Spiro-structure-containing compound, deuterated 8-hydroxyquinoline lithium and application of deuterated 8-hydroxyquinoline lithium

Abstract

The invention discloses a spiro-structure-containing compound, deuterated 8-hydroxyquinoline lithium and application thereof, and belongs to the technical field of display. The chemical structural formula of the compound containing the spiro structure is as follows: L1-L3 are single bonds, arylene of C6-C30 or heteroarylene of C3-C30, and the L1-L3 are not single bonds at the same time; ar is O, S or Se; z1, Z2, Z3 and Z4 are N or CR14; r1 to R14 are one of hydrogen, deuterium, halogen, a cyano group, an aryl group with 6 to 30 carbon atoms, a heteroaryl group with 3 to 30 carbon atoms, an alkyl group with 1 to 16 carbon atoms, an alkoxy group with 1 to 16 carbon atoms, and a cycloalkyl group with 3 to 16 carbon atoms; n is 0, 1, 2 or 3; and m is 0, 1, 2, 3 or 4. The compound is beneficial to reducing the working voltage of an OLED device, improving the current efficiency and the external quantum efficiency of the OLED device and prolonging the cycle service life of the OLED device.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of display, in particular to a compound containing a spiro structure, lithium deuterated 8-hydroxyquinoline and application thereof. BACKGROUND

[0002] An organic electroluminescence device (OLED), also known as an organic electroluminescence diode, has the advantages of self-illumination, low energy consumption, wide viewing angle, light weight, thin thickness, fast response, high contrast, low driving voltage, and bendable folding, and is widely used in display and lighting fields.

[0003] Generally, the OLED device includes a cathode, an anode, and an electron transport functional layer, a light-emitting layer, and a hole transport functional layer arranged in layers between the cathode and the anode.

[0004] At present, the electron transport capability of the electron transport material in the electron transport functional layer needs to be improved, so that it is not matched with the hole transport capability of the hole transport material, resulting in the problem of imbalance in the number of electrons and holes in the light-emitting layer of the OLED device, and further resulting in light-emitting quenching. SUMMARY

[0005] In view of this, the present application provides a compound containing a spiro structure, lithium deuterated 8-hydroxyquinoline and application thereof, which can solve the technical problems existing in the related art. Specifically, the technical solutions include the following:

[0006] In a first aspect, a compound containing a spiro structure is provided, and the chemical structural formula of the compound containing a spiro structure is as follows:

[0007]

[0008] wherein L1-L3 are each independently one of a single bond, a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C3-C30 heteroarylene group, and L1-L3 are not simultaneously a single bond;

[0009] Ar is

[0010] X is O, S or Se;

[0011] Z1, Z2, Z3, Z4 are each independently N or CR 14 ;

[0012] R1-R 14 are each independently one of hydrogen, deuterium, halogen, cyano, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group, a substituted or unsubstituted C1-C16 alkyl group, a substituted or unsubstituted C1-C16 alkoxy group, and a substituted or unsubstituted C3-C16 cycloalkyl group.

[0013] n is 0, 1, 2, or 3;

[0014] m is 0, 1, 2, 3, or 4.

[0015] In some possible implementations, L1-L3 are each independently one of a single bond, a deuterium atom-substituted or unsubstituted arylene group, a deuterium atom-substituted or unsubstituted heteroarylene group;

[0016] wherein the arylene group and the heteroarylene group comprise one of a phenylene group, a naphthylene group, a substituted or unsubstituted fluorenylene group having 6-30 carbon atoms, a dibenzothiophene group, a dibenzofuran group, a phenanthrene group, a fluoranthene group, an anthracene group, a biphenylene group, a pyridine group, a pyrimidine group, a pyrene group, a benzophenanthrene group, a benzofuran group, a benzothiophene group, a spiro[fluorene-9,9'-xanthene].

[0017] In some possible implementations, two of L1-L3 are single bonds, and the other one is the arylene group or the heteroarylene group.

[0018] Alternatively, one of L1-L3 is a single bond, and the other two are the arylene group or the heteroarylene group.

[0019] In some possible implementations, Z1, Z2, Z3, Z4 are all CH or all CD.

[0020] In some possible implementations, R1-R 14 are each independently one of hydrogen, deuterium, methyl, ethyl, propyl, isopropyl, tert-butyl, cyclohexane, adamantane, phenyl, tolyl, biphenyl, deuterated phenyl, naphthyl, deuterated naphthyl, tert-butylphenyl, adamantylphenyl, deuterated biphenyl.

[0021] In some possible implementations, R 14 is phenyl or deuterated phenyl.

[0022] In a second aspect, there is provided a deuterated lithium 8-hydroxyquinoline, the chemical structural formula of which is as shown below:

[0023]

[0024] R 101 -R 106 are each independently hydrogen, deuterium, cyano, halogen, C1-18alkyl, substituted or unsubstituted C6-C30aryl, substituted or unsubstituted C3-C30heteroaryl, and R 101 -R 106 at least one is a deuterium atom.

[0025] In a third aspect, an electron transport material is provided, the electron transport material comprising the compound of the first aspect, and / or the deuterated lithium 8-hydroxyquinoline of the second aspect.

[0026] In some possible implementation manners, the electron transport material comprises the compound of the first aspect and an organic metal complex, and a mass percentage of the organic metal complex is 20wt%-70wt%.

[0027] In some possible implementation manners, the organic metal complex is selected from at least one of lithium 8-hydroxyquinoline and deuterated lithium 8-hydroxyquinoline, wherein the deuterated lithium 8-hydroxyquinoline is as described in the second aspect.

[0028] In a fourth aspect, the compound containing a spiro structure of the first aspect and the deuterated lithium 8-hydroxyquinoline of the second aspect are applied in an organic electroluminescent device, an organic solar cell, an organic thin-film transistor, an organic photodetector, an organic field effect transistor, an organic integrated circuit, and an organic photoreceptor.

[0029] In a fifth aspect, an organic electroluminescent device is provided, the organic electroluminescent device comprising: a first electrode, a second electrode, an electron transport functional layer, a light-emitting layer, and a hole transport functional layer arranged in a stack between the first electrode and the second electrode.

[0030] The electron transport functional layer comprises the compound of the first aspect, and / or the deuterated lithium 8-hydroxyquinoline of the second aspect.

[0031] In some possible implementation manners, the electron transport functional layer comprises at least one of an electron transport layer and a hole blocking layer, and at least one of the electron transport layer and the hole blocking layer comprises the electron transport material.

[0032] In a fifth aspect, a display device is provided, the display device comprising the organic electroluminescent device of the fourth aspect.

[0033] The technical scheme provided by the embodiments of the present application has at least the following beneficial effects:

[0034] The compound provided by the embodiment of the present application contains a spiro structure, and an indolospirofluorene group with a specific chemical structure is connected to an Ar group through a connecting group, wherein the Ar group can be a benzoxazolyl group or a benzothiazolyl group. The benzoxazolyl group or the benzothiazolyl group has strong electron-withdrawing properties, excellent electron injection and transport capacity, and hole blocking capacity, and effectively increases the electron mobility of the compound. The indolospirofluorene group endows the compound with high stability and good film-forming property, which is beneficial to increasing the glass transition temperature of the compound and improving the service life of the device. Research shows that the embodiment of the present application makes the benzoxazolyl group or the benzothiazolyl group and the indolospirofluorene group synergize, which not only further increases the electron mobility of the compound, but also reduces the LUMO (Lowest Unoccupied Molecular Orbital) energy level of the compound, improves the charge injection capacity thereof, and ensures high stability of the compound. Therefore, the compound can be applied to an organic electroluminescent device, especially to an electron transport functional layer thereof, so as to ultimately achieve the purposes of reducing the working voltage of the organic electroluminescent device, improving the current efficiency and external quantum efficiency thereof, and prolonging the service life thereof. BRIEF DESCRIPTION OF DRAWINGS

[0035] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed in the embodiment description will be briefly introduced. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative effort.

[0036] Figure 1 The hydrogen spectrum graph of the compound 20 provided by the embodiment of the present application is shown in the following figure.

[0037] Figure 2 The hydrogen spectrum graph of the compound 31 provided by the embodiment of the present application is shown in the following figure.

[0038] Figure 3 The hydrogen spectrum graph of the compound 103 provided by the embodiment of the present application is shown in the following figure.

