Blue light material and use thereof

Abstract

The present invention provides an organic electroluminescent compound and the use thereof. The compound has a structure shown in formula 1 as follows, and as an organic electroluminescent blue light material, has a higher current efficiency and a longer service life while having a lower driving voltage.

Description

A Blue Light Material and Its Application

[0001] Cross-reference to related applications

[0002] This application claims priority to Chinese Patent Application No. 202410703834.2, filed on May 31, 2024, the entire contents of which are incorporated herein by reference. Technical Field

[0003] This invention belongs to the field of organic electroluminescence technology, specifically relating to an organic electroluminescent blue light material compound and its application in organic electroluminescent devices. Background Technology

[0004] Organic electroluminescent displays are hailed as the "third display technology revolution" due to their numerous advantages, including self-illumination, wide viewing angle, high contrast, fast response, low power consumption, thinner and lighter design, and the ability to achieve flexible displays. They are widely used in mobile phones, televisions, computers, automotive displays, and other display and lighting applications.

[0005] With the development of organic electroluminescent materials, red and green light-emitting materials have largely met the needs of displays. However, blue light-emitting materials, due to their wide bandgap characteristics and difficulty in charge injection, lag behind red and green light in terms of efficiency and lifetime. Nevertheless, the performance of blue light emission, especially deep blue light, has a significant impact on improving display quality and reducing power consumption.

[0006] Commercially viable blue luminescent materials require high efficiency and long lifespan. Chinese patent application CN103222082 discloses an aromatic vinyl compound for use as a blue electroluminescent material; however, this compound has poor heat resistance and is prone to decomposition during sublimation. Similarly, Chinese patent CN1394195 discloses a series of anthracene derivatives that can be used as OLED blue light materials, but these anthracene derivatives have low efficiency and cannot meet the requirements of current displays in practical applications. Furthermore, Chinese patent application CN101018760 discloses a series of aromatic amine derivatives, but due to the imbalance between their hole and electron transport properties, their lifespan remains unsatisfactory. Therefore, the development of high-efficiency and long-lifespan blue luminescent materials is of great significance for promoting the development of organic electroluminescent display and lighting technologies.

[0007] Therefore, existing technologies still need to be improved and developed.

[0008] Summary of the Invention

[0009] In view of the various defects and shortcomings existing in the prior art, the object of the present invention is to provide a suitable organic compound as an organic electroluminescent material. Therefore, in a first aspect, the present invention provides an organic electroluminescent compound having the structure shown in Formula 1:

[0010] In Equation 1, A1 to A 21 Each represents CR independently;

[0011] X1 and X2 may be the same or different, and each is independently selected from single bonds, O, S, Se, and NR. N , CRaRb, (CRaRb)2, RaC=CRb or SiRaRb;

[0012] According to some preferred embodiments of the present invention, one of X1 and X2 is (CRaRb)2 or RaC=CRb, and the other is selected from single bonds, O, S, Se, NR. N , CRaRb or SiRaRb;

[0013] According to some preferred embodiments of the present invention, one of X1 and X2 is (CRaRb)2 or RaC=CRb, and the other is selected from a single bond, O or S;

[0014] R, R N Ra, Rb, R N1 and R N2 Each time it appears, it is selected from the group consisting of the following, either identically or differently: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1-20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3-20 carbon atoms, substituted or unsubstituted heteroalkyl groups having 1-20 carbon atoms, substituted or unsubstituted heterocycloalkyl groups having 3-20 carbon atoms, substituted or unsubstituted aralkyl groups having 7-30 carbon atoms, substituted or unsubstituted alkoxy groups having 1-20 carbon atoms, substituted or unsubstituted aroxy groups having 6-30 carbon atoms, substituted or unsubstituted alkenyl groups having 2-20 carbon atoms, substituted or unsubstituted alkynyl groups having 2-20 carbon atoms, substituted... The substituted group may be an unsubstituted aryl group having 6-30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3-30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3-20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6-20 carbon atoms, an substituted or unsubstituted amino group, acyl group, carbonyl group, carboxylic acid group, ester group, cyano group, isocyano group, hydroxyl group, mercapto group, sulfinyl group, sulfonyl group, phosphinyl group, or a combination thereof having 0-20 carbon atoms; wherein the substituted group is selected from deuterium, halogen, alkyl group having 1-10 carbon atoms, cycloalkyl group having 3-10 carbon atoms, aryl group having 6-20 carbon atoms, or heteroaryl group having 3-20 carbon atoms.

[0015] According to some embodiments of the present invention, the compound has a structure represented by any one of Formulas 1-1 to 1-8:

[0016] According to some preferred embodiments of the present invention, the compound has a structure represented by any one of formulas 1-9 to 1-16:

[0017] In equations 1-1 to 1-16, A1 to A 21 R N1 and R N2 The definition is the same as in Formula 1; preferably, the definition of X is the same as X1 or X2, and is preferably selected from O or S.

[0018] In some preferred embodiments, R in the compound is selected from hydrogen, substituted or unsubstituted alkyl groups having 1-10 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3-10 carbon atoms, substituted or unsubstituted heteroalkyl groups having 1-10 carbon atoms, substituted or unsubstituted heterocycloalkyl groups having 3-10 carbon atoms, substituted or unsubstituted alkoxy groups having 1-10 carbon atoms, substituted or unsubstituted alkenyl groups having 2-10 carbon atoms, and substituted or unsubstituted alkynyl groups having 2-10 carbon atoms; the substituent used for substitution is selected from deuterium, halogen, alkyl groups having 1-10 carbon atoms, cycloalkyl groups having 3-10 carbon atoms, aryl groups having 6-20 carbon atoms, or heteroaryl groups having 3-20 carbon atoms;

[0019] In some preferred embodiments, R in the compound is selected from hydrogen, substituted or unsubstituted alkyl groups having 1-5 carbon atoms, substituted or unsubstituted alkoxy groups having 1-5 carbon atoms, and substituted or unsubstituted heteroalkyl groups having 1-5 carbon atoms; the substituent used for substitution is selected from deuterium, halogen, alkyl groups having 1-10 carbon atoms, cycloalkyl groups having 3-10 carbon atoms, aryl groups having 6-20 carbon atoms, or heteroaryl groups having 3-20 carbon atoms;

[0020] In some preferred embodiments, R in the compound is selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tert-butyl.

[0021] In some preferred embodiments, R in the compound N1 and R N2Each time it appears, it is selected from the group consisting of the following, either identically or differently: substituted or unsubstituted alkyl groups having 1-10 carbon atoms; substituted or unsubstituted cycloalkyl groups having 3-10 carbon atoms; substituted or unsubstituted heteroalkyl groups having 1-10 carbon atoms; substituted or unsubstituted heterocycloalkyl groups having 3-10 carbon atoms; substituted or unsubstituted aralkyl groups having 7-25 carbon atoms; substituted or unsubstituted alkoxy groups having 1-10 carbon atoms; substituted or unsubstituted aroxy groups having 6-20 carbon atoms; substituted or unsubstituted alkenyl groups having 2-10 carbon atoms; substituted or unsubstituted alkynyl groups having 2-10 carbon atoms; substituted or unsubstituted alkyne groups; and so on. The substituted aryl group having 6-25 carbon atoms, the substituted or unsubstituted heteroaryl group having 3-20 carbon atoms, the substituted or unsubstituted alkylsilyl group having 3-10 carbon atoms, the substituted or unsubstituted arylsilyl group having 6-10 carbon atoms, the substituted or unsubstituted amino group, acyl group, carbonyl group, carboxylic acid group, ester group, cyano group, isocyano group, hydroxyl group, mercapto group, sulfinyl group, sulfonyl group, phosphinyl group, and combinations thereof, having 0-10 carbon atoms; wherein the substituent used for the substitution is selected from deuterium, halogen, alkyl group having 1-10 carbon atoms, cycloalkyl group having 3-10 carbon atoms, aryl group having 6-20 carbon atoms, or heteroaryl group having 3-20 carbon atoms;

