Polycyclic compound, organic electroluminescent device and application thereof

Abstract

The embodiment of the invention provides a polycyclic compound, an organic electroluminescent device and application thereof. The organic light-emitting device comprises a cathode, an anode and a light-emitting layer located between the cathode and the anode, the light-emitting layer comprises a light-emitting main body material and a doping material, and the doping material comprises at least one polycyclic compound; wherein the polycyclic compound comprises a polycyclic aromatic skeleton and a spiro structure, a nitrogen atom and a carbonyl group are embedded in the polycyclic aromatic skeleton, the spiro structure comprises two Ar1, a spiro carbon atom connected with the two Ar1 respectively and a bridging group, the spiro carbon atom is connected with the polycyclic aromatic skeleton, and the bridging group is connected with the nitrogen atom. Ar1 is independently selected from a substituted or unsubstituted aromatic ring or a substituted or unsubstituted aromatic heterocyclic ring, and the half-peak width of an electroluminescent peak of the luminescent layer is less than or equal to 30nm. The light-emitting layer of the device contains the polycyclic compound, the light-emitting color purity is high, the external quantum efficiency of the device is high, and the display effect is good.

Description

Technical Field

[0001] The present application relates to the technical field of light-emitting devices, and in particular to a polycyclic compound, an organic electroluminescent device and applications thereof. Background Art

[0002] Organic light emission diodes (OLEDs) are energy conversion devices that use organic materials as luminescent materials and can convert applied electrical energy into light energy. They are widely used in display, lighting and other fields due to their high brightness, fast response, wide viewing angle and flexibility. However, the existing OLEDs have low luminous efficiency and insufficient luminous color purity, and cannot achieve higher display effects. Therefore, it is necessary to develop new OLEDs with excellent performance. Summary of the invention

[0003] In view of this, the embodiments of the present application provide a polycyclic compound, an organic electroluminescent device and its application. The light-emitting layer of the device adopts a specific polycyclic compound so that the half-peak width of the electroluminescent peak of the light-emitting layer can be below 30nm, and the luminescence efficiency of the device is relatively high.

[0004] Specifically, the first aspect of an embodiment of the present application provides an organic electroluminescent device, which includes a cathode and an anode, and a light-emitting layer located between the cathode and the anode, the light-emitting layer includes a light-emitting main material and a doping material, and the doping material includes at least one polycyclic compound; wherein the polycyclic compound includes a polycyclic aromatic skeleton and a spiro structure, the polycyclic aromatic skeleton is embedded with nitrogen atoms and carbonyl groups, the spiro structure includes two Ar1s, spiro carbon atoms respectively connected to the two Ar1s, and a bridging group, the spiro carbon atom is connected to the polycyclic aromatic skeleton, the Ar1 is independently selected from substituted or unsubstituted aromatic rings, or substituted or unsubstituted aromatic heterocycles, and the half-peak width of the electroluminescence peak of the light-emitting layer is less than or equal to 30nm.

[0005] The doping material in the light-emitting layer of the organic electroluminescent device adopts a polycyclic compound that meets the above requirements. The presence of the spirocyclic structure in the polycyclic compound can limit the vibration of its polycyclic aromatic skeleton, reduce the vibration relaxation of the excited state molecular structure of the polycyclic compound, and inhibit the half-peak width broadening of the electroluminescent spectrum, so that the half-peak width of the light-emitting layer can be below 30nm, thereby making the device have high color purity and high external quantum efficiency.

[0006] In the embodiment of the present application, the maximum external quantum efficiency of the organic electroluminescent device is above 18%, which is significantly higher than the device parameter made by using the existing polycyclic compounds with carbonyl and nitrogen atoms embedded in the skeleton.

[0007] In some embodiments of the present application, based on the total mass of the light-emitting layer, the mass proportion of the doping material is 0.3-30.0wt%, and the mass proportion of the light-emitting main material is 70.0-99.7wt%. Controlling the mass proportion of the light-emitting main material and the doping material in the light-emitting layer within the above range is conducive to ensuring a high energy transfer efficiency between the two, thereby making the device more efficient, and is also conducive to reducing the interaction between the doping material molecules, which is conducive to a narrow half-peak width of the light-emitting peak of the light-emitting layer.

[0008] In some other embodiments of the present application, the light-emitting layer further includes a sensitizer; based on the total mass of the light-emitting layer, the mass percentage of the doping material is 0.3-10.0wt%, the mass percentage of the light-emitting main material is 65.0-94.7wt%, and the weight percentage of the sensitizer is 5-25wt%. Controlling the mass percentage of the light-emitting main material, the doping material and the sensitizer in the light-emitting layer within the above range is conducive to ensuring a high energy transfer efficiency between the three, so that the luminescence potential of the doping material can be fully utilized, thereby making the device have a higher luminescence efficiency.

[0009] In an embodiment of the present application, the organic electroluminescent device further includes other functional layers, which may include one or more of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer, and an electron injection layer; and the other functional layers include the polycyclic compound.

[0010] In the embodiment of the present application, the bridging group is selected from any of the following structures:

[0011]

[0012] Wherein, the dotted line represents a bond; R2 is independently selected from one or more of a hydrogen atom, a deuterium atom, a tritium atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a sulfhydryl group, a carboxyl group, an amino group, a carbonyl group, an ester group, an amide group, a phosphoryl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, and a substituted or unsubstituted silane group, wherein when the bridging group is When R2 can also be connected with Ar1 to form a ring; when the bridging group is When the bridging group is When R2 is connected to form a ring or R2 is connected to Ar1. The presence of these bridging groups can make the steric hindrance effect and rigidity enhancement effect of the spiro ring structure more obvious, which is conducive to the excellent luminescent properties of the polycyclic compound.

[0013] In the embodiment of the present application, the polycyclic compound has the general formula as shown in formula (I):

[0014]

[0015] In formula (I), X represents the bridging group, and each occurrence of R1 is independently selected from one or more of a hydrogen atom, a deuterium atom, a tritium atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, a carboxyl group, an amino group, a carbonyl group, an ester group, an amide group, a phosphoryl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, and a substituted or unsubstituted silane group.

[0016] In some embodiments of the present application, the bridging group includes any structure shown in formula (i-1) to formula (i-23):

[0017]

[0018]

[0019] wherein each R' and R" are independently selected from one or more of a hydrogen atom, a deuterium atom, a tritium atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a sulfhydryl group, a carboxyl group, an amino group, a carbonyl group, an ester group, an amide group, a phosphoryl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, and a substituted or unsubstituted silane group.

[0020] In the structures shown in the above formulas (i-1) to (i-23), R2 in the corresponding bridging group is an independent substituted or unsubstituted phenyl group that does not participate in the ring formation, or R2 is connected to form a ring, which is beneficial to increase the rigidity and steric hindrance effect of the spiro structure in the polycyclic compound, making the half-peak width of the luminescence spectrum of the polycyclic compound narrower and the external quantum efficiency exhibited in the device higher.

[0021] In some embodiments of the present application, the general formula represented by formula (I) includes any one of formula (II-1) to formula (II-5):

[0022]

[0023] In formula (II-1) to formula (II-5), the selection range of each R' is the same as that of R1.

[0024] The structures shown in the above formulas (i-1) to (i-23) correspond to the situation where R2 and Ar1 in the bridging group are connected to form a ring, which is more conducive to increasing the rigidity and steric effect of the spiro structure in the polycyclic compound, making the half-peak width of the luminescence spectrum of the polycyclic compound narrower and the external quantum efficiency exhibited in the device higher.

[0025] In the embodiment of the present application, the substituents in the substituted alkyl, substituted cycloalkyl, substituted alkenyl, substituted alkynyl, substituted aryl, and substituted heteroaryl include deuterium atoms, tritium atoms, halogen atoms, cyano groups, nitro groups, hydroxyl groups, sulfhydryl groups, carboxyl groups, amino groups, carbonyl groups, ester groups, amide groups, phosphoryl groups, substituted or unsubstituted alkyl groups, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted alkynyl groups, substituted or unsubstituted aryl groups, substituted or unsubstituted heteroaryl groups, substituted or unsubstituted hydrocarbyl groups, substituted or unsubstituted hydrocarbyl groups, substituted or unsubstituted silyl groups, or one or more of these. The introduction of different substituents can obtain polycyclic compounds with more structures, further adjust their luminescent properties, and meet the needs of more different scenarios.

[0026] In the embodiment of the present application, the substituted or unsubstituted alkyl group is a substituted or unsubstituted C1~C 20 Alkyl; the substituted or unsubstituted cycloalkyl is a substituted or unsubstituted C3~C 20 Cycloalkyl; the substituted or unsubstituted alkenyl is a substituted or unsubstituted C2~C 20 The substituted or unsubstituted alkynyl group is a substituted or unsubstituted C2~C 20 Alkynyl; the substituted or unsubstituted aryl is a substituted or unsubstituted C6~C 30 Aryl; the substituted or unsubstituted heteroaryl is a substituted or unsubstituted C3~C 30 Heteroaryl. Each group has a suitable number of carbon atoms, which not only enables the above-mentioned polycyclic compound to have good luminescent properties, but also makes its preparation raw materials more readily available, thereby simplifying the preparation of the compound.

[0027] In the embodiment of the present application, in Ar1, the substituted or unsubstituted aromatic ring is a substituted or unsubstituted C6~C 30 Aromatic ring; the substituted or unsubstituted aromatic heterocyclic ring is a substituted or unsubstituted C3~C 30 Aromatic heterocycle; the heteroatom in the aromatic heterocycle is selected from one or more of nitrogen atom, oxygen atom, sulfur atom, selenium atom, boron atom and silicon atom. Ar1 has different carbon atoms, which can make the above polycyclic compound have good luminescence performance, and the raw materials are more easily available, which can simplify the preparation of the compound.

[0028] In some embodiments of the present application, in Ar1, the substituted or unsubstituted aromatic ring includes a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted anthracene ring, a substituted or unsubstituted phenanthrene ring, a substituted or unsubstituted triphenylene ring, a fluoranthene ring, a substituted or unsubstituted pyrene ring, a substituted or unsubstituted binaphthyl ring, a substituted or unsubstituted fluorene ring, and a substituted or unsubstituted spirofluorene ring; the substituted or unsubstituted aromatic heterocyclic ring includes a substituted or unsubstituted furan ring, a substituted or One of an unsubstituted pyrrole ring, a substituted or unsubstituted thiophene ring, a substituted or unsubstituted pyridine ring, a substituted or unsubstituted quinoline ring, a substituted or unsubstituted furanopyrrole ring, a substituted or unsubstituted benzopyrrole ring, a substituted or unsubstituted benzofuran ring, a substituted or unsubstituted dibenzofuran ring, a substituted or unsubstituted benzothiophene ring, a substituted or unsubstituted dibenzothiophene ring, a substituted or unsubstituted carbazole ring, a substituted or unsubstituted triazine ring, and a substituted or unsubstituted xanthone ring. Ar1 can be selected from a variety of different aromatic rings or aromatic heterocyclic structures, which can enrich the types of the above-mentioned polycyclic compounds and realize diversified regulation of luminescent properties.

[0029] The second aspect of the embodiment of the present application provides a polycyclic compound, wherein the polycyclic compound has the general formula as shown in formula (I):

[0030]

[0031] In formula (I), each occurrence of Ar1 is independently selected from a substituted or unsubstituted aromatic ring, or a substituted or unsubstituted aromatic heterocycle;

[0032] X is selected from any of the following structures:

[0033]

[0034] Wherein, the dotted line represents a bond; R1 and R2 are independently selected from one or more of hydrogen, deuterium, tritium, halogen, cyano, nitro, hydroxyl, sulfhydryl, carboxyl, amino, carbonyl, ester, amide, phosphoryl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkylthio, substituted or unsubstituted silane; wherein, when X is When R2 can also be connected with Ar1 to form a ring; when X is When the bridging group is When R2 is connected to each other to form a ring or R2 is connected to Ar1.

[0035] In the polycyclic compound shown in formula (I), the spirocyclic structure formed by two Ar1 and the spirocyclic carbon atoms connected thereto and the bridging group X can limit the vibration of the polycyclic aromatic skeleton containing carbonyl and nitrogen atoms in the skeleton, increase the rigidity of the overall compound, reduce the vibration relaxation of the excited state molecular structure of the polycyclic compound, narrow the half-peak width of the electroluminescent spectrum to less than 30nm, and improve the fluorescence quantum efficiency, thereby facilitating the polycyclic compound to effectively show good application effects in light-emitting devices. In particular, the above-mentioned specific selection of X is more conducive to the improvement of the luminescence performance of the polycyclic compound.

[0036] In some embodiments of the present application, X comprises any structure shown in formula (i-1) to formula (i-23):

[0037]

[0038] The selection range of each R and R" is the same as that of R1.

[0039] In some other embodiments of the present application, the general formula represented by formula (I) is represented by any one of formula (II-1) to formula (II-5):

[0040]

[0041] In formula (II-1) to formula (II-5), the selection range of each R' is the same as that of R1.

[0042] The third aspect of the embodiment of the present application provides a polymer, wherein at least one repeating unit of the polymer is connected to the polycyclic compound described in the second aspect of the embodiment of the present application. The repeating unit of the polymer is connected to the aforementioned polycyclic compound of the present application, which also has good luminescent properties.

[0043] The fourth aspect of the embodiments of the present application provides a mixture, which includes the polycyclic compound described in the second aspect of the embodiments of the present application or the polymer described in the third aspect of the embodiments of the present application, and at least one functional material; wherein the functional material includes a hole injection material, a hole transport material, an electron blocking material, a light-emitting main material, a hole blocking material, an electron transport material or an electron injection material.

