 aryloxycarbonyl, or a group represented by formula (5);

[0017] m, n, p and q are the same as or different from each other and are each independently selected from integers between 0 and 10; when any one of m, n, p and q is greater than 1, each of R1, R2, R3 and R4 is the same as or different from each other;

[0018]

[0019] In formula (5), L1 and L3 are each independently selected from a single bond, substituted or unsubstituted C6-C40 arylene, substituted or unsubstituted C2-C40 heteroarylene; L2 is selected from a nitrogen atom, substituted or unsubstituted C6-C40 arylene, substituted or unsubstituted C2-C40 heteroarylene; Ar is selected from substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C2-C40 heteroaryl; r is selected from 1 to 5 and is an integer; and when r≥2, each of the L3 and Ar groups is the same as or different from each other; * is a connection site.

[0020] On the other hand, the present invention provides an organic layer comprising the aforementioned spiro compound.

[0021] On the other hand, the present invention provides the use of the spiro compound as described above and / or the aforementioned organic layer in an organic electroluminescent device.

[0022] On the other hand, the present invention provides an organic electroluminescent device comprising a first electrode, a second electrode and an organic layer, wherein the organic layer is at least one of a hole injection layer, a hole transport layer, a light emitting layer, an electron injection layer or an electron transport layer, and the organic layer comprises the aforementioned spiro compound.

[0023] On the other hand, the present invention provides a display or lighting device comprising the organic electroluminescent device as described above.

[0024] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0025] By incorporating cycloalkyl or heterocycloalkyl at appropriate positions of the spiro compound, on the one hand, it can play the role of protecting functional groups at these sites, which is beneficial to improving the stability of the molecule; on the other hand, it can reduce the intermolecular interaction, which is beneficial to forming a stable amorphous thin film, thereby improving the lifespan of the OLED device. In addition, by connecting different substituents at different positions of such molecular fragments, the frontier orbital energy levels of the molecule can be adjusted significantly, so as to be applicable to the functional layers of OLED devices for various color lights such as red, green, and blue. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 It is a schematic structural diagram of an organic electroluminescent device in the embodiment.

[0027] Figure 2 It is another schematic structural diagram of an organic electroluminescent device in the embodiment.

[0028] In the figure:

[0029] 101 Substrate

[0030] 102 First electrode

[0031] 103 Hole injection layer

[0032] 104 First hole transport layer

[0033] 105 Second hole transport layer

[0034] 106 Light emitting layer

[0035] 107 Hole blocking layer

[0036] 108 Electron transport layer

[0037] 109 Second electrode

[0038] 110 Cover layer DETAILED DESCRIPTION OF THE EMBODIMENTS

[0039] Hereinafter, the embodiments of the specifically disclosed spiro compounds and their applications in organic electroluminescent devices will be described in detail. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and various details in this specification can also be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention.

[0040] Before further describing the specific embodiments of the present invention, it should be understood that the protection scope of the present invention is not limited to the following specific embodiments; it should also be understood that the terms used in the embodiments of the present invention are for describing specific embodiments, rather than for limiting the protection scope of the present invention; in the specification and claims of the present invention, unless otherwise clearly indicated in the text, the singular forms "a", "an" and "the" include plural forms.

[0041] When the embodiments give a numerical range, it should be understood that unless otherwise stated in the present invention, both endpoints of each numerical range and any value between the two endpoints can be selected. Unless otherwise defined, all technical and scientific terms used in the present invention have the same meaning as commonly understood by those skilled in the art of this technology. In addition to the specific methods, devices, and materials used in the embodiments, according to the knowledge of those skilled in the art of this technology and the description of the present invention, any methods, devices, and materials of the prior art similar or equivalent to those described in the embodiments of the present invention can also be used to implement the present invention.

[0042] Through a large amount of exploration and research, the inventors of the present invention aim to provide a class of spiro-based organic compounds. The spiro structure based on fluorene itself can provide good molecular thermal stability and charge carrier transport properties. Incorporating cycloalkyl or heterocycloalkyl groups at appropriate positions in the molecule can not only play the role of functional group protection, which is beneficial to improving the stability of the molecule; but also further reduce the intermolecular interaction, making it easier to obtain an amorphous organic molecule with a high glass transition temperature, thereby being beneficial to the improvement of the lifespan of OLED devices.

[0043] In addition, the spiro fragment provided by the present invention has moderate frontier orbital energy levels. By introducing different substituents, a large range of energy level regulation can be achieved, thereby obtaining various functional layer materials with excellent performance. For example, when connecting an electron-donating triarylamine group, the resulting molecule can be used as a hole transport material; while connecting an electron-deficient substituted s-triazine group or quinoxaline group, depending on the substituents on the electron-deficient group, the resulting molecule can be used as a light-emitting host material or an electron transport material. Based on this, this application is completed.

[0044] The first aspect of the present invention provides a spiro compound, and the chemical structure of the spiro compound is shown in formula (1):

[0045]

[0046] For the convenience of subsequent description, the five-membered ring and six-membered ring in the structure of formula (1) are numbered as follows:

[0047]

[0048] In some embodiments, the chemical structure of the spiro compounds is shown in Formulas (6)-(8):

[0049]

[0050] In Formulas (1), (6)-(8) of the present application, A is selected from O, S or NR0; wherein, R0 is selected from substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, or substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-30 heteroaryl;

[0051] In some embodiments, the R0 is selected from the following groups:

[0052]

[0053] In any of the above groups, only one carbon atom on any one aromatic ring is the bonding site, or any hydrogen atom can be replaced by one of deuterium, fluorine, chlorine, bromine, cyano, nitro, trifluoromethyl, methoxy, ethoxy, methylthio, ethylthio, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, tolyl, tert-butylphenyl, naphthyl, pyridyl, pyrazinyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, quinoxalinyl.

[0054] In Formulas (1), (6)-(8) of the present application, the rings G1 and G2, the same or different, each independently selected from substituted or unsubstituted C6-C18 aromatic rings, substituted or unsubstituted C3-C18 heteroaromatic rings.

[0055] In some embodiments of the present application, G1 and G2 each independently selected from the following groups, and G1 and G2 are the same or different from each other:

[0056] Wherein, Q is independently selected from N, CH, CR5 or C* a , and it is satisfied that there are exactly two adjacent Qs that are C* a ; C* a represents the shared connection site with the six-membered ring in Formula (1). Here, the shared connection site specifically refers to that in the G1 ring, two adjacent C* a correspond to the carbon atoms at the 3-position and 4-position on the six-membered ring in Formula (1). In the G2 ring, two adjacent C* a correspond to the carbon atoms at the 1-position and 2-position on the six-membered ring in Formula (1).

[0057] R5 is independently selected from deuterium, fluorine, chlorine, bromine, cyano, nitro, trifluoromethyl, C1-C12 alkyl, C3-C12 cycloalkyl, C1-C12 alkoxy, C1-C12 alkylthio, C6-C30 aryl, or C2-C30 heteroaryl, etc.

