A compound and use thereof

Abstract

The present application relates to a kind of compound and its application, the compound is by the mother nucleus shown in formula (1) And at least one substituent group shown in formula (H) Composed, and substituent group shown in formula (H) Substituted in the mother nucleus shown in formula (1) Any substitutable position;By introducing a kind of group containing spiroalkane structure in boron-containing mother nucleus, this kind of spiroalkane structure can effectively play steric hindrance, improve efficiency;In addition, this kind of spiroalkane structure, can effectively improve molecular transition dipole arrangement, realize better light extraction effect, these points jointly act, realize the technical advantage of device efficiency improvement.

Description

Technical Field

[0001] This invention relates to the field of organic electroluminescence technology, and more particularly to a compound and its applications. Background Technology

[0002] The primary way people acquire information is through vision; therefore, display devices are crucial in the process of human interaction with information. Organic light-emitting diodes (OLEDs) have become one of the mainstream display devices due to their numerous advantages, such as flexibility, self-illumination, high contrast, large size, and low power consumption.

[0003] Red and green dyes, as the three primary colors, generally contain heavy atoms such as Ir and Pt, and theoretically can achieve 100% internal quantum efficiency, resulting in high electroluminescence efficiency and low power consumption, making them the mainstream in current commercial display devices. However, the color saturation and lifespan of blue phosphorescent materials do not meet the current commercial display requirements. Currently, blue light devices still use traditional fluorescent materials to achieve high color purity and long device lifespan.

[0004] There is still much room for improvement in the luminescence performance of existing organic electroluminescent materials, and the industry urgently needs to develop new luminescent material systems to meet commercialization needs.

[0005] CN110662750A discloses a class of boron-containing organic materials. In this patent, cyclohexane is preferably used as a steric hindrance group, mainly to reduce concentration quenching in the device. However, the performance of organic electroluminescent devices using this organic material still needs to be improved.

[0006] Therefore, there is an urgent need in this field to develop a novel blue organic electroluminescent material to further improve device performance. Summary of the Invention

[0007] One of the objectives of this invention is to provide a compound, particularly a boron-containing compound, which is a blue fluorescent material. When applied to organic electroluminescent devices, the compound can improve device performance, reduce driving voltage, and increase device efficiency.

[0008] To achieve this objective, the present invention adopts the following technical solution:

[0009] The present invention provides a compound comprising a core represented by formula (1) and at least one (e.g., 1, 2, 3, 4, 5 or 6, etc.) substituent represented by formula (H), wherein the substituent represented by formula (H) substitutes at any substituted position of the core represented by formula (1);

[0010]

[0011] Where * represents the linking bond of a group;

[0012] In formula (1), ring D, ring G, and ring F are independently selected from one of substituted or unsubstituted C5-C60 aromatic rings or substituted or unsubstituted C3-C60 heteroaromatic rings. The substituted group is connected to the connected aromatic ring or heteroaromatic ring to form a ring or not connected to form a ring. The phrase "connected to form a ring or not connected to form a ring" means that when the C6-C60 aromatic ring or the C3-C60 heteroaromatic ring contains a substituent, the substituent can be connected to the substituted aromatic ring or heteroaromatic ring to form a ring structure, or it can be substituted on the aromatic ring or heteroaromatic ring by means of single bond substitution. The way of connecting to form a ring is not specifically limited. For example, it can be connected by a single bond or by a connecting group such as methylene. When similar expressions are mentioned below, they all have the same meaning and will not be described in detail.

[0013] In formula (1), X 1 and X 2 Independently selected from CR 1 R 2 NR 3 O, S or SiR 4 R 5 One of them, the R 1 R 2 R 3 R 4 and R 5 It can independently connect with adjacent rings D, G, or F to form a ring or not; when two Rs are present in the compound. 3 At that time, these two R 3 R can be selected from the same group or from different groups. 1 R 2 R 4 and R 5 Similarly;

[0014] The R 1 R 2 R 3 R 4 and R 5 The substituted group is independently selected from one of the following: substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, wherein the substituted group is connected to or not connected to the connected aromatic or heteroaromatic ring to form a ring.

[0015] In formula (H), ring A and ring E are independently selected from substituted or unsubstituted C3 to C8 aliphatic rings, wherein the substituted group is connected to the connected aliphatic ring to form a ring or not connected to the connected ring; wherein “C3 to C8” means that the aliphatic ring contains 3 to 8 carbon atoms, including the carbon atoms shared by ring A and ring E.

[0016] In formula (H), ring A and ring E are connected by sharing a single sp3 hybrid C atom; by sharing a single sp3 hybrid C atom, a spiral ring structure is formed.

[0017] Ring D, Ring G, Ring F, R 1 R 2 R 3 R 4 R 5 In rings A and E, the substituted groups are independently selected from one or a combination of at least two of the following: halogen, cyano, carbonyl, nitro, hydroxyl, amino, C1-C20 chain alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 silyl, C6-C60 arylamino, C3-C60 heteroarylamino, C6-C60 aryl, and C3-C60 heteroaryl.