[0044] The fifth aspect of the embodiment of the present application also provides the use of the polycyclic compound described in the second aspect of the embodiment of the present application, the polymer described in the third aspect of the embodiment of the present application, and the mixture described in the fourth aspect of the embodiment of the present application in the functional layer of the electronic device. The polycyclic compound of the embodiment of the present application has good luminescence performance and can improve the performance of the electronic device.

[0045] The sixth aspect of the embodiment of the present application provides an electronic device, the electronic device includes a functional layer, the functional layer includes the polycyclic compound described in the second aspect of the embodiment of the present application, or the polymer described in the third aspect of the embodiment of the present application, or the mixture described in the fourth aspect of the embodiment of the present application. The polycyclic compound of the embodiment of the present application has good structural stability and luminescent properties, and can improve the device performance of the electronic device.

[0046] In the embodiment of the present application, the electronic device includes an organic electroluminescent device, an organic field effect transistor, an organic solar cell, a light-emitting electrochemical cell, a laser, an optical sensor or a lighting element.

[0047] In some embodiments of the present application, the functional layer includes one or more of a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer or an electron injection layer.

[0048] The seventh aspect of the embodiments of the present application provides an organic electroluminescent device, which includes a cathode and an anode, and a functional layer located between the cathode and the anode, wherein the functional layer includes at least one polycyclic compound described in the second aspect of the embodiments of the present application, or includes at least one polymer described in the third aspect of the embodiments of the present application, or includes the mixture described in the fourth aspect of the embodiments of the present application.

[0049] The polycyclic compounds of the embodiments of the present application have good luminescent properties and can improve the performance of organic electroluminescent devices, especially improve the device efficiency and reduce the half-peak width of the luminescent peak. Wherein, the functional layer includes one or more of a hole injection layer, a hole transport layer, an electron blocking layer, a luminescent layer, a hole blocking layer, an electron transport layer, and an electron injection layer.

[0050] The embodiment of the present application also provides a display module, which includes a cover plate, a back plate, and an organic electroluminescent device as described in the first aspect of the embodiment of the present application or as described in the seventh aspect of the embodiment of the present application, wherein the organic electroluminescent device is located between the back plate and the cover plate. The organic electroluminescent device using the aforementioned polycyclic compound in the embodiment of the present application has good device luminescence performance, thereby making the display effect of the display module using the device better.

[0051] The embodiment of the present application also provides an electronic device, the electronic device comprises a housing and the display module of the embodiment of the present application, the display module is connected to the housing. The electronic device adopts a display module with good display effect and has outstanding market competitiveness. BRIEF DESCRIPTION OF THE DRAWINGS

[0052] Figure 1 A schematic structural diagram of an organic electroluminescent device provided in an embodiment of the present application is shown.

[0053] Figure 2A , Figure 2B Two exemplary structural schematic diagrams of the display module provided in the embodiments of the present application are shown.

[0054] Figure 3A It is a schematic diagram of the three-dimensional structure of an electronic device provided in one embodiment of the present application.

[0055] Figure 3B yes Figure 3A A schematic diagram of the exploded three-dimensional structure of the electronic device shown.

[0056] Figure 4 This is the carbon NMR spectrum of compound 45 in Example 1 of the present application.

[0057] Figure 5 This is the infrared spectrum of compound 45 in Example 1 of the present application.

[0058] Figure 6 This is the fluorescence spectrum of compound 45 in Example 1 of the present application in toluene solution.

[0059] Figure 7 Schematic diagram of the structure of the organic electroluminescent device in device embodiment 1. DETAILED DESCRIPTION

[0060] The embodiments of the present application will be described below in conjunction with the drawings in the embodiments of the present application.

[0061] Organic light-emitting diodes (OLEDs) are commonly used as display components in electronic devices such as mobile phones and televisions. Figure 1 , Figure 1 A schematic diagram of the structure of an organic electroluminescent device 100 provided in an embodiment of the present application. Figure 1The organic electroluminescent device 100 shown includes an anode 10, a cathode 20, and a functional layer 30 located between the anode 10 and the cathode 20, and the functional layer 30 includes a light-emitting layer 301. In some embodiments, the functional layer 30 may also include a first carrier transport layer 302 located between the anode 10 and the light-emitting layer 301, and a second carrier transport layer 303 located between the cathode 20 and the light-emitting layer 301. The first carrier transport layer 302 may be one or more of a hole injection layer 3021, a hole transport layer 3022, and an electron blocking layer 3023 located between the anode 10 and the light-emitting layer 301. The hole injection layer 3021 is located between the anode 10 and the hole transport layer 3022, and the electron blocking layer 3023 is located between the light-emitting layer 301 and the hole transport layer 3022. The second carrier transport layer 303 may be one or more of an electron injection layer 3031, an electron transport layer 3032, and a hole blocking layer 3033 located between the cathode 20 and the light-emitting layer 301. The electron injection layer 3031 is located between the cathode 20 and the electron transport layer 3032, and the hole blocking layer 3033 is located between the cathode 20 and the hole transport layer 3022.

[0062] After a certain voltage is applied between the anode 10 and the cathode 20 of the organic electroluminescent device 100, the light-emitting material in the light-emitting layer 301 is excited by the recombination of holes and electrons in the layer to emit light, thereby giving the OLEDs device a light-emitting function. However, the half-peak width of the light-emitting peak of the light-emitting material in the light-emitting layer 301 of existing OLEDs is not narrow enough, and the half-peak width is basically above 40nm, which makes the OLEDs have low luminous efficiency and low luminous color purity, making it difficult to meet higher display standards. To this end, an embodiment of the present application provides a polycyclic compound that can be used for the light-emitting layer 301 of the above-mentioned OLEDs and its application. The half-peak width of the polycyclic compound is extremely narrow, so that the OLEDs using it can obtain higher device efficiency, etc.

[0063] Specifically, the above-mentioned light-emitting layer 301 includes the polycyclic compound provided in the embodiment of the present application, and the polycyclic compound includes a polycyclic aromatic skeleton and a spirocyclic structure, wherein the polycyclic aromatic skeleton is embedded with a nitrogen atom (N) and a carbonyl group (-C(=O)-), and the spirocyclic structure includes two Ar1s, spiro carbon atoms and a bridging group respectively connected to the two Ar1s, and the spiro carbon atoms are connected to the polycyclic aromatic skeleton, and the Ar1 is independently selected from substituted or unsubstituted aromatic rings, or substituted or unsubstituted aromatic heterocycles, and the half-peak width of the light-emitting peak of the polycyclic compound is less than or equal to 30nm.

[0064] Wherein, the above-mentioned spirocyclic structure may include the following structural formula: X represents the bridging group, and the dotted line represents the bond between the spiro ring structure and the polycyclic aromatic skeleton. The spiro ring structure includes a cyclic structure formed by two Ar1 and the spiro carbon atoms connected thereto and the bridging group. Each Ar1 may have the same or different structures.

[0065] In the above-mentioned polycyclic compound, the polycyclic aromatic skeleton containing N atoms and -C(=O)- in the skeleton can be used as the light-emitting unit of the compound, and the compound is a multi-resonance effect thermally activated delayed fluorescent material due to the presence of the compound, and the internal quantum efficiency is high; and the above-mentioned spiro ring structure is connected to the polycyclic aromatic skeleton through its spiro carbon atom, which can greatly enhance the rigidity of the overall molecule, and based on the steric effect of the spiro ring structure, the vibration of the light-emitting unit can be well suppressed, the vibration relaxation of the excited state molecular structure of the compound can be effectively reduced, and the spectrum broadening effect caused by the interaction between molecules can be suppressed, thereby further improving its fluorescence quantum yield, so that the half-peak width (FWHM, Full Width at Half Maxima) of its electroluminescence spectrum can be further narrowed, and the half-peak width can be below 30nm. Therefore, the above-mentioned polycyclic compound is used in the light-emitting layer of the light-emitting device, which can make the device have a higher luminous efficiency (that is, external quantum efficiency), a higher luminous color purity, and a good display effect.

[0066] The multiple resonance effect of the above-mentioned polycyclic compound is mainly caused by the intramolecular push-pull electron system formed by the polycyclic aromatic skeleton and the electron-rich atoms (i.e., N atoms) and electron-deficient atoms (oxygen in the carbonyl group) embedded in the polycyclic aromatic skeleton. The multiple resonance effect enables the HOMO (Highest Occupied Molecular Orbital) and LUMO (Lowest Unoccupied Molecular Orbital) of the above-mentioned compound to be separated to different atoms, and the energy level difference between the singlet state and the triplet state of the molecule (i.e., ΔE ST ) is smaller, and the thermally activated delayed fluorescence (TADF) effect is more obvious, that is, it promotes the conversion of triplet excitons into singlet excitons through antisystem crossing, thereby emitting fluorescence and improving the internal quantum efficiency. The above-mentioned term "half-maximum width" refers to the peak width corresponding to half the peak height of the luminescence peak in the electroluminescence spectrum of the material.

[0067] In the embodiment of the present application, the bridging group X is selected from any of the following structures:

[0068]

[0069] Wherein, the dotted line represents a bond; R2 is independently selected from one or more of a hydrogen atom, a deuterium atom, a tritium atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a sulfhydryl group, a carboxyl group, an amino group, a carbonyl group, an ester group, an amide group, a phosphoryl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, and a substituted or unsubstituted silane group, wherein when the bridging group is When R2 can also be connected with Ar1 to form a ring; when the bridging group is When the bridging group is When R2 is connected to each other to form a ring or R2 is connected to Ar1.

[0070] Specifically, when the bridging group X is When the bridging group X is When the bridging group is When R2 is connected to each other to form a ring or R2 and Ar1 are connected to form a ring.

[0071] The specific selection of the bridging group X can make the steric hindrance effect and rigidity enhancement effect of the spiro ring structure more obvious, which is conducive to the excellent luminescent properties of the polycyclic compound. In particular, when X is When R2 is connected to form a ring or R2 and Ar1 are connected to form a ring, or X is When R2 and Ar1 are connected to form a ring, the steric hindrance and rigidity effects of the spirocyclic structure are better, so that the half-peak width of the polycyclic compound is narrower and the external quantum efficiency of the light-emitting device using it is higher.

[0072] In the above polycyclic aromatic skeleton, the N atom may be located at the center of the skeleton, and -C(=O)- may be located at the edge of the skeleton. The N atom may form another cyclic structure with the spiro carbon atom of the above spiro ring structure. In the embodiment of the present application, the above polycyclic compound may have a general formula as shown in formula (I):

[0073]

[0074] In formula (I), each occurrence of Ar1 is independently selected from a substituted or unsubstituted aromatic ring, or a substituted or unsubstituted aromatic heterocycle;

[0075] X represents the above-mentioned bridging group, and X includes any of the following structures:

[0076]

[0077] Wherein, the dotted line represents a bond; R1 and R2 are independently selected from one or more of hydrogen, deuterium, tritium, halogen, cyano, nitro, hydroxyl, sulfhydryl, carboxyl, amino, carbonyl, ester, amide, phosphoryl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkylthio, substituted or unsubstituted silane; wherein, when X is When R2 can also be connected with Ar1 to form a ring; when X is When the bridging group is When R2 is connected to each other to form a ring or R2 is connected to Ar1.

[0078] The polycyclic compound shown in formula (I) is an improved TADF compound containing carbonyl-nitrogen-spirocyclic carbon, wherein the polycyclic aromatic skeleton containing carbonyl-nitrogen serves as the luminescent unit of the compound, the nitrogen atom is located at the center of the skeleton, and the carbonyl group is located at the edge of the skeleton; the spirocyclic structure shown in the dashed frame (including a ring structure composed of two rigid Ar1 rings and spirocyclic carbon atoms and a bridging group X connecting them) is bonded to the polycyclic aromatic skeleton, specifically, the spirocarbon atom is respectively bonded to the two aromatic rings below the carbonyl nitrogen in the polycyclic aromatic skeleton, which can further enhance the rigidity of the overall compound molecule, and based on the steric effect of the spirocyclic structure, the vibration of the luminescent unit can be suppressed, and its luminescent characteristics can be enhanced, so that the radiation transition rate of the compound molecule is further improved, and the fluorescence quantum efficiency is further improved, so that the half-peak width of its electroluminescence spectrum can be below 30nm. In particular, when X is When one of the above-mentioned spirocyclic structures is selected and R2 participates in the ring formation, the steric hindrance and rigidity effects of the above-mentioned spirocyclic structure are better, and the half-peak width of the compound of formula (I) is narrower.

[0079] Therefore, the use of the compound of formula (I) in a light-emitting device can make the device have a higher external quantum efficiency, a higher purity of luminescent color, and a good display effect. In addition, by regulating the multiple R1s in formula (I) and the substituents on the two Ar1s, the luminescent position, half-peak width, etc. and solubility of the compound of formula (I) can be further regulated to obtain more diverse structural compounds and expand the scope of application.

[0080] In the embodiment of the present application, the above-mentioned polycyclic compound is used as the doping material in the light-emitting layer 301, so that the maximum external quantum efficiency of the organic electroluminescent device 100 is above 18%. It is significantly higher than the efficiency of the device made of the existing multi-resonance TADF material. Specifically, the maximum external quantum efficiency of the device can be above 19%, or above 20%, or above 22%, or above 25%, etc.

[0081] In this application, the above-mentioned "hydrogen atom" is also referred to as "protium atom ( 1 H)". Deuterium atom is also called "heavy hydrogen" and its chemical symbol is 2 H or D. The chemical symbol for tritium atom is 3 H. The halogen atom may be fluorine (F), chlorine (Cl), bromine (Br), or iodine (I). The chemical formula of a cyano group may be -CN, and the chemical formula of a nitro group may be -NO2.