[0058] In some specific embodiments of the present application, the ring G1 or G2 is independently selected from the following groups:

[0059]

[0060] In any of the above groups, any two and only two adjacent carbon atoms are the common connection sites with the six-membered ring in formula (1); specifically, the common connection site means that in the G1 ring, the two adjacent carbon atoms correspond to the 3-position carbon and 4-position carbon on the six-membered ring in formula (1). In the G2 ring, the two adjacent carbon atoms correspond to the 1-position carbon and 2-position carbon on the six-membered ring in formula (1). Or any hydrogen atom can be replaced by one of deuterium, fluorine, chlorine, bromine, cyano, nitro, trifluoromethyl, methoxy, methylthio, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, tolyl, tert-butylphenyl, naphthyl, pyridyl, pyrazinyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, quinoxalinyl.

[0061] In formula (1) of the present application, the rings G3 and G4, the same or different, are each independently selected from the groups shown in formula (2) to formula (4), or a benzene ring, and they are not both benzene rings at the same time;

[0062]

[0063] In formula (2) to formula (4), Z are the same or different, and each is independently selected from CR A R B 、NR C 、O or S; wherein, any two adjacent * carbons represent the common connection sites with the benzene ring in formula (1); specifically, the common connection site means that in the G3 ring, the two adjacent * carbons correspond to the 5-position carbon and 6-position carbon on the five-membered ring in formula (1). In the G4 ring, the two adjacent carbon atoms correspond to the 7-position carbon and 8-position carbon on the five-membered ring in formula (1).

[0064] Specifically, the R A 、R B are the same or different, and each is independently selected from hydrogen, deuterium, deuterated or non-deuterated methyl; the R CSelected from substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C1-C8 heteroalkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C3-C12 heterocycloalkyl, substituted or unsubstituted C6-C12 aryl, substituted or unsubstituted C2-C12 heteroaryl. The formula (1) satisfies the condition that at least one of G3 and G4 is selected from one of the formulas (2) to (4). Both G3 and G4 satisfy the condition that when the number of heteroatoms NR C , S or O is more than 1, any two heteroatoms NR C , S or O are separated by at least one CR A R B .

[0065] In the formula (1) of the present application, G5 and G6 are the same or different and each independently selected from the groups shown in the formulas (9) to (11):

[0066]

[0067] Among them, the selection of Z is the same as that of the formulas (2) to (4); * in the formula (9), (10) or (11) represents a connection site, and is respectively connected to any two adjacent unsubstituted carbon atoms on the benzene ring of any one of the formulas (6), (7) or (8).

[0068] In some embodiments of the present application, the ring G5 or G6 is independently selected from the following groups:

[0069]

[0070] Among them, the selection of R0 is the same as that of the formula (1). * represents a connection site, and is respectively connected to any two adjacent unsubstituted carbon atoms on the benzene ring of the formulas (6), (7) or (8).

[0071] Specifically, R0 is selected from the following groups:

[0072]

[0073] In any of the above groups, only one carbon atom on any one aromatic ring is the bonding site, or any hydrogen atom can be replaced by one of deuterium, fluorine, chlorine, bromine, cyano, nitro, trifluoromethyl, methoxy, ethoxy, methylthio, ethylthio, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, tolyl, tert-butylphenyl, naphthyl, pyridyl, pyrazinyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, quinoxalinyl.

[0074] In Formula (1), Formula (6) - Formula (8) of the present application, R1, R2, R3, and R4 are each independently selected from deuterium, fluorine, chlorine, bromine, cyano, isocyano, trifluoromethyl, nitro, substituted or unsubstituted C1 - C30 alkyl, substituted or unsubstituted C3 - C30 cycloalkyl, substituted or unsubstituted C1 - C30 alkoxy, substituted or unsubstituted C1 - C30 alkylthio, substituted or unsubstituted C6 - C40 aryl, substituted or unsubstituted C2 - C40 heteroaryl, substituted or unsubstituted C1 - C40 keto, substituted or unsubstituted C2 - C40 alkoxycarbonyl, substituted or unsubstituted C6 - C40 aryloxycarbonyl, or the group shown in Formula (5).

[0075]

[0076] In Formula (5), L1 and L3 are each independently selected from a single bond, substituted or unsubstituted C6 - C40 arylene, substituted or unsubstituted C2 - C40 heteroarylene; L2 is selected from a nitrogen atom, substituted or unsubstituted C6 - C40 arylene, substituted or unsubstituted C2 - C40 heteroarylene; Ar is selected from substituted or unsubstituted C6 - C40 aryl, substituted or unsubstituted C2 - C40 heteroaryl; r is selected from 1 - 5 and is an integer; and when r ≥ 2, each L3 and Ar group are the same as or different from each other; * is a connection site.

[0077] In some embodiments of the present application, r can be 1, 2, 3, 4, 5, etc.

[0078] In some embodiments of the present application, the group shown in Formula (5) is selected from one or more of the following structures:

[0079]

[0080] In Formula (12), L2 is not a single bond, and the definitions of L3, Ar, * are the same as those in Formula (5), and r is selected from 1 - 5 and is an integer;

[0081] In Formula (13), neither L1 nor L2 is selected from a single bond, and the definitions of L3, Ar, * are the same as those in Formula (5), and r is selected from 1 - 5 and is an integer;

[0082] In Formula (14), the definitions of L1, L3, Ar, * are the same as those in Formula (5), and r is selected from 1 - 5 and is an integer.

[0083] In some embodiments of the present application, L1 and L3 are each independently selected from a single bond or the following groups; L2 is selected from a nitrogen atom or the following groups; and L1, L2, and L3 are the same as or different from each other:

[0084]

[0085] Wherein, U is independently selected from N, CH, CR6 or C* b , and it is satisfied that there are exactly two Us being C* b ; R6 is independently selected from deuterium, fluorine, chlorine, bromine, cyano, nitro, trifluoromethyl, C1-C12 alkyl, C3-C12 cycloalkyl, C1-C12 alkoxy, C1-C12 alkylthio, C6-C30 aryl, C2-C30 heteroaryl; * b is the bonding site of Ar, or * b corresponds to * in formula (5);

[0086] V is selected from O, S, NR7, CR8R9, SiR 10 R 11 ; R7-R 11 are each independently selected from C1-C12 alkyl, C3-C12 cycloalkyl, C6-C30 aryl, C2-C30 heteroaryl; alternatively, R8 and R9 are bonded to form a C5-C12 aliphatic ring, or are bonded to form a C12-C30 aromatic fused ring.

[0087] In some specific embodiments of the present application, L1 and L3 are each independently selected from a single bond or the following groups; L2 is selected from a nitrogen atom or the following groups. And, L1, L2, and L3 are the same as or different from each other:

[0088]

[0089] In any of the above groups, carbon atoms on any two and only two aromatic rings are bonding sites; or any hydrogen atom can be replaced by one of deuterium, fluorine, chlorine, bromine, cyano, nitro, trifluoromethyl, methoxy, methylthio, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, tolyl, tert-butylphenyl, naphthyl, pyridyl, pyrazinyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, quinoxalinyl.