[0018] In this invention, "substituted group" refers to the range of substituents to be selected when a "substituted or unsubstituted" group is substituted. The number is not specifically limited, as long as the requirements of the compound bond are met. For example, it can be 1, 2, 3, 4 or 5 substituents. When the number of substituents is 2 or more, these 2 or more substituents can be the same or different.

[0019] In this invention, when the core shown in formula (1) is substituted with at least two substituents shown in formula (H), the structures of these at least two substituents may be the same or different.

[0020] In this invention, halogens represent chlorine atoms, fluorine atoms, bromine atoms, etc.

[0021] In this invention, the expression of Ca to Cb represents that the group has a to b carbon atoms. Unless otherwise specified, the number of carbon atoms generally does not include the number of carbon atoms of the substituents.

[0022] In this invention, the way the ring structure is represented by "—" indicates that the connection point is located at any position on the ring structure where bonding can occur.

[0023] In this specification, aryl includes monocyclic aryl or fused-ring aryl, and heteroaryl includes monocyclic heteroaryl or fused-ring heteroaryl.

[0024] In the present invention, the C6 (or C5) - C60 (such as C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C30, C32, C34, C36, C38, C40, C42, C44, C46, C48, C50, C52, C54, C56, C58, etc.) aryl (or aromatic ring) is preferably a substituted or unsubstituted C6 - C30 aryl (aromatic ring), more preferably a substituted or unsubstituted C6 - C20 aryl (aromatic ring), and still more preferably a group selected from the group consisting of phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, indenyl, fluorenyl and its derivatives, fluoranthenyl, triphenylenyl, pyrenyl, perylenyl, and groups in the group consisting of quaterphenyl. Specifically, biphenyl is selected from 2-biphenyl, 3-biphenyl and 4-biphenyl; terphenyl includes p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl and m-terphenyl-2-yl; the naphthyl includes 1-naphthyl and 2-naphthyl; anthryl is selected from 1-anthryl, 2-anthryl and 9-anthryl; the fluorenyl is selected from 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl; the fluorenyl derivatives are selected from 9,9'-dimethylfluorene, 9,9'-spirobifluorene and benzofluoren; the pyrenyl is selected from 1-pyrenyl, 2-pyrenyl and 4-pyrenyl; quaterphenyl is selected from 1-quaterphenyl, 2-quaterphenyl and 9-quaterphenyl.

[0025] In the present invention, C6 - C60 arylamino represents a group formed by connecting a C6 - C60 aryl and an amino group through a single bond, and the C6 - C60 aryl therein is as described in the above paragraph.

[0026] In the present invention, the heteroatom generally refers to an atom or atomic group selected from N, O, S, P, Si and Se, and is preferably selected from N, O, S. The atomic names in the present invention include their corresponding various isotopes. For example, hydrogen (H) includes 1 H (protium or H), 2 H (deuterium or D), etc.; carbon (C) includes 12 C, 13 C, etc.

[0027] In this invention, the C3-C60 (e.g., C4, C5, C6, C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C30, C32, C34, C36, C38, C40, C42, C44, C46, ​​C48, C50, C52, C54, C56, C58, etc.) heteroaryl (heteroaryl rings) are preferably C3-C30 heteroaryl (heteroaryl rings). The preferred step is using a C4-C20 heteroaryl group (heteroary ring), more preferably a nitrogen-containing heteroaryl group, an oxygen-containing heteroaryl group, a sulfur-containing heteroaryl group, etc. Specific examples include: furanyl, thiophene, pyrrole, benzofuranyl, benzothiophene, isobenzofuranyl, indolyl, dibenzofuranyl, dibenzothiophene, carbazole and its derivatives, wherein the carbazole derivative is preferably 9-phenylcarbazole, 9-naphthylcarbazole, benzocarbazole, dibenzocarbazole, or indolocarbazole.

[0028] In this invention, C3-C60 heteroaryl represents a group formed by C3-C60 heteroaryl and an amino group connected by a single bond, wherein the C3-C60 heteroaryl is as described in the previous paragraph.

[0029] In this invention, the C1-C20 chain alkyl group is preferably a C1-C10 chain alkyl group, more preferably a C1-C6 chain alkyl group, such as methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, isopropyl, isobutyl, tert-butyl, etc.

[0030] In this specification, C3 to C20 cycloalkyl groups include monocycloalkyl and polycycloalkyl groups, wherein polycycloalkyl refers to an alkyl group containing at least two ring structures.

[0031] In this invention, the C3-C20 cycloalkyl group is preferably a C3-C12 cycloalkyl group, and more preferably a C3-C10 cycloalkyl group, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, etc.

[0032] In this invention, C1-C20 alkoxy groups are preferably C1-C10 alkoxy groups, more preferably C1-C6 alkoxy groups, such as methoxy and ethoxy groups.

[0033] In this invention, C1-C20 silane is preferably C1-C10 silane, more preferably C1-C6 silane, such as methylsilane, ethylsilane, isopropylsilane, tert-butylsilane, phenylsilane, etc.