[0039] Figure 4 The hydrogen spectrum graph of the compound 130 provided by the embodiment of the present application is shown in the following figure. DETAILED DESCRIPTION

[0040] The technical solutions in the embodiments of the present application will be described clearly and completely with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only some embodiments of the present application, rather than all the embodiments. Based on the embodiments in the embodiments of the present application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present application.

[0041] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in the description of the application herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.

[0042] As used herein, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise.

[0043] In the embodiments of the present application, "first aspect", "second aspect", "third aspect", "fourth aspect" and the like are only for the purpose of description, and cannot be understood as indicating or implying relative importance or quantity, nor can they be understood as implicitly indicating the importance or quantity of the technical features indicated. Moreover, "first", "second", "third", "fourth" and the like only serve the purpose of non-exhaustive enumeration and description, and should be understood as not constituting a closed limitation on the quantity.

[0044] In the embodiments of the present application, among the technical features described in an open manner, a closed technical solution composed of the enumerated features is also included, as well as an open technical solution including the enumerated features.

[0045] In the embodiments of the present application, when a numerical interval is involved, unless otherwise specified, the numerical interval is considered to be continuous and includes the minimum value and the maximum value of the range, as well as every value between the minimum value and the maximum value. Further, when the range refers to integers, every integer between the minimum value and the maximum value of the range is included. In addition, when multiple ranges are provided to describe a feature or a characteristic, the ranges can be combined. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all sub-ranges encompassed therein.

[0046] In the embodiments of the present application, the percentage concentration, unless otherwise specified, refers to the final concentration. The final concentration refers to the proportion of the added ingredient in the system after the ingredient is added.

[0047] In the embodiments of the present application, the temperature parameter, unless otherwise specified, allows both constant temperature treatment and treatment within a certain temperature range. The constant temperature treatment allows the temperature to fluctuate within the accuracy range controlled by the instrument. The room temperature in the embodiments of the present application generally refers to 4-30℃, preferably 20±5℃.

[0048] Organic electroluminescent device (OLED), also known as organic electroluminescent diode, has the advantages of self-emission, low energy consumption, wide viewing angle, light weight, thin thickness, fast response, high contrast, low driving voltage, and can be bent and folded, and is widely used in display and lighting fields.

[0049] In a first aspect, embodiments of the present application provide a spiro-containing compound, the chemical structure of which is shown as follows:

[0050]

[0051] wherein L1-L3 are each independently one of a single bond, a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C3-C30 heteroarylene group, and L1-L3 are not simultaneously a single bond.

[0052] Ar is

[0053] X is O, S, or Se.

[0054] Z1, Z2, Z3, Z4 are each independently N or CR 14 .

[0055] R1-R 14 are each independently one of hydrogen, deuterium, halogen, cyano, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group, a substituted or unsubstituted C1-C16 alkyl group, a substituted or unsubstituted C1-C16 alkoxy group, and a substituted or unsubstituted C3-C16 cycloalkyl group.

[0056] n is 0, 1, 2, or 3; and m is 0, 1, 2, 3, or 4. The (D)n and (D)m mentioned above each refer to a deuterium substituent.

[0057] It should be noted that the term “substituted or unsubstituted ZZ group” or “unsubstituted ZZ group” in embodiments of the present application means that the hydrogen atoms of the “ZZ group” are not substituted by a substituent. The “substituted ZZ group” means that at least one hydrogen atom of the “ZZ group” is substituted by a substituent, and when multiple hydrogens are replaced by multiple substituents, the multiple substituents can be the same or different.

[0058] The term “CXX-CYY ZZ group” in embodiments of the present application means the number of carbon atoms contained in the “ZZ group” without substitution, and when the “ZZ group” has a substituent, the number of carbon atoms should not include the number of carbon atoms in the substituent.

[0059] The "substituent" involved in the embodiments of the present application includes, but is not limited to, deuterium, tritium, cyano, halogen, nitro, C1-C15 alkyl, C3-C15 cycloalkyl, C2-C15 heterocyclyl, C6-C20 aryl, C2-C20 heteroaryl, fused ring group of C3-C15 alicyclic ring and C6-C20 aromatic ring, fused ring group of C3-C15 alicyclic ring and C2-C20 heteroaromatic ring, and the like. Further, for example, the substituent can be deuterium, tritium, cyano, halogen, nitro, methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, phenyl, biphenyl, naphthyl, phenanthryl, triphenylenyl, anthryl, pyrenyl, fluoranthenyl, benzothienyl, indolyl, carbazolyl, pyridyl, pyrimidyl, pyrazinyl, pyridazinyl, triazinyl, quinolyl, isoquinolyl, quinazolyl, and the like.

[0060] For the above-mentioned C1-C16 alkyl, the alkyl group can be a straight-chain alkyl group or a branched-chain alkyl group, and when the number of carbon atoms of the straight-chain alkyl group is three or more, isomers thereof are included, for example, propyl includes n-propyl and isopropyl; and butyl includes n-butyl, isobutyl, sec-butyl, t-butyl, and the like. Examples of the above-mentioned alkyl group include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and the like.

[0061] For the above-mentioned C1-C16 alkyl, the alkyl group can be a straight-chain alkyl group or a branched-chain alkyl group, and when the number of carbon atoms of the straight-chain alkyl group is three or more, isomers thereof are included, for example, propyl includes n-propyl and isopropyl; and butyl includes n-butyl, isobutyl, sec-butyl, t-butyl, and the like. Examples of the above-mentioned alkyl group include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and the like.

[0062] For the above-mentioned C1-C16 alkyl, the alkyl group can be a straight-chain alkyl group or a branched-chain alkyl group, and when the number of carbon atoms of the straight-chain alkyl group is three or more, isomers thereof are included, for example, propyl includes n-propyl and isopropyl; and butyl includes n-butyl, isobutyl, sec-butyl, t-butyl, and the like. Examples of the above-mentioned alkyl group include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and the like.

[0063] The compound provided by the embodiment of the present application connects the indolospirofluorene group with a specific chemical structure to the Ar group through a connecting group, wherein the Ar group can be a benzoxazolyl group or a benzothiazolyl group. The benzoxazolyl group or the benzothiazolyl group has strong electron-withdrawing properties, excellent electron injection and transport capacity, and hole blocking capacity, and effectively increases the electron mobility of the compound. The indolospirofluorene group gives the compound higher stability and good film-forming property, which is beneficial to increase the glass transition temperature of the material and improve the service life of the device. Research shows that the embodiment of the present application makes the benzoxazolyl group or the benzothiazolyl group and the indolospirofluorene group synergize, which not only further increases the electron mobility of the compound, but also reduces the LUMO (Lowest Unoccupied Molecular Orbital) energy level of the compound, improves the charge injection capacity, and also ensures that the compound has high stability. Therefore, the compound can be applied to an organic electroluminescent device, especially to an electron transport functional layer thereof, so as to ultimately achieve the purposes of reducing the working voltage of the organic electroluminescent device, improving the current efficiency and external quantum efficiency thereof, and prolonging the service life thereof.

[0064] In some examples, for the Ar group, Z1, Z2, Z3, and Z4 are all CH or all CD.

[0065] When Z1, Z2, Z3, and Z4 are all CH, the Ar group is a benzoxazolyl group or a benzothiazolyl group. When Z1, Z2, Z3, and Z4 are all CD, the Ar group is a deuterated benzoxazolyl group or a deuterated benzothiazolyl group, which is beneficial to further increase the thermal stability and electron mobility of the compound molecule and improve the comprehensive performance of the OLED device.

[0066] L1-L3 are used to realize the connection between the benzoxazolyl group or the benzothiazolyl group and the indolospirofluorene group. In some examples, L1-L3 are each independently one of the following groups: a single bond, a deuterium atom-substituted or unsubstituted arylene group, and a deuterium atom-substituted or unsubstituted heteroarylene group. The arylene group and the heteroarylene group include one of the following groups: a phenylene group, a naphthylene group, a substituted or unsubstituted fluorenylene group having 6-30 carbon atoms, a dibenzothiophene group, a dibenzofuran group, a phenanthrene group, a fluoranthene group, an anthracene group, a biphenylene group, a pyridine group, a pyrimidine group, a pyrene group, a benzophenanthrene group, a benzofuran group, a benzothiophene group, and a spiro[fluorene-9,9'-xanthene].

[0067] L1-L3 are selected from the above groups, which is conducive to further increasing the stability of the compound, and at the same time, the spatial structure and the molecular energy level of the compound molecule can be adjusted, so as to improve the film-forming property and the stability of the compound, and the electron transport capability and the hole blocking performance of the compound can be improved. Finally, the purpose of improving the efficiency of the OLED device, reducing the power consumption of the OLED device, and prolonging the service life of the OLED device is achieved.