[0082] The amino group can be represented by -N(R a )2, each R a can be independently selected from one of hydrogen atoms, deuterium atoms, tritium atoms, substituted or unsubstituted hydrocarbon groups; wherein the substituted or unsubstituted hydrocarbon group includes one of substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl. a ) Two R in 2 a When each of the following is independently selected from a hydrogen atom, a deuterium atom, or a tritium atom, it may be referred to as a primary amino group, and R a It is more common to be a hydrogen atom. a When one of them is a hydrogen atom or an isotope atom thereof (such as a deuterium atom or a tritium atom), and the other is a substituted or unsubstituted hydrocarbon group as described above, the -N(R a )2 can be called a secondary amino group; when two N(R a ) Two R in 2 a When all are independently selected from the substituted or unsubstituted hydrocarbon groups mentioned above, the -N(R a )2 can be called a tertiary amino group.

[0083] The above hydroxyl group can be represented as -OR a , where R a is a hydrogen atom, a deuterium atom or a tritium atom. The chemical formula of a thiol group (i.e., a thiol group) can be represented by -SR a , where R a It is a hydrogen atom, a deuterium atom or a tritium atom. The chemical formula of the carboxyl group can be expressed as -COOR a , where R a A hydrogen atom, a deuterium atom or a tritium atom.

[0084] The above substituted or unsubstituted alkoxy group can be represented by -OR a , where R a is a substituted or unsubstituted hydrocarbon group as described above. The number of carbon atoms of the substituted or unsubstituted hydrocarbon group is described below in this application. a When it is a substituted or unsubstituted alkyl group, the -OR a Specifically, it is a substituted or unsubstituted alkoxy group; when R a When it is a substituted or unsubstituted cycloalkyl group, the -OR a Specifically, it is a substituted or unsubstituted cycloalkoxy group; when R a When it is a substituted or unsubstituted alkenyl group, the -OR a Specifically, it is a substituted or unsubstituted alkenyloxy group; when R a When it is a substituted or unsubstituted alkynyl group, the -OR a Specifically, it is a substituted or unsubstituted alkynyloxy group; when R a When it is a substituted or unsubstituted aryl group, the -OR a Specifically, it is a substituted or unsubstituted aryloxy group; when R a When it is a substituted or unsubstituted heteroaryl group, the -OR a Specifically, it is a substituted or unsubstituted heteroaryloxy group. In the embodiment of the present application, R a It is usually a substituted or unsubstituted alkyl group, or a substituted or substituted aryl group.

[0085] The above substituted or unsubstituted hydrocarbon thio group can be represented by -SR a , where R a is a substituted or unsubstituted hydrocarbon group as described above. The number of carbon atoms of the substituted or unsubstituted hydrocarbon thio group is described below in this application for the corresponding substituted or unsubstituted hydrocarbon group. a When -SR is a substituted or unsubstituted alkyl group, a Specifically, it is a substituted or unsubstituted alkylthio group; when R a When -SR is a substituted or unsubstituted cycloalkyl group, a Specifically, it is a substituted or unsubstituted cycloalkylthio group; when R a When -SR is a substituted or unsubstituted alkenyl group, a Specifically, it is a substituted or unsubstituted alkenylthio group; when R a When -SR is a substituted or unsubstituted alkynyl group, the a Specifically, it is a substituted or unsubstituted alkynylthio group; when R a When -SR is a substituted or unsubstituted aryl group, a Specifically, it is a substituted or unsubstituted arylthio group; when R a When -SR is a substituted or unsubstituted heteroaryl group, the aSpecifically, it is a substituted or unsubstituted heteroarylthio group. In the embodiment of the present application, R a Substituted or unsubstituted alkyl, substituted or substituted aryl are more common.

[0086] The carbonyl group (also called "acyl") can be represented by -C(=O)R a , where R a It can be a hydrogen atom, a deuterium atom, a tritium atom, a halogen atom, or a substituted or unsubstituted hydrocarbon group. a When it is a hydrogen atom or a deuterium atom or a tritium atom, the group is specifically a formyl group. a Substituted or unsubstituted hydrocarbon groups are more common, and substituted or unsubstituted alkyl groups are the most common.

[0087] The above ester group can be represented by -C(=O)OR a or -OC(=O)R a , where R a The ester group may be a substituted ester group or an unsubstituted ester group, specifically R a For example, when R a When it is an unsubstituted hydrocarbon group, the group -C(=O)OR a or -OC(=O)R a Specifically, it is an unsubstituted ester group; when R a When it is a substituted hydrocarbon group, the group -C(=O)OR a or -OC(=O)R a In some embodiments, R a Substituted or unsubstituted alkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl are more common.

[0088] The amide group can be represented by -C(=O)N(R a )2 or -N(H)C(=O)R a . Among them -N(H)C(=O)R a R a is a substituted or unsubstituted hydrocarbon group as above; -C(=O)N(R a ) The two R in 2 a can be independently selected from a hydrogen atom, a deuterium atom, a tritium atom, a substituted or unsubstituted hydrocarbon group, for example, one R a It can be a hydrogen atom, a deuterium atom or a tritium atom, and the other R a is a substituted or unsubstituted hydrocarbon group as above, or two R a Each of them is a substituted or unsubstituted hydrocarbon group as mentioned above.

[0089] The above-mentioned phosphoryl group (also known as phosphoryl group) can be represented by the above-mentioned group -P(=O)-R a , where R a It can be selected from a hydrogen atom, a deuterium atom, a tritium atom, a halogen atom, or a substituted or unsubstituted hydrocarbon group. a The substituted or unsubstituted hydrocarbon groups mentioned above are more common, and the substituted or unsubstituted aryl groups and substituted or unsubstituted heteroaryl groups are more common.

[0090] The above substituted or unsubstituted silyl group can be represented by -Si(R a )3, the three Rs here a Can be independently selected from one or more of hydrogen atoms, deuterium atoms, tritium atoms, halogen atoms, substituted or unsubstituted hydrocarbon groups mentioned above. In some embodiments, each R a may be independently selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. a )3 can specifically be trimethylsilyl, phenylsilyl, tert-butyldiphenylsilyl, etc.

[0091] In the present application, the substituted or unsubstituted alkyl mentioned above is a chain alkyl, which can be a straight chain alkyl or a branched chain alkyl. The substituted or unsubstituted alkyl can be a substituted or unsubstituted C1~C 20 In some embodiments, the substituted or unsubstituted alkyl group is a substituted or unsubstituted C1-C 10 Alkyl, substituted or unsubstituted C1-C6 alkyl, for example, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted isopropyl (i-Pr), substituted or unsubstituted isobutyl, substituted or unsubstituted tert-butyl (t-Bu), etc.

[0092] The substituted or unsubstituted cycloalkyl mentioned above may be a substituted or unsubstituted C3-C 20 In some embodiments, the substituted or unsubstituted cycloalkyl group is a substituted or unsubstituted C3-C 10 Specific examples of the cycloalkyl group include substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, and substituted or unsubstituted adamantyl.

[0093] The substituted or unsubstituted alkenyl group may be a substituted or unsubstituted C2 to C 20 Alkenyl; can be a chain alkenyl or a cyclic alkenyl. In some embodiments, the substituted or unsubstituted alkenyl can be a substituted or unsubstituted C2-C 10The chain alkenyl group and the substituted or unsubstituted C2-C6 chain alkenyl group may be, for example, a substituted or unsubstituted vinyl group, a substituted or unsubstituted propenyl group, a substituted or unsubstituted butenyl group, or the like.

[0094] The substituted or unsubstituted alkynyl group may be a substituted or unsubstituted C2 to C 20 Alkynyl; can be a chain alkynyl or a cyclic alkynyl. In some embodiments, the substituted or unsubstituted alkenyl can be a substituted or unsubstituted C2-C 10 Alkynyl, substituted or unsubstituted C2-C6 alkynyl; for example, substituted or unsubstituted ethynyl, substituted or unsubstituted propynyl, substituted or unsubstituted butynyl, etc.

[0095] The substituted or unsubstituted aryl group mentioned above may be a substituted or unsubstituted C6~C 30 Aryl. The aryl may be a monocyclic aryl or a polycyclic aryl; the polycyclic aryl may be a condensed ring type or a non-condensed ring type (such as biphenyl). In some embodiments, the substituted or unsubstituted aryl may be a substituted or unsubstituted C6~C 24 Aryl, further may be substituted or unsubstituted C6~C 20 Aryl, substituted or unsubstituted C6~C 12 Aryl, etc. For example, the substituted or unsubstituted aryl group may be specifically substituted or unsubstituted following groups: phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, fluorenyl, spirofluorenyl, binaphthyl, etc.

[0096] The substituted or unsubstituted heteroaryl mentioned above may be a substituted or unsubstituted C3-C 30 Heteroaryl. The heteroatom in the heteroaryl may be one or more selected from nitrogen atom (N), oxygen atom (O), sulfur atom (S), selenium atom (Se), boron atom (B), silicon atom (Si). In some embodiments, the substituted or unsubstituted heteroaryl may be a substituted or unsubstituted C5-C 30 Heteroaryl, further may be substituted or unsubstituted C5~C 20 Heteroaryl, substituted or unsubstituted C6~C 12 Heteroaryl, etc. For example, the substituted or unsubstituted heteroaryl group may be a substituted or unsubstituted pyridyl group, a substituted or unsubstituted quinolyl group, a substituted or unsubstituted furyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted dibenzothienyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted triazinyl group, etc.

[0097] In the embodiment of the present application, the substituents in the above-mentioned substituted alkyl, substituted cycloalkyl, substituted alkenyl, substituted alkynyl, substituted aryl, and substituted heteroaryl may include deuterium atoms, tritium atoms, halogen atoms, cyano, nitro, hydroxyl, sulfhydryl, carboxyl, amino, carbonyl, ester, amide, phosphoryl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted hydrocarbyl, substituted or unsubstituted hydrocarbylthio, substituted or unsubstituted silane. The introduction of substituents in each group can enrich the types of polycyclic compounds, obtain compound products with slightly different properties, and better realize applications. Among them, the chemical expressions of cyano, nitro, hydroxyl, thiol, carboxyl, amino, carbonyl, ester, amide, phosphoryl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkylthio, substituted or unsubstituted silyl, etc. can refer to the description in the previous text of this application. The number of carbon atoms of substituted or unsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryloxy, etc. can refer to the description in the previous text of this application.

[0098] Among them, the substituents in the above-mentioned substituted alkyl groups generally include one or more of deuterium atoms, tritium atoms, halogen atoms, cyano groups, nitro groups, hydroxyl groups, sulfhydryl groups, carboxyl groups, amino groups, carbonyl groups, ester groups, amide groups, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted aryl groups, substituted or unsubstituted heteroaryl groups, substituted or unsubstituted hydrocarbyl groups (such as alkoxy groups, aryloxy groups), substituted or unsubstituted hydrocarbylthio groups, substituted or unsubstituted silyl groups, and halogen atoms, substituted or unsubstituted hydrocarbyl groups, substituted or unsubstituted aryl groups, substituted or unsubstituted heteroaryl groups, etc. are more common. For example, the substituted alkyl groups can be deuterated methyl groups, tritiated methyl groups, trifluoromethyl groups (CF3), deuterated ethyl groups, tritiated ethyl groups, deuterated isopropyl groups, tritiated isopropyl groups, deuterated tert-butyl groups, tritiated tert-butyl groups, phenyl-substituted methyl groups, etc.

[0099] Among them, the substituents in the substituted cycloalkyl, substituted alkenyl, substituted alkynyl, substituted aryl, and substituted heteroaryl generally include one or more of deuterium atoms, tritium atoms, halogen atoms, cyano, nitro, hydroxyl, sulfhydryl, carboxyl, amino, carbonyl, ester, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted hydrocarbonoxy (such as alkoxy, aryloxy), substituted or unsubstituted silane, etc. Exemplarily, the substituted cycloalkyl can be deuterated cyclopentyl, tritiated cyclopentyl, methyl substituted cyclopentyl, etc. Exemplarily, the substituted alkenyl can be deuterated vinyl, tritiated vinyl, fluoro vinyl, fluoro propenyl, etc. Exemplarily, the substituted alkynyl can be deuterated ethynyl, tritiated ethynyl, fluoro ethynyl, fluoro propynyl, etc. Illustratively, the substituted aryl group may be deuterated phenyl, tritiated phenyl, methyl substituted phenyl, ethyl substituted phenyl, isopropyl substituted phenyl, tert-butyl substituted phenyl, methyl substituted biphenyl, tert-butyl substituted biphenyl, deuterated isopropyl substituted biphenyl, diphenyl ether (two benzene rings connected by an oxygen atom), etc. Illustratively, the substituted heteroaryl group may be a triazinyl substituted by diphenyl, a triazinyl substituted by di-p-tert-butylphenyl, a phenyl substituted pyridyl, a tert-butyl substituted dibenzofuranyl, etc.

