Heteroatom-containing spirocyclic derivatives and their applications

Abstract

The invention discloses a spiro derivative containing heteroatoms, the general formula of which is: The purpose of the spiro derivative containing heteroatoms is to prepare organic photoelectric devices, that is, to serve as a material for the light-emitting layer of organic photoelectric devices.

Description

Technical Field

[0001] The present invention belongs to the field of organic optoelectronics, and particularly relates to spiro derivatives containing heteroatoms and applications thereof. Background Art

[0002] Organic Light-Emitting Diode (OLED), also known as organic electric laser display or organic light-emitting semiconductor, refers to the phenomenon in which organic semiconductor materials and luminescent materials emit light through carrier injection and recombination under the drive of an electric field. In terms of commercial applications, OLED has gradually become market-oriented and scaled in the field of information display, and has also entered the fast lane of industrialization in the fields of solid-state lighting and flexible displays. Although it already has the technical foundation for industrialization, OLED technology has not yet reached perfection, and some technical links need to be improved urgently, especially the development of high-efficiency, stable and long-life blue light devices. One way to achieve high-performance blue fluorescent materials is to design a bipolar molecular structure with a bipolar (DA) system. Diphenylamine and carbazole are both excellent blue luminophores and good electron donor elements. The phenanthroimidazole group is a common electron acceptor blue light chromophore with multiple sites for structural modification. At the same time, electron donor / acceptor groups are introduced to raise the highest occupied molecular orbital (HOMO) energy level and lower the lowest unoccupied molecular orbital (LUMO) energy level to reduce the carrier injection barrier, balance carrier transport, and make the HOMO and LUMO energy levels partially overlap to adjust the fluorescence quantum efficiency. However, this often leads to the occurrence of charge transfer transitions between the electron donor / acceptor groups, resulting in a red shift in the luminescence spectrum.

[0003] Spiroaromatic hydrocarbons (spirobifluorene and spirofluorene heteroanthracene) are important building blocks for organic semiconductor materials. Spiro[fluorene-9,9'-heteroanthracene] (SFX) boasts a one-pot synthesis strategy, a cross-orthogonal structure similar to SBF, spectral properties, and thermal stability. In recent years, it has seen rapid development in applications such as undoped blue-emitting OLED materials and host materials. The development of new host materials requires excellent bipolar carrier injection and transport properties (holes and electrons) to prevent carrier accumulation between the emissive layer and the charge transport layer, which can lead to exciplex luminescence at the interface. This can result in low device parameters such as external quantum efficiency, power efficiency, and current efficiency, high turn-on voltage, and spectral instability. The highly rigid spirocyclic structure not only reduces molecular aggregation beneath the film but also dampens molecular vibration, preventing the release of excitation energy as heat due to vibration, thereby enhancing fluorescence. The 9-position substitution of the fluorene with an aromatic hydrocarbon avoids the formation of fluorenone defects caused by oxidation of the carbon atom.

[0004] Boron, due to its unique valence shell electronic structure—the number of valence electrons is less than the number of valence orbitals, resulting in a vacant p orbital—can effectively conjugate tri-coordinate compounds with adjacent π systems and easily complex with Lewis bases to form tetra-coordinate compounds. Introducing boron into traditional optoelectronic functional molecules often imparts unique optoelectronic properties to the overall system, making it an important strategy for the design of novel organic optoelectronic functional molecules.

[0005] The nitrogen-containing spiro compound BiBSTPA has the structural formula Although the spectrum of this compound is in the blue light region, its fluorescence quantum efficiency is low. When used in device preparation, the turn-on voltage is high and the efficiency roll-off is severe (J. Mater. Chem. C, 2013, 1, 463–469). Summary of the Invention

[0006] The technical problem to be solved by the present invention is to provide spirocyclic derivatives and applications thereof.