[0022] In some preferred embodiments, R in the compound N1 and R N2 Each time it appears, it is selected from the group consisting of: substituted or unsubstituted aralkyl groups having 7-25 carbon atoms, substituted or unsubstituted aryloxy groups having 7-20 carbon atoms, substituted or unsubstituted aryl groups having 6-25 carbon atoms, and substituted or unsubstituted heteroaryl groups having 3-20 carbon atoms; wherein the substituent used for the substitution is selected from deuterium, halogen, alkyl groups having 1-10 carbon atoms, cycloalkyl groups having 3-10 carbon atoms, aryl groups having 6-20 carbon atoms, or heteroaryl groups having 3-20 carbon atoms;

[0023] In some preferred embodiments, R in the compound N1 and R N2 Each of them is independently selected from the following structure:

[0024] In some preferred embodiments, the compound is selected from compounds numbered C1 to C124:

[0025] Secondly, the present invention provides the application of the above-mentioned compounds in the preparation of organic electroluminescent devices.

[0026] According to some preferred embodiments of the present invention, the compound is used as a blue light doping material for the light-emitting layer in an organic electroluminescent device.

[0027] In some embodiments, the doping concentration (mass percentage) of the doped material is 1 wt% to 20 wt% relative to the host material in the light-emitting layer, preferably 1 wt% to 10 wt%, more preferably 2 wt% to 8 wt%.

[0028] Thirdly, the present invention provides an organic electroluminescent device, including a light-emitting layer, wherein the doping material of the light-emitting layer contains the compounds described above in the present invention.

[0029] According to some preferred embodiments of the present invention, the organic electroluminescent device includes: an anode, a cathode, and a light-emitting layer disposed between the anode and the cathode. In some embodiments, the light-emitting layer further includes a dopant material.

[0030] According to some preferred embodiments of the present invention, the organic electroluminescent device further includes one or more of the following: 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.

[0031] Fourthly, the present invention provides a display component / device comprising the compound described in the first aspect of the present invention or the organic electroluminescent device described in the third aspect of the present invention. Attached Figure Description

[0032] Figure 1 is a schematic diagram of an organic light-emitting device according to a specific embodiment of the present invention.

[0033] Figure 2 is a schematic diagram of an organic light-emitting device in another specific embodiment of the present invention.

[0034] The reference numerals in the attached figures are as follows: 100, first organic light-emitting device; 101, substrate; 110, anode; 120, hole injection layer; 130, hole transport layer; 140, electron blocking layer; 150, light-emitting layer; 160, hole blocking layer; 170, electron transport layer; 180, electron injection layer; 190, cathode; 102, encapsulation layer; 200, second organic light-emitting device. Detailed Implementation

[0035] The technical solution of the present invention will be described in detail below through specific embodiments. The following embodiments are used to illustrate the present invention, but are not intended to limit the scope of the present invention. All equivalent changes or modifications made without departing from the spirit disclosed in the present invention should be included within the scope of the claims.

[0036] OLEDs can be fabricated on various substrates, such as glass, plastic, and metal. Figure 1 schematically and non-limitingly illustrates a first organic light-emitting device 100. The figure is not necessarily drawn to scale, and some layer structures may be omitted as needed. Device 100 may include a substrate 101, an anode 110, a hole injection layer 120, a hole transport layer 130, an electron blocking layer 140, a light-emitting layer 150, a hole blocking layer 160, an electron transport layer 170, an electron injection layer 180, and a cathode 190. Device 100 can be fabricated by sequentially depositing the described layers. The properties and functions of each layer, as well as exemplary materials, are described in more detail in columns 6-10 of U.S. Patent 7,279,704B2, the entire contents of which are incorporated herein by reference.

[0037] Each of these layers has numerous examples. For instance, a flexible and transparent substrate-anode combination is disclosed in U.S. Patent No. 5,844,363, which is incorporated herein by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated herein by reference in its entirety. An example of a host material is disclosed in U.S. Patent No. 6,303,238 to Thompson et al., which is incorporated herein by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003 / 0230980, which is incorporated herein by reference in its entirety. Examples of cathodes are disclosed in U.S. Patent Nos. 5,703,436 and 5,707,745, which are incorporated herein by reference in their entirety. These cathodes comprise composite cathodes having a thin metal layer, such as Mg:Ag, overlaid with a transparent, conductive, sputter-deposited ITO layer. The principles and use of barrier layers are described in more detail in U.S. Patent No. 6,097,147 and U.S. Patent Application Publication No. 2003 / 0230980, which are also incorporated herein by reference in their entirety. Examples of implantation layers are provided in U.S. Patent Application Publication No. 2004 / 0174H6, which is incorporated herein by reference in its entirety. A description of protective layers can be found in U.S. Patent Application Publication No. 2004 / 0174H6, which is incorporated herein by reference in its entirety.

[0038] The layered structure described above is provided through non-limiting embodiments. The functionality of an OLED can be achieved by combining the various layers described above, or some layers can be omitted entirely. It may also include other layers not explicitly described. Within each layer, a single material or a mixture of multiple materials can be used to achieve optimal performance. Any functional layer may include several sublayers. For example, a light-emitting layer may have two different light-emitting materials to achieve a desired emission spectrum.

[0039] In one embodiment, an OLED can be described as having an "organic layer" disposed between a cathode and an anode. This organic layer may include one or more layers.

[0040] OLEDs also require an encapsulation layer. Figure 2 schematically and non-limitingly illustrates a second organic light-emitting device 200, which, unlike Figure 1, may include an encapsulation layer 102 above the cathode 190 to protect against harmful substances from the environment, such as moisture and oxygen. Any material capable of providing encapsulation can be used as the encapsulation layer, such as glass or an organic-inorganic hybrid layer. The encapsulation layer should be placed directly or indirectly on the outside of the OLED device. Multilayer thin-film encapsulation is described in U.S. Patent 7,968,146B2, the entire contents of which are incorporated herein by reference.

[0041] Devices manufactured according to embodiments of the present invention can be incorporated into a variety of consumer products having one or more electronic component modules (or units). Some examples of such consumer products include flat panel displays, monitors, medical monitors, televisions, billboards, lights for indoor or outdoor lighting and / or signaling, head-up displays, fully or partially transparent displays, flexible displays, smartphones, tablet computers, phablets, wearable devices, smartwatches, laptop computers, digital cameras, portable camcorders, viewfinders, microdisplays, 3D displays, vehicle displays, and taillights.

[0042] The materials and structures described in this article can also be used in other organic electronic devices listed above.

[0043] Definition of the term "substituent group"

[0044] The term “halogen or halide” as used in this article includes fluorine, chlorine, bromine, and iodine.

[0045] As used herein, the term "alkyl" includes both straight-chain and branched alkyl groups. An alkyl group can be an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 12 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isolaryl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecanyl, n-hexadecyl, n-heptadecyl, n-octadecyl, neopentyl, 1-methylpentyl, 2-methylpentyl, 1-pentylhexyl, 1-butylpentyl, 1-heptyloctyl, and 3-methylpentyl. Furthermore, the alkyl group may optionally be substituted. Among the above, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, and n-hexyl are preferred. Additionally, the alkyl group may optionally be substituted.