[0100] In some embodiments of the present application, each occurrence of R1 and R2 is independently selected from hydrogen atoms, deuterium atoms, tritium atoms, halogen atoms, cyano groups (-CN), nitro groups (-NO2), -N(R a )2.-OR a 、-SR a 、-C(=O)R a 、-C(=O)OR a 、-C(=O)N(R a )2, -N(H)C(=O)R a 、-P(=O)-R a 、-Si(R a )3. Being R d Substituted or unsubstituted C1~C 20 Alkyl, R d Substituted or unsubstituted C3~C 20 Cycloalkyl, R d Substituted or unsubstituted C2~C 20 Alkenyl, R d Substituted or unsubstituted C2~C 20 Alkynyl, R d Substituted or unsubstituted C6~C 30 Aryl, R d Substituted or unsubstituted C3~C 30 One or more heteroaryl groups; wherein R aEach occurrence is independently selected from hydrogen atoms, deuterium atoms, tritium atoms, d Substituted or unsubstituted C1~C 20 Alkyl, R d Substituted or unsubstituted C3~C 20 Cycloalkyl, R d Substituted or unsubstituted C2~C 20 Alkenyl, R d Substituted or unsubstituted C2~C 20 Alkynyl, R d Substituted or unsubstituted C6~C 30 Aryl, R d Substituted or unsubstituted C3~C 30 One or more heteroaryl groups, R d The occurrences are independently selected from deuterium atoms, tritium atoms, halogen atoms, cyano groups, nitro groups, -N(R c )2.-OR c 、-SR c 、-C(=O)R c 、-C(=O)OR c 、-C(=O)N(R c )2, -N(H)C(=O)R c 、-P(=O)-R c 、-Si(R c )3. Being R b Substituted or unsubstituted C1~C 20 Alkyl, R b Substituted or unsubstituted C3~C 20 Cycloalkyl, R b Substituted or unsubstituted C2~C 20 Alkenyl, R b Substituted or unsubstituted C2~C 20 Alkynyl, R b Substituted or unsubstituted C6~C 30 Aryl, R b Substituted or unsubstituted C3~C 30 Heteroaryl; wherein R c Each occurrence is independently selected from hydrogen atoms, deuterium atoms, tritium atoms, b Substituted or unsubstituted C1~C 20 Alkyl, R b Substituted or unsubstituted C3~C 20 Cycloalkyl, R b Substituted or unsubstituted C2~C 20 Alkenyl, R b Substituted or unsubstituted C2~C 20 Alkynyl, R b Substituted or unsubstituted C6~C30 Aryl, R b Substituted or unsubstituted C3~C 30 One or more heteroaryl groups, R b Each occurrence is independently selected from a deuterium atom, a tritium atom, a halogen atom, a cyano group, a nitro group, an unsubstituted alkoxy group, an unsubstituted C1-C 20 Alkyl, unsubstituted C3~C 20 Cycloalkyl, unsubstituted C2~C 20 Alkenyl, unsubstituted C2~C 20 Alkynyl, unsubstituted C6~C 30 Aryl, C3~C 30 One or more heteroaryl groups.

[0101] In the present application, in the above formula (I), the three R1s may be the same or different groups, specifically, the R1s at all positions may be the same, or the R1s at all positions may be different, or the R1s at some positions may be the same. For example, in some embodiments, all R1s in formula (I) are hydrogen atoms, or are tert-butyl groups; or two R1s are trifluoromethyl groups, and the remaining R1s are tert-butyl groups; or two R1s are tert-butyl groups, and the remaining R1 is a triazine group substituted with diphenyl, or a phenyl group substituted with a tert-butyl group, or a triazine group substituted with a tert-butylphenyl group. In some embodiments of the present application, the three R1s in formula (I) are not simultaneously selected from one of hydrogen atoms, deuterium atoms, and tritium atoms. This is more conducive to the electroluminescence spectrum of the compound shown in formula (I) having a narrower half-peak width.

[0102] In some embodiments of the present application, the above R2 can be selected from substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, adjacent R2 can be connected to form a ring or R2 can be connected to Ar1 in formula (Ⅰ) to form a ring. This is more conducive to the above-mentioned spirocyclic structure to enhance the rigidity of the compound represented by formula (Ⅰ), and the steric hindrance effect of the spirocyclic structure is more obvious, which is more conducive to the improvement of the luminescent properties of the compound. Specifically, in some embodiments of the present application, when the bridging group X is -P(R2)- or -B(R2)-, R2 is selected from substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, and R2 can be connected to Ar1 to form a ring. When X is When X is When R2 is selected from substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, R2 are connected to form a ring or R2 and Ar1 are connected to form a ring, and further R2 are connected to form a ring.

[0103] Wherein, when adjacent R2 are connected to form a ring, the connecting bond between adjacent R2 may include one or more of a single bond, an ether bond (-O-), a thioether bond (-S-), -Se-, a carbonyl group (-C(=O)-), a sulfone group (-S(=O)2-), a triple bridging group (such as a substituted or unsubstituted imino group—-NH-, -NR"-), a quadruple bridging bond (-C(R") (R")-), etc. The selection range of R" is the same as that of the above R a When R2 and Ar1 are connected to form a ring, the atom connected to R2 (such as a B atom, a C atom, a P atom, etc.), the substituent in R2 (such as a substituent in a substituted aryl group / substituted heteroaryl group), and Ar1 may form a ring structure, but is not limited thereto.

[0104] In some embodiments of the present application, the above-mentioned bridging group X may include any group represented by formula (i-1) to formula (i-23):

[0105]

[0106]

[0107] Among them, the selection range of each R' and R" is the same as that of R1 mentioned above. That is, each R' and R" is independently selected from one or more of hydrogen atom, deuterium atom, tritium atom, halogen atom, cyano group, nitro group, hydroxyl group, sulfhydryl group, carboxyl group, amino group, carbonyl group, ester group, amide group, phosphoryl group, substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, substituted or unsubstituted hydrocarbonoxy group, substituted or unsubstituted hydrocarbonthio group, substituted or unsubstituted silane group.

[0108] X is a different general structure, which can enrich the types of the above polycyclic compounds and obtain a variety of different luminescent materials with good luminescent properties. When R2 is a substituted or unsubstituted phenyl group, and R2 does not participate in the ring formation. The presence of rigid R2 is beneficial to increase the rigidity and steric effect of the above-mentioned spirocyclic structure, and inhibit the vibration of the light-emitting unit. The above formulas (i-4) to (i-23) show that X is When such X is connected to the compound represented by the above formula (I), the steric hindrance effect and rigidity enhancement effect of the above spiro ring structure are more obvious, the half-peak width of the luminescence spectrum of the compound represented by the formula (I) is narrower, and the external quantum efficiency in the device is higher.

[0109] In some embodiments of the present application, each R' and each R" are independently selected from one or more of a hydrogen atom, a deuterium atom, a tritium atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heteroaryl group. Further, each R' and each R" are independently selected from one of a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or substituted aryl group, and a substituted or unsubstituted heteroaryl group. In this case, the synthesis of the above-mentioned polycyclic compound with the bridging group X is easier and the structure is more stable.

[0110] In some other embodiments of the present application, the general formula shown in the above formula (I) can be expressed as any one of formulas (II-1) to (II-5):

[0111]

[0112]

[0113] In formula (II-1) to formula (II-5), the selection range of each R' is the same as that of R1 described above.

[0114] In other words, in some other embodiments of the present application, the spiro ring structure includes any of the following structures:

[0115]

[0116] Among them, the structures shown in the above formulas (II-1) to (II-3) show the case where R2 is connected to Ar1 to form a ring when X is -B(R2)-; formulas (II-4) and (II-5) show the case where R2 is connected to Ar1 to form a ring when X is -C(R2)2-. The connection of R2 and Ar1 to form a ring is more conducive to ensuring that the steric hindrance effect of the above-mentioned spirocyclic structure is greater and the rigidity is stronger, and its effect on suppressing the vibration of the light-emitting unit and improving its light-emitting performance is more obvious, and thus the half-peak width of the light-emitting spectrum of the compound shown in formula (I) is narrower, and its external quantum efficiency in the device is higher.

[0117] In some embodiments, in formula (II-1) to formula (II-5), each R' is independently selected from one or more of hydrogen atom, deuterium atom, tritium atom, halogen atom, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl. In this case, the synthesis of the above-mentioned polycyclic compound with the bridging group X is easier and the structure is more stable.

[0118] In the present application, each Ar1 mentioned above is independently selected from a substituted or unsubstituted aromatic ring or a substituted or unsubstituted aromatic heterocycle. 30 The substituted or unsubstituted aromatic heterocyclic ring may be a substituted or unsubstituted C3~C 30 Aromatic heterocycle. The heteroatom in the aromatic heterocycle can be selected from one or more of nitrogen atom, oxygen atom, sulfur atom, selenium atom, boron atom and silicon atom. The substituents in the substituted aromatic ring and substituted aromatic heterocycle can refer to the description of the substituents in the substituted aryl and substituted heteroaryl in the previous text of this application.

[0119] In some embodiments, the substituted or unsubstituted aromatic ring may be a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted anthracene ring, a substituted or unsubstituted phenanthrene ring, a substituted or unsubstituted triphenylene ring, a fluoranthene ring, a substituted or unsubstituted pyrene ring, a substituted or unsubstituted biphenyl ring, a substituted or unsubstituted terphenyl ring, a substituted or unsubstituted binaphthyl ring, a substituted or unsubstituted fluorene ring, a substituted or unsubstituted spirofluorene ring, and the like.

[0120] Wherein, the substituted or unsubstituted aromatic heterocycle may be a substituted or unsubstituted C3-C 30 Aromatic heterocycle; specifically, for example, it can be a substituted or unsubstituted furan ring, a substituted or unsubstituted pyrrole ring, a substituted or unsubstituted thiophene ring, a substituted or unsubstituted pyridine ring, a substituted or unsubstituted quinoline ring, a substituted or unsubstituted furanopyrrole ring, a substituted or unsubstituted benzopyrrole ring, a substituted or unsubstituted benzofuran ring, a substituted or unsubstituted dibenzofuran ring, a substituted or unsubstituted benzothiophene ring, a substituted or unsubstituted dibenzothiophene ring, a substituted or unsubstituted carbazole ring, a substituted or unsubstituted triazine ring, or a substituted or unsubstituted xanthone ring.

[0121] In some embodiments of the present application, each occurrence of Ar1 is independently selected from any of the following structures:

[0122]

[0123]

[0124] wherein Z is independently selected at each occurrence from a nitrogen atom or C(R 1 ), Y is independently selected from O, S, Se, B, sulfoxide (-S(=O)-), sulfone (-S(=O)2-), carbonyl (-C(=O)-), N(R 2 )、C(R 2 )(R 2 )、Si(R 2 )(R 2 ), wherein each R1 , R 2 The selection range is the same as that of R1 above.

[0125] In some embodiments of the present application, each R 1 , R 2 Each occurrence is independently selected from one or more of a hydrogen atom, a deuterium atom, a tritium atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, and a substituted or unsubstituted heteroaryloxy group.

[0126] Among them, formula (d) and formula (e), formula (f) and formula (g), formula (j) and formula (k), formula (l) and formula (m), formula (n), formula (o) and formula (p), formula (q), formula (r) and formula (s), and formula (v), formula (w) and formula (x) are homologous structures, except that the positions at which Ar1 is connected to the spiro carbon atom and X are different.

[0127] Wherein, the structure represented by formula (h) is C(R 1 ) when it represents a substituted or unsubstituted benzene ring. In the unsubstituted benzene ring, the four Zs are all C(H). In the substituted benzene ring, the four R 2 At least one of them is not a hydrogen atom. For example, in some specific embodiments, the substituent in the substituted benzene ring is a substituted or unsubstituted phenyl. In this case, the substituted benzene ring is specifically a biphenyl ring, and the four R 2 In another specific embodiment, the substituent in the substituted benzene ring is a substituted or unsubstituted heteroaryl group, such as carbazolyl

[0128] Wherein, the structure represented by formula (i) is C(R 1 ) in the form of, it may represent a substituted or unsubstituted naphthalene ring. The structure represented by formula (l) or formula (m) is C(R 1 ) in the form of, it may represent a substituted or unsubstituted triphenylene ring. The structures represented by formula (n), formula (o), and formula (p) are all C(R 1 ) in the form of, it may represent a substituted or unsubstituted fluoranthene ring. The structures represented by formula (q), formula (r) and formula (s) are all C(R 1 ) in the form of, it may represent a substituted or unsubstituted phenanthrene ring. The structures represented by formula (t) and formula (u) are C(R 1 ) in the form of , it may represent a substituted or unsubstituted pyrene ring.

[0129] In some embodiments of the present application, the polycyclic compound represented by formula (I) can be specifically selected from any one of the following compounds:

[0130]

[0131]

[0132]

[0133]

[0134] It should be noted that the above compounds 1 to 76 are only specific examples, and it should not be understood that the polycyclic compounds represented by the above formula (I) can only be selected from these.

[0135] The above-mentioned polycyclic compounds of the embodiments of the present application can be prepared by various chemically feasible methods. The above-mentioned polycyclic compounds of the present application have high structural stability, and the half-peak width of the electroluminescence spectrum is narrow, reaching less than 30nm. The polycyclic compound has a high fluorescence quantum yield and can be used in various electronic devices with light-emitting, display, lighting and other functions to improve the luminous efficiency, luminous color purity and device life of the device. For example, when the above-mentioned polycyclic compound is used as a doping material in the light-emitting layer 301 of OLEDs, the half-peak width of the electroluminescence spectrum presented by the light-emitting layer can be less than 30nm, and the maximum external quantum efficiency of OLEDs is more than 18%.

[0136] The above-mentioned polycyclic compound of the embodiment of the present application can be specifically used as a doping material (also referred to as a "guest material") in the light-emitting layer 301. At this time, the light-emitting layer 301 includes a light-emitting main material and a doping material, and the doping material includes at least one polycyclic compound mentioned above in the embodiment of the present application. The main material performs an energy transfer function. The polycyclic compound mentioned above in the present application is used as the doping material of the light-emitting layer 301. It can be excited by the main material and sensitized and emit light, thereby improving the luminous efficiency of the device; the half-peak width of the polycyclic compound itself is narrow, which is more conducive to improving the luminous efficiency of the device, as well as the purity of the luminous color, so that the device can meet higher display standards.