[0007] In order to solve the above technical problems, the present invention provides a spiro derivative containing a heteroatom, which has the following general formula:

[0008]

[0009] In the general formula:

[0010] Ar1 represents a deuterated, substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C60 aryl group, or a substituted or unsubstituted 1- to 30-membered heteroaryl group; or is linked with adjacent substituents to form a monocyclic or polycyclic ring, specifically a C3-C60 aliphatic or aromatic ring, wherein the carbon atoms of the ring are optionally replaced by at least one heteroatom selected from nitrogen, oxygen, and sulfur; or at least one of an unsubstituted C12-C40 carbazolyl group and its derivatives, a substituted or unsubstituted C12-C40 diphenylamino group and its derivatives, and a C13-C40 acridinyl group and its derivatives; and at least one, more, or all of the deuterated hydrogen atoms are deuterated (i.e., the hydrogen atoms on Ar1 are optionally substituted with deuterium, and at least one, more, or all of the deuterated hydrogen atoms are deuterated);

[0011] R1 and R2 are independently selected from any one of hydrogen, deuterium, CN, halogen, C1-C60 alkyl, C1-C60 alkoxy, C1-C60 alkylsilyl, C1-C60 alkoxysilyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C1-C60 heteroaryl, substituted or unsubstituted alkenyl, substituted or unsubstituted arylether, substituted or unsubstituted heteroarylether, substituted or unsubstituted arylamine, substituted or unsubstituted heteroarylamine, substituted or unsubstituted arylsilyl, substituted or unsubstituted heteroarylsilyl, substituted or unsubstituted aryloxysilyl, substituted or unsubstituted arylacyl, substituted or unsubstituted heteroarylacyl, and substituted or unsubstituted phosphinyl; heteroaryl refers to a group containing at least one heteroatom selected from B, N, O, S, P(=O), and Si;

[0012] Ar2 and Ar3 are independently selected from a group having 1 to 60 carbon atoms, the group including alkyl, substituted or unsubstituted arylalkyl, alkoxy, substituted or unsubstituted aryloxy, alkylsilyl, alkoxy, alkylsiloxy, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, alkylamino, substituted or unsubstituted arylamino, substituted or unsubstituted heteroarylamino, and combinations thereof; substituted or unsubstituted C10-C60 condensed aryl, substituted or unsubstituted C10-C60 condensed heteroaryl, substituted or unsubstituted C12-C40 carbazolyl and derivatives thereof, substituted or unsubstituted C12-C40 diphenylamine and derivatives thereof, substituted or unsubstituted C18-C60 triphenylamine and derivatives thereof, C12-C40 acridinium and derivatives thereof at least one group;

[0013] The hydrogen atoms on Ar2 and Ar3 may be fully deuterated, partially deuterated, or not deuterated;

[0014] X is O or S or B or P(═O) or N or C;

[0015] Y is C or Si;

[0016] G may be present or absent. When present, G is O or S or Se or Te or O=S=O;

[0017] h is 0, 1, or 2. When X is O or S, h is 0. When X is B, P (=O), or N, h is 1. When X is C, h is 2.

[0018] a and b are each independently an integer from 0 to 4. In the same structural formula, a and b may be the same or different at the same time;

[0019] m and n are each independently an integer from 0 to 4. In the same structural formula, m and n may be the same or different at the same time, and m+n≥1.

[0020] As an improvement of the heteroatom-containing spiro derivative of the present invention: as a preferred embodiment: Y is C, G is absent, and X is B.

[0021] As a further improvement of the heteroatom-containing spiro derivative of the present invention, it has the following structural formula:

[0022]

[0023] As a further improvement of the heteroatom-containing spiro derivative of the present invention: h=1, a=b=0, m+n=1 or 2.

[0024] As a further improvement of the heteroatom-containing spiro derivative of the present invention: the substitution positions of Ar2 and Ar3 are the 3-position and 6-position of fluorene.

[0025] As a further improvement of the heteroatom-containing spiro derivatives of the present invention, the structures shown in Chemical Formula III and Chemical Formula IV are as follows:

[0026]

[0027] As a further improvement of the heteroatom-containing spiro derivative of the present invention: Ar1 is any one of the following:

[0028]

[0029] Ar2 and Ar3 are any of the following (and hydrogen on the aromatic ring may be replaced by deuterium):

[0030]

[0031] Ar4 may or may not exist. When it exists, it is:

[0032] In the above structure, · represents a connection point with an adjacent atom.