[0046] As used herein, the term "alkenyl" includes a straight-chain, branched, or cyclic non-aromatic hydrocarbon group with one or more carbon-carbon double bonds. An alkenyl group can be a straight-chain, branched, or cyclic non-aromatic hydrocarbon group with 2-20 carbon atoms and having one or more carbon-carbon double bonds, preferably an alkenyl group with 2-12 carbon atoms, including but not limited to vinyl, propenyl, isopropenyl, 1-butenyl, 2-butenyl, isobutenyl, butadienyl, 1-pentenyl, 2-pentenyl, isopentenyl, 1,3-pentadienyl, 1,4-pentadienyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 1,3-hexadienyl, 1,4-hexadienyl, 1,5-hexadienyl, 2,4-hexadienyl, or 1,3,5-hextrienyl, etc. Furthermore, the alkenyl group may optionally be substituted.

[0047] As used herein, the term "cycloalkyl" includes cyclic alkyl groups. A cycloalkyl group can be a cycloalkyl group having 3 to 20 carbon atoms, preferably a cycloalkyl group having 4 to 10 carbon atoms. Examples of cycloalkyl groups include cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4,4-dimethylcyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl, etc. Among the above, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, and 4,4-dimethylcyclohexyl are preferred. Furthermore, the cycloalkyl group may optionally be substituted.

[0048] As used herein, the term "heteroalkyl" refers to an alkyl chain in which one or more carbon atoms are substituted with heteroatoms selected from the group consisting of nitrogen, oxygen, sulfur, selenium, phosphorus, silicon, germanium, and boron atoms. Heteroalkyl groups can be of 1 to 20 carbon atoms, preferably of 1 to 10 carbon atoms, and more preferably of 1 to 6 carbon atoms. Examples of heteroalkyl groups include methoxymethyl, ethoxymethyl, ethoxyethyl, methylthiomethyl, ethylthiomethyl, ethylthioethyl, methoxymethoxymethyl, ethoxymethoxymethyl, ethoxyethoxyethyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, mercaptomethyl, mercaptoethyl, mercaptopropyl, aminomethyl, aminoethyl, aminolactone, dimethylaminomethyl, trimethylsilyl, dimethylethylsilyl, dimethylisolactone, tert-butyldimethylsilyl, triethylsilyl, triisolactone, trimethylsilylmethyl, trimethylsilylethyl, and trimethylsilylisolactone. In addition, heteroalkyl groups may be optionally substituted.

[0049] The terms "carbocyclic group" and "carbocyclic group" used herein are used interchangeably to refer to non-aromatic saturated or partially unsaturated monocyclic or polycyclic systems composed of carbon atoms as ring atoms, including aromatic rings composed of carbon atoms as ring atoms. Furthermore, the carbocyclic group may be optionally substituted.

[0050] The term "heterocyclic group" as used herein is used interchangeably with "heterocycle," "carbon heterocycle," and "carbon heterocyclic group," and includes both aromatic and non-aromatic cyclic groups. Aromatic cyclic groups include heteroaromatic groups having 3-18 ring atoms, wherein at least one ring atom is selected from the group consisting of nitrogen, oxygen, sulfur, selenium, silicon, phosphorus, germanium, and boron atoms. Non-aromatic heterocyclic groups include saturated heterocyclic groups having 3-30 ring atoms and unsaturated non-aromatic heterocyclic groups having 3-30 ring atoms, wherein at least one ring atom is selected from the group consisting of nitrogen, oxygen, sulfur, selenium, silicon, phosphorus, germanium, and boron atoms. Preferred non-aromatic heterocyclic groups are those having 3 to 7 ring atoms, which include at least one heteroatom such as nitrogen, oxygen, silicon, or sulfur. Non-aromatic heterocyclic groups include ethylene oxide, oxetane, tetrahydrofuranyl, tetrahydropyranyl, dioxopentacycloyl, dioxahexacycloyl, acridineyl, dihydropyrroleyl, tetrahydropyrroleyl, piperidinyl, oxazolyl, morpholinyl, piperazineyl, oxetane-heptanetrienyl, thioheptanetrienyl, azirane-heptanetrienyl, and tetrahydrothiopyrroleyl. Furthermore, the heterocyclic group may optionally be substituted.

[0051] The term "aryl or aromatic group" as used herein includes both non-fused and fused systems. The aryl group can be an aryl group having 6 to 30 carbon atoms, preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms. Examples of aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenanthrene, fluorene, pyrene, etc. Perylene and azulene, preferably phenyl, biphenyl, triphenylene, fluorene, and naphthalene. Additionally, the aryl group may optionally be substituted. Examples of non-fused aryl groups include phenyl, biphenyl-2-yl, biphenyl-3-yl, biphenyl-4-yl, p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl, m-terphenyl-2-yl, o-tolyl, m-tolyl, p-tolyl, p-(2-phenylpropyl)phenyl, 4'-methyldiphenyl, 4”-tert-butyl-p-terphenyl-4-yl, o-cumyl, m-cumyl, p-cumyl, 2,3-xylyl, 3,4-xylyl, 2,5-xylyl, mesitylene, and m-tetraphenyl. Additionally, the aryl group may optionally be substituted.

[0052] As used herein, the term "heteroaryl" includes non-fused and fused heteroaryl groups with 1 to 5 heteroatoms, wherein at least one heteroatom is selected from the group consisting of nitrogen, oxygen, sulfur, selenium, silicon, phosphorus, germanium, and boron. Isoaryl also refers to heteroaryl. Heteroaryl can be a heteroaryl having 3 to 30 carbon atoms, preferably a heteroaryl having 3 to 20 carbon atoms, and more preferably a heteroaryl having 3 to 12 carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridoindole, pyrrolopyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxtriazole, dioxazole, thiadiazol, pyridine, pyrazine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzoisoxazole, benzothiazole, quinoline, iso Quinoline, cyclophosphine, quinazolin, quinoxaline, naphthidine, phthalazine, pteridine, guarbenzine, acridine, phenazine, phenothiazine, benzofuranopyridine, furanodipyridine, benzothiophenopyridine, thiophenodipyridine, benzoselenophenopyridine, selenobenzodipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborane, 1,3-azaborane, 1,4-azaborane, boronazole and its aza analogues. Additionally, the heteroaryl group may optionally be substituted.

[0053] As used herein, the term "alkoxy" is represented by -O-alkyl, -O-cycloalkyl, -O-heteroalkyl, or -O-heterocyclic. Examples and preferred examples of alkyl, cycloalkyl, heteroalkyl, and heterocyclic groups are the same as described above. An alkoxy group can be an alkoxy group having 1 to 20 carbon atoms, preferably an alkoxy group having 1 to 6 carbon atoms. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, cyclopropyloxy, cyclobutyloxy, cyclopentoxy, cyclohexyloxy, tetrahydrofuranyloxy, tetrahydropyranyloxy, methoxypropyloxy, ethoxyethyloxy, methoxymethyloxy, and ethoxymethyloxy. Additionally, the alkoxy group may optionally be substituted.

[0054] As used herein, the term "aryloxy group" is denoteed by -O-aryl or -O-heteroaryl. Examples and preferred examples of aryl and heteroaryl groups are the same as described above. An aryloxy group can be an aryloxy group having 6 to 30 carbon atoms, preferably an aryloxy group having 6 to 20 carbon atoms. Examples of aryloxy groups include phenoxy and biphenyloxy groups. Additionally, aryloxy groups may optionally be substituted.