[0034] This invention provides a novel boron-containing compound that introduces a group containing a spiroalkane structure into a boron-containing core. This spiroalkane structure can effectively act as a steric hindrance, thereby improving efficiency. In addition, this spiroalkane structure can effectively improve the molecular transition dipole arrangement, thereby achieving better light extraction. These factors work together to achieve the technical advantage of improved device efficiency.

[0035] Furthermore, the preparation process of the compounds of this invention is simple and easy, the raw materials are readily available, and it is suitable for mass production scale-up.

[0036] Preferably, the compound consists of a core represented by formula (1) and one or two substituents represented by formula (H), wherein the substituents represented by formula (H) substitute at any substituted position of the core represented by formula (1).

[0037] Preferably, the X 1 and X 2 Independently selected from NR 3 One of O or S, with NR being the most preferred. 3 .

[0038] The present invention preferably contains X in the parent nucleus 1 and X 2 The presence of nitrogen atoms at certain positions, along with the resonance effect between boron atoms and nitrogen atoms within the same ring, gives this series of materials narrow spectral density and thermally activated delayed fluorescence emission, thereby further improving device performance.

[0039] Preferably, the parent core shown in formula (1) is specifically the structure shown in formula (1-1);

[0040]

[0041] In equation (1-1), rings D, G, F, and R... 3 All have the same selection range as in equation (1);

[0042] The R 3 'Having R 3 Same selection range. R 3 'With R 3 You can choose the same group or different groups.

[0043] The compounds provided by this invention have the following structures depending on the substitution site of the (H) group:

[0044]

[0045] When the (H) group is substituted in R 3 When it is above, the substitution site is also arbitrary.

[0046] Preferably, ring D, ring G, and ring F are independently selected from one of substituted or unsubstituted C5-C30 aromatic rings or substituted or unsubstituted C3-C30 heteroaromatic rings, more preferably one of substituted or unsubstituted C5-C14 aromatic rings or substituted or unsubstituted C3-C14 heteroaromatic rings, and even more preferably one of substituted or unsubstituted C5-C8 aromatic rings or substituted or unsubstituted C5-C8 heteroaromatic rings.

[0047] Preferably, ring D, ring G, and ring F are independently selected from the groups shown in formula (b);

[0048]

[0049] The ring D is connected to other parts of the parent nucleus through shared chemical bonds c and d;

[0050] The rings G and F are independently connected to other parts of the parent nucleus via shared chemical bond c or chemical bond d;

[0051] In equation (b), Z 1 Z 2 Z 3 and Z 4 Independently selected from CR 6 Or N, the R 6 Independently selected from one of hydrogen, halogen, cyano, carbonyl, nitro, hydroxyl, amino, C1-C20 chain alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 silyl, C6-C60 arylamino, C3-C60 heteroarylamino, C6-C60 aryl, and C3-C60 heteroaryl, wherein R 6 It can independently connect with connected aromatic or heteroaromatic rings to form a ring or not connect to form a ring. When there are two or more R in equation (b). 6 At that time, two or more R 6 They can be the same or different.

[0052] Preferably, the core shown in formula (1) is specifically the structure shown in formula (1-1-1), formula (1-1-2) or formula (1-1-3), with the structure shown in formula (1-1-1) being preferred;

[0053]

[0054] The Z 1 Z 1 '、Z 1 Z 2 Z 2 '、Z 2 Z 3 Z 3 '、Z 3 Z 4and Z 4 'Independently selected from CR 6 Or N, the R 6 Independently selected from one of hydrogen, halogen, cyano, carbonyl, nitro, hydroxyl, amino, C1-C20 chain alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 silyl, C6-C60 arylamino, C3-C60 heteroarylamino, C6-C60 aryl, and C3-C60 heteroaryl, wherein R 6 It can independently connect with connected aromatic or heteroaromatic rings to form a ring or not connect to form a ring;

[0055] The Z 5 Z 5 '、Z 6 Z 6 '、Z 7 Z 7 '、Z 8 and Z 8 'Independently selected from CR 7 Or N, the R 7 Independently selected from one of hydrogen, halogen, cyano, carbonyl, nitro, hydroxyl, amino, C1-C20 chain alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 silyl, C6-C60 arylamino, C3-C60 heteroarylamino, C6-C60 aryl, and C3-C60 heteroaryl, wherein R 7 Independently linked to an aromatic ring or heteroaromatic ring to form a ring or not; when two or more Rs exist in the parent nucleus 7 At that time, two or more R 7 They can be the same or different;

[0056] The R 3 Having the same selection range as in equation (1), the R 3 'Having R 3 Same selection range.

[0057] Preferably, the Z 5 Z 6 Z 7 and Z 8 At most two of them are N, and / or, the Z 5 '、Z 6 '、Z 7 'and Z 8 At most two of them are N.