[0033] As a further improvement of the heteroatom-containing spiro derivative of the present invention, the specific structural formula of the spiro compound is any of the following:

[0034]

[0035]

[0036]

[0037]

[0038]

[0039] Wherein: R3 and R4 may exist at the same time or not exist at the same time. When they exist, R3 and R4 are the same and are any of the following groups:

[0040]

[0041] The present invention also provides a use of the above-mentioned spiro derivative containing heteroatoms: preparing organic photoelectric devices.

[0042] An improvement on the use of the heteroatom-containing spiro derivative of the present invention: as a material for the light-emitting layer of an organic optoelectronic device (as a light-emitting host material or a light-emitting guest material).

[0043] The organic semiconductor luminescent materials of the present invention can be used in organic light-emitting diodes (OLEDs). In OLED applications, an OLED light-emitting device generally comprises a substrate material, an anode, a cathode, and an organic semiconductor (e.g., an electron injection layer between the luminescent layer and the cathode, and a hole injection layer between the luminescent layer and the anode). The luminescent layer contains a luminescent dopant mixed with a host material to form the luminescent layer. Typically, the luminescent dopant material is doped into the host material at a concentration of 1-50% (by weight).

[0044] The excitation relaxation time of TADF luminescent materials (thermally activated delayed fluorescence luminescent materials) is generally in the order of microseconds and sub-microseconds, which is longer than that of general fluorescent luminescent materials (in the order of nanoseconds), or the intermolecular exciton transmission distance is longer. Therefore, TADF luminescent materials use general cyano, methyl, ethyl, tert-butyl, methoxy, phosphine, halogen, etc. substitutions or it is difficult to effectively reduce the annihilation of excitons between luminescent molecules. The present invention uses cyclic alkyl substitutions, or even spirocycloalkane substitutions, and unexpectedly found that the organic luminescent boron compounds so substituted can reduce the annihilation of excitons between luminescent molecules, increase the molecular distance, inhibit molecular stacking and Dexter energy transfer, and thus improve the efficiency roll-off problem of organic electroluminescent devices using such compounds, and improve the luminous efficiency. The organic molecular semiconductor formed has improved TADF material OLED device luminous efficiency, especially when applied to organic electroluminescent blue light OLED, to obtain improved luminous efficiency or increased life OLED devices.

[0045] The present invention aims to provide a spirocyclic organic compound and its application. The spirocyclic organic compound of the present invention has good rigidity and conjugation, strong hole and electron transport capabilities, good thermal stability, and the prepared device has a long life and high current efficiency.

[0046] The present invention also provides a mixture comprising the above-mentioned spirocyclic organic compound and at least one organic functional material, wherein the organic functional material is selected from at least one of hole injection materials, hole transport materials, electron transport materials, electron injection materials, electron blocking materials, hole blocking materials, luminophores, host materials and organic dyes.

[0047] The present invention also provides a composition comprising one of the above-mentioned spirocyclic organic compounds or a combination of the above-mentioned organic compounds.

[0048] The present invention also provides an organic electronic device, wherein the raw materials for preparing the electronic device include at least one of the above-mentioned spirocyclic organic compounds, or the above-mentioned mixture, or the above-mentioned combination.

[0049] In one embodiment, the compound of the present invention can be applied to organic optoelectronic devices, specifically organic light emitting diodes, organic field effect transistors, organic solar cells, dye-sensitized cells, optical storage devices, optical sensors, organic nonlinear devices, and the like.

[0050] In one embodiment, the organic light-emitting device includes an anode and a cathode disposed opposite to each other, and a light-emitting layer located between the anode and the cathode, wherein the light-emitting layer includes a host material and a guest material.

[0051] In one embodiment, the light-emitting layer includes a host material and a guest material selected from the above-mentioned specific compounds.

[0052] In one embodiment, the present invention relates to an organic photoelectric device, which includes an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode.

[0053] In one embodiment of the present specification, other layers in the organic light-emitting device can be made of any known material if they are used in their respective layers. Preferred materials suitable for the organic layer are exemplified below, but are not limited thereto.

[0054] The anode material is generally preferably a material with a large work function in order to facilitate hole injection into the organic layer. Specific examples of anode materials that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO2:Sb; and conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole, and polyaniline, but are not limited thereto.