[0055] As used herein, the term "aralkyl" encompasses aryl-substituted alkyl groups. Aralkyl groups can be aralkyl groups having 7 to 30 carbon atoms, preferably aralkyl groups having 7 to 20 carbon atoms, and more preferably aralkyl groups having 7 to 13 carbon atoms. Examples of aralkyl groups include benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl, 2-phenylisopropyl, phenyl tert-butyl, α-naphthylmethyl, 1-α-naphthylethyl, 2-α-naphthylethyl, 1-α-naphthylisopropyl, 2-α-naphthylisopropyl, β-naphthylmethyl, 1-β-naphthyl-ethyl, 2-β-naphthyl-ethyl, 1-β-naphthylisopropyl, 2-β-naphthylisopropyl, p-methylbenzyl, m-methylbenzyl The compounds include alkyl groups, such as o-methylbenzyl, p-chlorobenzyl, m-chlorobenzyl, o-chlorobenzyl, p-bromobenzyl, m-bromobenzyl, o-bromobenzyl, p-iodobenzyl, m-iodobenzyl, o-iodobenzyl, p-hydroxybenzyl, m-hydroxybenzyl, o-hydroxybenzyl, p-aminobenzyl, m-aminobenzyl, o-aminobenzyl, p-nitrobenzyl, m-nitrobenzyl, o-nitrobenzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-hydroxy-2-phenylisopropyl, and 1-chloro-2-phenylisopropyl. Among the above, benzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl, and 2-phenylisopropyl are preferred. Additionally, the alkyl group may optionally be substituted.

[0056] As used herein, the term "alkylsilyl or silyl" encompasses silyl groups substituted with groups listed in the above alkyl groups, such as methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, tert-butyldimethylsilyl, tert-butyldiphenylsilyl, etc.

[0057] As used in this article, the term "arylsilyl" refers to a group consisting of any of the aforementioned aryl and silyl groups.

[0058] As used herein, the term "aza" in terms such as "azadibenzofuran" and "azadibenzothiophene" refers to a cyclic aromatic segment in which one or more CH groups are replaced by nitrogen atoms. For example, azatriphenylene includes dibenzo[f,h]quinoline, dibenzo[f,h]quinoline, and other analogs having two or more nitrogen atoms in the ring system. Other nitrogen analogs of the aforementioned aza derivatives will readily conceive of those skilled in the art, and all such analogs are identified as being included in the terminology used herein.

[0059] In this disclosure, unless otherwise defined, when any of the terms consisting of the group consisting of, for example, substituted alkyl, substituted cycloalkyl, substituted heteroalkyl, substituted heterocyclic, substituted aralkyl, substituted alkoxy, substituted aryloxy, substituted alkenyl, substituted alkynyl, substituted aryl, substituted heteroaryl, substituted alksilyl, substituted arylsilyl, substituted amino, substituted acyl, substituted carbonyl, substituted carboxylic acid, substituted ester, substituted sulfinyl, substituted sulfonyl, substituted phosphinyl, refers to any one of the following groups: alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, alkenyl, aryl, heteroaryl, alksilyl, arylsilyl, amino, acyl, carbonyl, carboxylic acid, ester, sulfinyl, sulfonyl, and phosphinyl, which may be one or more groups selected from deuterium, halogen, unsubstituted alkyl having 1-20 carbon atoms, and unsubstituted... The substituted cycloalkyl group having 3-20 carbon atoms, the unsubstituted heteroalkyl group having 1-20 carbon atoms, the unsubstituted heterocyclic group having 3-20 carbon atoms, the unsubstituted aralkyl group having 7-30 carbon atoms, the unsubstituted alkoxy group having 1-20 carbon atoms, the unsubstituted aryl group having 6-30 carbon atoms, the unsubstituted alkenyl group having 2-20 carbon atoms, the unsubstituted alkynyl group having 2-20 carbon atoms, the unsubstituted aryl group having 6-30 carbon atoms, the unsubstituted heteroaryl group having 3-30 carbon atoms, the unsubstituted alksilyl group having 3-20 carbon atoms, the unsubstituted arylsilyl group having 6-20 carbon atoms, and the unsubstituted amino, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, hydroxyl, mercapto, sulfinyl, sulfonyl, phosphin, and combinations thereof having 0-20 carbon atoms.

[0060] It should be understood that when a molecular segment is described as a substituent or otherwise attached to another part, its name may be written according to whether it is a segment (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or according to whether it is a whole molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of specifying substituents or attaching segments are considered equivalent.

[0061] In the compounds mentioned in this disclosure, hydrogen atoms can be partially or completely replaced by deuterium. Other atoms such as carbon and nitrogen can also be replaced by their other stable isotopes. Substitution with other stable isotopes in the compounds may be preferred due to their ability to enhance device efficiency and stability. In the compounds mentioned in this disclosure, multiple substitution refers to the range including disubstitution, up to the maximum number of available substitutions. When a substituent in a compound mentioned in this disclosure represents multiple substitution (including disubstitution, trisubstitution, tetrasubstitution, etc.), it means that the substituent can be present at multiple available substitution positions in its linkage structure. The substituent present at multiple available substitution positions can be of the same structure or different structures.

[0062] In the compounds mentioned in this disclosure, unless explicitly specified, for example, that adjacent substituents can optionally connect to form a ring, adjacent substituents in the compounds cannot connect to form a ring. In the compounds mentioned in this disclosure, the optional connection of adjacent substituents to form a ring includes both cases where adjacent substituents can connect to form a ring and cases where adjacent substituents do not connect to form a ring. When adjacent substituents can optionally connect to form a ring, the resulting ring can be a monocyclic or polycyclic ring, and can be an alicyclic, heterocyclic, aromatic, or heteroaromatic ring. In this context, adjacent substituents can refer to substituents bonded to the same atom, substituents bonded to carbon atoms directly bonded to each other, or substituents bonded to carbon atoms further away. Preferably, adjacent substituents refer to substituents bonded to the same carbon atom and substituents bonded to carbon atoms directly bonded to each other.

[0063] The materials described in this invention for specific layers in organic light-emitting devices can be used in combination with a variety of other materials present in the device. These combinations of materials are described in detail in paragraphs 0132-0161 of U.S. Patent Application US2016 / 0359122M, the entire contents of which are incorporated herein by reference. The materials described or mentioned herein are non-limiting examples of materials that can be used in combination with the compounds disclosed herein, and those skilled in the art can readily consult the literature to identify other materials that can be used in combination.

[0064] Materials described herein for use in specific layers in organic light-emitting devices can be used in combination with a variety of other materials present in said devices. For example, the compounds disclosed herein can be used in combination with a variety of host layers, delivery layers, barrier layers, injection layers, electrodes, and other possible layers. These combinations of materials are described in detail in paragraphs 0080-0101 of U.S. Patent Application US2015 / 0349273M, the entire contents of which are incorporated herein by reference. The materials described or mentioned herein are non-limiting examples of materials that can be used in combination with the compounds disclosed herein, and those skilled in the art can readily consult the literature to identify other materials that can be used in combination.