[0090] In some embodiments of the present application, Ar is selected from the following groups, and when the number of Ar is more than 1, different Ars are the same as or different from each other:

[0091]

[0092] Wherein, X is independently selected from N, CH, CR 12 or C *c ; and one of Xs is selected from C *c ; R 12Independently selected from deuterium, fluorine, chlorine, bromine, cyano, nitro, C1-C12 alkyl, C3-C12 cycloalkyl, C1-C12 alkoxy, C1-C12 alkylthio, C6-C30 aryl, C2-C30 heteroaryl; * c is the bonding site of L3;

[0093] Y is selected from O, S, NR 13 , CR 14 R 15 , SiR 16 R 17 ; R 13 ~R 17 are each independently selected from C1-C12 alkyl, C3-C12 cycloalkyl, C6-C30 aryl, C2-C30 heteroaryl; or, R 14 , R 15 bond to form a C5-C12 aliphatic ring, or bond to form a C12-C30 aromatic fused ring.

[0094] In some specific embodiments of the present application, Ar is selected from the following groups, and when the number of Ar is more than 1, different Ar are the same or different from each other:

[0095]

[0096]

[0097] In any of the above groups, only one carbon atom on any aromatic ring is the bonding site, or any hydrogen atom can be replaced by one of deuterium, fluorine, chlorine, bromine, cyano, nitro, trifluoromethyl, methoxy, ethoxy, methylthio, ethylthio, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, tolyl, tert-butylphenyl, naphthyl, pyridyl, pyrazinyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, quinoxalinyl.

[0098] In formula (1), formula (6) - formula (8) of the present application, m, n, p, q are the same or different from each other, and are each independently selected from integers between 0 and 10; when any one of m, n, p, q is greater than 1, each of the substituents R1, R2, R3, R4 is the same or different from each other. Taking R1 as an example, that is, if m is greater than 1, multiple R1 are the same or different from each other.

[0099] Among them, m is the number of the group R1. In some embodiments, m can be selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, etc.

[0100] n is the number of the group R2. In some embodiments, n may be selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, etc.

[0101] p is the number of the group R3. In some embodiments, p may be selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, etc.

[0102] q is the number of the group R3. In some embodiments, q may be selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, etc.

[0103] In this application, in the description of the number of carbons, for example, C1-C12 means having 1 to 12 carbon atoms. Another example, C2-C30 means having 2 to 30 carbon atoms. The same applies to others and will not be elaborated here.

[0104] In the spiro compounds provided by this application, in the formulas (1), (5)-(8), for the substituted or unsubstituted, the substituents of the substitution are selected from one or more of deuterium, halogen groups (such as fluorine, chlorine, bromine, etc.), cyano group, nitro group, trifluoromethyl group, C1-C12 alkyl group, C3-C12 cycloalkyl group, C1-C12 alkoxy group, C1-C12 alkylthio group, C6-C30 aryl group, C2-C30 heteroaryl group; and, the substituents in R0, R1, R2, R3, R4, L1, L2, L3, Ar are the same or different from each other.

[0105] Among the spiro compounds provided by the present invention, the spiro compounds are selected from any one of the following chemical structures:

[0106]

[0107]

[0108]

[0109]

[0110]

[0111]

[0112]

[0113]

[0114]

[0115]

[0116]

[0117]

[0118]

[0119] Specifically, the above structure may be unsubstituted or substituted with one or more substituents selected from the following. For example, it may be deuterium, a halogen group, a nitrile group, a nitro group, a hydroxyl group, a carbonyl group, an ester group, an imide group, an amine group, a phosphine oxide group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, a silyl group, a boron group, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, an aralkenyl group, an alkylaryl group, an alkylamino group, an aralkylamino group, a heteroarylamino group, an arylamino group, an arylheteroarylamino group, an arylphosphino group, and a heteroaryl, etc.

[0120] The second aspect of the present invention provides an organic layer comprising the spiro compound described in the first aspect of the present invention.

[0121] The third aspect of the present invention provides the use of the spiro compound described in the first aspect of the present invention and / or the organic layer described in the second aspect of the present invention in an organic electroluminescent device.

[0122] The fourth aspect of the present invention provides an organic electroluminescent device comprising a first electrode, a second electrode, and one or more organic layers disposed between the first electrode and the second electrode, which is a bottom or top emission device structure. The organic layer may be a single-layer structure or a multi-layer tandem structure laminated with two or more organic layers. The organic layer has at least one layer including a hole injection layer, a hole transport layer, a light-emitting layer, an electron injection layer, or an electron transport layer. It can be prepared using common methods and materials for preparing organic electroluminescent devices. The organic layer includes the spiro compound described in the first aspect of the present invention.

[0123] In the organic electroluminescent device provided by the present invention, the first electrode serves as an anode layer, and the anode material may be, for example, a material having a large work function, so that holes can be smoothly injected into the organic layer. More specifically, it may be a metal, a metal oxide, a combination of a metal and an oxide, a conductive polymer, etc. The metal oxide may be, for example, indium tin oxide (ITO), zinc oxide, indium oxide, and indium zinc oxide (IZO), etc.

[0124] In the organic electroluminescent device provided by the present invention, the second electrode serves as a cathode layer, and the cathode material may be, for example, a material having a small work function, so that electrons can be smoothly injected into the organic layer. The cathode material may be, for example, a metal or a multi-layer structure material. The metal may be, for example, magnesium, silver, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, tin, and lead, or an alloy thereof. The cathode material is preferably selected from magnesium and silver.

[0125] In the organic electroluminescent device provided by the present invention, as the material of the hole injection layer, a material with the highest occupied molecular orbital (HOMO) between the work function of the anode material and the HOMO of the surrounding organic layer is preferably used as the material that can advantageously receive holes from the anode at low voltage.

[0126] In the organic electroluminescent device provided by the present invention, the material of the hole transport layer is a material with a high hole mobility and is suitable as a material for receiving holes from the anode or the hole injection layer and transporting the holes to the light-emitting layer. The materials of the hole transport layer include, but are not limited to, organic materials of arylamines, conductive polymers, block copolymers having both a conjugated part and a non-conjugated part, and the like.

[0127] In the organic electroluminescent device provided by the present invention, the material of the light-emitting layer can generally be selected from materials with good quantum efficiency for fluorescence or phosphorescence as materials that can emit light in the visible light region by receiving holes and electrons from the hole transport layer and the electron transport layer respectively and combining the holes and electrons.

[0128] In the organic electroluminescent device provided by the present invention, the material of the electron transport layer is a material with a high electron mobility and is suitable as a material for advantageously receiving electrons from the cathode and transporting the electrons to the light-emitting layer.

[0129] In the organic electroluminescent device provided by the present invention, the material of the cover layer generally has a high refractive index, so it can contribute to the improvement of the light efficiency of the organic light-emitting device, especially to the improvement of the external light-emitting efficiency.

[0130] In the organic electroluminescent device provided by the present invention, the organic electroluminescent device is an organic photovoltaic device, an organic light-emitting device, an organic solar cell, an electronic paper, an organic photoreceptor, an organic thin-film transistor, etc.

[0131] On the other hand, the present invention provides a display or lighting device including the organic electroluminescent device described in the present invention.