[0058] Preferably, the R 3It is selected from one of substituted or unsubstituted C6-C60 aryl and substituted or unsubstituted C3-C60 heteroaryl, preferably substituted or unsubstituted C6-C30 aryl; more preferably substituted or unsubstituted phenyl.

[0059] Preferably, R 3 In this context, the substituted group is selected from any one or at least two combinations of C1-C20 chain alkyl or C6-C60 aryl, preferably any one or at least two combinations of methyl, isopropyl, tert-butyl, and phenyl.

[0060] Preferably, the substituent represented by formula (H) specifically has the structure represented by formula (H');

[0061]

[0062] In formula (H'), * represents the linking bond of a group;

[0063] In equation (H'), m and n are independent integers from 0 to 5, such as 1, 2, 3 or 4, and r and s are each independent integers from 0 to 6, such as 1, 2, 3, 4 or 5. For example, when m or n is 0, it is a ternary ring; when it is 1, it is a quaternary ring; when it is 2, it is a quinary ring, and so on.

[0064] In formula (H'), R a and R b Independently selected from one of halogen, cyano, carbonyl, nitro, hydroxyl, amino, C1-C20 chain alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 silyl, C6-C60 arylamino, C3-C60 heteroarylamino, C6-C60 aryl, and C3-C60 heteroaryl, wherein R a and R b It may connect independently to the connected adipose ring to form a ring or not connect independently to form a ring.

[0065] When there are two or more R in equation (H') a At that time, two or more R a They can be the same or different, R b Similarly.

[0066] Preferably, the substituent represented by formula (H) is one of the structures represented by formulas (H-1) to (H-6), with the structure represented by formula (H-1) being preferred;

[0067]

[0068] In this context, * represents the linking bond of a group; and in (H-2), (H-4), and (H-6), the straight lines that pass through both rings indicate that the linking bond can be on either ring.

[0069] The R a R b r and s all have the same range of choices as in equation (H').

[0070] Preferably, the R a and R b It is independently selected from C1 to C20 chain alkyl groups, preferably methyl or n-butyl.

[0071] Preferably, r and s are independently 0 to 2, for example 1, and preferably 0.

[0072] Preferably, the substituent represented by formula (H) is specifically selected from one of the following groups:

[0073]

[0074] In this context, * represents the linking bond of a group.

[0075] Preferably, the compound has any one of the structures described in M1-M104;

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082] A second objective of this invention is to provide an application of the compound described in one objective, wherein the compound is used in an organic electroluminescent device.

[0083] Preferably, the compound is used as a light-emitting layer material in the organic electroluminescent device, and is preferably a light-emitting dye.

[0084] A third objective of this invention is to provide an organic electroluminescent device, the organic electroluminescent device comprising a substrate, and a first electrode, an organic layer, and a second electrode sequentially formed on the substrate, wherein the organic layer contains the compound described in one of the objectives.

[0085] OLED devices prepared using the compounds of this invention have low start-up voltage and better lifespan, which can meet the current requirements of panel manufacturers for high-performance materials.

[0086] Preferably, the organic layer includes a light-emitting layer containing one of the compounds described in the objectives.

[0087] An OLED includes a first electrode and a second electrode, and an organic material layer located between the electrodes. This organic material layer can be further divided into multiple regions. For example, the organic material layer may include a hole transport region, a light-emitting layer, and an electron transport region.

[0088] In specific embodiments, a substrate can be used below the first electrode or above the second electrode. The substrate is typically made of glass or polymer material with excellent mechanical strength, thermal stability, water resistance, and transparency. Furthermore, thin-film transistors (TFTs) can also be incorporated into the substrate used for displays.

[0089] The first electrode can be formed by sputtering or depositing the material to be used as the first electrode on a substrate. When the first electrode is used as the anode, it can be a transparent conductive oxide material such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), zinc oxide (ZnO), or any combination thereof. When the first electrode is used as the cathode, it can be a metal or alloy such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), ytterbium (Yb), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), or any combination thereof.

[0090] Organic material layers can be formed on electrodes using methods such as vacuum thermal evaporation, spin coating, and printing. The compounds used as organic material layers can be small organic molecules, large organic molecules, polymers, and combinations thereof.

[0091] The hole transport region is located between the anode and the emissive layer. The hole transport region can be a single-layer hole transport layer (HTL), including single-layer hole transport layers containing only one compound and single-layer hole transport layers containing multiple compounds. Alternatively, the hole transport region can be a multilayer structure including at least one of a hole injection layer (HIL), a hole transport layer (HTL), and an electron blocking layer (EBL); wherein the HIL is located between the anode and the HTL, and the EBL is located between the HTL and the emissive layer.

[0092] The material for the hole transport region may be selected from, but is not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or polymers containing conductive dopants such as polyphenylene ethylene, polyaniline / dodecylbenzenesulfonic acid (Pani / DBSA), poly(3,4-ethylenedioxythiophene) / poly(4-styrenesulfonate) (PEDOT / PSS), polyaniline / camphorsulfonic acid (Pani / CSA), polyaniline / poly(4-styrenesulfonate) (Pani / PSS), aromatic amine derivatives as shown in HT-1 to HT-51 below; or any combination thereof.