[0068] Further, as a preferred scheme, two of L1-L3 can be a single bond, and the other one can be an arylene group or a heteroarylene group. Alternatively, one of L1-L3 can be a single bond, and the other two can be an arylene group or a heteroarylene group. Wherein, the "arylene group or heteroarylene group" involved herein is as described above, which is not repeated here.

[0069] In some examples, R1-R 14 Each is independently one of hydrogen, deuterium, methyl, ethyl, propyl, isopropyl, tert-butyl, cyclohexyl, adamantyl, phenyl, tolyl, biphenyl, deuterated phenyl, naphthyl, deuterated naphthyl, tert-butylphenyl, adamantylphenyl, deuterated biphenyl.

[0070] R1-R 14 When the above groups are selected, the spatial stability of the indole spirofluorene group is increased, the stability of the compound is further increased, and the purpose of prolonging the service life of the organic electroluminescent device is achieved.

[0071] For the R 14 group involved in the Ar group, R 14 may be a phenyl group or a deuterated phenyl group, which has the effects of simplifying the structure and preparation process and cost of the compound on the basis of the above-mentioned effects.

[0072] For the above-mentioned compound containing a spiro structure, the embodiment of the present application provides some examples of compounds containing a spiro structure, as shown in the following compounds 1-147.

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082] The application also provides the application of the compound with the spiro structure in the electronic transmission material, and the electronic transmission material has all the advantages of the compound with the spiro structure.

[0083] For the electronic transmission material, in some cases, due to the limitation of electron injection and transmission, lithium 8-hydroxyquinoline needs to be doped to improve the electron mobility and the electron injection capacity. However, the stability of the OLED device needs to be improved, and therefore, the lithium 8-hydroxyquinoline is further improved in the embodiment of the application to solve the above technical problems.

[0084] In the second aspect, the embodiment of the application provides a deuterated lithium 8-hydroxyquinoline, and the chemical structural formula of the deuterated lithium 8-hydroxyquinoline is as follows:

[0085]

[0086] R 101 -R 106 Each is independently hydrogen, deuterium, cyano, halogen, C1-18alkyl, substituted or unsubstituted C6-C30aryl, substituted or unsubstituted C3-C30heteroaryl, and R 101 -R 106 At least one is a deuterium atom.

[0087] It should be noted that the specific selection of the alkyl group, the aryl group, the heteroaryl group and the like involved herein can refer to the selection of the related groups in the compound with the spiro structure involved in the first aspect.

[0088] The deuterated lithium 8-hydroxyquinoline with the above chemical structure can be used as an electronic transmission material, has the advantages of improving the electron mobility and the electron injection capacity, and in particular, the deuterated lithium 8-hydroxyquinoline, compared with the lithium 8-hydroxyquinoline, can reduce the chemical vibration energy loss of the C-H bond due to the fact that deuterium is heavier than hydrogen, so that the stability is stronger, and the stability and the cycle life of the OLED device are improved.

[0089] The number of deuterium atoms contained in the deuterated lithium 8-hydroxyquinoline can be 1-6, and in some examples, some examples of the deuterated lithium 8-hydroxyquinoline can be as follows:

[0090]

[0091] The embodiment of the present application also provides application of the deuterated 8-hydroxyquinoline lithium in the electronic transport material, and further, the deuterated 8-hydroxyquinoline lithium can be used in combination with the known electronic transport material (ETL material) and the compound with the spiro structure according to the first aspect of the embodiment of the present application.

[0092] In particular, when the deuterated 8-hydroxyquinoline lithium is used in combination with the compound with the spiro structure according to the embodiment of the present application, the electronic transport performance of the formed electronic transport material is not only improved, but also the stability of the OLED device is greatly improved, and the cycle life is significantly improved. That is, the working voltage, the current efficiency and the cycle life of the OLED device can be simultaneously improved, and in particular, the improvement of the cycle life is greater.

[0093] In the third aspect, the embodiment of the present application provides an electronic transport material, which comprises any one of the compounds according to the first aspect and / or the deuterated 8-hydroxyquinoline lithium according to the second aspect.

[0094] The electronic transport material according to the embodiment of the present application has all the advantages of the compound with the spiro structure and the deuterated 8-hydroxyquinoline lithium according to the embodiment of the present application.

[0095] Specifically, the compound according to the first aspect can increase the electron mobility by introducing the benzoxazole or benzothiazole group, which is an electron-withdrawing group, and the nitrogen atom participates in conjugation. Therefore, the use of the compound as the electronic transport material can improve the efficiency of the electron transport to the light-emitting layer, thereby improving the performance of the organic electroluminescent device.

[0096] In some examples, the electronic transport material can be used to prepare the electron transport layer of the OLED device.

[0097] In other examples, the electronic transport material can be used to prepare the hole blocking layer of the OLED device.

[0098] Further, the electronic transport material according to the embodiment of the present application not only comprises any one of the compounds according to the first aspect, but also can comprise an organometallic complex, and the mass percentage of the organometallic complex can be 20wt%-70wt%, which includes but is not limited to 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt% and the like.

[0099] The organic metal complex generally has a suitable electron affinity and excellent electron transport properties, and by synergizing the organic metal complex with the compound, the electron injection efficiency and transport rate to the light-emitting layer can be further improved.

[0100] Some applicable organic metal complexes can be metal quinoline complexes, metal pyrazole / triazole complexes, metal phthalocyanine complexes, metal imidazole / benzimidazole complexes, etc.

[0101] Further, a metal quinoline complex can be used to synergize with any of the compounds according to the first aspect, to achieve better electron transport effect.

[0102] For example, the metal quinoline complex is selected from at least one of lithium 8-hydroxyquinoline and deuterated lithium 8-hydroxyquinoline according to the second aspect.

[0103] The chemical structural formula of lithium 8-hydroxyquinoline is

[0104] In a fourth aspect, the present application provides any of the compounds according to the first aspect, and the deuterated lithium 8-hydroxyquinoline according to the second aspect for use in an organic electroluminescence device, an organic solar cell, an organic thin-film transistor, an organic photodetector, an organic field-effect transistor, an organic integrated circuit, and an organic photoreceptor.

[0105] In a fifth aspect, the present application provides an organic electroluminescence device, comprising: a first electrode, a second electrode, an electron transport functional layer, a light-emitting layer, and a hole transport functional layer, which are arranged in a stack between the first electrode and the second electrode; wherein the electron transport functional layer comprises any of the compounds according to the first aspect, and / or the deuterated lithium 8-hydroxyquinoline according to the second aspect.

[0106] The organic electroluminescence device provided by the embodiments of the present application has all the advantages of the compound containing a spiro structure according to the embodiments of the present application.

[0107] In some examples, the organic electroluminescence device provided by the embodiments of the present application has an electron transport functional layer comprising at least one of an electron transport layer and a hole blocking layer, and at least one of the electron transport layer and the hole blocking layer comprises an electron transport material.

[0108] When the electron transport layer contains the compound according to the first aspect, the compound can transport electrons, thereby improving the electron transport rate. When the hole blocking layer contains the compound according to the first aspect, the compound can block holes from entering the electron transport layer while transporting electrons, thereby improving the electron transport rate.

[0109] Further, the electron transport function layer can also include an electron injection layer.

[0110] The organic electroluminescent device provided by the embodiment of the present application has a hole transport function layer including at least one of a hole injection layer, a hole transport layer and an electron blocking layer.

[0111] In one example, the organic electroluminescent device includes a first electrode, a second electrode, and a light-emitting unit disposed between the first electrode and the second electrode, the light-emitting unit including a hole transport layer, a light-emitting layer and an electron transport layer arranged in sequence.

[0112] In another example, the organic electroluminescent device includes a first electrode, a second electrode, and a light-emitting unit disposed between the first electrode and the second electrode, the light-emitting unit including a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer and an electron injection layer arranged in sequence. Based on this example, only one of the hole injection layer and the hole transport layer can be provided, and / or only one of the electron transport layer and the electron injection layer can be provided.

[0113] In yet another example, the organic electroluminescent device includes a first electrode, a second electrode, and a light-emitting unit disposed between the first electrode and the second electrode, the light-emitting unit including a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer arranged in sequence. Based on this example, only one or any two of the hole injection layer, the hole transport layer and the electron blocking layer can be provided, and / or only one or any two of the hole blocking layer, the electron transport layer and the electron injection layer can be provided.