[0065] In the examples of material synthesis, unless otherwise stated, all reactions were carried out under nitrogen protection. All reaction solvents were anhydrous and used as is from commercial sources. The synthesized products were structurally confirmed and characterized using one or more instruments conventional in the art (including but not limited to Agilent liquid chromatographs, liquid chromatography-mass spectrometers, gas chromatography-mass spectrometers, differential scanning calorimeters, fluorescence spectrophotometers, electrochemical workstations, sublimation apparatuses, etc.) in methods well known to those skilled in the art. In the examples of devices, the characteristics of the devices were also tested using conventional instruments in the art (including but not limited to vapor deposition machines manufactured by Nanjing Institute of Microelectronics, optical testing systems and lifetime testing systems manufactured by Suzhou Fushida, ellipsometers manufactured by Wuhan Yiguang Technology, etc.) in methods well known to those skilled in the art. Since those skilled in the art are familiar with the use of the above-mentioned equipment, testing methods, and other related content, and can obtain the inherent data of the samples definitively and unaffected, the above-mentioned related content will not be elaborated further in this patent.

[0066] The preparation methods of the compounds of this invention are not limited. Typical but not limited examples are the following compounds, whose synthetic routes and preparation methods are as follows:

[0067] Synthesis Example 1: Synthesis of Compound C1

[0068] The synthesis route is as follows:

[0069] Specific synthesis steps:

[0070] (1) Under nitrogen protection, 200 mL of toluene, 16.9 g (0.1 mol) of 2-aminobiphenyl, 21.3 g (0.1 mol) of 4-tert-butylbromobenzene, 14.4 g (0.15 mol) of sodium tert-butoxide, 0.3 g of tris(dibenzylacetone)dipalladium, and 0.3 g of 2-dicyclohexylphospho-2',4',6'-triisopropylbiphenyl were added to a 500 mL three-necked flask. The mixture was stirred and slowly heated to 95-100 °C for 2 hours. After cooling, 8 mL of hydrochloric acid and 100 mL of water were added to adjust the pH to acidic, and the mixture was separated. The organic phase was washed with water until neutral, subjected to column chromatography, recrystallized, and dried to obtain 25.6 g of product C1-1, with a yield of 85%. MS (m / e): 301.

[0071] (2) Under nitrogen protection, 200 mL of xylene was added to a 500 mL three-necked flask, and 12.2 g (0.127 mol) of sodium tert-butoxide was added with stirring. Then, 25.6 g (0.085 mol) of intermediate C1-1, 31.9 g (0.085 mol) of 3,4-dibromo-5-iodotoluene, 0.12 g of tris(dibenzylacetone)dipalladium, and 0.15 g of tri-tert-butylphosphine were added. The temperature was slowly raised to 110 °C, and after stabilization, it was raised to 130 °C and reacted for 2 hours. The reaction solution was cooled to 50 °C, 40 mL of water was added, and the mixture was washed with water. The mixture was then subjected to column chromatography, recrystallized, and dried to obtain 40 g of product C1-2, with a yield of 86%. MS (m / e): 549.

[0072] (3) Under nitrogen protection, 250 mL of tetrahydrofuran and 26.7 g (0.1 mol) of 2'-bromo-4-chlorobiphenyl were added sequentially to a 500 mL three-necked flask. Under nitrogen protection, the temperature was lowered to -80 °C. 60 mL of 2 mol / L n-butyllithium was added dropwise at -80 to -70 °C. The addition was completed in about 30 minutes. The reaction was maintained at -80 to -70 °C for 1.5 hours. 20.8 g (0.1 mol) of 10,11-dihydrodibenzo[a,b]cyclohepten-5-one was added in batches at -70 to -60 °C. After the addition was completed, the reaction was maintained at -70 to -60 °C for 1.5 hours. Add 40 mL of concentrated hydrochloric acid and 80 mL of water to the reaction solution until the pH is acidic. Allow the solution to stand and separate the phases. Extract with ethyl acetate, combine the organic phases, wash with water until neutral, and desolvate under negative pressure to obtain 45 g of yellow viscous liquid of C1-3 with a purity of 85%. Proceed directly to the next step.

[0073] (4) Under nitrogen protection, 45 g of intermediate C1-3 yellow viscous liquid, 160 mL of glacial acetic acid, and 12 mL of concentrated hydrochloric acid were added sequentially to a 500 mL three-necked flask. The mixture was stirred and heated to 105–110 °C, then refluxed for 4 hours. 200 mL of toluene was added to the reaction mixture. The mixture was separated, washed with water until neutral, dissolved, subjected to column chromatography, recrystallized, and dried to obtain 30.2 g of C1-4 pale yellow solid. MS (m / e): 378.5.

[0074] (5) Under nitrogen protection, 200 mL of xylene, 13.5 g (0.08 mol) of 2-aminobiphenyl, 0.2 g (0.08 mol) of intermediate C1-43, 13.4 g (0.12 mol) of potassium tert-butoxide, 0.36 g of tris(dibenzylacetone)dipalladium, and 0.36 g of 2-dicyclohexylphospho-2',4',6'-triisopropylbiphenyl were added to a 500 mL three-necked flask. The mixture was stirred and slowly heated to 105-110 °C and reacted for 2 hours. After cooling, 8 mL of hydrochloric acid and 100 mL of water were added to adjust the pH to acidic, and the mixture was separated. The organic phase was washed with water until neutral, subjected to column chromatography, recrystallized, and dried to obtain 33.5 g of C1-5 product, with a yield of 82%. MS (m / e): 511.

[0075] (6) Under nitrogen protection, 200 mL of xylene was added to a 500 mL three-necked flask, and 7.2 g (0.75 mol) of sodium tert-butoxide was added with stirring. Then, 27.5 g (0.05 mol) of intermediate C1-2, 25.6 g (0.05 mol) of intermediate C1-5, 0.09 g of tris(dibenzylacetone)dipalladium, and 0.11 g of tri-tert-butylphosphine were added. The temperature was slowly raised to 110 °C, and after stabilization, it was raised to 130 °C and reacted for 4 hours. The reaction solution was cooled to 50 °C, 40 mL of water was added, and the mixture was washed with water. Column chromatography was performed, recrystallized, and dried to obtain 39.2 g of compound C1-6, with a yield of 80%. MS (m / e): 980.

[0076] (7) Under nitrogen protection, 160 mL of analytical grade xylene was added to a 250 mL reaction flask, and 9.8 g (0.01 mol) of intermediate C1-6 was added with stirring. The mixture was heated to approximately 55 °C, and after dissolution, it was cooled to -30 °C. Nitrogen was purged three times, and 6 mL of 2 mol / L n-butyllithium was added dropwise. The temperature was slowly increased to 75 °C, and the reaction was allowed to proceed for 2 hours. The temperature was then lowered to -25 °C, and 3.0 g (0.012 mol) of boron tribromide was added. The temperature was then slowly increased to 60 °C and held for 3 hours. The temperature was then lowered to -20 °C, and 2.3 g of N,N-diisopropylethylamine was added dropwise. The temperature was then slowly increased to 80 °C and held for 1 hour. The temperature was then increased to 130 °C, and the reaction was allowed to proceed for 12 hours. The reaction solution was cooled to 50 °C, subjected to column chromatography, recrystallized, and dried to obtain 2.7 g of the target compound C1, with a yield of 30%.

[0077] Product MS (m / e): 908; 1H NMR (400MHz, CDCl3): δ7.75-7.70(m,3H),7.58-7.55(dd,1H),7.48-7.43(m,4H),7.40-7.34(m,10H),7.34-7.32(m,1H),7.31-7.26(m,4 H),7.25-7.15(m,7H),7.06(ddt,2H),7.02-6.98(m,2H),6.88-6.85(dd,1H),6.74-6.68(dd,2H),2.95(m,4H),2.29(s,3H),1.34(d,9H).