[0132] Hereinafter, the specific preparation methods of the above new compounds of the present invention will be described in detail with multiple synthesis examples. However, the preparation methods of the present invention are not limited to these multiple synthesis examples. Those skilled in the art can make any modifications, equivalent replacements, improvements, etc. on the basis thereof without departing from the principles of the present invention, and extend the method to the scope of the technical solutions claimed in the claims of the present invention.

[0133] Taking the structural formula (6) as an example, the present invention gives a representative synthesis route of the compounds of the present invention. The same can be referred to for the preparation of other structures:

[0134]

[0135] When A is O, A1 in compound i is OH;

[0136] When A is S, A1 in compound i is SH;

[0137] When A is NR0, A1 in compound i is NR0H;

[0138] The main reactions involved in synthesizing the compounds of the present invention are as follows: In the first step, one of the starting compounds i and ii has a halogen functional group iodine, and the other has a functional group containing active hydrogen (hydroxyl group, mercapto group or amino group). They react under an appropriate catalytic system to form an intermediate compound iii; in the second step, the intermediate compound iii forms an aryl carbanion under the action of n-butyllithium, and further reacts with 9-fluorenone or its derivative (compound iv) to generate the target compound.

[0139] Furthermore, the synthesis method of the 9-fluorenone derivative iv can refer to the non-patent literature Org. Lett. 2021, 23, 8688 - 8693.

[0140] The specific steps are as follows:

[0141]

[0142] Synthesis of intermediate compound vii:

[0143] Under a nitrogen atmosphere, add meta-chloroperoxybenzoic acid (9.5 g, 55.0 mmol, 1.1 eq) to a dry three-necked flask and dissolve it in anhydrous dichloromethane (250 mL). Subsequently, add the iodide compound v (50.0 mmol, 1 eq) and boron trifluoride diethyl etherate (17.7 g, 125.0 mmol, 2.5 eq) sequentially at room temperature, and observe that the color of the reaction system turns yellow. Stir the reaction system at room temperature for 1 hour, then cool it to 0 °C, and add the borate compound vi (55 mmol, 1.1 eq). After the feeding is completed, slowly restore the reaction system to room temperature and continue stirring for 30 minutes. Then cool the reaction system to 0 °C, dropwise add trifluoromethanesulfonic acid (8.3 g, 55.0 mmol, 1.1 eq), and continue stirring at 0 °C for 15 minutes. After the reaction is completed, remove most of the solvent by rotary evaporation, add anhydrous ether to precipitate a solid, collect the obtained solid and dry it under vacuum to obtain compound vii. The obtained solid is directly used in the next step of the reaction without post-treatment.

[0144] Synthesis of 9-fluorenone derivative iv:

[0145] In a nitrogen atmosphere, carboxylic acid compound viii (20.0mmol, 1eq), diaryl iodide vii (50.0mmol, 2.5eq), palladium acetate (449mg, 2.0mmol, 10%eq) sodium tert-butoxide (1.9g, 20.0mmol, 1eq) and anhydrous xylene (Xylene, 120mL) were added to a dry three-necked flask in sequence. After stirring evenly, the mixture was reacted at 110°C in a nitrogen atmosphere for 24 hours. Thin layer chromatography analysis showed that there was basically no raw material remaining, and most of the solvent was removed by vacuum distillation. Ethyl acetate (80mL) and deionized water (100mL) were then added to the reaction flask in sequence, the mixture was allowed to stand for stratification, the organic phase was collected, the aqueous phase was extracted with ethyl acetate (3×30mL), the organic phases were combined, dried with anhydrous magnesium sulfate, filtered, and the solvent was removed by vacuum distillation. The crude product was separated by rapid silica gel column chromatography (the mobile phase was a mixed solvent of n-hexane / ethyl acetate) to obtain a 9-fluorenone derivative iv.

[0146] In particular, for some embodiments where A is NR0, compound i can be synthesized by a one-step Ullmann coupling reaction, and the synthesis route is as follows:

[0147]

[0148] The specific steps of the synthetic reaction are: under a nitrogen atmosphere, add bromoaryl compound x (1 eq), amino compound R0-NH2 (compound xi, 1 eq) and anhydrous toluene in a dry three-necked flask in sequence, stir evenly, then add sodium tert-butoxide (1.5 eq), tris(dibenzylideneacetone)dipalladium (0.5% eq), and tri-tert-butylphosphine (1.5% eq) in sequence. The above system is mixed evenly, and the temperature is raised to reflux under a nitrogen atmosphere, and the reaction is overnight. By thin layer chromatography analysis, there is basically no raw material remaining, and heating is stopped. When the reaction solution is cooled to below 45°C, a mixed solution of 5mL concentrated hydrochloric acid (37% aqueous solution) and 100mL deionized water is added to the reaction system, stirred and then allowed to stand, separated with a separatory funnel, the organic phase is retained, the aqueous phase is extracted with toluene, combined with the aforementioned retained organic phase, dried over anhydrous magnesium sulfate, filtered, and the solvent is removed by reduced pressure distillation. The crude product is purified by rapid silica gel column chromatography to obtain compound i.

[0149] In particular, for some embodiments, for example, when the R1 group is an aryl group, a heteroaryl group, or a group described in formula (3), the following synthetic route can also be used. The chlorine-substituted raw material compound i is used to retain the substitution site of R1 as a chlorine atom, and the intermediate compound v is synthesized by the aforementioned "two-step method", and then the R1 group is connected through a Suzuki coupling reaction or an Ullmann coupling reaction to obtain the target product.

[0150]

[0151] Similarly, for some other embodiments, for example, when the R3 or R4 group is an aryl group, a heteroaryl group, or a group represented by formula (3), fluorenone can also be used as the starting material, and the R3 or R4 group can be connected through a Suzuki coupling reaction or an Ullmann coupling reaction to obtain the intermediate compound iv.

[0152] More specifically, the synthesis methods of the representative compounds of the present invention are given below. Unless otherwise specified, the compounds for which the synthesis methods are not mentioned in the present invention are commercially available products; in the present invention, the mass spectrometry is measured by a ZABHS type mass spectrometer (manufactured by Micromass, UK), and the nuclear magnetic resonance is measured by a Bruker 400MHz type nuclear magnetic resonance spectrometer (manufactured by Bruker, Germany);

[0153] Synthesis of compound H14:

[0154]

[0155] 1. Synthesis of compound iii-H14

[0156] Under a nitrogen atmosphere, diphenylamine (compound i-H14, 6.0 g, 35.3 mmol, 1 eq) and anhydrous tetrahydrofuran (350 mL) were successively added to a dry flask and stirred evenly. Subsequently, sodium hydride (1.7 g, 70.8 mmol, 2 eq) was slowly added to the aforementioned three-necked flask in batches at room temperature to avoid violent generation of bubbles. After the addition of sodium hydride was completed, the reaction system turned yellow. At room temperature, 1-bromo-2-iodobenzene (compound ii-H14, 10.0 g, 35.3 mmol, 1 eq) was slowly added dropwise to the reaction system, and the reaction was continued at room temperature for 12 hours. The resulting reaction system was filtered, and the filtrate was collected. The filter residue was washed with anhydrous tetrahydrofuran, and the washing solution was combined with the aforementioned filtrate. The combined organic phase was concentrated by rotary evaporation to remove the solvent. The resulting crude product was purified by flash silica gel column chromatography (the mobile phase was a mixed solvent of n-hexane / ethyl acetate) to obtain compound iii-H14 (7.2 g, yield 62.9%). Mass spectrometry (m / z) = 324.03 [M+H] +

[0157] 2. Synthesis of compound iv-H14

[0158]

[0159] First, compound ix-H14 (4.9 g, yield 78.2%) was synthesized by referring to the preparation method of the aforementioned 9-fluorenone derivative iv. Mass spectrometry (m / z) = 313.01 [M+H] + .