[0137] It should be noted that when the doping material of the light-emitting layer 301 includes only the above-mentioned polycyclic compound of the embodiment of the present application, the half-peak width of the electroluminescent peak of the light-emitting layer 301 is the half-peak width of the above-mentioned polycyclic compound. Of course, in other embodiments of the present application, the doping material of the light-emitting layer 301 may also include one or more of the above-mentioned polycyclic compounds of the embodiment of the present application and other doping materials at the same time. Other doping materials may be various doping materials available in the art, which can be selected according to actual needs. In addition, the light-emitting main material of the light-emitting layer 301 may include one or more, and the main material may be various main materials available in the art, which can be selected according to actual needs.

[0138] In the embodiment of the present application, in the light-emitting layer 301, the mass proportion of the above-mentioned polycyclic compound can be 0.3wt%-30wt%. When the mass proportion of the polycyclic compound is within this range, the maximum external quantum efficiency of the organic electroluminescent device 100 can be above 18%, and further can be above 19%, above 20%, above 25%, etc. In some embodiments, the mass proportion of the above-mentioned polycyclic compound is 0.3wt%-10.0wt%.

[0139] In some embodiments of the present application, based on the total mass of the luminescent host material and the doping material, the mass proportion of the doping material is 0.3-30.0wt%, and the mass proportion of the luminescent host material is 70.0-99.7wt%. In this case, the material in the luminescent layer 301 can be composed only of the luminescent host material and the doping material. The host material, as the main material of the luminescent layer material, has a high mass proportion, and is mainly responsible for transferring energy; the doping material is mixed with the luminescent host material in an appropriate proportion, which is conducive to the high energy transfer efficiency between the two, thereby making the device more efficient in luminescence and also conducive to a narrow half-peak width. Specifically, the mass proportion of the doping material can be 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, etc. The mass percentage of the luminescent host material may be 75%, 80%, 85%, 90%, 93%, 95%, 98%, 99%, 99.5%, etc. In some embodiments, the mass percentage of the polycyclic compound in the luminescent layer 301 is 0.3-30.0 wt%.

[0140] In some other embodiments of the present application, the light-emitting layer 301 also includes a sensitizer. That is, the light-emitting layer 301 includes a light-emitting main material, a doping material and a sensitizer. The presence of the sensitizer can promote the transfer of energy from the light-emitting main material to the guest material (i.e., the doping material), promote the luminescence of the doping material, and improve the luminescence efficiency of the device. Among them, based on the total mass of the light-emitting main material, the doping material and the sensitizer, the mass proportion of the doping material is 0.3-10.0wt%, the mass proportion of the light-emitting main material is 65.0-94.7wt%, and the weight percentage of the sensitizer is 5-25wt%. The appropriate content of the light-emitting main material, the doping material and the sensitizer is conducive to the high energy transfer efficiency between the three of them, so that the luminescence potential of the doping material can be fully utilized, and the luminescence efficiency of the device is higher. Specifically, the mass proportion of the doping material can be 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc.; the mass proportion of the luminescent host material can be 68%, 70%, 80%, 85%, 90%, 92%, 94%, 94.5%, etc.; the mass proportion of the sensitizer can be 5%, 6%, 8%, 10%, 15%, 20%, 22%, 24%, etc. In some embodiments, the mass proportion of the above-mentioned polycyclic compound in the light-emitting layer 301 is 0.3-10.0wt%.

[0141] The present application also provides a polymer, the repeating unit of which is connected to the polycyclic compound shown in the above formula (I) provided in the present application. The above polycyclic compound is specifically connected to the side chain of the repeating unit of the polymer. Among them, one or more repeating units of the polymer may be connected to the above polycyclic compound of the present application embodiment.

[0142] In the embodiment of the present application, the weight average molecular weight of the above polymer may be in the range of 50,000-500,000; further in the range of 100,000-400,000, or in the range of 100,000-300,000. The polymer has a suitable molecular weight so that it has suitable mechanical and optical properties.

[0143] The present application also provides a mixture, which includes the above-mentioned polycyclic compound provided in the embodiment of the present application, or the above-mentioned polymer, and at least one functional material. Each functional material can be selected according to the functional layer in which the mixture is to be used. Exemplarily, the functional material may include a hole injection material, a hole transport material, an electron blocking material, a luminescent host material, a hole blocking material, an electron transport material or an electron injection material, but is not limited thereto. Accordingly, the mixture can be used to make a hole injection layer, a hole transport layer, an electron blocking layer, a luminescent layer, a hole blocking layer, an electron transport layer or an electron injection layer, etc.

[0144] In some embodiments of the present application, the mixture includes the above-mentioned polycyclic compound or polymer of the embodiment of the present application and a luminescent host material. The mixture can be used to make a luminescent layer of a luminescent device. The luminescent performance of the luminescent layer is relatively excellent.

[0145] The embodiments of the present application provide the use of the above-mentioned polycyclic compound, the above-mentioned polymer, and the above-mentioned mixture in electronic devices. Among them, the above-mentioned polycyclic compound, or the above-mentioned polymer, or the above-mentioned mixture can be used as a material for the functional layer of the electronic device. Among them, the electronic device includes but is not limited to an organic electroluminescent device, an organic field effect transistor (especially an organic light-emitting field effect transistor), an organic solar cell, a light-emitting electrochemical cell (such as an organic light-emitting cell), a laser, an optical sensor or a lighting element, etc.

[0146] In the embodiment of the present application, the functional layer may include one or more of 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, but is not limited thereto. For example, the above-mentioned polycyclic compound can be used in an organic electroluminescent device, specifically as a material for its light-emitting layer, which can improve the luminous efficiency and luminescent color purity of the device.

[0147] Correspondingly, an embodiment of the present application further provides an electronic device, which has a functional layer, and the functional layer includes the above-mentioned polycyclic compound of the embodiment of the present application, or includes the above-mentioned polymer of the embodiment of the present application, or includes the above-mentioned mixture of the embodiment of the present application.

[0148] In the embodiment of the present application, the electronic device includes but is not limited to an organic electroluminescent device, an organic field effect transistor, an organic solar cell, a light-emitting electrochemical cell, a laser, an optical sensor or a lighting element.

[0149] In some embodiments of the present application, the electronic device is an organic electroluminescent device. The organic electroluminescent device includes a cathode and an anode, and a functional layer located between the cathode and the anode, wherein the functional layer includes at least one polycyclic compound as shown in formula (I), or includes at least one of the aforementioned polymers, or includes the aforementioned mixture, and preferably includes the aforementioned polycyclic compound. Among them, there may be one or more functional layers. For example, the functional layer of the organic electroluminescent device may include one or more of 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.

[0150] In some cases, each functional layer includes other functional materials in addition to the above-mentioned polycyclic compound or the above-mentioned polymer of the embodiment of the present application; other functional materials may include hole injection materials, hole transport materials, electron blocking materials, luminescent host materials, hole blocking materials, electron transport materials or electron injection materials. For example, when the functional layer is specifically a luminescent layer, the other functional materials in the luminescent layer may include a luminescent host material; or include a luminescent host material and a sensitizer.

[0151] The foregoing Figure 1 A schematic diagram of the structure of an organic electroluminescent device (OLEDs) is shown. Figure 1 The organic electroluminescent device 100 shown includes an anode 10, a cathode 20 and a functional layer 30 located between the anode 10 and the cathode 20. In some embodiments of the present application, the functional layer 30 includes a light-emitting layer 301, and the light-emitting layer 301 includes the above-mentioned polycyclic compound, polymer, or mixture provided in the embodiments of the present application.

[0152] As described above, in the embodiment of the present application, the light-emitting layer 301 includes a light-emitting main material and a doping material, wherein the doping material includes at least one of the polycyclic compounds or polymers described above in the embodiment of the present application.

[0153] In some embodiments of the present application, the material in the light-emitting layer 301 is composed of a light-emitting main material and a doping material. Among them, based on the total mass of the light-emitting layer 301, the mass proportion of the doping material is 0.3-30.0wt%, and the mass proportion of the light-emitting main material is 70.0-99.7wt%. The doping material is mixed with the light-emitting main material in an appropriate proportion, which is conducive to a high energy transfer efficiency between the two, thereby making the device more efficient. The specific enumerated values ​​within each mass proportion range can be found in the previous description of this application.

[0154] In some other embodiments of the present application, the material in the light-emitting layer 301 is composed of a light-emitting main material, a doping material and a sensitizer. Wherein, based on the total mass of the light-emitting layer 301, the mass proportion of the doping material is 0.3-10.0wt%, the mass proportion of the light-emitting main material is 65.0-94.7wt%, and the weight percentage of the sensitizer is 5-25wt%. The introduction of a proper amount of sensitizer as an energy transfer link between an appropriate amount of light-emitting main material and a doping material is conducive to a high energy transfer efficiency between the three, so that the luminous potential of the doping material can be fully utilized, and the luminous efficiency of the device is higher. The specific enumerated values ​​within each mass percentage range can be found in the previous description of this application.

[0155] In the foregoing text of the present application, the light-emitting layer 301 includes the above-mentioned polycyclic compound in the embodiment of the present application. However, it is understandable that other functional layers may also include the polycyclic compound. In some embodiments, for example Figure 1 As shown, the organic electroluminescent device 100 includes an anode 10, a hole injection layer 3021, a hole transport layer 3022, an electron blocking layer 3023, a light-emitting layer 301, a hole blocking layer 3033, an electron transport layer 3032, and an electron injection layer 3031, which are arranged in sequence. Among them, in addition to the light-emitting layer 301 including the above-mentioned polycyclic compound or polymer of the embodiment of the present application, one or more of the hole injection layer 3021, the hole transport layer 3022, the electron blocking layer 3023, the hole blocking layer 3033, the electron transport layer 3032, or the electron injection layer 3031 may include the above-mentioned polycyclic compound or the above-mentioned polymer of the embodiment of the present application. For example, when the above-mentioned polycyclic compound is used in the hole injection layer 3021, it can be used as a hole injection material, and other hole injection materials can also be included in the layer. When the above-mentioned polycyclic compound is used in the hole transport layer 3022, it can be used as a hole transport material, and other hole transport materials can also be included in the layer. When the above-mentioned polycyclic compound is used in the electron blocking layer 3023, it can be used as an electron blocking material, and other electron blocking materials can also be included in the layer. When the above-mentioned polycyclic compound is used in the hole blocking layer 3033, it can be used as a hole blocking material, and other hole blocking materials can also be included in the layer. When the above-mentioned polycyclic compound is used in the electron transport layer 3032, it can be used as an electron transport layer material, and other electron transport materials can also be included in the layer. When the above-mentioned polycyclic compound is used in the electron injection layer 3031, it can be used as an electron injection material, and other electron injection materials can also be included in the layer.

[0156] It should be noted that not all layers of the functional layer 30 are required, but the light-emitting layer 301 is required. For example, the functional layer 30 may also include, in sequence, a stacked structure of "light-emitting layer 301 / electron transport layer 3032" along the direction from the anode 10 to the cathode 20, or a stacked structure of "light-emitting layer 301 / electron injection layer 3031", or a stacked structure of "hole injection layer 3021 / light-emitting layer 301 / electron transport layer 3032", or a stacked structure of "hole injection layer 3021 / light-emitting layer 301 / electron injection layer 3031", or a stacked structure of "hole transport layer 3022 / light-emitting layer 301 / electron transport layer 3032", or a stacked structure of "hole injection layer 3021 / light-emitting layer 301 / electron injection layer 3031". The stacked structure includes "hole injection layer 3021 / hole transport layer 3022 / light-emitting layer 301 / electron transport layer 3032", or the stacked structure includes "hole injection layer 3021 / hole transport layer 3022 or electron blocking layer 3023 / light-emitting layer 301 / hole blocking layer 3033 or electron transport layer 3032 / electron injection layer 3031", or the stacked structure includes "hole injection layer 3021 / hole transport layer 3022 / electron blocking layer 3023 / light-emitting layer 301 / hole blocking layer 3033 or electron transport layer 3032 / electron injection layer 3031", etc. Wherein " / " indicates the boundary between each layer. In the present application, there is no specific limitation on the thickness of the above layers, and those skilled in the art can determine it according to actual needs. The materials of the above layers are conventionally selected in the field and are not specifically limited in the present application.

[0157] In the present application, the constituent materials of the anode 10 and the cathode 20 are conductive materials, which can be independently selected from conductive metals, conductive metal oxides, conductive polymers, etc. Among them, the conductive metal can include one or more of metal elements such as magnesium (Mg), aluminum (Al), gold (Au), silver (Ag), platinum (Pt), target (Pd) and their alloys; the conductive metal oxide includes but is not limited to one or more of indium tin oxide (ITO), indium zinc oxide (IZO), aluminum-doped zinc oxide (AZO), fluorine-doped tin dioxide (FTO), phosphorus-doped tin dioxide (PTO), etc.; the conductive polymer includes but is not limited to polythiophene, polypyrrole, polyaniline, etc.

[0158] In some embodiments, the organic electroluminescent device 100 may further include a substrate 40 (eg Figure 1 The substrate 40 may be located on the side of the anode 10 away from the functional layer 30 (eg Figure 1As shown), in this case, the organic electroluminescent device 100 is a bottom-emitting device. The substrate 40 may also be located on the side of the cathode 20 away from the functional layer 30. In this case, the organic electroluminescent device 100 is a top-emitting device, and the top-emitting device includes a cathode 20, a functional layer 30, and an anode 10 sequentially arranged on the substrate 40. In some embodiments, the substrate 40 is glass or plastic that is transparent to light. The shape of the substrate 40 can be determined according to the specific application scenario, for example, it can be formed into a plate, a film, or a sheet.