[0114] In some examples, the light-emitting layer includes a light-emitting host material and a light-emitting dopant material, and various desired light emission can be adjusted by changing the light-emitting host material, so that the light-emitting layer has good light-emitting properties.

[0115] The light-emitting layer can include one or more of the following compounds: naphthalene compounds, pyrene compounds, fluorene compounds, phenanthrene compounds, chrysene compounds, fluoranthene compounds, anthracene compounds, pentacene compounds, perylene compounds, diarylethene compounds, triphenylamine ethylene compounds, amine compounds, carbazole compounds, benzimidazole compounds, furan compounds, metal organic fluorescent complexes, metal organic phosphorescent complexes (such as Ir, Pt, Os, Cu, Au), boron-nitrogen compounds, polyvinyl carbazole, polyorganosilicon compounds, polythiophene, etc. The light-emitting layer can also include other compounds, which are not specifically limited.

[0116] Organic layers in organic electroluminescent devices can be prepared by vacuum evaporation, molecular beam evaporation, solvent-based dip coating, spin coating, rod coating, or inkjet printing. Electrodes can be prepared by evaporation or sputtering.

[0117] In a sixth aspect, embodiments of the present invention also provide a display device, which includes the organic electroluminescent device provided in the fifth aspect of embodiments of the present invention.

[0118] For example, the display device may be a mobile phone, tablet, laptop, wearable device, television, electronic screen, vehicle display, special display device, etc.

[0119] The specific embodiments of the present invention will now be described in more detail. While specific embodiments of the present invention are described below, it should be understood that the present invention can be implemented in various forms and should not be limited to the embodiments set forth herein. Where specific techniques or conditions are not specified in the embodiments, they are performed in accordance with the techniques or conditions described in the literature in the art or according to the product instructions. Reagents or instruments whose manufacturers are not specified are all conventional products that can be obtained commercially.

[0120] It should be noted that the serial numbers of the compounds provided in the following embodiments are the same as the compounds with the same serial numbers among the aforementioned compounds 1-147.

[0121] The intermediates or products synthesized in the following specific examples were separated by column chromatography, followed by nuclear magnetic resonance mass spectrometry (NMR mass spectrometry). 1 HNMR), high-resolution mass spectrometry (HNMR), 1 Molecular structure characterization was performed using HRMS.

[0122] Example 1

[0123] Example 1 provides compound 1, the synthetic route and method of which are shown below:

[0124]

[0125] Into a three-necked flask, 2-(4-bromophenyl)benzo[d]oxazole (1.0 g, 3.45 mmol), 2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-spiro[fluorene-9,10'-indolo[1,2- a]indole] (1.74 g, 3.61 mmol) and potassium carbonate (0.71 g, 5.14 mmol) were stirred uniformly. Then toluene (10 mL), ethanol (5 mL) and deionized water (5 mL) were added. Under nitrogen protection, di-triphenylphosphine palladium chloride (0.05 g, 0.07 mmol) was added, and the reaction was continued for 5 h under reflux. After the reaction was completed, the reaction mixture was separated, and the organic phase was concentrated to dryness. The crude product was separated by column chromatography with dichloromethane: petroleum ether (v / v = 1:2) as the eluent to obtain 1.52 g of white product, with a yield of 78%.

[0126] The related characterization of compound 1 is shown as follows: 1 H NMR (400 MHz, CDC13, δ): 8.01-8.03 (m, 1H), 7.91-7.93 (m, 1H), 7.83-7.85 (m, 1H), 7.71-7.74 (m, 3H), 7.66-7.68 (m, 1H), 7.59-7.61 (m, 2H), 7.44-7.55 (m, 4H), 7.28-7.42 (m, 8H), 7.22-7.23 (m, 1H), 7.02-7.03 (m, 1H), 6.28-6.29 (m, 1H). HRMS (ESI, m / z): [M+H]+calcd for: C 40 H 25 N2S, 565.1733, found, 565.1735. Anal.: calcd: C, 85.08; H, 4.28; N, 4.96; S, 5.68; found: C, 85.15; H, 4.20; N, 4.89; S, 5.72.

[0127] Example 2

[0128] Example 2 provides compound 20, the synthetic route and the synthetic method thereof as shown below:

[0129]

[0130] Synthesis of intermediate 20-1

[0131] Synthesis of intermediate 20-1 2-bromospiro[fluorene-9,10'-indeno[l,2-a]indole] (2.0 g, 4.60 mmol), 4-chlorobenzoic acid (0.79 g, 5.05 mmol) and potassium carbonate (0.95 g, 6.87 mmol) were placed in a three-necked flask and stirred well. Toluene (20 mL), ethanol (10 mL) and deionized water (10 mL) were then added. Palladium di-triphenylphosphine chloride (0.1 g, 0.14 mmol) was added under nitrogen protection and the reaction was continued at reflux for 5 h. After the reaction was completed, the mixture was separated and the organic phase was concentrated to dryness. The crude product was separated by column chromatography using dichloromethane: petroleum ether (v / v = 1 :5) as eluent to obtain the white product 1.81 g in 84% yield. The relevant characterization of intermediate 20-1 is shown below: 1 H NMR (400 MHz, CDC13, δ): 7.83-7.85 (m, 1H), 7.71-7.74 (m, 2H), 7.50-7.56 (m, 4H), 7.34-7.40 (m, 7H), 7.27-7.32 (m, 4H), 6.98-7.00 (m, 1H), 6.43-6.44 (m, 1H).

[0132] Synthesis of intermediate 20-2

[0133] Intermediate 20-1 (1.5 g, 3.22 mmol), bis(pinacolato)diboron (0.98 g, 3.86 mmol), potassium acetate (0.63 g, 6.42 mmol) and anhydrous toluene (30 mL) were placed in a three-necked flask. Pd2(dba)3(0.03 g) and X-phos (0.06 g) were added under nitrogen protection and the reaction was continued at reflux for 10 h. After the reaction was completed, the potassium acetate was filtered off and the solvent was concentrated to dryness. The crude product was separated by column chromatography using dichloromethane: petroleum ether (v / v = 1 :3) as eluent to obtain the white product 1.48 g in 82% yield. The relevant characterization of intermediate 20-2 is shown below: 1 H NMR (400 MHz, CDC13, δ): 7.83-7.88 (m, 3H), 7.67-7.70 (m, 2H), 7.44-7.52 (m, 4H), 7.28-7.41 (m, 8H), 7.26-7.27 (m, 1H), 7.02-7.03 (m, 1H), 6.43-6.44 (m, 1H), 1.27 (s, 6H), 1.21 (s, 6H).

[0134] Synthesis of compound 20

[0135] The synthesis method is the same as that of compound 1. The relevant characterization of compound 20 is shown below and can be seen in Figure 1 : 1H NMR (400 MHz, CDC13, δ): 8.24-8.26 (m, 3H), 7.87-7.94 (m, 4H), 7.71-7.76 (m, 4H), 7.54-7.63 (m, 6H), 7.36-7.47 (m, 4H), 7.17-7.21 (m, 3H), 6.92-7.00 (m, 2H), 6.72-6.74 (m, 1H), 6.14-6.16 (m, 1H). HRMS (ESI, m / z): [M+H]+calcd for: C 46 H 29 N2S, 641.2046, found, 641.2048. Anal.: calcd: C, 86.22; H, 4.40; N, 4.37; S, 5.00; found: C, 86.26; H, 4.34; N, 4.45; S, 4.91.