[0160] Under nitrogen atmosphere, add diphenyl-4-ylamine (compound xii-H14, 4.8g, 15.0mmol, 1eq), compound ix-H14 (4.7g, 15.0mmol, 1eq) and anhydrous toluene (80mL) to a dry three-necked flask in sequence, stir evenly, then add sodium tert-butoxide (2.2g, 22.5mmol, 1.5eq), bis(dibenzylideneacetonepalladium) (85.0mg, 0.15mmol, 1%eq), and tri-tert-butylphosphine (10% n-hexane solution, 0.5mL, 0.23mmol, 1.5%eq) in sequence. Mix the above system evenly, heat to reflux under nitrogen atmosphere, and stop heating after 7 hours of reaction. When the reaction solution was cooled to room temperature, a mixed solution of 5 mL of concentrated hydrochloric acid (37% aqueous solution) and 100 mL of deionized water was added to the reaction system, stirred and then allowed to stand, separated using a separatory funnel, the organic phase was retained, the aqueous phase was extracted with toluene (3×30 mL), combined with the above-retained organic phase, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by reduced pressure distillation. The crude product was purified by rapid silica gel column chromatography (the mobile phase was a mixed solvent of n-hexane / ethyl acetate) to obtain compound iv-H14 (6.8 g, yield 81.8%). Mass spectrum (m / z) = 554.24 [M+H] +

[0161] 3. Synthesis of compound H14

[0162] Under a nitrogen atmosphere, compound iii-H14 (3.9 g, 12.0 mmol, 1 eq) was dissolved in anhydrous tetrahydrofuran (120 mL). The solution was placed in a -78 °C bath and, after sufficient cooling, a solution of n-butyllithium in hexane (concentration 2.5 M, 4.8 mL, 12.0 mmol, 1 eq) was slowly added dropwise at this temperature under a nitrogen atmosphere. Stirring was continued at -78 °C for 1 hour. Subsequently, a solution of compound iv-H14 (6.6 g, 12.0 mmol, 1 eq) in anhydrous tetrahydrofuran (30 mL) was added dropwise to the reaction system at -78 °C under a nitrogen atmosphere. After the addition was complete, the reaction system was slowly allowed to return to room temperature and the reaction was carried out for 8 hours. Deionized water (80 mL) was slowly added to the reaction system in sequence to quench the reaction, and then ethyl acetate (150 mL) was added. After stirring, the mixture was allowed to stand and separate into layers. The organic phase was collected using a separatory funnel, and the aqueous phase was extracted with ethyl acetate (3 × 50 mL). The organic phases were combined and the solvent was removed by rotary evaporation. Subsequently, the obtained crude product was dissolved in glacial acetic acid (60 mL), the temperature was raised to 80 °C, and 0.2 mL of concentrated sulfuric acid was added dropwise. Stirring was continued at 80 °C for 4 hours. Subsequently, the reaction system was cooled to room temperature, distilled water (150 mL) was added, and a white solid precipitated. The mixture was filtered, the filter cake was collected, washed with deionized water, and dried. The obtained crude product was purified by flash silica gel column chromatography (mobile phase: a mixed solvent of n-hexane / toluene) to obtain compound H14 (6.7 g, yield 71.5%). Mass spectrometry (m / z) = 781.35 [M + H] + . Starting from compound i-H14, compound H14 was obtained via compound iii-H14, and the total yield of the two-step reaction was 45.0%.

[0163] The following compounds (x): H37, H56, H142, H168, H175, H196, H205, H213 were synthesized by referring to the preparation method of compound H14, with the difference that raw material compounds i-x, ii-x, v-x, viii-x, and ix-x were used to equivalently replace compound i-H4, ii-H4, v-14, viii-H4, and ix-H4, respectively. Among them, the main raw materials used, the synthesized intermediates, the yields, and the mass spectrometry characterization data are shown in Table 1. The NMR characterization data are shown in Table 2.

[0164] Table 1

[0165]

[0166]

[0167] Table 2

[0168]

[0169]

[0170] Synthesis of Compound H13:

[0171]

[0172] The synthesis method of compound iv-H13 is as follows:

[0173]

[0174] First, compound ix-H13 (4.8 g, yield 79.7%) was synthesized by referring to the preparation method of the aforementioned 9-fluorenone derivative iv. Mass spectrum (m / z) = 300.98 [M+H] + 。

[0175] Under a nitrogen atmosphere, compound ix-H13 (4.5 g, 15.0 mmol, 1 eq), compound xii-H13 (6.6 g, 15.0 mmol, 1 eq) and degassed toluene (120 mL) were successively added to a three-necked flask. After mixing evenly, potassium carbonate (5.2 g, 37.5 mmol, 2.5 eq), tetrakis(triphenylphosphine)palladium (173.3 mg, 0.15 mmol, 1% eq), degassed ethanol (40 mL) and deionized water (40 mL) were successively added. Stirring was started, and the above system was fully mixed and heated to reflux under a nitrogen atmosphere. The reaction was carried out for 10 hours. Analysis by thin-layer chromatography showed that there was basically no raw material remaining, and heating was stopped. After the reaction system was cooled to room temperature, it was poured into 80 mL of toluene, allowed to stand for liquid separation, extracted with toluene (3 × 30 mL), and the combined organic phases were dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure to remove the solvent. The obtained crude product was separated by flash silica gel column chromatography (mobile phase: a mixed solvent of n-hexane / dichloromethane) to obtain compound iv-H13 (7.2 g, yield 77.7%). Mass spectrum (m / z) = 618.24 [M+H] + 。

[0176] Referring to the preparation method of compound H14, compound H13 was synthesized. The difference is that compound i-H13, ii-H13 and xii-H13 were used equivalently to replace compound i-H14, ii-H14 and xii-H14 respectively, and the target compound H13 was obtained through a two-step reaction. The total yield of the two-step reaction was 46.9%. The mass spectrum of compound H13 (m / z) = 898.40 [M+H] + 。

[0177] With reference to the preparation method of reference compound H13, the following compounds (x) were synthesized: H46, H118, H155, H188, E2, E7, E11, E28, E38, E56, E61, E70, E84, E90, E105, except that starting materials compound i-x, ii-x, v-x, viii-x and ix-x were used to equivalently replace compound i-H13, ii-H13, v-13, viii-H13 and ix-H13, respectively. Among them, the main starting materials used, the synthesized intermediates, the yields and the mass spectrometry characterization data are shown in Table 3. The nuclear magnetic resonance characterization data are shown in Table 4.