[0078] Example 2: Synthesis of compound C2

[0079] Specific synthesis steps:

[0080] Using compounds replace By selecting a suitable material ratio, and with other raw materials and steps being the same as in Example 1, compound C2 was obtained; product MS (m / e): 906.

[0081] Example 3: Synthesis of compound C45

[0082] The synthesis route is as follows:

[0083] Specific synthesis steps:

[0084] (1) Under nitrogen protection, 200 mL of toluene, 14.9 g (0.1 mol) of 4-amino-tert-butylbenzene, 21.3 g (0.1 mol) of 4-tert-butylbromobenzene, 14.4 g (0.15 mol) of sodium tert-butoxide, 0.3 g of tris(dibenzylacetone)dipalladium, and 0.3 g of 2-dicyclohexylphospho-2',4',6'-triisopropylbiphenyl were added to a 500 mL three-necked flask. The mixture was stirred and slowly heated to 95-100 °C for 2 hours. After cooling, 8 mL of hydrochloric acid and 100 mL of water were added to adjust the pH to acidic, and the mixture was separated. The organic phase was washed with water until neutral, subjected to column chromatography, recrystallized, and dried to obtain 23.6 g of product C45-1, with a yield of 84%. MS (m / e): 281.

[0085] (2) Under nitrogen protection, 200 mL of xylene was added to a 500 mL three-necked flask, and 12.2 g (0.127 mol) of sodium tert-butoxide was added with stirring. Then, 23.9 g (0.085 mol) of intermediate C45-1, 35.5 g (0.085 mol) of 3,4-dibromo-5-iodotert-butylbenzene, 0.12 g of tris(dibenzylacetone)dipalladium, and 0.15 g of tritert-butylphosphine were added. The temperature was slowly raised to 110 °C, and after stabilization, it was raised to 130 °C and reacted for 2 hours. The reaction solution was cooled to 50 °C, 40 mL of water was added, and the mixture was washed with water. The mixture was then subjected to column chromatography, recrystallized, and dried to obtain 40.8 g of product C45-2, with a yield of 84%. MS (m / e): 529.

[0086] (3) Under nitrogen protection, 250 mL of tetrahydrofuran and 24.9 g (0.1 mol) of 1-bromo-2-phenoxybenzene were added sequentially to a 500 mL three-necked flask. Under nitrogen protection, the temperature was lowered to -80 °C. 60 mL of 2 mol / L n-butyllithium was added dropwise at -80 to -70 °C. The addition was completed in about 30 minutes. The reaction was maintained at -80 to -70 °C for 1.5 hours. 24.2 g (0.1 mol) of 3-chloro-10,11-dihydrodibenzo[a,b]cyclohepten-5-one was added in batches at -70 to -60 °C. After the addition was completed, the reaction was maintained at -70 to -60 °C for 1.5 hours. Add 40 mL of concentrated hydrochloric acid and 80 mL of water dropwise to the reaction solution until the pH is acidic. Allow the solution to stand and separate the layers. Extract with ethyl acetate, combine the organic phases, wash with water until neutral, and desolvate under negative pressure to obtain 46 g of yellow viscous liquid of C45-3 with a purity of 82%.

[0087] (4) Under nitrogen protection, 46 g of intermediate C45-3 yellow viscous liquid, 160 mL of glacial acetic acid, and 12 mL of concentrated hydrochloric acid were added sequentially to a 500 mL three-necked flask. The mixture was stirred and heated to 105–110 °C, then refluxed for 4 hours. 200 mL of toluene was added to the reaction mixture. The mixture was separated, washed with water until neutral, dissolved, and subjected to column chromatography. The solution was recrystallized and dried to obtain 26 g of C45-4 pale yellow solid. MS (m / e): 394.

[0088] (5) Under nitrogen protection, 200 mL of xylene, 13.2 g (0.08 mol) of 4-tert-butylaniline, 31.5 g (0.08 mol) of intermediate C45-4, 13.4 g (0.12 mol) of potassium tert-butoxide, 0.36 g of tris(dibenzylacetone)dipalladium, and 0.36 g of 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl were added to a 500 mL three-necked flask. The mixture was stirred and slowly heated to 105-110 °C and reacted for 2 hours. After cooling, 8 mL of hydrochloric acid and 100 mL of water were added to adjust the pH to acidic, and the mixture was separated. The organic phase was washed with water until neutral, subjected to column chromatography, recrystallized, and dried to obtain 29.2 g of product C45-5, with a yield of 72%. MS (m / e): 507.

[0089] (6) Under nitrogen protection, 200 mL of xylene was added to a 500 mL three-necked flask, and 7.2 g (0.75 mol) of sodium tert-butoxide was added with stirring. Then, 26.5 g (0.05 mol) of intermediate C45-2, 25.4 g (0.05 mol) of intermediate C45-5, 0.09 g of tris(dibenzylacetone)dipalladium, and 0.11 g of tri-tert-butylphosphine were added. The temperature was slowly raised to 110 °C, and after stabilization, it was raised to 130 °C and reacted for 4 hours. The reaction solution was cooled to 50 °C, 40 mL of water was added, and the mixture was washed with water. The mixture was then subjected to column chromatography, recrystallized, and dried to obtain 31.5 g of product C45-6, with a yield of 66%. MS (m / e): 956.

[0090] (7) Under nitrogen protection, 160 mL of analytical grade xylene was added to a 250 mL reaction flask, and 9.6 g (0.01 mol) of intermediate C45-6 was added with stirring. The mixture was heated to approximately 55 °C to dissolve, then cooled to -30 °C, purged with nitrogen three times, and 6 mL of 2 mol / L n-butyllithium was added dropwise. The temperature was slowly increased to 75 °C, and the reaction was carried out for 2 hours. The temperature was then lowered to -25 °C, and 3.0 g (0.012 mol) of boron tribromide was added. The temperature was then slowly increased to 60 °C and held for 3 hours. The temperature was then lowered to -20 °C, and 2.3 g of N,N-diisopropylethylamine was added dropwise. The temperature was then slowly increased to 80 °C and held for 1 hour, then increased to 130 °C and the reaction was carried out for 12 hours. The reaction solution was cooled to 50 °C, subjected to column chromatography, recrystallized, and dried to obtain 3.2 g of C45 product, with a yield of 36%.

[0091] Product MS (m / e): 884. 1 H NMR (400MHz, CDCl3): δ7.36-7.32(m,3H),7.29-7.25(m,5H),7.22-6.98(m, 17H),6.73-6.68(dd,2H),2.96-2.84(ddt,4H),2.29(s,3H),1.34(d,27H).

[0092] Example 4: Synthesis of compound C46

[0093] Specific synthesis steps:

[0094] Using compounds replace By selecting a suitable material ratio, and with other raw materials and steps being the same as in Example 3, compound C46 was obtained; product MS (m / e): 882.

[0095] Example 5: Synthesis of compound C65

[0096] The synthesis route is as follows:

[0097] Specific synthesis steps:

[0098] Using compounds replace Using compounds replace By selecting a suitable material ratio, and with other raw materials and steps being the same as in Example 1, compound C65 was obtained in a yield of 26%; MS (m / e) of the product: 798.

[0099] Example 6: Synthesis of compound C66

[0100] Specific synthesis steps:

[0101] Using compounds replace By selecting a suitable material ratio, and with other raw materials and steps being the same as in Example 5, compound C66 was obtained; MS (m / e) of the product: 796.