[0055] The cathode material is preferably a material with a small work function in order to facilitate electron injection into the organic layer. Specific examples of cathode materials include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, but are not limited thereto.

[0056] The aforementioned electron / hole injection layer materials generally have the following requirements for the electron injection layer and the hole injection layer: lowering the barrier for electron injection from the cathode, allowing electrons to be efficiently injected into the OLED device from the cathode; and lowering the barrier for hole injection from the anode, allowing holes to be efficiently injected into the OLED device from the anode. Therefore, when selecting materials for the electron / hole injection layer, it is preferable to consider the matching of the material energy level with the anode material. Specific examples of materials for the electron / hole injection layer include: LiF, MgP, MgF2, Al2O3, MnO, etc.; and hole injection layer materials include: CuPc (polyester carbonate), TiOPc, m-MTDATA, 2-TNATA, aromatic amine derivatives, hexaazatriphenylene derivatives, dibenzoindenofluoreneamine, or spirobifluoreneamine, etc., but are not limited to these.

[0057] The aforementioned electron / hole transport layer materials typically have a higher hole transport rate than electrons in OLED organic materials. To ensure that electrons and holes injected from the electrodes recombine in the light-emitting layer, the electron and hole transport layer structures must be designed. Factors to consider include: a suitable material energy level structure that matches the energy level structure of the electron / hole transport layer and the light-emitting layer; a suitable material electron / hole migration rate; and a suitable film thickness. Specific examples of electron / hole transport layer materials include, but are not limited to, Al complexes of 8-hydroxyquinoline, complexes containing Alq3, organic free radical compounds, and hydroxyflavone-metal complexes. Common hole transport layer materials include, but are not limited to, TPD, NPB, PVK, Spiro-TPD, Spiro-NPB, indolocarbazole derivatives, conductive polymers, phthalocyanine, or porphyrin derivatives.

[0058] The above-mentioned electron / hole blocking layer materials, usually when electrons and holes migrate into the light-emitting layer, due to the presence of the electric field, electrons can continue to migrate to the anode and holes can continue to migrate to the cathode, resulting in a decrease in the electron / hole concentration in the light-emitting area and a decrease in the luminous efficiency. The electron / hole blocking layer, due to its special energy level structure, can form a barrier to the migration of electrons / holes, preventing them from further migration. Preferably, as a specific example of the electron / hole injection layer material, the electron blocking layer material is: aromatic derivatives or spirobifluorenamine; the hole blocking layer material is azine, phenanthroline, triphenylene derivatives, or benzimidazole, etc., but is not limited to this.

[0059] Preferably, in one embodiment, the material used for the cathode is: indium tin oxide, indium zinc oxide, or tin dioxide.

[0060] Preferably, in one embodiment, the material used for the electron injection layer is: LiF or Al2O3 or MnO, etc.

[0061] Preferably, in one embodiment, the material used for the electron transport layer is: a metal complex, a benzimidazole derivative, a pyrimidine derivative, a pyridine derivative, or a quinoline.

[0062] Preferably, in one embodiment, the material used for the hole blocking layer is triazine, phenanthroline, triphenylene derivative, benzimidazole, etc.

[0063] Preferably, in one embodiment, the material used for the light-emitting layer is: the organic molecules involved in the present invention.

[0064] Preferably, in one embodiment, the material used for the electron blocking layer is: aromatic derivatives or spirobifluoreneamine.

[0065] Preferably, in one embodiment, the material used for the hole transport layer is: indolecarbazole derivatives, conductive polymers, phthalocyanine, porphyrin derivatives, etc.

[0066] Preferably, in one embodiment, the material used for the hole injection layer is: aromatic amine derivatives, hexaazatriphenylene derivatives, dibenzoindenofluoreneamine, spirodifluoreneamine, etc.

[0067] Preferably, in one embodiment, the material used for the anode is: indium tin oxide, indium zinc oxide, or tin dioxide.