[0178] Table 3

[0179]

[0180]

[0181]

[0182] Table 4

[0183]

[0184]

[0185]

[0186]

[0187] Synthesis of compound H74:

[0188]

[0189] First, with reference to the preparation method of reference compound H14, compound v-H74 was synthesized, except that starting materials compound i-H74, ii-74 and iv-H74 were used to equivalently replace compound i-H14, ii-H14 and iv-H14, respectively, and the intermediate compound v-H74 was obtained through two-step reactions. Among them, intermediate compound iv-H74 was synthesized with reference to the preparation method of iv-H14. Subsequently, with reference to the preparation method of compound iv-H14, the target compound H74 was synthesized, except that compound v-H74 and xii-H74 were used to equivalently replace compound ix-H14 and xii-H14, respectively. The total yield of the three-step reaction was 35.0%. Mass spectrometry (m / z) = 788.38 [M+H] + 。

[0190] In addition, compounds H83 and H88 can also be synthesized with reference to the preparation method of compound H74.

[0191] The synthetic route of compound H83 is as follows. Among them, the intermediate compound iv-H83 was synthesized with reference to the preparation method of iv-H14.

[0192]

[0193] The total yield of the three-step reaction was 35.6%. Mass spectrometry (m / z) = 895.36 [M+H] + .

[0194] The synthetic route of compound H88 is as follows. Among them, the intermediate compound iv-H88 was synthesized with reference to the preparation method of iv-H14.

[0195]

[0196] The total yield of the three-step reaction was 36.5%. Mass spectrometry (m / z) = 969.42 [M+H] + .

[0197] With reference to the preparation method of compound H74, the following compounds (x) were synthesized: H90, H114, H138, H199. The difference is that the raw material compounds i-x, ii-x, v-x, viii-x and ix-x were used to equivalently replace the compounds i-H74, ii-H74, v-74, viii-H74 and ix-H74, respectively. Among them, the main raw materials used, the synthesized intermediates, the yields and the mass spectrometry characterization data are shown in Table 5. The nuclear magnetic resonance characterization data are shown in Table 6.

[0198] Table 5

[0199]

[0200]

[0201] Table 6

[0202]

[0203]

[0204] Synthesis of compound H136

[0205]

[0206] First, referring to the preparation method of compound H14, compound v-H136 was synthesized. The difference is that compound i-H136, ii-H136, and iv-H136 were used to equivalently replace compound i-H14, ii-H14, and iv-H14 respectively, and the intermediate compound v-H136 was obtained through two-step reactions. In particular, compound iv-136 was synthesized referring to the preparation method of compound iv-H14. Subsequently, referring to the preparation method of compound iv-H13, the target compound H136 was synthesized. Using the same solvent and catalytic system, the stopping time point of the reaction was judged by thin-layer chromatography. The difference is that compound v-H136 and xii-H136 were used to equivalently replace compound ix-H13 and xii-H13 respectively. The total yield of the three-step reaction was 35.5%. Mass spectrometry (m / z) = 884.38 [M+H] + 。

[0207] Referring to the preparation method of compound H136, the following compounds (x) were synthesized: E123, E136, E138, E147, E156, E177. The difference is that starting materials compound i-x, ii-x, v-x, vii-x, and xii-x were used to equivalently replace compound i-H136, ii-H136, v-H136, vii-136, and xii-H116 respectively. Among them, the main starting materials used, the synthesized intermediates, the yields, and the mass spectrometry characterization data are shown in Table 7. The nuclear magnetic resonance characterization data are shown in Table 8.

[0208] Table 7

[0209]

[0210]

[0211] Table 8

[0212]

[0213]

[0214]

[0215] Synthesis of compound E112

[0216]

[0217] The total yield of the three-step reaction was 37.5%. Mass spectrometry (m / z) = 849.33 [M+H] + 。Nuclear magnetic data 11H NMR (400 MHz, DMSO-d6) δ 9.20 (d, J = 1.4 Hz, 2H), 8.68–8.59 (m, 8H), 8.47 (dt, J = 7.5, 1.5 Hz, 2H), 8.34–8.28 (m, 4H), 7.91–7.85 (m, 3H), 7.57–7.41 (m, 6H), 7.27 (td, J = 7.5, 1.6 Hz, 1H), 7.22 (d, J = 7.5 Hz, 1H), 7.18 (dd, J = 7.5, 1.6 Hz, 1H), 7.14–7.08 (m, 2H), 7.05 (td, J = 7.5, 1.5 Hz, 1H), 6.99 (dd, J = 7.5, 1.5 Hz, 1H), 3.00–2.93 (m, 2H), 2.78–2.70 (m, 2H), 1.81–1.68 (m, 4H).

[0218] Device embodiments:

[0219] The compounds of the present invention used in the device are purified by sublimation, and the purity is greater than 99.98%.

[0220] Among the compounds involved in the present invention, some embodiments can be used as hole transport materials for blue, green, and red OLED devices; some other embodiments can be used as electron transport materials for blue OLED devices; and some other embodiments can be used as host emitting materials for red phosphorescent OLED devices.

[0221] Blue device embodiment: Preparation of blue organic electroluminescent device (as hole transport material)

[0222] According to Figure 1The structure shown is used to fabricate a blue top-emitting organic electroluminescent device. The fabrication process is as follows: On a glass substrate 101, a transparent anode ITO film layer (with a thickness of 150 nm) is formed through a magnetron sputtering process to obtain a first electrode 102 as the anode. On the surface of the anode, a mixed material of compound 1 and compound 1-1 is evaporated as a hole injection layer 103, with a mixing ratio of 3:97 (by mass) and a thickness of 10 nm. Subsequently, on the surface of the hole injection layer, compound H13 of the present invention (with a thickness of 100 nm) and compound 1-2 (with a thickness of 20 nm) are successively evaporated to obtain a first hole transport layer 104 and a second hole transport layer 105 respectively. Next, on the surface of the second hole transport layer 105, compound 1-3 and compound 1-4 (with a thickness of 30 nm and a mass ratio of 95:5) are co-evaporated to form a blue light-emitting layer 106. Subsequently, compound 5 (with a thickness of 10 nm) is evaporated to form a hole blocking layer 107, and a compound 6 and LiQ with a mixing ratio of 4:6 (by mass) are evaporated to form an electron transport layer 108 (with a thickness of 30 nm). Then, ytterbium (Yb) with a thickness of 3 nm, magnesium (Mg) with a thickness of 10 nm, and silver (Ag) are successively vacuum-evaporated onto the electron injection layer at an evaporation rate of 1:9 as a second electrode 109. Finally, 70 nm of compound 7 is evaporated as a covering layer material to complete the fabrication of the organic light-emitting device.

[0223] Table 9

[0224]

[0225] Examples 2 - 7 of blue devices

[0226] An organic electroluminescent device is fabricated using the same method as in Example 1 of the blue light device, except that when forming the hole injection layer and the hole transport layer, the compounds in Table 10 below are used to replace compound H13 respectively.

[0227] Comparative Example 1

[0228] An organic electroluminescent device is fabricated using the same method as in Example 1 of the blue light device, except that when forming the hole injection layer and the hole transport layer, compound 1-1 is used to replace compound H13.

[0229] The chemical structures of the compounds 1, 1-1, 1-2, 1-3, 1-4, 5, 6, 7, and LiQ are shown in Table 9.