[0102] Example 7: Synthesis of compound C109

[0103] The synthesis route is as follows:

[0104] Specific synthesis steps:

[0105] (1) Using compounds replace Select a suitable material ratio, and keep the other raw materials and steps the same as in Example 1. Refer to steps (1) and (2) of Example 1 to obtain intermediate C109-2;

[0106] (2) Referring to step (5) of Example 1, C1-4 and The reaction yields intermediate C109-3;

[0107] (3) Referring to steps (6) and (7) of Example 1, the target product C109 was obtained with a yield of 40%.

[0108] Product MS (m / e): 1056; 1 H NMR (400MHz, CDCl3): δ7.72(s,1H),7.58-7.54(dd,1H),7.50-7.48(t,1H),7.4-7.25(m,11H),7.23-7.16(m,6 H),7.07-6.97(m,6H),6.88-6.85(dd,1H),6.73-6.68(dd,2H),2.96(t,4H),2.29(s,3H),1.36-1.33(dd,45H).

[0109] Example 8: Synthesis of compound C123

[0110] Using compounds replace By selecting a suitable material ratio, and with other raw materials and steps being the same as in Example 7, the target compound C123 was obtained; the MS (m / e) of the product was 1098.

[0111] Example 9: Synthesis of compound C110

[0112] Specific synthesis steps:

[0113] Using compounds replace By selecting a suitable material ratio, and with other raw materials and steps being the same as in Example 7, compound C110 was obtained; the product MS (m / e) was 1054.

[0114] Example 10: Synthesis of compound C115

[0115] The synthesis route is as follows:

[0116] Specific synthesis steps:

[0117] (1) Refer to steps (3) and (4) of Example 1. and The reaction yields intermediate C115-2;

[0118] (2) Referring to step (5) of Example 1, C115-2 and The reaction yields intermediate C115-3;

[0119] (3) Referring to step (6) of Example 1, C115-3 reacts with C109-2 to obtain intermediate C115-4;

[0120] (4) Referring to step (7) of Example 1, C115-4 was reacted with boron tribromide to close the ring and obtain the target compound C115 with a yield of 26%.

[0121] Product: MS (m / e): 1056. 1H NMR (400MHz, CDCl3): δ7.86-7.82(dd,2H),7.50-7.48(t,1H),7.41-7.25(m,12H),7.23-7.16(m,5H),7.07- 6.97(m,5H),6.84-6.81(dd,2H),6.73-6.68(dd,2H),3.00-2.84(m,4H),2.29(s,3H),1.37-1.32(dd,45H).

[0122] Example 11. Synthesis of compound C116

[0123] Specific synthesis steps:

[0124] Using compounds replace By selecting a suitable material ratio, and keeping other raw materials and steps the same as in Example 10, compound C116 was obtained; product MS (m / e): 1054.

[0125] Example 12. Synthesis of compound C121

[0126] The synthesis route is as follows:

[0127] Synthesis steps:

[0128] (1) Referring to step (6) of Example 1, C45-2 reacts with C1-5 to obtain intermediate C121-1;

[0129] (2) Referring to step (7) of Example 1, C121-1 was reacted with boron tribromide to close the ring and obtain the target compound C121 with a yield of 28%.

[0130] Product MS (m / e): 888; 1 H NMR (400MHz, CDCl3): δ7.75-7.70(m,2H),7.58-7.54(dd,1H),7.47-7.42(m,2H),7.40-7.16(m,18H) ,7.07-6.98(m,6H),6.88-6.85(dd,1H),6.73-6.68(dd,2H),2.96(t,4H),2.29(s,3H),1.34(d,18H).

[0131] Example 13. Synthesis of compound C122

[0132] Using compounds replace By selecting an appropriate material ratio, and with other raw materials and steps being the same as in Example 12, the target compound C122 was obtained with a yield of 24%.

[0133] Product MS (m / e): 930. 1 H NMR (400MHz, CDCl3): δ7.75-7.70(m,2H),7.58-7.54(dd,1H),7.47-7.42(m,2H),7.40-7. 16(m,18H),7.07-7.98(m,6H),6.90-6.85(m,3H),2.96(t,4H),1.36(s,9H),1.33(d,18H).

[0134] Example 14. Synthesis of compound C124

[0135] Using compounds replace C109-3 was substituted for C1-5, and all other raw materials and steps were the same as in Example 12 to obtain the target compound C124, with a yield of 29%.

[0136] Product MS (m / e): 910. 1 H NMR (400MHz, CDCl3): 7.72 (s, 1H), 7.58-7.54 (dd, 1H), δ7.41-7.24 (m, 9H), 7.22-7.16 (m,5H),7.09-6.97(m,8H),6.89-6.84(m,3H),2.96(t,4H),1.36(s,9H),1.34(d,27H).

[0137] Those skilled in the art should understand that the above preparation method is merely an exemplary example, and they can obtain other compound structures of the present invention by improving it.

[0138] Device Example 1

[0139] First, the glass substrate, which has a 120 nm thick indium tin oxide (ITO) anode, is cleaned and then treated with UV ozone and oxygen plasma. After treatment, the substrate is dried in a nitrogen-filled glove box to remove moisture, and then mounted on a substrate holder and placed in a vacuum chamber. The organic layer specified below is applied at a vacuum degree of approximately 10... -8 In the case of Torr, The deposition rate was achieved sequentially on the ITO anode via thermal vacuum. Simultaneously, the deposition compounds HT and NDP-9 (weight ratio 97:3) were used as a hole injection layer (HIL) with a thickness of [missing information]. Compound HT is used as a hole transport layer (HTL) with a thickness of [missing information]. Compound EB is used as an electron blocking layer (EBL) with a thickness of [missing information]. Then, BH, which serves as the blue light source, and C1, the compound of the present invention, which serves as a dopant (weight ratio 98:2), are co-deposited as an emissive layer (EML) with a thickness of [missing information]. Compound HB was used as the hole blocking layer (HBL), with a thickness of [missing information]. On the hole-blocking layer, compound ET and 8-hydroxyquinoline-lithium (Liq) were co-deposited (weight ratio 50:50) as an electron transport layer (ETL), with a thickness of [missing information]. Finally, vapor deposition Thick 8-hydroxyquinoline-lithium (Liq) was used as the electron injection layer (EIL) and deposited by evaporation. Aluminum was used as the cathode. The device was then transferred back to the glove box and sealed with a glass cover to complete the device.

[0140] Device Examples 2 to 14

[0141] The method is the same as in Device Example 1, except that in the light-emitting layer (EML), the compounds C2, C45, C46, ​​C65, C66, C109, C110, C115, C116, C121, C122, C123 and C124 of the present invention listed in Table 2 are used instead of compound C1 as the doping material.

[0142] Device Comparison Example 1

[0143] The method is the same as in Device Example 1, except that compound A is used instead of compound C1 of the present invention as the dopant material in the light-emitting layer (EML).

[0144] The material structure used in the device is shown below:

[0145] Table 1 lists the values ​​at 10 mA / cm 2 Under the given conditions, the voltage (V), external quantum efficiency (EQE), and lifetime (T) were measured. To better illustrate the data comparison, the voltage, efficiency, and lifetime of Comparative Example 1 were set to 100%. The voltage, efficiency, and lifetime data of Device Examples 1 to 14 were all converted relative to the corresponding data of Comparative Example 1. The relevant data and conversion results are shown in Table 1.