[0093]

[0094]

[0095]

[0096]

[0097] The hole injection layer is located between the anode and the hole transport layer. The hole injection layer can be a single compound material or a combination of multiple compounds. For example, the hole injection layer can be one or more compounds of HT-1 to HT-51 mentioned above, or one or more compounds of HI-1 to HI-3 mentioned below; it can also be one or more compounds of HT-1 to HT-51 doped with one or more compounds of HI-1 to HI-3 mentioned below.

[0098]

[0099] The emissive layer includes luminescent dyes (i.e., dopants) that can emit different wavelengths of light, and may also include a host material. The emissive layer can be a monochromatic emissive layer emitting a single color such as red, green, or blue. Multiple monochromatic emissive layers of different colors can be arranged in a planar pattern according to pixel design, or they can be stacked together to form a colored emissive layer. When different colored emissive layers are stacked together, they can be separated from each other or connected to each other. The emissive layer can also be a single colored emissive layer that can simultaneously emit different colors such as red, green, and blue.

[0100] Depending on the technology used, the light-emitting layer material can be various, including fluorescent electroluminescent materials, phosphorescent electroluminescent materials, and thermally activated delayed fluorescence materials. An OLED device can employ a single light-emitting technology or a combination of different technologies. These different light-emitting materials, categorized by technology, can emit light of the same color or different colors.

[0101] In one aspect of the invention, the light-emitting layer employs fluorescent electroluminescence technology. The fluorescent host material of the light-emitting layer may be selected from, but is not limited to, one or more combinations of BFH-1 to BFH-17 listed below.

[0102]

[0103] In one aspect of the present invention, an electron blocking layer (EBL) is located between the hole transport layer and the light-emitting layer. The electron blocking layer may employ, but is not limited to, one or more compounds of HT-1 to HT-51 described above, or one or more compounds of PH-47 to PH-77 described below; or a mixture of one or more compounds of HT-1 to HT-51 and one or more compounds of PH-47 to PH-77 may be employed.

[0104]

[0105]

[0106]

[0107] The OLED organic material layer may also include an electron transport region between the light-emitting layer and the cathode. The electron transport region can be a single-layer electron transport layer (ETL), including single-layer electron transport layers containing only one compound and single-layer electron transport layers containing multiple compounds. Alternatively, the electron transport region can be a multilayer structure including at least one of an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL).

[0108] In one aspect of the present invention, the electron transport layer material may be selected from, but not limited to, one or more combinations of ET-1 to ET-65 listed below.

[0109]

[0110]

[0111]

[0112]

[0113] In one aspect of the present invention, a hole blocking layer (HBL) is located between the electron transport layer and the light-emitting layer. The hole blocking layer may employ, but is not limited to, one or more compounds of ET-1 to ET-65 described above, or one or more compounds of PH-1 to PH-46 described below; or a mixture of one or more compounds of ET-1 to ET-65 and one or more compounds of PH-1 to PH-46 may be employed.

[0114]

[0115]

[0116]

[0117] The device may also include an electron injection layer located between the electron transport layer and the cathode, and the electron injection layer material includes, but is not limited to, one or more combinations of the following.

[0118] LiQ, LiF, NaCl, CsF, Li2O, Cs2CO3, BaO, Na, Li, Ca, Mg, Yb.

[0119] The fourth objective of this invention is to provide a display screen or display panel, wherein the display screen or display panel employs the organic electroluminescent device as described in the third objective; preferably, the display screen or display panel is an OLED display.

[0120] A fifth objective of the present invention is to provide an electronic device having the display screen or display panel described in objective four.

[0121] Compared with the prior art, the present invention has the following beneficial effects:

[0122] (1) The present invention introduces a group containing a spiroalkane structure into a boron-containing compound. This spiroalkane structure can effectively play a steric hindrance role and improve efficiency. In addition, this spiroalkane structure can effectively improve the molecular transition dipole arrangement and achieve better light extraction effect. These factors work together to achieve the technical advantage of improving device efficiency.

[0123] (2) The preparation process of the compound of the present invention is simple and easy to carry out, the raw materials are readily available, and it is suitable for mass production scale-up. Detailed Implementation

[0124] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0125] The representative synthetic route of the novel boron-containing compound provided by this invention is as follows:

[0126] Method 1:

[0127]

[0128] Method 2:

[0129]

[0130] Method 3:

[0131]

[0132] The above symbols all have the same meaning as in equations (1) and (H).

[0133] It should be noted that obtaining the compounds of this invention is not limited to the synthetic methods and raw materials used in this invention. Those skilled in the art can also select other methods or routes to obtain the compounds proposed in this invention. The compounds synthesized by methods not mentioned in this invention are all raw material products obtained through commercial means, or prepared in-house using these raw material products according to known methods.

[0134] The following synthetic examples exemplify the synthetic methods of specific compounds, wherein the analysis and detection of intermediates and compounds were performed using an ABSCIEX mass spectrometer (4000QTRAP).