[0230] For the organic light-emitting device prepared as above, its operating voltage and efficiency were calculated using a computer-controlled Keithley 2400 test system. The device lifetime under dark conditions was obtained using a Polaronix (McScience Co.) lifetime measurement system equipped with a power supply and a photodiode as the detection unit. Each device in the blue device examples of each group was produced and tested in the same batch as the device of Comparative Example 1. The operating voltage, efficiency, and lifetime of the device of Comparative Example 1 were each recorded as 1, and the ratios of the corresponding indexes of the devices of Examples 1-7 of the blue device to those of the device of Comparative Example 1 were calculated respectively, as shown in Table 10.

[0231] Table 10

[0232] Hole transport layer Relative operating voltage Relative efficiency Relative lifetime Comparative example 1 1-1 1 1 1 Example 1 of blue light device H13 0.960 1.067 1.580 Example 2 of blue light device H14 0.958 1.059 1.684 Example 3 of blue light device H88 0.946 1.095 1.365 Example 4 of blue light device H114 0.932 1.076 1.431 Example 5 of blue light device H142 0.977 1.063 1.712 Example 6 of blue light device H168 0.942 1.081 1.830 Example 7 of blue light device H205 0.951 1.054 1.778

[0233] Example 1 of the red device: Preparation of a red organic light-emitting device (as a hole transport material)

[0234] According to the Figure 2 shown structure, a red bottom-emitting organic light-emitting device was fabricated. The preparation process was as follows: On a glass substrate 101, a transparent ITO film layer (thickness 150 nm) was formed by magnetron sputtering to obtain a first electrode 102 as the anode. A mixed material of Compound 1 and Compound 1-1 was evaporated on the surface of the anode as a hole injection layer 103, with a mixing ratio of 3:97 (mass ratio) and a thickness of 10 nm. Subsequently, Compound 1-1 (thickness 100 nm) and the compound H56 of the present invention (thickness 10 nm) were successively evaporated on the surface of the hole injection layer to obtain a first hole transport layer 104 and a second hole transport layer 105 respectively. Next, on the surface of the second hole transport layer 105, Compound 2-3 and Compound 2-4 were co-evaporated at a mass ratio of 95:5 to form an organic light-emitting layer 106 (thickness 40 nm). Subsequently, Compound 5 was evaporated on the surface of the organic light-emitting layer to form a hole blocking layer 107 (thickness 10 nm), and a compound 6 and LiQ with a mixing ratio of 4:6 (mass ratio) were evaporated to form an electron transport layer 108 (thickness 30 nm). Finally, magnesium (Mg) and silver (Ag) were co-deposited on the surface of the electron transport layer 108 at an evaporation rate ratio of 1:9 to form a second electrode 109 with a thickness of 10 nm as the cathode, completing the fabrication of the organic light-emitting device.

[0235] Examples 2-7 of the red device

[0236] Except that when forming the second hole transport layer, the compounds in Table 12 below were used to replace Compound H4 respectively, an organic light-emitting device was fabricated using the same method as in Example 1 of the red light device.

[0237] Comparative Example 2

[0238] An organic electroluminescent device was fabricated using the same method as in Example 1 of the red light device, except that compound HTB was used to replace compound H4 when forming the second hole transport layer.

[0239] The chemical structures of the aforementioned compounds 1, 5, 6, 7, and LiQ have been described previously. The chemical structures of compounds 2-3, 2-4, and HTB are shown in Table 11.

[0240] Table 11

[0241]

[0242] For the organic electroluminescent device fabricated as above, its operating voltage and efficiency were calculated using a computer-controlled Keithley 2400 test system. The device lifetime under dark conditions was obtained using a Polaronix (McScience Co.) lifetime measurement system equipped with a power supply and a photodiode as the detection unit. Each device in each group of red device examples was produced and tested in the same batch as the device of Comparative Example 2. The operating voltage, efficiency, and lifetime of the device of Comparative Example 2 were each recorded as 1, and the ratios of the corresponding indices of the devices of Red Examples 1-7 to those of the device of Comparative Example 2 were calculated respectively, as shown in Table 12.

[0243] Table 12

[0244] Second hole transport layer Relative operating voltage Relative efficiency Relative lifetime Comparative example 2 HTB 1 1 1 Example 1 of red light device H56 0.929 1.088 1.654 Example 2 of red light device H118 0.961 1.075 1.700 Example 3 of red light device H155 0.905 1.062 1.735 Example 4 of red light device H175 0.940 1.105 1.447 Example 5 of red light device H188 0.952 1.047 1.801 Example 6 of red light device H196 0.901 1.096 1.665 Example 7 of red light device H213 0.934 1.059 1.960

[0245] Example 1 of the green device: Preparation of a green organic electroluminescent device (as a hole transport material)

[0246] According to Figure 2Fabricate a green bottom-emitting organic electroluminescent device with the shown structure. The preparation process is as follows: On a glass substrate 101, form a transparent ITO film layer (with a thickness of 150 nm) through magnetron sputtering to obtain the first electrode 102 as the anode. Evaporate a mixture of compound 1 and compound 1-1 on the surface of the anode as the hole injection layer 103, with a mixing ratio of 3:97 (mass ratio) and a thickness of 10 nm. Subsequently, evaporate compound 1-1 (with a thickness of 100 nm) and the compound H37 of the present invention (with a thickness of 40 nm) successively on the surface of the hole injection layer to obtain the first hole transport layer 104 and the second hole transport layer 105 respectively. Next, on the surface of the second hole transport layer 105, co-evaporate compound 3-3 and compound 3-4 at a mass ratio of 90:10 to form an organic light-emitting layer 106 (with a thickness of 40 nm). Subsequently, evaporate compound 5 on the surface of the organic light-emitting layer to form a hole blocking layer 107 (with a thickness of 10 nm), and evaporate a mixture of compound 6 and LiQ with a mixing ratio of 4:6 (mass ratio) to form an electron transport layer 108 (with a thickness of 30 nm). Finally, deposit a mixture of magnesium (Mg) and silver (Ag) at an evaporation rate ratio of 1:9 on the surface of the electron transport layer 108 to form a second electrode 109 with a thickness of 10 nm as the cathode, completing the fabrication of the organic light-emitting device.

[0247] Examples 2 - 7 of Green Devices

[0248] Fabricate an organic electroluminescent device using the same method as in Example 1 of the green light device, except that when forming the second hole transport layer, replace compound H37 with the compounds in Table 14 below respectively.

[0249] Comparative Example 3

[0250] Fabricate an organic electroluminescent device using the same method as in Example 1 of the green light device, except that when forming the second hole transport layer, replace compound H37 with compound HTC.

[0251] The structures of the main materials used in the above Examples of green devices and Comparative Example 3 are shown in Table 13 below:

[0252] Table 13

[0253]

[0254] For the organic light-emitting devices prepared as above, their operating voltages and efficiencies were calculated using a computer-controlled Keithley 2400 test system. The device lifetime under dark conditions was obtained using a Polaronix (McScience Co.) lifetime measurement system equipped with a power supply and a photodiode as the detection unit. The devices of each group of green device examples were produced and tested in the same batch as the devices of Comparative Example 3. The operating voltage, efficiency, and lifetime of the devices of Comparative Example 3 were each recorded as 1, and the ratios of the corresponding indexes of the devices of green device examples 1 to 7 and the devices of Comparative Example 3 were calculated respectively, as shown in Table 14.