[0159] In the present application, there is no particular restriction on the preparation process of each layer of the anode 10, cathode 20 and functional layer 30, and they can be prepared by physical vapor deposition, chemical vapor deposition or coating. Among them, the physical vapor deposition method can include one or more of vacuum evaporation (such as resistance evaporation source evaporation method, electron beam evaporation source evaporation method, pulsed laser deposition method, etc.), sputtering method (such as magnetron sputtering method), etc.; the coating method can include one or more of solution spin coating, dip coating, blade coating, spray coating, roller coating, inkjet printing, screen printing, etc. Figure 1 Taking the organic electroluminescent device shown as an example, the anode 10 may be first formed on the substrate 40 , and then the functional layer 30 including the light-emitting layer 301 may be sequentially formed on the anode 10 , and then the cathode 20 may be formed on the functional layer 30 .

[0160] The electronic devices provided in the embodiments of the present application, especially the organic electroluminescent devices, can be used in display modules, lighting equipment, etc. Among them, the lighting device can include automobile taillights, automobile headlights, automobile fog lights, indoor lighting devices (including commercial or household lighting, such as table lamps, ceiling lamps, etc.), outdoor lighting devices (such as street lamps), or backlight sources of display devices, etc.

[0161] The embodiment of the present application further provides a display module, which includes the electronic device described above in the embodiment of the present application, and specifically may include the organic electroluminescent device described above in the embodiment of the present application.

[0162] See also Figure 2A The embodiment of the present application provides a display module 200, which includes the electronic device described above in the embodiment of the present application, and specifically includes the organic electroluminescent device 100 described above. The display module 200 may include a cover plate 21, a back plate 22, and the organic electroluminescent device 100 described above in the embodiment of the present application, and the organic electroluminescent device 100 is located between the cover plate 21 and the back plate 22.

[0163] The cover plate 21 can cover the organic electroluminescent device 100 to protect it. The cover plate 21 can be a glass cover plate, a transparent plastic cover plate or a composite material cover plate (such as a composite material of glass and plastic). The back plate 22 can support the organic electroluminescent device 100. The back plate 22 can be made of titanium alloy, copper alloy, or stainless steel. The display module 200 can be used to display images, etc., specifically by emitting light from the organic electroluminescent device 100 to display images, etc.

[0164] In some embodiments, the display module 200 may further include a polarizer 23 (eg, Figure 2B As shown in the figure), the polarizer 23 is located between the cover plate 21 and the organic electroluminescent device 100. At this time, the display module 200 includes the cover plate 21, the polarizer 23, the organic electroluminescent device 100 and the back plate 22 which are stacked in sequence. Among them, the polarizer 23 can be used to improve the display contrast and reduce the influence of the reflection of the OLED device on the display contrast when the external light is irradiated on the OLED device, especially when the external light is very bright, the content displayed by the display module 200 can also be seen clearly. In addition, an adhesive layer (not shown in the figure) can be provided between the cover plate 21 and the polarizer 23, between the polarizer 23 and the organic electroluminescent device 100, and between the organic electroluminescent device 100 and the back plate 22 to achieve a stable connection between them, and specifically, a pressure-sensitive adhesive or an optical adhesive can be used. In addition, the display module 200 may further include a touch device (not shown), and the location of the touch device is not limited, for example, it may be integrated on the cover plate 21, or integrated on the polarizer 23, or arranged in or below the light-emitting layer 301 of the OLED device, etc. The touch device may be used to implement the touch function of the display module 200, and may specifically receive information input on the display module 200, and then the display module 200 responds to it, outputs display content, etc.

[0165] The display module 200 can be applied to electronic devices such as mobile phones, tablet computers, etc. The electronic device can include one or more display modules 200 .

[0166] The present application also provides an electronic device using the organic electroluminescent device. Figure 3A and Figure 3B , Figure 3A is a three-dimensional structural diagram of an electronic device 300 provided in an embodiment of the present application, Figure 3B yes Figure 3AThe three-dimensional structure of the electronic device 300 is shown as an exploded schematic diagram. The electronic device 300 can be a mobile phone, a tablet computer, a laptop computer, a personal computer, a wearable device (such as a smart watch, a smart bracelet, etc.), an augmented reality (AR) device, a virtual reality (VR) device, a television, a digital camera, a camcorder, a video player, a video recorder, a vehicle-mounted device, and other electronic products, which are not limited in this application. This embodiment is described by taking the electronic device 300 as a mobile phone as an example.

[0167] The electronic device 300 may include a housing 31 and a display module 200, and the display module 200 is connected to the housing 31. Specifically, the display module 200 is mounted on the housing 31, and the display module 200 and the housing 31 jointly enclose a receiving space. The electronic device 300 also includes a circuit board assembly 33, which is fixedly received in the receiving space enclosed by the display module 200 and the housing 31. The circuit board assembly 33 is electrically connected to the display module 200. In some embodiments, the electronic device 300 also includes a battery 34, which is fixedly received in the receiving space and electrically connected to the circuit board assembly 33. The battery 34 is used to power various electronic devices in the electronic device 300 (for example, the display module 200, the processor in the circuit board assembly 33 and other electronic devices).

[0168] The display module 200 is used to display a graphical user interface such as an image, information, and menu. In some embodiments, the display module 200 may also integrate a touch function, that is, the display module 200 is a touch display module. As described above, the display module 200 may include a touch device, and the setting position of the touch device is not limited, and it may be electrically connected to the circuit board assembly 33. Among them, the touch device is used to receive information input by the user on the display module 200, and output a touch signal to the circuit board assembly 33. After receiving the touch signal, the circuit board assembly 33 controls the display module 200 to respond to it and output the display content according to the touch signal.

[0169] In some embodiments, the housing 31 includes a middle frame 310 and a back cover 320. One side of the middle frame 310 is connected to the back cover 320, and the middle frame 310 and the back cover 320 together enclose a first space. The first space can be used to accommodate electronic components such as a circuit board assembly 33, a battery 34, a camera, and a sound device. Among them, the back cover 320 can be made of materials including but not limited to metal, glass, plastic or ceramic, and this application does not specifically limit this.

[0170] In some embodiments, the middle frame 310 includes a metal middle plate 311 and a frame, and the frame is arranged along the periphery of the metal middle plate 311. Exemplarily, the frame may include a top frame 312 and a bottom frame 313 that are arranged opposite to each other, and a first side frame 314 and a second side frame 315 that are located between the top frame 312 and the bottom frame 313 and are arranged opposite to each other. Among them, the connection method between each frame (top frame 312, bottom frame 313, first side frame 314 and second side frame 315) and the metal middle plate 311 includes but is not limited to welding, clamping and integral injection molding. The metal middle plate 311 can be made of materials including but not limited to aluminum, aluminum alloy, stainless steel and the like. Each frame can be made of materials including but not limited to metal, glass, plastic or ceramic and the like.

[0171] The display module 200 can be specifically connected to the side of the middle frame 310 away from the back cover 320, that is, the middle frame 310 is arranged between the display module 200 and the back cover 320. Specifically, the display module 200 is connected to the side of the frame of the middle frame 310 away from the back cover 320, and the middle frame 310 supports the display module 200. The display module 200 and the middle frame 310 jointly enclose a second space, and the second space and the first space jointly enclosed by the middle frame 310 and the back cover 320 jointly constitute the aforementioned receiving space. In some other embodiments, the housing 31 includes the back cover 320, and the outer periphery of the back cover 320 is provided with a frame. The display module 200 is connected to one side of the frame of the back cover 320, and the closed space jointly enclosed by the back cover 320 is also the receiving space.

[0172] In some embodiments, the circuit board assembly 33 can be specifically accommodated in the first space enclosed by the middle frame 310 and the back cover 320. The circuit board assembly 33 is fixed on the surface of the metal middle plate 311 facing the back cover 320; or fixed on the surface of the back cover 320 facing the middle frame 310. In other embodiments, the circuit board assembly 33 can also be accommodated in the closed space enclosed by the display module 200 and the middle frame 310.

[0173] It is to be understood that the structure illustrated in the embodiment of the present application does not constitute a specific limitation on the electronic device 300. In other embodiments of the present application, the electronic device 300 may include more or fewer components than shown in the figure, or combine certain components, or separate certain components, or arrange the components differently. For example, the electronic device 300 may also include devices such as a microphone, a speaker, a camera (such as a front camera and a rear camera), and a flash.

[0174] The embodiments of the present application are further described below with reference to a plurality of embodiments.

[0175] Example 1

[0176] A polycyclic compound, the structure of which is shown in the aforementioned reference numeral 45, and the synthesis route of the compound is as follows:

[0177]

[0178] The preparation of the above-mentioned polycyclic compound 45 specifically includes:

[0179] 1) Synthesis of compound B3:

[0180] Under nitrogen protection, compound B1 (3.0 g), compound B2 (2.87 g), copper powder (0.035 g), cuprous iodide (CuI, 0.15 g), 2,2,6,6-tetramethylheptane-3,5-dione (abbreviated as ( t BuCO)2OCH2, 0.15g), potassium carbonate (molecular formula K2CO3, 1.65g) and 50mL of n-butyl ether (abbreviated as n-Bu2O) were added to a 100mL double-necked flask with a stirrer, the reaction material system was stirred, and heated to 160°C for 3 days. After cooling to room temperature, the filtrate was filtered off, the filter cake was washed with dichloromethane, and the organic phases were combined. The organic phase was distilled under reduced pressure to remove the solvent to obtain a crude product. The crude product was purified by a silica gel column, and the eluent was dichloromethane and petroleum ether in a volume ratio of 2:3. Finally, 4.3g of compound B3 was obtained with a yield of 88.6%. Among them, the mass spectrometry test results of compound B3 were measured as follows: MS (EI) m / z: 608.6 [M + ], and according to the molecular formula C 34 H 42 The calculated values ​​of BrNO4 are basically consistent.

[0181] 2) Synthesis of compound B4:

[0182] The above-mentioned compound B3 (3.5g), sodium hydroxide (chemical formula is NaOH, 4.6g), 100mL water and 100mL ethanol (ie, EtOH) are added to a 500mL double-necked bottle with a stirrer, and the reaction material system is stirred and heated to 100°C for reflux reaction for 2 days. After cooling to room temperature, the obtained reaction solution is concentrated by vacuum distillation to remove most of the ethanol, and the pH of the obtained concentrated reaction solution is adjusted to strong acidity with concentrated hydrochloric acid to precipitate the product. The filtrate is then removed by vacuum filtration to obtain a crude product. After the crude product is dried in an oven, 2.9g of compound B4 is finally obtained with a yield of 86.9%. Among them, the mass spectrometry test results of compound B4 are: MS (EI) m / z: 580.6 [M + ], and according to the molecular formula C 32 H 38 The calculated values ​​of BrNO4 are basically consistent.

[0183] 3) Synthesis of compound B5:

[0184] Compound B4 (2.5 g) and 60 mL of dichloromethane were added to a 250 mL double-necked flask with a stirrer. After stirring and heating to 50 °C, N, N-dimethylformamide (DMF, two drops, catalytic amount) and oxalyl chloride (chemical formula C2Cl2O2, 0.9 mL) were added dropwise in sequence. The reaction was continued for 1 h. After the system was clarified, anhydrous tin tetrachloride (chemical formula SnCl4, 1.2 mL) was added dropwise, and then the reaction was continued for another 5 h. After the reaction was completed, the obtained reaction solution was poured into an aqueous sodium hydroxide solution, and extracted with dichloromethane for several times and the organic phases were combined. The organic phase was distilled under reduced pressure to remove the solvent to obtain a crude product. The crude product was purified by a silica gel column, wherein the eluent was dichloromethane and petroleum ether in a volume ratio of 4:1, and finally 2.0 g of compound B5 was obtained with a yield of 85%. Among them, the mass spectrometry test results of compound B5 were: MS (EI) m / z: 544.5 [M + ], and according to the molecular formula C 32 H 34 The calculated values ​​of BrNO2 are basically consistent.

[0185] 4) Synthesis of compound B6:

[0186] Under nitrogen protection, compound B5 (1.8 g) was added to a 250 mL double-necked flask with a stirrer, and 200 mL of anhydrous and oxygen-free tetrahydrofuran (abbreviated as THF) and 13 mL of 1 M tetrahydrofuran·borane complex (chemical formula: BH3˙THF) were added in sequence. The reaction material system was stirred and heated to 70°C for 4 h. After cooling to room temperature, a small amount of saturated brine was slowly added dropwise to quench the reaction. Subsequently, 50 mL of sodium hydroxide aqueous solution was added, and then the organic phase was separated by a separatory funnel. After the aqueous phase was extracted with anhydrous ether, the organic phases were combined. The organic phase was distilled under reduced pressure to remove the solvent to obtain a crude product. The crude product was purified by a silica gel column, and the eluent was dichloromethane and petroleum ether in a volume ratio of 1:1. Finally, 1.5 g of compound B6 was obtained with a yield of 87.8%. Among them, the mass spectrometry test results of compound B6 were: MS (EI) m / z: 516.6 [M + ], and according to the molecular formula C 32 H 38 The calculated values ​​of BrN are basically consistent.

[0187] 5) Synthesis of compound 45:

[0188] Under nitrogen protection, the above compound B6 (1.5g, 1 equivalent) was added to a 100mL Shrek reaction tube with a stirrer, and 30mL of anhydrous and oxygen-free tetrahydrofuran was added. The reaction tube was placed in a low-temperature reactor at -78°C, and 1.4mL of 2.5M n-butyl lithium (n-BuLi) solution (1.2 equivalents) was added dropwise, and the temperature was kept at -78°C for 1h. Compound B7 (1.1g, 1 equivalent) was then added, and the temperature was slowly raised to room temperature, and the reaction was continued overnight. A small amount of methanol was then added to quench the reaction to obtain a reaction solution. The reaction solution was subjected to reduced pressure distillation to remove the solvent to obtain the first intermediate product.