[0146] Table 1

[0147] Discussion: As shown in Table 1, at 10 mA / cm 2At the specified current density, compared to Comparative Example 1, Device Examples 1 to 14 exhibit a voltage reduction of 0-14%, an external quantum efficiency increase of 2%-30%, and a device lifetime extension of 1%-22% in examples 1 to 14. These data demonstrate that the compounds of this invention, which are formed by connecting a spirocyclic structure and a boron-containing heterocyclic structure through a specific structure, exhibit higher current efficiency and lifetime than Comparative Example Compound A due to the introduction of a spirocyclic structure. This structural change unexpectedly leads to superior device performance, proving the unique advantages of the compounds of this invention.

[0148] It should be understood that the various embodiments described herein are merely examples and are not intended to limit the scope of the invention. Therefore, as will be apparent to those skilled in the art, the claimed invention may include variations of the specific embodiments and preferred embodiments described herein. Many of the materials and structures described herein can be substituted with other materials and structures without departing from the spirit of the invention. It should be understood that various theories regarding why the invention works are not intended to be limiting.

Claims

1. An organic electroluminescent compound, characterized by has a structure represented by the following formula 1: wherein, in formula 1, A1to A 21 each independently represents CR; X1, X2are the same or different, each independently selected from a single bond, O, S, Se, NR N , CRaRb, (CRaRb)2, RaC=CRb, or SiRaRb; Preferably, one of X1and X2is (CRaRb)2or RaC=CRb, and the other is selected from a single bond, O, S, Se, NR N , CRaRb, or SiRaRb; more preferably, one of X1and X2is (CRaRb)2or RaC=CRb, and the other is selected from a single bond, O, or S; R, R N Ra, Rb, R N1 and R N2 are the same or different at each occurrence and are selected from the group consisting of hydrogen, deuterium, halogen, substituted or unsubstituted alkyl of 1-20 carbon atoms, substituted or unsubstituted cycloalkyl of 3-20 carbon atoms, substituted or unsubstituted heteroalkyl of 1-20 carbon atoms, substituted or unsubstituted heterocycloalkyl of 3-20 carbon atoms, substituted or unsubstituted aralkyl of 7-30 carbon atoms, substituted or unsubstituted alkoxy of 1-20 carbon atoms, substituted or unsubstituted aryloxy of 6-30 carbon atoms, substituted or unsubstituted alkenyl of 2-20 carbon atoms, substituted or unsubstituted alkynyl of 2-20 carbon atoms, substituted or unsubstituted aryl of 6-30 carbon atoms, substituted or unsubstituted heteroaryl of 3-30 carbon atoms, substituted or unsubstituted alkylsilyl of 3-20 carbon atoms, substituted or unsubstituted arylsilyl of 6-20 carbon atoms, substituted or unsubstituted amino of 0-20 carbon atoms, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, hydroxyl, thiol, sulfinyl, sulfonyl, phosphino, and combinations thereof; the substituents employed in the substitutions are selected from deuterium, halogen, alkyl of 1-10 carbon atoms, cycloalkyl of 3-10 carbon atoms, aryl of 6-20 carbon atoms, or heteroaryl of 3-20 carbon atoms.

2. The compound of claim 1, wherein The compounds have a structure represented by any one of: Preferably, the compound has a structure represented by any one of Formulae 1-9 to 1-16: In formulae 1-1 to 1-16, A1to A 21 , R N1 and R N2 are defined as in formula 1; preferably, X is defined as in X1or X2, preferably selected from O or S.

3. The compound of claim 1, wherein R in said compound is selected from hydrogen, substituted or unsubstituted alkyl having 1-10 carbon atoms, substituted or unsubstituted cycloalkyl having 3-10 carbon atoms, substituted or unsubstituted heteroalkyl having 1-10 carbon atoms, substituted or unsubstituted heterocycloalkyl having 3-10 carbon atoms, substituted or unsubstituted alkoxy having 1-10 carbon atoms, substituted or unsubstituted alkenyl having 2-10 carbon atoms, substituted or unsubstituted alkynyl having 2-10 carbon atoms; the substituents used in said substitution are selected from deuterium, halogen, alkyl having 1-10 carbon atoms, cycloalkyl having 3-10 carbon atoms, aryl having 6-20 carbon atoms or heteroaryl having 3-20 carbon atoms; Preferably, R in said compound is selected from hydrogen, substituted or unsubstituted alkyl having 1-5 carbon atoms, substituted or unsubstituted alkoxy having 1-5 carbon atoms, substituted or unsubstituted heteroalkyl having 1-5 carbon atoms; More preferably, R in said compound is selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl; R in the compound N1 and R N2 are, at each occurrence, the same or different, selected from the group consisting of substituted or unsubstituted alkyl of 1-10 carbon atoms, substituted or unsubstituted cycloalkyl of 3-10 carbon atoms, substituted or unsubstituted heteroalkyl of 1-10 carbon atoms, substituted or unsubstituted heterocycloalkyl of 3-10 carbon atoms, substituted or unsubstituted aralkyl of 7-25 carbon atoms, substituted or unsubstituted alkoxy of 1-10 carbon atoms, substituted or unsubstituted aryloxy of 6-20 carbon atoms, substituted or unsubstituted alkenyl of 2-10 carbon atoms, substituted or unsubstituted alkynyl of 2-10 carbon atoms, substituted or unsubstituted aryl of 6-25 carbon atoms, substituted or unsubstituted heteroaryl of 3-20 carbon atoms, substituted or unsubstituted alkylsilyl of 3-10 carbon atoms, substituted or unsubstituted arylsilyl of 6-10 carbon atoms, substituted or unsubstituted amino of 0-10 carbon atoms, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, hydroxyl, thiol, sulfinyl, sulfonyl, phosphino, and combinations thereof; the substitution employing substituents selected from deuterium, halogen, alkyl of 1-10 carbon atoms, cycloalkyl of 3-10 carbon atoms, aryl of 6-20 carbon atoms, or heteroaryl of 3-20 carbon atoms; Preferably, R in the compound is N1 and R N2 are, on each occurrence, identically or differently selected from the group consisting of substituted or unsubstituted aralkyl having 7 to 25 carbon atoms, substituted or unsubstituted aryloxy having 7 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 25 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 20 carbon atoms; the substitution employed being selected from deuterium, halogen, alkyl having 1 to 10 carbon atoms, cycloalkyl having 3 to 10 carbon atoms, aryl having 6 to 20 carbon atoms or heteroaryl having 3 to 20 carbon atoms; More preferably, R N1 and R N2 are each independently selected from the following structures:

4. The compound of claim 1, wherein said compound is selected from the group consisting of the compounds corresponding to Number C1 to Number C124:

5. Use of a compound according to any one of claims 1 to 4 in the manufacture of an organic electroluminescent device.

6. An organic electroluminescent device comprising: an anode, a cathode, and a light-emitting layer disposed between the anode and the cathode; the light-emitting layer further comprises a dopant material, the dopant material of the light-emitting layer comprising a compound according to any one of claims 1 to 4.

7. The organic electroluminescent device according to claim 6, characterized in that The compound according to any one of claims 1 to 4 is used as a blue dopant material for a light-emitting layer in an organic electroluminescent device.

8. The organic electroluminescent device according to claim 6, characterized in that, The dopant concentration of the dopant material is 1 wt% to 20 wt%, preferably 1 wt% to 10 wt%, more preferably 2 wt% to 8 wt% relative to the host material in the light-emitting layer.

9. The organic electroluminescent device according to claim 6, characterized in that, The organic electroluminescent device further comprises one or more of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer, an electron injection layer.

10. A display assembly / device comprising a compound according to any one of claims 1 to 4 or an organic electroluminescent device according to any one of claims 6 to 9.

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