[0255] Table 14

[0256] Second hole transport layer Relative operating voltage Relative efficiency Relative lifetime Comparative example 3 HTC 1 1 1 Example 1 of green light device H37 0.954 1.061 1.187 Example 2 of green light device H46 0.948 1.079 1.175 Example 3 of green light device H74 0.929 1.180 1.202 Example 4 of green light device H83 0.933 1.088 1.251 Example 5 of green light device H90 0.917 1.085 1.315 Example 6 of green light device H138 0.936 1.073 1.289 Example 7 of green light device H199 0.943 1.066 1.277

[0257] Blue device Example 8: Preparation of a blue organic light-emitting device (as an electron transport material)

[0258] Referring to the preparation method of the organic light-emitting device in Blue device Example 1, the device in this example was prepared. The difference is that the compound E11 of the present invention and LiQ (the mixing ratio is 4:6 by mass) were co-evaporated to form the electron transport layer 108 (thickness 30 nm).

[0259] Blue device Examples 9 to 16

[0260] Except that when forming the electron transport layer, the compounds in Table 15 below were used to replace compound E11 respectively, the organic light-emitting device was fabricated using the same method as in Blue device Example 1.

[0261] Comparative Example 4

[0262] Except that when forming the electron transport layer, ETA was used to replace compound E11, the organic light-emitting device was fabricated using the same method as in Blue device Example 1. The structure of compound ETA is as follows:

[0263]

[0264] Table 15

[0265]

[0266]

[0267] Red device Example 8: Preparation of a red organic light-emitting device (as a host material for the light-emitting layer)

[0268] Referring to the preparation method of the red organic electroluminescent device in Comparative Example 2 of the reference device, the device in this example was prepared, except that the compound E2 and the compound 2-4 of the present invention were co-evaporated at a mass ratio of 95:5 to form an organic light-emitting layer 106 with a thickness of 40 nm.

[0269] Examples 9-17 of Red Devices

[0270] Except that when forming the electron transport layer, the compounds in Table 16 below were used to replace the compound E2 respectively, the organic electroluminescent device was fabricated by the same method as in Example 1 of the red light device.

[0271] Comparative Example 5

[0272] Except that when forming the electron transport layer, HOSTA was used to replace the compound E2, the organic electroluminescent device was fabricated by the same method as in Example 1 of the red light device. The structure of the compound HOSTA is as follows:

[0273]

[0274] Table 16

[0275]

[0276]

[0277] As described above, the above are only the preferred specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention, according to the technical solution and inventive concept of the present invention, makes equivalent substitutions or changes, and all should be covered by the protection scope of the present invention.

Claims

1. A spiro compound, the chemical structure of the spiro compound is shown in formula (1): In formula (1), A is selected from O, S or NR0; wherein, R0 is selected from substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl; The rings G1, G2, which may be the same or different, are each independently selected from The rings G3 and G4, the same or different, each independently selected from the groups shown in formula (2)-(3), or a benzene ring, and not both are benzene rings at the same time; In formulas (2) to (3), Zs are the same as or different from each other, and each independently selected from CR A R B , NR C , O or S; wherein any two adjacent * carbons represent a common connection site with the five-membered ring in formula (1); The R A , R B are the same or different and each independently selected from hydrogen, deuterium, methyl which is deuterated or not deuterated; the R C is selected from substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C1-C8 heteroalkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C3-C12 heterocycloalkyl; Formula (1) satisfies the condition: at least one of G3 and G4 is selected from one of formula (2)-(3); Both G3 and G4 satisfy the condition that when the number of heteroatoms NR C , S or O is more than 1, there is at least one CR A R B spaced between any two heteroatoms NRc, S or O; R1, R2, R3, and R4 are each independently selected from C1-C30 alkyl, C6-C40 aryl or the group shown in formula (5), and at least one of R1, R2, R3, and R4 is selected from the group shown in formula (5); m, n, p, and q are the same or different from each other, each independently selected from integers between 0 and 10, and m, n, p, and q are not all 0 at the same time; when any one of m, n, p, and q is greater than 1, each of R1, R2, R3, and R4 is the same or different from each other; *-L1-L2-(L3-Ar) r (5) In formula (5), L1 and L3 are each independently selected from a single bond or the following groups; L2 is selected from a nitrogen atom, In any group, carbon atoms on any two and only two aromatic rings are bonding sites; Ar is selected from In any group, only one carbon atom on any aromatic ring is the bonding site, and any hydrogen atom can be replaced by one of trifluoromethyl, methyl, tert-butyl, and cyclohexyl; r is selected from 1-5 and is an integer; and when r≥2, each of the L3 and Ar groups is the same or different from each other; * is the connection site; In formula (1), among the substituted or unsubstituted, the substituents of the substitution are selected from one or more of deuterium, halogen groups, cyano groups, nitro groups, trifluoromethyl, C1-C12 alkyl, C3-C12 cycloalkyl, C1-C12 alkoxy, C1-C12 alkylthio, C6-C30 aryl, and C2-C30 heteroaryl.

2. The spiro compound according to claim 1, wherein The chemical structure of the spiro compound is shown in formula (6)-(8): Among them, the selection of A, R1, R2, R3, R4, G1, and G2 is the same as that in formula (1); the G5 and G6, the same or different, each independently selected from the groups shown in formula (9)-(10): Among them, the selection of Z is the same as that in formula (2)-(3); in formula (9) and (10), * represents the connection site, connecting any two adjacent unsubstituted carbon atoms on the benzene ring of any one of formula (6), (7), or (8).

3. The spiro compound according to claim 2, characterized in that, The ring G5 or G6 is independently selected from the following groups: wherein, R c is selected in the same manner as in formula (1); * represents a linking site, respectively linking any two adjacent unsubstituted carbon atoms on the benzene ring in formula (6), (7) or formula (8).

4. A spiro compound, characterized in that, The spiro compound is selected from any one of the following chemical structures:

5. An organic layer, comprising the spiro compound according to any one of claims 1-4.

6. Use of the spiro compound according to any one of claims 1-4 or the organic layer according to claim 5 in an organic electroluminescent device.

7. An organic electroluminescent device, comprising a first electrode, a second electrode, and an organic layer, wherein the organic layer is at least one of a hole injection layer, a hole transport layer, a light-emitting layer, an electron injection layer, or an electron transport layer, and the organic layer comprises the spiro compound according to any one of claims 1-4.

8. The organic electroluminescent device according to claim 7, characterized in that, The organic electroluminescent device includes an organic photovoltaic device, an organic light-emitting device, an electronic paper, an organic photoreceptor, or an organic thin-film transistor.

9. The organic electroluminescent device according to claim 7, wherein The organic electroluminescent device includes an organic solar cell.

10. A display or lighting device, characterized in that, It includes the organic electroluminescent device according to any one of claims 7 to 9.

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