[0135] Synthesis Example 1: Synthesis of M-17

[0136]

[0137] Preparation of intermediate M17-1:

[0138] Add 50 g (264.19 mmol, 1 eq) of 4-(4-aminophenyl)cyclohexanone to a 1 L single-necked flask at room temperature. Replace the nitrogen atmosphere three times with 500 mL of anhydrous diethyl ether. Add 158.5 mL (317.03 mmol, 2 mol / L cyclohexane solution, 1.2 eq) of allephemeral magnesium chloride dropwise to the system under ice bath conditions. React at room temperature for 2 h. Filter, concentrate the filtrate to remove the solvent.

[0139] Under ice bath conditions, phosphoric acid (200 mL) and water (100 mL) were added to the residue and refluxed for 5 h. The mixture was then neutralized to a weakly alkaline state by adding sodium hydroxide aqueous solution under ice bath conditions. The mixture was extracted with ethyl acetate (500 mL), concentrated, and subjected to column chromatography to obtain 60 g of a pale yellow oily substance.

[0140] Synthesis of intermediate M17-2:

[0141] Intermediate M17-1 (24.3 g, 100 mmol, 1 eq) was dissolved in 300 mL of DMF. A DMF solution (100 mL) containing NBS (35.5 g, 200 mmol, 2 eq) was slowly added at -40 °C. After the addition was complete, the mixture was allowed to react at low temperature for 0.5 h. The reaction mixture was then added to water and extracted with dichloromethane (300 mL). The extract was first washed with sodium sulfite solution, then washed several times with water, and the mixture was separated and evaporated to dryness under reduced pressure to obtain 28.9 g of a white solid.

[0142] Synthesis of intermediate M17-3:

[0143] 20.12 g (195.07 mmol, 3 eq) of tert-butyl nitrite and 19.31 g (195.07 mmol, 3 eq) of cuprous chloride were added to a 1 L single-necked flask and dissolved in 100 mL of acetonitrile. The mixture was heated at 50 °C under nitrogen protection for 1 h. Then, intermediate M17-2 (26.06 g, 65 mmol, 1 eq) was dissolved in 200 mL of acetonitrile and slowly added dropwise to the reaction mixture. The reaction was stopped after 2 h at 50 °C, filtered, evaporated to dryness, and subjected to column chromatography with silica gel and pure petroleum ether. 13.5 g of a white solid was obtained.

[0144] Synthesis of intermediate M17-4:

[0145] At room temperature, M17-3 (8.4 g, 20 mmol), 3,6-di-tert-butylaniline (16 g, 64 mmol), tris(dibenzylacetone)dipalladium (Pd2(dba)3, 0.56 g, 0.6 mmol), 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl (s-Phos, 0.24 g, 0.6 mmol), sodium tert-butoxide (6.7 g, 70 mmol), and xylene (300 mL) were added to a 1 L single-necked flask. The mixture was purged with nitrogen three times and heated to 130 °C overnight. The reaction solution was cooled to room temperature, extracted with ethyl acetate, washed thoroughly with water, dried, concentrated, and subjected to column chromatography to give 10.1 g of a white solid.

[0146] Synthesis of compound M-17:

[0147] M17-4 (8.2 g, 10 mmol) was added to a 500 mL three-necked flask, followed by p-tert-butylbenzene (t-BuPh, 150 mL). After stirring for 20 minutes, the reaction mixture was cooled to 0 °C, and then 15 mmol of tert-butyllithium (t-BuLi) was added. The mixture was stirred for another 30 minutes while maintaining the low temperature. The temperature was then gradually increased to 60 °C and maintained for 3 hours. Finally, the reaction mixture was cooled back to -20 °C, and boron tribromide (5.1 g, 20 mmol) was added under nitrogen protection. After stirring for 30 minutes, diisopropylethylamine (NEt(i-Pr)2, 13 g, 80 mmol) was added. The reaction mixture was then heated to 110 °C and reacted for 12 hours. After cooling to room temperature, the organic phase was evaporated to dryness under reduced pressure. The mixture was extracted three times with ethyl acetate (200 mL), and the combined organic phases were dried over anhydrous sodium sulfate. Organic phase was concentrated with silica gel, and column chromatography yielded 2.7 g of crude product. Recrystallization from toluene / n-hexane gave 1.65 g of yellow solid with a purity of 99.45%. Mass spectrometry analysis determined the molecular ion mass to be 795.22 (theoretical value: 795.01).

[0148] Synthesis Example 2: Synthesis of M-69

[0149]

[0150] Preparation of intermediate M69-1:

[0151] The synthesis scheme was the same as that for M17-3, except that 65 mmol of M17-2 was replaced with M17-1, and 12.7 g of white solid was obtained after column chromatography.