[0136] Example 3

[0137] Example 3 provides compound 27, the synthetic route and the synthetic method thereof as shown below:

[0138]

[0139] Synthesis of intermediate 27-1

[0140] The synthetic method is the same as intermediate 20-1. The related characterization of intermediate 27-1 is shown as follows: 1 H NMR (400 MHz, CDC13, δ): 8.24-8.26 (m, 3H), 7.87-7.94 (m, 4H), 7.71-7.76 (m, 4H), 7.54-7.63 (m, 6H), 7.36-7.47 (m, 4H), 7.17-7.21 (m, 3H), 6.92-7.00 (m, 2H), 6.72-6.74 (m, 1H), 6.14-6.16 (m, 1H). HRMS (ESI, m / z): [M+H]+calcd for: C

[0141] Synthesis of intermediate 27-2

[0142] The synthetic method is the same as intermediate 20-2. The related characterization of intermediate 27-2 is shown as follows: 1 H NMR (400 MHz, CDC13, δ): 8.24-8.26 (m, 3H), 7.87-7.94 (m, 4H), 7.71-7.76 (m, 4H), 7.54-7.63 (m, 6H), 7.36-7.47 (m, 4H), 7.17-7.21 (m, 3H), 6.92-7.00 (m, 2H), 6.72-6.74 (m, 1H), 6.14-6.16 (m, 1H). HRMS (ESI, m / z): [M+H]+calcd for: C

[0143] Synthesis of compound 27

[0144] Synthetic method is the same as compound 1. The relevant characterization of compound 27 is shown as follows: 1 H NMR (400 MHz, CDC13, δ): 8.00-8.03 (m, 1H), 7.83-7.87 (m, 2H), 7.73-7.75 (m, 1H), 7.66-7.69 (m, 1H), 7.44-7.49 (m, 3H), 7.28-7.40 (m, 9H), 7.19-7.21 (m, 1H), 6.97-6.99 (m, 1H), 6.22-6.23 (m, 1H). HRMS (ESI, m / z): [M+H]+calcd for: C 46 H 21 D8N2S, 649.2548, found, 649.2545. Anal.: calcd: C, 85.15; H, 5.59; N, 4.32; S, 4.94; found: C, 85.09; H, 5.64; N, 4.27; S, 4.99.

[0145] Example 4

[0146] Example 4 provides compound 31, the synthetic route and synthetic method thereof as shown below:

[0147]

[0148] Synthesis of intermediate 31-1

[0149] Synthetic method is the same as intermediate 20-1. The relevant characterization of intermediate 31-1 is shown as follows: 1 H NMR (400 MHz, CDC13, δ): 8.00-8.03 (m, 1H), 7.83-7.87 (m, 2H), 7.73-7.75 (m, 1H), 7.66-7.69 (m, 1H), 7.44-7.49 (m, 3H), 7.28-7.40 (m, 9H), 7.19-7.21 (m, 1H), 6.97-6.99 (m, 1H), 6.22-6.23 (m, 1H). HRMS (ESI, m / z): [M+H]+calcd for: C

[0150] Synthesis of intermediate 31-2

[0151] Synthetic method is the same as intermediate 20-2. The relevant characterization of intermediate 31-2 is shown as follows: 1H NMR (400 MHz, CDC13, δ): 7.83-7.85 (m, 1H), 7.73-7.75 (m, 2H), 7.67-7.70 (m, 1H), 7.60-7.62 (m, 1H), 7.46-7.52 (m, 4H), 7.28-7.41 (m, 9H), 7.02-7.03 (m, 1H), 6.43-6.44 (m, 1H), 1.27 (s, 6H), 1.21 (s, 6H).

[0152] Synthesis of compound 31

[0153] Synthetic method is the same as compound 1. The relevant characterization of compound 31 is shown below and can be seen in Figure 2 : 1 H NMR (400 MHz, CDC13, δ): 8.07-8.14 (m, 3H), 7.86-7.94 (m, 4H), 7.67-7.74 (m, 5H), 7.33-7.56 (m, 9H), 7.16-7.21 (m, 3H), 6.91-6.96 (m, 2H), 6.71-6.73 (m, 1H), 6.14-6.16 (m, 1H). HRMS (ESI, m / z): [M+H]+calcd for: C 46 H 29 N2S, 641.2046, found, 641.2042. Anal.: calcd: C, 86.22; H, 4.40; N, 4.37; S, 5.00; found: C, 86.14; H, 4.44; N, 4.42; S, 4.95.

[0154] Example 5

[0155] Example 5 provides compound 37, the synthetic route and synthetic method of which are shown as follows:

[0156]

[0157] Synthesis of intermediate 37-1

[0158] Synthetic method is the same as intermediate 20-1. The relevant characterization of intermediate 37-1 is shown as follows: 1 H NMR (400 MHz, CDC13, δ): 7.80-7.85 (m, 3H), 7.71-7.73 (m, 1H), 7.66-7.68 (m, 1H), 7.54-7.57 (m, 2H), 7.50-7.53 (m, 4H), 7.30-7.41 (m, 10H), 7.24-7.25 (m, 1H), 7.02-7.03 (m, 1H), 6.43-6.44 (m, 1H).

[0159] Synthesis of intermediate 37-2

[0160] Synthetic method is same as intermediate 20-2. The related characterization of intermediate 37-2 is shown as follows: 1 H NMR (400 MHz, CDC13, δ): 7.77-7.85 (m, 5H), 7.71-7.73 (m, 1H), 7.66-7.69 (m, 1H), 7.55-7.57 (m, 2H), 7.47-7.51 (m, 4H), 7.28-7.40 (m, 9H), 6.97-6.99 (m, 1H), 6.22-6.23 (m, 1H), 1.27 (s, 6H), 1.21 (s, 6H).

[0161] Synthesis of compound 37

[0162] Synthetic method is same as compound 1. The related characterization of compound 37 is shown as follows: 1 H NMR (400 MHz, CDC13, δ): 8.01-8.02 (m, 1H), 7.91-7.94 (m, 3H), 7.83-7.85 (m, 1H), 7.64-7.73 (m, 6H), 7.49-7.58 (m, 10H), 7.28-7.38 (m, 8H), 7.24-7.25 (m, 1H), 7.00-7.01 (m, 1H), 6.24-6.25 (m, 1H). HRMS (ESI, m / z): [M+H]+calcd for: C 52 H 33 N2S, 717.2359, found, 717.2355. Anal.: calcd: C, 87.12; H, 4.50; N, 3.91; S, 4.47; found: C, 87.03; H, 4.63; N, 3.82; S, 4.49.

[0163] Example 6

[0164] Example 6 provides compound 41, the synthetic route and synthetic method of which are shown as follows:

[0165]

[0166] Synthesis of intermediate 41-1

[0167] Synthetic method is same as intermediate 20-1. The related characterization of intermediate 41-1 is shown as follows: 1H NMR (400 MHz, CDC13, δ): 7.79-7.80 (m, 1H), 7.71-7.74 (m, 1H), 7.59-7.61 (m, 1H), 7.50-7.54 (m, 2H), 7.46-7.47 (m, 1H), 7.28-7.40 (m, 11H), 7.21-7.22 (m, 1H), 6.98-7.00 (m, 1H), 6.43-6.44 (m, 1H).

[0168] Synthesis of intermediate 41-2

[0169] The synthesis method is the same as intermediate 20-2. The relevant characterization of intermediate 41-2 is shown as follows: 1 H NMR (400 MHz, CDC13, δ): 7.79-7.80 (m, 1H), 7.71-7.74 (m, 1H), 7.59-7.61 (m, 1H), 7.50-7.54 (m, 2H), 7.46-7.47 (m, 1H), 7.28-7.40 (m, 11H), 7.21-7.22 (m, 1H), 6.98-7.00 (m, 1H), 6.43-6.44 (m, 1H).

[0170] Synthesis of compound 41

[0171] The synthesis method is the same as compound 1. The relevant characterization of compound 41 is shown as follows: 1 H NMR (400 MHz, CDC13, δ): 7.79-7.80 (m, 1H), 7.71-7.74 (m, 1H), 7.59-7.61 (m, 1H), 7.50-7.54 (m, 2H), 7.46-7.47 (m, 1H), 7.28-7.40 (m, 11H), 7.21-7.22 (m, 1H), 6.98-7.00 (m, 1H), 6.43-6.44 (m, 1H). 46 H 29 N2S, 641.2046, found, 641.2046. Anal.: calcd: C, 86.22; H, 4.40; N, 4.37; S, 5.00; found: C, 86.28; H, 4.35; N, 4.35; S, 4.39.

[0172] Example 7

[0173] Example 7 provides a compound 42, a synthesis route and a synthesis method thereof as shown below:

[0174]

[0175] Synthesis of intermediate 42-1

[0176] The synthesis method is the same as intermediate 20-1. The relevant characterization of intermediate 42-1 is shown as follows: 1 H NMR (400 MHz, CDC13, δ): 7.77-7.78 (m, 1H), 7.71-7.74 (m, 1H), 7.59-7.61 (m, 1H), 7.55-7.57 (m, 1H), 7.50-7.52 (m, 3H), 7.34-7.41 (m, 7H), 7.28-7.32 (m, 4H), 6.98-7.00 (m, 1H), 6.43-6.44 (m, 1H).