[0189] Afterwards, the first intermediate product was added to a 250 mL two-necked bottle with a stirrer, and 100 mL of glacial acetic acid (ie, HOAc) and 5 mL of concentrated hydrochloric acid (HCl) were added in sequence, and the reaction material system was stirred and heated to 110° C. to react overnight. After cooling to room temperature, the resulting reaction solution was poured into an appropriate amount of ice water, and then filtered to obtain a second intermediate product.

[0190] Afterwards, the second intermediate product was added to a 250 mL double-necked flask with a stirrer, and 80 mL of dioxane (English name: 1,4-dioxane), 40 mL of dichloromethane (abbreviated as DCM), 10 mL of water and 4.0 g of dichlorodicyanobenzoquinone (abbreviated as DDQ, 6 equivalents) were added in sequence, and reacted at room temperature for 2 days. The resulting reaction solution was separated by a separatory funnel to obtain an organic phase, and the aqueous phase was extracted with dichloromethane, and the organic phases were combined. The organic phase was distilled under reduced pressure to remove the solvent to obtain a crude product. The crude product was purified by a silica gel column, and the eluent was dichloromethane and petroleum ether in a volume ratio of 4:1. Finally, 1.5 g of compound 45 was obtained, and the yield was 63%. Among them, the mass spectrometry test results of compound 45 were: MS (EI) m / z: 824.1 [M + ], and according to the molecular formula C 58 H 49 The calculated values ​​of NO2S are basically consistent.

[0191] The obtained compound 45 was subjected to carbon nuclear magnetic resonance spectrum test and infrared spectrum test, and the results were as follows: Figure 4 , Figure 5 As shown. Among them, the characteristic signal peak with a chemical shift between 40 and 60 ppm in the nuclear magnetic resonance carbon spectrum corresponds to the spiro carbon atom in the general formula (I) above. In the infrared spectrum, the wave number is between 1750 and 1680 cm -1 The high intensity peaks between Figure 5 Specifically, the wave number is 1643cm -1The peak corresponding to the carbonyl stretching vibration absorption peak corresponds to the peak at the position of the carbonyl group. These two test results indicate that the provided compound is an organic material containing a carbonyl nitrogen system with a spirocyclic structure. In addition, the fluorescence spectrum test of the above compound 45 is performed, and the results are as follows Figure 6 As shown. Figure 6 It can be seen that the luminescence peak of this compound is 463 nm, and the half-peak width of the luminescence peak is only 22 nm, which can determine that it is a multiple resonance thermally activated delayed fluorescence material.

[0192] Example 2

[0193] A polycyclic compound, the structure of which is shown as the aforementioned reference numeral 51. The synthesis route of the compound 51 is as follows:

[0194]

[0195] The preparation of the polycyclic compound 51 specifically comprises the following steps:

[0196] 1) Synthesis of compounds C3, C4, C5:

[0197] The synthesis steps of compounds C3, C4 and C5 are similar to those of compounds B3, B4 and B5 in Example 1, the main difference being that reactant B1 is replaced by compound C1.

[0198] 2) Synthesis of compound C6:

[0199] Under nitrogen protection, compound C5 (1.0 g), biboronic acid pinacol ester (0.52 g), methoxy (cyclooctadiene) iridium dimer (abbreviated as [Ir (COD) (OMe)] 2, 0.07 g), 4,4'-di-tert-butyl-2,2'-dipyridine (English name 4,4'-di-tert-butyl-2,2'-dipyridyl, 0.055 g) and 100 mL of tetrahydrofuran (abbreviated as THF) were added to a 100 mL double-necked flask with a stirrer, and the reaction material system was stirred and heated to 70 ° C for 1 day. After cooling to room temperature, the reaction solution was distilled under reduced pressure to remove the solvent to obtain a crude product. The crude product was purified by silica gel column, and the eluent was dichloromethane and petroleum ether in a volume ratio of 4:1. Finally, 1.1 g of compound C6 was obtained with a yield of 87%. Among them, the mass spectrometry test result of compound C6 was measured as follows: MS (EI) m / z: 614.4 [M + ], and according to the molecular formula C 34 H 37 The calculated values ​​of BBrNO4 are basically consistent.

[0200] 3) Synthesis of compound C8:

[0201] Under nitrogen protection, compound C6 (1.0 g) and compound C7 (molecular formula: C 15 H 10 N3Cl, 0.4g), tetrakis(triphenylphosphine)palladium (abbreviated as Pd(PPh3)4, 0.056g), potassium carbonate (chemical formula K2CO3, 2.25g), 100mL tetrahydrofuran (abbreviated as THF) and 10mL water (abbreviated as H2O) were added to a 250mL double-necked flask with a stirrer, the reaction material system was stirred, and heated to 70°C for 12h. After cooling to room temperature, dichloromethane was used for extraction and separation, and the organic phase was distilled under reduced pressure to remove the solvent to obtain a crude product. The crude product was purified by a silica gel column, and the eluent was dichloromethane and petroleum ether in a volume ratio of 2:3. Finally, 1.0g of compound C8 was obtained with a yield of 85%. Among them, the mass spectrometry test results of compound C8 were measured as follows: MS (EI) m / z: 719 [M + ], and according to the molecular formula C 43 H 35 The calculated values ​​of BrN4O2 are basically consistent.

[0202] 4) Synthesis of compound 51:

[0203] The steps for synthesizing compound C9 from compound C8 are similar to the steps for synthesizing compound B6 from compound B5 in Example 1; the steps for synthesizing compound 23 from compound C9 are similar to the steps for synthesizing compound 45 from compound B6 in Example 1.

[0204] Example 3

[0205] A polycyclic compound, the structure of which is shown in the above reference numeral 49, specifically The synthetic route of this compound is similar to that of compound 51 in Example 2, except that reactant B7 is replaced by the following raw materials:

[0206] Example 4

[0207] A polycyclic compound, the structure of which is shown in the above reference numeral 52, specifically The synthetic route of this compound is similar to that of compound 51 in Example 2, except that reactant B7 is replaced by the following raw materials:

[0208] Example 5

[0209] A polycyclic compound, the structure of which is shown in the above reference numeral 48, specifically The synthetic route of compound 48 is similar to that of compound 51 in Example 1, except that reactant B7 is replaced by the following raw materials:

[0210] Example 6

[0211] A polycyclic compound, the structure of which is shown in the above reference numeral 47, specifically The synthetic route of this compound is similar to that of compound 51 in Example 2, except that reactant B7 is replaced by the following raw materials:

[0212] Example 7

[0213] A polycyclic compound, the structure of which is shown in the above reference numeral 50, specifically The synthetic route of this compound is similar to that of compound 51 in Example 2, except that reactant B7 is replaced by the following raw materials:

[0214] Example 8

[0215] A polycyclic compound, the structure of which is shown in the aforementioned reference numeral 23, and the synthesis route of the compound is as follows:

[0216]

[0217] The steps for synthesizing compound 23 from compound C9 are similar to those for synthesizing compound 51 from compound C9 in Example 2, the main difference being that compound B7 is replaced by compound C10.

[0218] Example 9

[0219] A polycyclic compound, the structure of which is shown in the above reference numeral 24, specifically The synthetic route of this compound is similar to that of compound 23, the main difference being that reactant C10 is replaced by the following raw material

[0220] Example 10

[0221] A polycyclic compound, the structure of which is shown in the above reference numeral 25, specifically The synthetic route of this compound is similar to that of compound 23, the main difference being that reactant C10 is replaced by the following raw material

[0222] Embodiment 11

[0223] A polycyclic compound, the structure of which is shown in the above reference numeral 26, specifically The synthetic route of this compound is similar to that of compound 23, the main difference being that reactant C10 is replaced by the following raw material

[0224] Example 12

[0225] A polycyclic compound, the structure of which is shown in the above reference numeral 27, specifically The synthetic route of this compound is similar to that of compound 23, the main difference being that reactant C10 is replaced by the following raw material

[0226] Embodiment 13

[0227] A polycyclic compound, the structure of which is shown in the above reference numeral 28, specifically The synthetic route of this compound is similar to that of compound 23, the main difference being that reactant C10 is replaced by the following raw material

[0228] Embodiment 14

[0229] A polycyclic compound, the structure of which is shown in the aforementioned reference numeral 18. The synthetic route of the compound 18 is as follows:

[0230]

[0231] Among them, the main differences between the synthesis steps of compound 18 and compound 23 are: the reaction raw material C10 is replaced by compound D10, and the raw material C9 is replaced by compound D9; the synthesis of compound D9 is similar to the synthesis of C7 from compound C6 in Example 2, the main difference is that the raw material C7 is replaced by compound D7.

[0232] Embodiment 15

[0233] A polycyclic compound, the structure of which is shown in the aforementioned reference numeral 3, and the synthetic route of the compound is as follows:

[0234]

[0235] The synthesis of compound 3 may specifically include the following steps:

[0236] 1) Compound C9 was synthesized by referring to the method described in Example 2; Compound C12 was synthesized using Compound C9, and the synthesis steps were similar to those of Compound 23 in Example 7, with the main difference being that reactant C10 was replaced by C11.

[0237] 2) Synthesis of compound 3:

[0238] Under nitrogen protection, compound C12 (1.0 g, 1 equivalent) was dissolved in 300 mL of dichloromethane (abbreviated as DCM), and then meta-chloroperbenzoic acid (abbreviated as mCPBA, 0.3 g, 1.5 equivalents) was added to react at room temperature for 1 hour. The reaction was monitored by thin layer chromatography, and 30 mL of saturated sodium bicarbonate solution was added after the reaction was complete to quench the reaction. The organic phase was extracted and separated by dichloromethane, and the solvent was removed by vacuum distillation to obtain a crude product. The crude product was purified by silica gel column, and the eluent was dichloromethane and petroleum ether in a volume ratio of 4:1. Finally, 0.8 g of compound 3 was obtained with a yield of 79%. Among them, the mass spectrometry test results of compound 3 were measured as follows: MS (EI) m / z: 851 [M+], which is consistent with the molecular formula C 56 H 42 The calculated value of N4O3S is 851.

[0239] Example 16

[0240] A polycyclic compound, the structure of which is shown in the above reference numeral 8, specifically The synthetic route of this compound is similar to that of compound 45 in Example 1, except that reactant B7 is replaced by the following raw materials:

[0241] Embodiment 17

[0242] A polycyclic compound, the structure of which is shown in the above reference numeral 57, specifically The synthetic route of this compound is similar to that of compound 45 in Example 1, except that reactant B7 is replaced by the following raw materials:

[0243] Embodiment 18

[0244] A polycyclic compound, the structure of which is shown in the above reference numeral 58, specifically The synthetic route of this compound is similar to that of compound 45 in Example 1, except that reactant B7 is replaced by the following raw materials:

[0245] Embodiment 19

[0246] A polycyclic compound, the structure of which is shown in the above reference numeral 68, specifically The synthetic route of this compound is similar to that of compound 45 in Example 1, except that reactant B7 is replaced by the following raw materials:

[0247] The application effects of the polycyclic compounds prepared above in the present application in organic electroluminescent devices are described in detail below through device examples.

[0248] Device Example 1

[0249] A method for preparing an organic electroluminescent device (OLED) comprises the following steps:

[0250] With a thickness of The glass substrate with an indium tin oxide (ITO) layer was placed in distilled water dissolved with a detergent for ultrasonic washing. After washing the ITO for 30 minutes, ultrasonic washing was repeated twice with distilled water for 10 minutes, and then ultrasonic washing was performed in sequence with isopropyl alcohol, acetone and methanol solvents, and dried, and then the substrate was transferred to an oxygen plasma cleaner to clean the substrate for 6 minutes, and then transferred to a vacuum evaporator.

[0251] 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HAT-CN) was vacuum deposited on the ITO electrode after the above treatment, wherein the deposition rate was / sec, and the vacuum degree during deposition was maintained at 1 × 10 -7 Up to 5×10 -6 Support, forming a thickness of of film as a hole injection layer.

[0252] The compound 4,4'-cyclohexylbis[N,N-di(4-methylphenyl)aniline] (TAPC) as a hole transport material was vacuum deposited on the hole injection layer at a deposition rate of / sec, and the vacuum degree during deposition was maintained at 1 × 10 -7 Up to 5×10 -6 Support, forming a thickness of hole transport layer.

[0253] Then, the compound 4,4',4"-tris(carbazol-9-yl)triphenylamine (TCTA) as an electron blocking material was added to The deposition rate of / second is vacuum deposited on the hole transport layer, wherein the deposition rate is / sec, and the vacuum degree during deposition was maintained at 1 × 10 -7 Up to 5×10 -6 Support, forming a thickness of electron blocking layer.

[0254] Next, compound 3,3'-bis(N-carbazole)-1,1'-biphenyl (mCBP) was used as the main luminescent material and compound 45 was used as the doping material. The two were vacuum deposited on the electron blocking layer at a mass ratio of (100-x):x, wherein the deposition rate was / sec, and the vacuum degree during deposition was maintained at 1 × 10 -7 Up to 5×10 -6 Support, forming a thickness of light-emitting layer; x is 2, 5, and 7 respectively.

[0255] Then, the compound 1,3,5-tris[(3-pyridyl)-3-phenyl]benzene (TmPyPB) is vacuum deposited on the above-mentioned light-emitting layer, wherein the deposition rate is / sec, and the vacuum degree during deposition was maintained at 1 × 10 -7 Up to 5×10 -6 Support, forming a thickness of electron transport layer.