[0152] Synthesis of intermediate M69-2:

[0153] At room temperature, M69-1 (10.4 g, 40 mmol), M17-1 (13.8 g, 60 mmol), Pd2(dba)3 (0.56 g, 0.6 mmol), sP hos (0.24 g, 0.6 mmol), sodium tert-butoxide (NaOBut, 6.7 g, 70 mmol), and xylene (300 mL) were added to a 1 L single-necked flask. The mixture was purged with nitrogen three times and heated to 130 °C overnight. The reaction solution was cooled to room temperature, extracted with ethyl acetate, washed thoroughly with water, dried, concentrated, and subjected to column chromatography to give 13.7 g of a white solid.

[0154] Synthesis of intermediate M69-3:

[0155] At room temperature, M69-2 (10.4 g, 40 mmol), 1,3-dibromo-2-chloro-5-methylbenzene (14 g, 50 mmol), Pd2(dba)3 (0.56 g, 0.6 mmol), sP hos (0.24 g, 0.6 mmol), sodium tert-butoxide (6.7 g, 70 mmol), and xylene (300 mL) were added to a 1 L single-necked flask. The mixture was purged with nitrogen three times and heated to 130 °C overnight. The reaction solution was cooled to room temperature, extracted with ethyl acetate, washed thoroughly with water, dried, concentrated, and subjected to column chromatography to give 17.7 g of a white solid.

[0156] Synthesis of intermediate M69-4:

[0157] At room temperature, M69-3 (13.4 g, 20 mmol), diphenylamine (6.8 g, 40 mmol), Pd2(dba)3 (0.28 g, 0.3 mmol), sP hos (0.12 g, 0.3 mmol), sodium tert-butoxide (3.4 g, 35 mmol), and xylene (200 mL) were added to a 500 mL single-necked flask. The mixture was purged with nitrogen three times and heated to 130 °C overnight. The reaction solution was cooled to room temperature, extracted with ethyl acetate, washed thoroughly with water, dried, concentrated, and subjected to column chromatography to give 10.7 g of a white solid.

[0158] Synthesis of compound M-69:

[0159] The synthesis scheme was the same as that for M-17, except that M17-4 was replaced with M69-4 (10 mmol). After purification, 1.46 g of yellow solid was obtained with a purity of 99.78%. The molecular ion mass determined by mass spectrometry was 734.56 (theoretical value: 734.87).

[0160] The synthesis of other compounds was similar, based on the relevant general synthetic formulas, and confirmed by mass spectrometry. The results are shown in the table below:

[0161] Compound numbering theoretical value of mass spectrometry Mass spectrometry test data M-1 570.32 570.47 M-13 570.32 570.39 M-24 710.47 710.56 M-41 622.35 622.57 M-50 772.49 772.83 M-57 874.44 874.74 M-66 734.47 734.58 M-85 838.53 838.67 M-89 674.38 674.49 M-2 556.30 556.44 M-6 542.28 542.67 M-8 542.28 542.39 M-7 514.25 514.45 M-9 528.27 528.32 M-11 598.35 598.45 M-101 528.39 528.55 M-102 593.36 593.73 M-103 508.24 508.76 M-104 627.37 627.53

[0162] Device Example 1

[0163] The glass plate coated with the ITO transparent conductive layer was ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in a acetone:ethanol mixed solvent, baked in a clean environment until all moisture was removed, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam.

[0164] The glass substrate with the anode was placed in a vacuum chamber and evacuated to a vacuum level of <1×10⁻⁶. -5 Pa, on the aforementioned anolyte film, a 10 nm HT-4:HI-3 (97 / 3, w / w) mixture was vacuum thermally deposited as a hole injection layer, a 60 nm HT-4 compound as a hole transport layer, and a 5 nm HT-14 compound as an electron blocking layer; a 20 nm BFH-4:M-1 (100:3, w / w) binary mixture was deposited as a light-emitting layer ("100:3, w / w" refers to the weight ratio of the two substances being 100:3); a 5 nm ET-23 was deposited as a hole blocking layer; a 25 nm ET-61:ET-57 (50 / 50, w / w) mixture was deposited as an electron transport layer; a 1 nm LiF layer was deposited as an electron injection layer; and a 150 nm aluminum metal was deposited as a cathode. The total deposition rate of all organic layers and LiF was controlled at 0.1 nm / s, and the deposition rate of the metal electrode was controlled at 1 nm / s.

[0165] Device Examples 2 to 21 were fabricated using the same method as Device Example 1, except that the dye M-1 in the light-emitting layer was replaced, while other parameters remained unchanged. See Table 1 for details.

[0166] Comparative Examples 1 and 2 were fabricated using the same method as Comparative Example 1, except that dye M-1 in the light-emitting layer was replaced with ref-1 and ref-2 (CN110662750A), respectively.

[0167]

[0168] Device performance testing:

[0169] The organic electroluminescent devices prepared by the above process were subjected to the following performance measurements:

[0170] At the same brightness, the driving voltage and external quantum efficiency of the organic electroluminescent devices prepared in the above-described device embodiments and comparative examples were measured using a digital source meter and a PR650. Specifically, the voltage was increased at a rate of 0.1 V per second, and the driving voltage and external quantum efficiency were measured when the brightness of the organic electroluminescent device reached 1000 cd / m². 2 The voltage at that time is the driving voltage at the corresponding brightness, and the external quantum efficiency (EQE%) of the device can be directly measured on the PR650.