[0177] Synthesis of intermediate 42-2

[0178] The synthesis method is the same as intermediate 20-2. The relevant characterization of intermediate 42-2 is shown as follows: 1 H NMR (400 MHz, CDC13, δ): 7.77-7.78 (m, 1H), 7.71-7.74 (m, 1H), 7.59-7.61 (m, 1H), 7.55-7.57 (m, 1H), 7.50-7.52 (m, 3H), 7.34-7.41 (m, 7H), 7.28-7.32 (m, 4H), 6.98-7.00 (m, 1H), 6.43-6.44 (m, 1H).

[0179] Synthesis of compound 42

[0180] The synthesis method is the same as compound 1. The relevant characterization of compound 42 is shown as follows: 1 H NMR (400 MHz, CDC13, δ): 7.77-7.78 (m, 1H), 7.71-7.74 (m, 1H), 7.59-7.61 (m, 1H), 7.55-7.57 (m, 1H), 7.50-7.52 (m, 3H), 7.34-7.41 (m, 7H), 7.28-7.32 (m, 4H), 6.98-7.00 (m, 1H), 6.43-6.44 (m, 1H). 46 H 29N2S, 641.2046, found, 641.2041. Anal.: calcd: C, 86.22; H, 4.40; N, 4.37; S, 5.00; found: C, 86.18; H, 4.46; N, 4.43; S, 4.90.

[0181] Example 8

[0182] Example 8 provides compound 48, the synthetic route and the synthetic method thereof as shown below:

[0183]

[0184] Synthesis of intermediate 48-1

[0185] The synthetic method is the same as intermediate 20-1. The related characterization of intermediate 48-1 is shown as follows: 1 H NMR (400 MHz, CDC13, δ): 7.71-7.74 (m, 1H), 7.61-7.63 (m, 1H), 7.54-7.56 (m, 1H), 7.46-7.51 (m, 3H), 7.42-7.45 (m, 1H), 7.34-7.40 (m, 7H), 7.28-7.32 (m, 3H), 7.01-7.03 (m, 1H), 6.95-6.97 (m, 1H), 6.43-6.44 (m, 1H).

[0186] Synthesis of intermediate 48-2

[0187] The synthetic method is the same as intermediate 20-2. The related characterization of intermediate 20-1 is shown as follows: 1 H NMR (400 MHz, CDC13, δ): 7.88-7.90 (m, 2H), 7.67-7.70 (m, 1H), 7.58-7.60 (m, 1H), 7.50-7.55 (m, 3H), 7.47-7.48 (m, 1H), 7.28-7.45 (m, 9H), 6.99-7.02 (m, 2H), 6.42-6.43 (m, 1H), 1.27 (s, 6H), 1.21 (s, 6H).

[0188] Synthesis of compound 48

[0189] The synthetic method is the same as compound 1. The related characterization of compound 48 is shown as follows: 1H NMR (400 MHz, CDC13, δ): 8.05-8.07 (m, 1H), 7.97-7.98 (m, 1H), 7.87-7.89 (m, 4H), 7.83-7.85 (m, 1H), 7.71-7.73 (m, 1H), 7.66-7.69 (m, 2H), 7.54-7.56 (m, 1H), 7.47-7.49 (m, 1H), 7.28-7.40 (m, 9H), 6.97-6.99 (m, 1H), 6.22-6.23 (m, 1H). HRMS (ESI, m / z): [M+H]+ calcd for: C 46 H 29 N2S, 641.2046, found, 641.2044. Anal.: calcd: C, 86.22; H, 4.40; N, 4.37; S, 5.00; found: C, 86.30; H, 4.30; N, 4.32; S, 5.01.

[0190] Example 9

[0191] Example 9 provides compound 56, its synthetic route and synthetic method as shown below:

[0192]

[0193] Synthesis of compound 56

[0194] The synthetic method is the same as compound 1. The relevant characterization of compound 56 is shown below: 1 H NMR (400 MHz, CDC13, δ): 8.05-8.07 (m, 1H), 7.97-7.98 (m, 1H), 7.87-7.89 (m, 4H), 7.83-7.85 (m, 1H), 7.71-7.73 (m, 1H), 7.66-7.69 (m, 2H), 7.54-7.56 (m, 1H), 7.47-7.49 (m, 1H), 7.28-7.40 (m, 9H), 6.97-6.99 (m, 1H), 6.22-6.23 (m, 1H). HRMS (ESI, m / z): [M+H]+ calcd for: C 46 H 24 D5N2S, 646.2360, found, 646.2363. Anal.: calcd: C, 85.55; H, 5.15; N, 4.34; S, 4.96; found: C, 85.59; H, 5.20; N, 4.22; S, 4.97.

[0195] Example 10

[0196] Example 10 provides compound 70, its synthetic route and synthetic method as shown below:

[0197]

[0198] Synthesis of intermediate 70-1

[0199] The synthesis method is the same as intermediate 20-1. The relevant characterization of intermediate 70-1 is shown as follows: 1 H NMR (400 MHz, CDC13, δ): 7.83-7.85 (m, 1H), 7.71-7.74 (m, 1H), 7.59-7.60 (m, 1H), 7.49-7.53 (m, 2H), 7.45-7.47 (m, 2H), 7.28-7.38 (m, 7H), 7.23-7.26 (m, 2H), 7.02-7.03 (m, 1H), 6.37-6.38 (m, 1H), 1.34 (s, 9H), 1.33 (s, 9H).

[0200] Synthesis of intermediate 70-2

[0201] The synthesis method is the same as intermediate 20-2. The relevant characterization of intermediate 70-2 is shown as follows: 1 H NMR (400 MHz, CDC13, δ): 7.83-7.85 (m, 1H), 7.71-7.74 (m, 1H), 7.59-7.60 (m, 1H), 7.49-7.53 (m, 2H), 7.45-7.47 (m, 2H), 7.28-7.38 (m, 7H), 7.23-7.26 (m, 2H), 7.02-7.03 (m, 1H), 6.37-6.38 (m, 1H), 1.34 (s, 9H), 1.33 (s, 9H).

[0202] Synthesis of compound 70

[0203] The synthesis method is the same as compound 1. The relevant characterization of compound 70 is shown as follows: 1 H NMR (400 MHz, CDC13, δ): 7.83-7.85 (m, 1H), 7.71-7.74 (m, 1H), 7.59-7.60 (m, 1H), 7.49-7.53 (m, 2H), 7.45-7.47 (m, 2H), 7.28-7.38 (m, 7H), 7.23-7.26 (m, 2H), 7.02-7.03 (m, 1H), 6.37-6.38 (m, 1H), 1.34 (s, 9H), 1.33 (s, 9H). HRMS (ESI, m / z): [M+H]+calcd for: C54 H 45 N2S,753.3298,found,753.3299.Anal.:calcd:C,86.13;H,5.89;N,3.72;S,4.36;found:C,86.02;H,5.92;N,3.75;S,4.39。

[0204] Example 11

[0205] Example 11 provides compound 81, the synthetic route and the synthetic method thereof as shown below:

[0206]

[0207] Synthesis of intermediate 81-1

[0208] The synthetic method is the same as intermediate 20-1. The related characterization of intermediate 81-1 is shown as follows: 1 H NMR (400 MHz, CDC13, δ): 7.89-7.90 (m, 1H), 7.71-7.72 (m, 1H), 7.67-7.69 (m, 1H), 7.58-7.61 (m, 3H), 7.54-7.56 (m, 1H), 7.50-7.52 (m, 2H), 7.29-7.45 (m, 10H), 6.38-6.39 (m, 1H).

[0209] Synthesis of intermediate 81-2

[0210] The synthetic method is the same as intermediate 20-2. The related characterization of intermediate 81-2 is shown as follows: 1 H NMR (400 MHz, CDC13, δ): 7.73-7.75 (m, 2H), 7.67-7.70 (m, 1H), 7.57-7.60 (m, 2H), 7.49-7.52 (m, 2H), 7.44-7.46 (m, 1H), 7.30-7.43 (m, 10H), 7.27-7.28 (m, 1H), 6.42-6.43 (m, 1H), 1.27 (s, 6H), 1.21 (s, 6H).

[0211] Synthesis of compound 81

[0212] The synthetic method is the same as compound 1. The related characterization of compound 81 is shown as follows: 1H NMR (400 MHz, CDC13, δ): 7.99-8.02 (m, 2H), 7.70-7.74 (m, 2H), 7.63-7.69 (m, 4H), 7.56-7.60 (m, 2H), 7.49-7.53 (m, 2H), 7.44-7.48 (m, 2H), 7.27-7.40 (m, 13H), 6.22-6.23 (m, 1H). HRMS (ESI, m / z): [M+H]+calcd for: C 46 H 29 N2O, 625.2274, found, 625.2279. Anal.: calcd: C, 88.44; H, 4.52; N, 4.48; O, 2.56; found: C, 88.40; H, 4.47; N, 4.55; O, 2.54.