[0256] On the electron transport layer The compound 8-hydroxyquinoline lithium (Liq) was vacuum deposited at a deposition rate of / s to form a layer with a thickness of The electron injection layer is then Aluminum was deposited in vacuum at a deposition rate of 1 × 10 / s, and the vacuum degree during deposition was maintained at 1 × 10 -7 Up to 5×10 -6 Support, forming a thickness of A cathode is provided to obtain an organic electroluminescent device.

[0257] The structure of the resulting OLED is as follows Figure 7 As shown, it is Figure 1 The device comprises a substrate 40 (specifically transparent glass), and an anode 10 (specifically ITO, with a thickness of 1000 mm) stacked on the substrate 40. ), hole injection layer 3021 (thickness is Specifically HAT-CN material), hole transport layer 3022 (thickness Specifically TAPC), electron blocking layer 3023 (thickness is Specifically TCTA material), light-emitting layer 301 (thickness mCBP is used as the main material, compound 45 is used as the doping material, the mass ratio of the main material to the doping material is (100-x):x), the electron transport layer 3032 (thickness is Specifically, TmPyPB material), electron injection layer 3031 (thickness The specific material is 8-hydroxyquinoline lithium (Liq)) and the cathode 20 (specifically metal aluminum with a thickness of ).

[0258] The structural formula of the relevant materials is shown below:

[0259]

[0260] After the preparation of the organic electroluminescent device is completed as described above, the anode 10 and the cathode 20 are connected using a known driving circuit (such as Keithley 2400 universal source meter), and the electroluminescent performance of the entire device is measured using a spectroradiometer PR745. The peak-to-peak value, half-peak width and maximum external quantum efficiency of the device are summarized in the following Table 1.

[0261] Table 1

[0262]

[0263] It can be seen from Table 1 that the OLED device prepared by using the polycyclic compound provided in the embodiment of the present application as the light-emitting layer doping material has an extremely narrow half-width of the electroluminescent peak of the device (not exceeding 30 nm), which can ensure that the luminescent color purity of the device is high. At the same time, the maximum external quantum efficiency of the device is high, at more than 18%.

[0264] In addition, according to the device preparation method described in the device embodiment 1 of the present application, other polycyclic compounds provided in the present application are used as light-emitting layer doping materials to prepare OLED devices, and the difference is mainly in the different light-emitting layer composition. The specific differences and related test results of the devices are summarized in the following Table 2.

[0265] Table 2

[0266]

[0267] It can be seen from Table 2 that other polycyclic compounds provided in the embodiments of the present application also achieve high device efficiency and high color purity in electroluminescent devices.

[0268] It should be noted that the words "set", "connect", and "install" in this application should be understood in a broad sense. For example, they can be directly set, connected, or installed, or they can be indirectly set, connected, or installed through an intermediate medium. The directional terms mentioned in this application, such as "upper", "lower", "front", "back", "left", "right", "inner", "outer", "front", "back", "bottom", "top", etc., are only for better and clearer explanation and understanding of this application, and do not indicate or imply that the referred parts must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as limitations on this application.

[0269] It should be understood that the terms "first", "second", etc. used in this application are used to distinguish different objects rather than to describe a specific order. In the description of this application, unless otherwise specified, the meaning of "multiple (kinds)" refers to greater than or equal to two (kinds). "At least one (kind)" refers to one (kind) or more (kinds). "At least one of the following (individuals)" or its similar expressions refers to any combination of these items, including any combination of single items (individuals) or plural items (individuals). For example, "at least one of a, b, or c", or "at least one of a, b, and c", can all represent: a, b, c, ab (i.e., a and b), ac, bc, or abc, wherein a, b, c can be single or multiple, respectively.

[0270] In addition, the numerical range represented by "-" in the present application refers to the range including the numerical values ​​recorded before and after "-" as the minimum value and the maximum value, respectively. In the present application, expressions about parameter ranges, such as "greater than or equal to (≥)", "less than or equal to (≤)", "above...", and "below..." all include the number itself.

Claims

1. An organic electroluminescent device, characterized in that: It includes a cathode and an anode, and a light-emitting layer located between the cathode and the anode, the light-emitting layer includes a light-emitting main material and a doping material, and the doping material includes at least one polycyclic compound; wherein the polycyclic compound includes a polycyclic aromatic skeleton and a spiro structure, the polycyclic aromatic skeleton is embedded with nitrogen atoms and carbonyl groups, the spiro structure includes two Ar1s, spiro carbon atoms respectively connected to the two Ar1s, and a bridging group, the spiro carbon atom is connected to the polycyclic aromatic skeleton, the Ar1 is independently selected from substituted or unsubstituted aromatic rings, or substituted or unsubstituted aromatic heterocycles, and the half-peak width of the electroluminescent peak of the light-emitting layer is less than or equal to 30nm.

2. The organic electroluminescent device according to claim 1, characterized in that: The maximum external quantum efficiency of the organic electroluminescent device is above 18%.

3. The organic electroluminescent device according to claim 1 or 2, characterized in that: Based on the total mass of the light-emitting layer, the mass proportion of the doping material is 0.3-30.0 wt %, and the mass proportion of the light-emitting host material is 70.0-99.7 wt %.

4. The organic electroluminescent device according to claim 1 or 2, characterized in that: The light-emitting layer also includes a sensitizer; based on the total mass of the light-emitting layer, the mass proportion of the doping material is 0.3-10.0wt%, the mass proportion of the light-emitting main material is 65.0-94.7wt%, and the weight percentage of the sensitizer is 5-25wt%.

5. The organic electroluminescent device according to any one of claims 1 to 4, characterized in that: The bridging group is selected from any of the following structures: Wherein, the dotted line represents a bond; R2 is independently selected from one or more of a hydrogen atom, a deuterium atom, a tritium atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a sulfhydryl group, a carboxyl group, an amino group, a carbonyl group, an ester group, an amide group, a phosphoryl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, and a substituted or unsubstituted silane group, wherein when the bridging group is When R2 can also be connected with Ar1 to form a ring; when the bridging group is When the bridging group is When R2 is connected to each other to form a ring or R2 is connected to Ar1.

6. The organic electroluminescent device according to any one of claims 1 to 5, characterized in that: The polycyclic compound has the general formula as shown in formula (I): In formula (I), X represents the bridging group, and each occurrence of R1 is independently selected from one or more of a hydrogen atom, a deuterium atom, a tritium atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, a carboxyl group, an amino group, a carbonyl group, an ester group, an amide group, a phosphoryl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, and a substituted or unsubstituted silane group.

7. The organic electroluminescent device according to any one of claims 1 to 6, characterized in that: The bridging group includes any structure shown in formula (i-1) to formula (i-23): wherein each R' and R" are independently selected from one or more of a hydrogen atom, a deuterium atom, a tritium atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a sulfhydryl group, a carboxyl group, an amino group, a carbonyl group, an ester group, an amide group, a phosphoryl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, and a substituted or unsubstituted silane group.

8. The organic electroluminescent device according to any one of claims 6, characterized in that: The general formula represented by the formula (I) includes any one of formula (II-1) to formula (II-5): In formula (II-1) to formula (II-5), the selection range of each R' is the same as that of R1.

9. The organic electroluminescent device according to any one of claims 5 to 8, characterized in that: The substituents in the substituted alkyl, substituted cycloalkyl, substituted alkenyl, substituted alkynyl, substituted aryl and substituted heteroaryl include one or more of a deuterium atom, a tritium atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, a carboxyl group, an amino group, a carbonyl group, an ester group, an amide group, a phosphoryl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted hydrocarbyl group, a substituted or unsubstituted hydrocarbyl group, and a substituted or unsubstituted silyl group.

10. The organic electroluminescent device according to any one of claims 5 to 9, characterized in that: The substituted or unsubstituted alkyl group is a substituted or unsubstituted C1-C 20 Alkyl; the substituted or unsubstituted cycloalkyl is a substituted or unsubstituted C3~C 20 Cycloalkyl; the substituted or unsubstituted alkenyl is a substituted or unsubstituted C2~C 20 The substituted or unsubstituted alkynyl group is a substituted or unsubstituted C2~C 20 Alkynyl; the substituted or unsubstituted aryl is a substituted or unsubstituted C6~C 30 Aryl; the substituted or unsubstituted heteroaryl is a substituted or unsubstituted C3~C 30 Heteroaryl.

11. The organic electroluminescent device according to any one of claims 1 to 10, characterized in that: In Ar1, the substituted or unsubstituted aromatic ring is a substituted or unsubstituted C6 to C 30 Aromatic ring; the substituted or unsubstituted aromatic heterocyclic ring is a substituted or unsubstituted C3~C 30 Aromatic heterocycle; the heteroatom in the aromatic heterocycle is selected from one or more of nitrogen atom, oxygen atom, sulfur atom, selenium atom, boron atom and silicon atom.

12. The organic electroluminescent device according to any one of claims 1 to 11, characterized in that: The substituted or unsubstituted aromatic ring includes a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted anthracene ring, a substituted or unsubstituted phenanthrene ring, a substituted or unsubstituted triphenylene ring, a fluoranthene ring, a substituted or unsubstituted pyrene ring, a substituted or unsubstituted binaphthyl ring, a substituted or unsubstituted fluorene ring, and a substituted or unsubstituted spirofluorene ring; the substituted or unsubstituted aromatic heterocyclic ring includes a substituted or unsubstituted furan ring, a substituted or unsubstituted pyrrole ring, a substituted or unsubstituted The ring may be selected from the group consisting of a substituted or unsubstituted thiophene ring, a substituted or unsubstituted pyridine ring, a substituted or unsubstituted quinoline ring, a substituted or unsubstituted furanopyrrole ring, a substituted or unsubstituted benzopyrrole ring, a substituted or unsubstituted benzofuran ring, a substituted or unsubstituted dibenzofuran ring, a substituted or unsubstituted benzothiophene ring, a substituted or unsubstituted dibenzothiophene ring, a substituted or unsubstituted carbazole ring, a substituted or unsubstituted triazine ring, and a substituted or unsubstituted xanthone ring.

13. The organic electroluminescent device according to any one of claims 1 to 12, characterized in that: The polycyclic compound is selected from any one of the following compounds:

14. The organic electroluminescent device according to any one of claims 1 to 13, characterized in that: The organic electroluminescent device further comprises other functional layers, wherein the other functional layers comprise the polycyclic compound; wherein the other functional layers comprise one or more of a hole injection layer, a hole transport layer, an electron blocking layer, an electron injection layer, an electron transport layer, and a hole blocking layer.

15. A polycyclic compound, characterized in that The polycyclic compound has the general formula as shown in formula (I): In formula (I), each occurrence of Ar1 is independently selected from a substituted or unsubstituted aromatic ring, or a substituted or unsubstituted aromatic heterocycle; X is selected from any of the following structures: Wherein, the dotted line represents a bond; R1 and R2 are independently selected from one or more of hydrogen, deuterium, tritium, halogen, cyano, nitro, hydroxyl, sulfhydryl, carboxyl, amino, carbonyl, ester, amide, phosphoryl, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkylthio, substituted or unsubstituted silane; wherein, when X is When R2 can also be connected with Ar1 to form a ring; when X is When the bridging group is When R2 is connected to each other to form a ring or R2 is connected to Ar1.

16. The polycyclic compound according to claim 15, characterized in that The X includes any structure shown in formula (i-1) to formula (i-23): The selection range of each R and R" is the same as that of R1.

17. The polycyclic compound according to claim 15, characterized in that The general formula represented by the formula (I) is any one of formula (II-1) to formula (II-5): In formula (II-1) to formula (II-5), the selection range of each R' is the same as that of R1.

18. A polymer, characterized in that At least one repeating unit of the polymer is connected with the polycyclic compound according to any one of claims 15 to 17.

19. A mixture, characterized in that The mixture comprises the polycyclic compound described in any one of claims 15 to 17 or the polymer described in claim 18, and at least one functional material; wherein the functional material comprises a hole injection material, a hole transport material, an electron blocking material, a light-emitting host material, a hole blocking material, an electron transport material or an electron injection material.

20. Use of the polycyclic compound according to any one of claims 15 to 17, or the polymer according to claim 18, or the mixture according to claim 19 in a functional layer of an electronic device.

21. The use according to claim 20, characterized in that The functional layer includes one or more of a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting host layer, a hole blocking layer, an electron transport layer or an electron injection layer.

22. An electronic device, characterized in that: The electronic device comprises a functional layer, wherein the functional layer comprises the polycyclic compound according to any one of claims 15 to 17, or comprises the polymer according to claim 18, or comprises the mixture according to claim 19.

23. The electronic device according to claim 22, characterized in that The electronic device comprises an organic electroluminescent device, an organic field effect transistor, an organic solar cell, a light-emitting electrochemical cell, a laser, an optical sensor or a lighting element.

24. An organic electroluminescent device, characterized in that: It comprises a cathode and an anode, and a functional layer located between the cathode and the anode, wherein the functional layer comprises at least one polycyclic compound as described in any one of claims 15 to 17, or comprises at least one polymer as described in claim 18, or comprises a mixture as described in claim 19.

25. The organic electroluminescent device according to claim 24, characterized in that: The functional layer includes one or more of a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer or an electron injection layer.

26. A display module, characterized in that: The invention comprises a cover plate, a back plate and an organic electroluminescent device according to any one of claims 1 to 14 or any one of claims 24 to 25, wherein the organic electroluminescent device is located between the back plate and the cover plate.

27. An electronic device, characterized in that: The electronic device comprises a housing and a display module as claimed in claim 26, wherein the display module is connected to the housing.

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