[0171] The performance of organic electroluminescent devices is shown in Table 1.

[0172] Table 1

[0173]

[0174]

[0175] The above results show that the novel organic material of the present invention can be used in organic electroluminescent devices. Compared with comparative devices 1-2, the devices in Examples 1-21 can effectively reduce the operating voltage and improve the external quantum efficiency, and are high-performance blue light materials.

[0176] The present invention has been illustrated with the above embodiments to explain the detailed method of the present invention. However, the present invention is not limited to the detailed method described above, that is, it does not mean that the present invention must rely on the detailed method described above to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A compound, characterized in that, The compound consists of a core represented by formula (1) and one or two substituents represented by formula (H), wherein the substituents represented by formula (H) substitute at any substituted position of the core represented by formula (1); Where * represents the linking bond of a group; In formula (1), ring D, ring G and ring F are independently selected from the groups shown in formula (b); （b） The ring D is connected to other parts of the parent nucleus through shared chemical bonds c and d; The rings G and F are independently connected to other parts of the parent nucleus via shared chemical bond c or chemical bond d; In equation (b), Z 1 Z 2 Z 3 and Z 4 Independently selected from CR 6 The R 6 The R is independently selected from one or a combination of at least two of hydrogen, C1-C10 chain alkyl, and C6-C20 aryl, wherein the R 6 It does not independently connect with the aromatic rings to form a ring; In equation (1), X 1 and X 2 Independently selected from CR 1 R 2 NR 3 S or SiR 4 R 5 One of them, the R 1 R 2 R 3 R 4 and R 5 It can be independently connected to adjacent rings G or F to form a ring, or it can remain unconnected to form a ring. The R 1 R 2 R 4 and R 5 Independently selected from C1-C10 chain alkyl groups, R 3 It is selected from one of substituted or unsubstituted C6-C20 aryl groups and substituted or unsubstituted C3-C10 heteroaryl groups, wherein the substituted group is not connected to the connected aromatic or heteroaryl ring to form a ring; R 3 In this context, the substituted groups are independently selected from C1-C10 chain alkyl groups; The substituents shown in formula (H) are specifically selected from one of the following groups: ； In this context, * represents the linking bond of a group.

2. The compound according to claim 1, characterized in that, The X 1 and X 2 Independently selected from NR 3 Or one of S.

3. The compound according to claim 2, characterized in that, The X 1 and X 2 Independently selected from NR 3 .

4. The compound according to claim 1, characterized in that, The parent nucleus shown in formula (1) is specifically the structure shown in formula (1-1); In equation (1-1), rings D, G, F, and R... 3 All have the same scope of definition as claim 1; The R 3 'Having R 3 Same scope.

5. The compound according to claim 1, characterized in that, The parent core shown in formula (1) is specifically the structure shown in formula (1-1-1), formula (1-1-2), or formula (1-1-3); ； The Z 1 Z 1 '、Z 1 ''、Z 2 Z 2 '、Z 2 ''、Z 3 Z 3 '、Z 3 ''、Z 4 and Z 4 'Independently selected from CR 6 The R 6 Independently selected from hydrogen, C1-C10 chain alkyl, and C6-C20 aryl, wherein R 6 It does not independently connect with the aromatic rings to form a ring; The Z 5 Z 5 '、Z 6 Z 6 '、Z 7 Z 7 '、Z 8 and Z 8 'Independently selected from CR 7 Or N, the R 7 Independently selected from hydrogen, C1-C10 chain alkyl, and C6-C20 aryl, wherein R 7 It does not independently connect with the aromatic rings to form a ring; The R 3 Having the same scope as claim 1, the R 3 'Having R 3 Same scope.

6. The compound according to claim 5, characterized in that, The core shown in formula (1) is specifically the structure shown in formula (1-1-1).

7. The compound according to claim 5, characterized in that, The Z 5 Z 6 Z 7 and Z 8 At most two of them are N, and / or, the Z 5 '、Z 6 '、Z 7 'and Z 8 At most two of them are N.

8. The compound according to claim 1, characterized in that, The R 3 The substituted or unsubstituted phenyl group is selected from C1-C10 chain alkyl groups.

9. The compound according to claim 1, characterized in that, R 3 In this context, the substituted group is selected from any one or at least a combination of two of methyl, isopropyl, and tert-butyl groups.

10. A compound, characterized in that, The compound has any one of the structures described in M1-M104; 。 11. The use of a compound according to any one of claims 1-10, characterized in that, The compound is used as a luminescent dye in organic electroluminescent devices, serving as the luminescent layer.

12. An organic electroluminescent device, characterized in that, The organic electroluminescent device includes a substrate, and a first electrode, an organic layer, and a second electrode sequentially formed on the substrate; The organic layer includes a light-emitting layer, which contains the compound according to any one of claims 1-10.

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