[0213] Example 12

[0214] Example 12 provides compound 89, the synthetic route and the synthetic method thereof as shown below:

[0215]

[0216] Synthesis of compound 89

[0217] The synthetic method is the same as compound 1. The relevant characterization of compound 89 is shown below: 1 H NMR (400 MHz, CDC13, δ): 7.99-8.02 (m, 2H), 7.70-7.74 (m, 2H), 7.63-7.69 (m, 4H), 7.56-7.60 (m, 2H), 7.49-7.53 (m, 2H), 7.44-7.48 (m, 2H), 7.27-7.40 (m, 13H), 6.22-6.23 (m, 1H). HRMS (ESI, m / z): [M+H]+calcd for: C 49 H 33 N2O, 665.2587, found, 665.2588. Anal.: calcd: C, 88.53; H, 4.85; N, 4.21; O, 2.41; found: C, 88.48; H, 4.81; N, 4.32; O, 2.38.

[0218] Example 13

[0219] Example 13 provides compound 103, the synthetic route and the synthetic method thereof as shown below:

[0220]

[0221] Synthesis of compound 103

[0222] Synthetic method is the same as compound 1. The relevant characterization of compound 103 is shown below and can be seen in Figure 3 : 1 H NMR (400 MHz, CDC13, δ): 8.30-8.32 (m, 2H), 7.86-7.95 (m, 3H), 7.78-7.80 (m, 1H), 7.71-7.74 (m, 5H), 7.52-7.61 (m, 3H), 7.34-7.48 (m, 7H), 7.16-7.21 (m, 3H), 6.91-6.96 (m, 2H), 6.71-6.73 (m, 1H), 6.14-6.16 (m, 1H). HRMS (ESI, m / z): [M+H]+calcd for: C 46 H 29 N2O, 625.2274, found, 625.2277. Anal.: calcd: C, 88.44; H, 4.52; N, 4.48; O, 2.56; found: C, 88.51; H, 4.44; N, 4.52; O, 2.51.

[0223] Example 14

[0224] Example 14 provides compound 114, the synthetic route and synthetic method thereof as shown below:

[0225]

[0226] Synthesis of compound 114

[0227] Synthetic method is the same as compound 1. The relevant characterization of compound 114 is shown below: 1 H NMR (400 MHz, CDC13, δ): 8.30-8.32 (m, 2H), 7.86-7.95 (m, 3H), 7.78-7.80 (m, 1H), 7.71-7.74 (m, 5H), 7.52-7.61 (m, 3H), 7.34-7.48 (m, 7H), 7.16-7.21 (m, 3H), 6.91-6.96 (m, 2H), 6.71-6.73 (m, 1H), 6.14-6.16 (m, 1H). HRMS (ESI, m / z): [M+H]+calcd for: C 46 H 29N2O, 625.2274, found, 625.2270. Anal.: calcd: C, 88.44; H, 4.52; N, 4.48; O, 2.56; found: C, 88.50; H, 4.45; N, 4.43; O, 2.59.

[0228] Example 15

[0229] Example 15 provides compound 130, a synthetic route and a synthetic method thereof as shown below:

[0230]

[0231] Synthesis of compound 130

[0232] The synthetic method is the same as compound 1. The related characterization of compound 130 is shown below and can be seen in Figure 4 : 1 H NMR (400 MHz, CDC13, δ): 8.20-8.23 (m, 2H), 7.93-7.95 (m, 2H), 7.86-7.89 (m, 2H), 7.70-7.82 (m, 4H), 7.46-7.52 (m, 7H), 7.32-7.43 (m, 4H), 7.23-7.25 (m, 1H), 7.14-7.19 (m, 2H), 6.88-6.95 (m, 2H), 6.71-6.73 (m, 1H), 6.13-6.15 (m, 1H). HRMS (ESI, m / z): [M+H]+calcd for: C 46 H 29 N2O, 625.2274, found, 625.2270. Anal.: calcd: C, 88.44; H, 4.52; N, 4.48; O, 2.56; found: C, 88.50; H, 4.45; N, 4.43; O, 2.59.

[0233] Example 16

[0234] Example 16 provides compound LiQ-D6 (molecular weight is 157), a synthetic route and a synthetic method thereof as shown below:

[0235]

[0236] In a reaction bottle, under nitrogen protection, deuterated 8-hydroxyquinoline (7.5 g, 50 mmol) and 100 ml deuterated acetonitrile were added, heated to 50 degrees, lithium hydroxide (2.3 g, 100 mmol) was slowly added, heated to reflux for 5 hours, cooled, filtered, the filter cake was washed with anhydrous ether (100 ml), and then recrystallized with 25 ml deuterated tetrahydrofuran, filtered to obtain 5.3 g of compound LiQ-D6, with a yield of 67%. The relevant characterization of compound LiQ-D6 is shown below: HRMS (ESI, m / z): [M+H]+calcd for: C9D6LiNO, 157.0986, found, 157.0989.

[0237] Application Examples

[0238] The structures and properties of the organic electroluminescent devices prepared by using each of the above compounds are further described in detail below by applying application examples 1-27. The corresponding preparation method can also be used to prepare the samples required in subsequent test examples.

[0239] Among them, application examples 1-15, 23, 24 and 25 use each of the above compounds to prepare electron transport layer materials. Application examples 16-22, 26 and 27 use each of the above compounds to prepare hole blocking layers.

[0240] The structure of the above-mentioned organic electroluminescent device is shown below: glass / anode (ITO) / hole injection layer (HIL) / hole transport layer (HTL) / electron blocking layer (EBL) / light-emitting layer (EML, host material BH: red light-emitting material BD) / hole blocking layer (HBL) / electron transport layer (ETL) / electron injection layer (EIL) / cathode. Each layer is arranged in the above order.

[0241] The preparation method of the organic electroluminescent device is as follows:

[0242] The transparent conductive ITO glass substrate (with an anode on the top) (China South Glass Co., Ltd.) was ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, and then sequentially washed with ethanol, acetone and deionized water, baked in a clean environment until all the water was removed, treated with ultraviolet light and ozone, and then treated with oxygen plasma for 30 seconds. The glass substrate with an anode was placed in a vacuum chamber and vacuumized.

[0243] Hole injection layer: HIL (10 nm thick) was evaporated on the ITO surface as a hole injection layer, with an evaporation rate of 0.1 nm / s.

[0244] A hole transport layer was formed by evaporating compound HT on the surface of the hole injection layer to a thickness of 100 nm at an evaporation rate of 0.1 nm / s.

[0245] An electron blocking layer was formed by evaporating EB on the surface of the hole transport layer to a thickness of 10 nm at an evaporation rate of 0.1 nm / s.

[0246] A light-emitting layer was formed by evaporating a light-emitting layer having a thickness of 25 nm on the surface of the electron blocking layer, wherein BH was a host light-emitting material, and BD was a dopant guest material at a weight ratio of 3%, at an evaporation rate of 0.1 nm / s.

[0247] A hole blocking layer was formed by evaporating a hole blocking material on the surface of the light-emitting layer to a thickness of 5 nm at an evaporation rate of 0.1 nm / s. When the compound containing a spiro structure was not applied to the hole blocking layer, the hole blocking material of the hole blocking layer was compound HB. When the compound containing a spiro structure was applied to the hole blocking layer, the hole blocking material of the hole blocking layer was the corresponding compound containing a spiro structure. The compositions of the hole blocking layers of the devices can be found in Table 1 below.

[0248] An electron transport layer was formed by evaporating an electron transport layer having a thickness of 25 nm on the surface of the light-emitting layer at an evaporation rate of 0.1 nm / s. When the compound containing a spiro structure was applied to the electron transport layer, some specific embodiments of the electron transport layer included the compound containing a spiro structure and lithium quinolate (LiQ) at a weight ratio of 5:5, and some other specific embodiments of the electron transport layer included the compound containing a spiro structure and deuterated lithium quinolate (LiQ-D6) at a weight ratio of 5:5. When the compound containing a spiro structure was not applied to the electron transport layer, the electron transport layer included compound ET and lithium quinolate (LiQ) at a weight ratio of 5:5. The compositions of the electron transport layers of the devices can be found in Table 1 below.

[0249] Yb was evaporated to a thickness of 1 nm as an electron injection layer.

[0250] Aluminum (Al) was evaporated to a thickness of 120 nm as a cathode of the device.

[0251] For application examples 1-15, application comparative examples 1-8 are also provided, for application examples 16-22, application comparative examples 9-12 are also provided, and application examples 23-27 use LiQ-D6 as a metal complex applied to the electron transport layer.

[0252] The compositions of the layers of the organic electroluminescent devices involved in the above application examples and application comparative examples are shown in Table 1 below, and some raw material compounds involved in the preparation process of the above organic electroluminescent devices are shown as follows:

[0253]

[0254]

[0255] Table 1

[0256]

[0257]

[0258]

[0259]

[0260] In Table 1, the percentage content ratio of two raw materials in the EML refers to the weight percentage, such as the weight percentage of BH and BD in Application Example 1 is 97%:3% respectively. The percentage content ratio of two raw materials in the ETL also refers to the weight percentage, such as the weight percentage of compound 1 and LiQ in Application Example 1 is 50%:50% respectively.

[0261] The performance of each organic electroluminescent device involved in Table 1 was tested, and in the testing process, the anode and cathode were connected by using a known driving circuit, and the Photo Research PR655 spectrometer was used for testing to measure the operating voltage, current efficiency at 1000 cd / cm2brightness, and the lifetime (T95) at 50 mA / cm2current density under room temperature environment when the brightness decayed to 95% of the original brightness. 2 2 The performance of each organic electroluminescent device involved in Table 1 was tested, and in the testing process, the anode and cathode were connected by using a known driving circuit, and the Photo Research PR655 spectrometer was used for testing to measure the operating voltage, current efficiency at 1000 cd / cm2brightness, and the lifetime (T95) at 50 mA / cm2current density under room temperature environment when the brightness decayed to 95% of the original brightness.

[0262] The relevant test data is shown in Table 2:

[0263] Table 2

[0264]

[0265]

[0266] As can be seen from Table 2, compared with Application Comparative Examples 1-8, the devices involved in Application Examples 1-15 have lower operating voltage, higher current efficiency, and longer service life, by using the compound containing a spiro structure provided in the embodiments of the present application as the electron transport layer. This is because the compound containing a spiro structure provided in the embodiments of the present application has higher electron mobility and stability.

[0267] ​Specifically, the application examples 1 and 7 use compounds ETL-1 and ETL-7, respectively, although both of them have a spiro structure, compared with them, the application examples further introduce an indole group into the spiro structure, which can effectively improve the conductivity of the compound.

[0268] The application examples 2 and 3 use compounds ETL-2 and ETL-3, respectively, although both of them introduce an indole group, however, compound ETL-2 combines the spiro structure with the introduction of the indole group with a benzimidazole group, and compound ETL-3 combines the spiro structure with the introduction of the indole group with a triazine group. The application examples combine the spiro structure with the introduction of the indole group with a benzothiazole group or a benzoxazole group (unsubstituted or deuterated), which contains O and S atoms, and researches have found that such compounds are more conducive to adjusting the energy level and increasing the electron transport capacity.

[0269] The application examples 4-6 use compounds ETL4-ETL6 and TPBi, respectively, although these compounds contain a benzothiazole group or a benzoxazole group, but do not contain a spiro structure. The compound of the application example is based on the presence of the spiro structure, which is conducive to improving the thermal stability of the compound, and thus conducive to prolonging the service life of the device.

[0270] For the application examples 16-22, which use the compound containing the spiro structure provided by the application example as a hole blocking layer, compared with the application examples 9-10, the device involved in the application examples 16-22 has a lower working voltage, a higher current efficiency, and a longer service life. This is because the compound containing the spiro structure provided by the application example can reduce the conjugated system based on the spiro structure, reduce the HOMO energy level, and be more conducive to blocking holes, plus its good electron transport performance, thereby effectively improving the overall performance of the device.

[0271] For the application examples 23-27, compared with using LiQ and the various compounds containing the spiro structure provided by the application example to form an electron transport layer, these examples use LiQ-D6 to replace LiQ. Since D is heavier than hydrogen, it can reduce the chemical vibration energy loss of the C-H bond, and compared with the scheme using LiQ, the cycle life is more obviously improved by more than 50%.

[0272] The above is only to facilitate those skilled in the art to understand the technical solutions of the present application, and does not limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A compound containing a spirostructure, characterized in that, The chemical structural formula of the spiro compound is shown below: Among them, L1-L3 are each independently one of a single bond, a substituted or unsubstituted C6-C30 arylene, or a substituted or unsubstituted C3-C30 heteroarylene, and L1-L3 are not all single bonds at the same time; Ar for or X is O, S, or Se; Z1, Z2, Z3, and Z4 are each independently N or CR. 14 ; R1-R 14 Each of the following is independently one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C1-C16 alkyl, substituted or unsubstituted C1-C16 alkoxy, or substituted or unsubstituted C3-C16 cycloalkyl. n can be 0, 1, 2, or 3; m can be 0, 1, 2, 3, or 4.

2. The spiro-containing compound according to claim 1, characterized in that, L1-L3 are each independently one of the following groups: single bond, deuterium-substituted or unsubstituted aryl group, or deuterium-substituted or unsubstituted heteroaryl group; Wherein, the arylene and the heteroarylene include one of the following groups: phenylene, naphthylene, substituted or unsubstituted fluorene group having 6-30 carbon atoms, dibenzothiophene group, dibenzofuran group, phenanthrene group, fluorenylene group, anthracene group, biphenylene group, pyridinyl group, pyrimidinyl group, benzophenanthrene group, benzothiophene group, benzofuran group, spiro[fluorene-9,9'-oxazanthene].

3. The spiro-containing compound according to claim 2, characterized in that, Two of L1-L3 are single bonds, and the other is the arylene or the heteroarylene; Alternatively, one of L1-L3 may be a single bond, and the other two may be either the aryl group or the heteroaryl group.

4. The spiro-containing compound according to any one of claims 1-3, characterized in that, Z1, Z2, Z3, and Z4 are all CH or all CD.

5. The spiro-containing compound according to any one of claims 1-3, characterized in that, R1-R 14 Each of the following is independently one of hydrogen, deuterium, methyl, ethyl, propyl, isopropyl, tert-butyl, cyclohexyl, adamantyl, phenyl, tolyl, biphenyl, deuterated phenyl, naphthyl, deuterated naphthyl, tert-butylphenyl, adamantylphenyl, and deuterated biphenyl.

6. The spiro-containing compound according to any one of claims 1-3, characterized in that, R 14 It is either phenyl or deuterated phenyl.

7. A deuterated 8-hydroxyquinoline lithium, characterized in that, The chemical structural formula of the deuterated 8-hydroxyquinoline lithium is shown below: R 101 -R 106 Each is independently hydrogen, deuterium, cyano, halogen, C1-18 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, and R 101 -R 106 At least one of them is a deuterium atom.

8. An electron transport material, characterized in that, The electron transport material includes the compound according to any one of claims 1-6, and / or the deuterated 8-hydroxyquinoline lithium according to claim 7.

9. The electron transport material according to claim 8, characterized in that, The electron transport material comprises the compound and organometallic complex according to any one of claims 1-6, wherein the organometallic complex has a mass percentage of 20wt%-70wt%.

10. The electron transport material according to claim 9, characterized in that, The organometallic complex is selected from at least one of lithium 8-hydroxyquinoline and lithium deuterated 8-hydroxyquinoline, wherein the lithium deuterated 8-hydroxyquinoline is as described in claim 7.

11. The spiro-containing compound according to any one of claims 1-6, and the use of the deuterated 8-hydroxyquinoline lithium according to claim 7 in organic electroluminescent devices, organic solar cells, organic thin-film transistors, organic photodetectors, organic field-effect transistors, organic integrated circuits, and organic photoreceptors.

12. An organic electroluminescent device, characterized in that, The organic electroluminescent device includes: a first electrode, a second electrode, an electron transport functional layer, a light-emitting layer, and a hole transport functional layer stacked between the first electrode and the second electrode; The electron transport functional layer includes the spiro-containing compound of any one of claims 1-6, and / or the deuterated 8-hydroxyquinoline lithium of claim 7.

13. The organic electroluminescent device according to claim 12, characterized in that, The electron transport functional layer includes at least one of an electron transport layer and a hole blocking layer, and at least one of the electron transport layer and the hole blocking layer includes the electron transport material.

14. A display device, characterized in that, The display device includes the organic electroluminescent device according to any one of claims 12-13.

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