[0068] The organic layer of the organic light-emitting device described herein may be a single-layer structure or a multilayer structure comprising two or more organic layers. For example, the organic layer between the anode and the light-emitting layer may be a hole injection layer, a hole transport layer, a layer that simultaneously transports and injects holes, or a hole regulation layer. The organic layer between the cathode and the light-emitting layer may be an electron regulation layer, an electron transport layer, an electron injection layer, or a layer that simultaneously transports and injects electrons. The organic light-emitting device described above may include more than one layer having the same function.

[0069] In one embodiment of the present specification, the compound represented by Chemical Formula I is contained in a light-emitting layer. The organic light-emitting device may further include another light-emitting layer that does not include the compound represented by Chemical Formula I. In one embodiment, when two or more light-emitting layers are included, the respective light-emitting layers may contain the same or different substances and emit the same or different colors.

[0070] In one embodiment of the present specification, the compound represented by the above Chemical Formula I may be included in an amount of 50 parts by weight or more and 100 parts by weight or less relative to 100 parts by weight of the total weight of the light-emitting layer.

[0071] The structures of the devices involved can be combined as follows:

[0072] (1) anode / luminescent layer / cathode;

[0073] (2) anode / hole transport layer / light-emitting layer / cathode;

[0074] (3) anode / light-emitting layer / electron transport layer / cathode;

[0075] (4) anode / hole transport layer / light-emitting layer / electron transport layer / cathode;

[0076] (5) anode / hole injection layer / hole transport layer / light-emitting layer / electron transport layer / cathode;

[0077] (6) anode / hole injection layer / hole transport layer / light-emitting layer / electron transport layer / electron injection layer / cathode;

[0078] (7) anode / hole injection layer / hole transport layer / electron blocking layer / luminescent layer / electron transport layer / electron injection layer / cathode;

[0079] (8) Anode / hole injection layer / hole transport layer / electron blocking layer / light-emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode.

[0080] When the organic light-emitting device includes a plurality of organic layers, the organic layers may be formed of the same material or different materials.

[0081] The organic layer of the organic light-emitting device can be formed by various methods.

[0082] Preferably, in one embodiment, an anode can be formed by vapor-depositing a metal or a conductive metal oxide or an alloy thereof on a substrate, and then an organic layer including a hole injection layer, a hole transport layer, a light-emitting layer and an electron transport layer is formed on the anode, and then a substance that can be used as a cathode is vapor-deposited on the organic layer to manufacture an organic light-emitting device.

[0083] Each organic layer can be formed by any conventional deposition technique, such as evaporation, liquid deposition (continuous and discontinuous techniques), and thermal transfer. Continuous deposition techniques include, but are not limited to, spin coating, gravure coating, curtain coating, dip coating, slot coating, spray coating, and continuous nozzle coating. Discontinuous deposition techniques include, but are not limited to, inkjet printing, gravure printing, and screen printing.

[0084] Preferably, in one embodiment, the compound represented by the above Chemical Formula I is used to form a light-emitting layer by a solution coating method when manufacturing an organic light-emitting device.

[0085] The organic light emitting device according to the present specification may be a top emission type, a bottom emission type, or a bi-directional emission type according to the materials used.

[0086] The spirocyclic organic compound (or spirocyclic derivative containing heteroatom) of the present invention has the following beneficial effects:

[0087] (1) Using a spirocyclic structure in the main body of the molecule gives the molecule a non-planar rigid structure, reduces molecular aggregation quenching, and ensures that the LUMO and HOMO can be effectively separated;

[0088] (2) Introducing B or P(=O) units into the molecule increases the hole transport capacity of the molecule while ensuring the fluorescence quantum efficiency, which is conducive to the construction of blue light-emitting materials with thermally excited delayed fluorescence (TADF) characteristics;

[0089] (3) Deuterium atoms are introduced into the main body of the molecule. Deuterated materials have lower internal energy than non-deuterated materials, and the CD and CH bonds have significantly smaller stretching and bending vibrations. These factors have significantly improved the stability and service life of deuterated materials.

[0090] (4) Substitution is selected at the 3 and 6 positions of the spirocyclic fluorene to ensure the triplet energy level of the material.

[0091] Spirocyclic aromatic compounds have a larger conjugated system and a unique spiroconjugated effect. This unique structural characteristic causes entanglement of molecules in the solid state, effectively preventing the formation of crystals. Therefore, almost all materials with such amorphous spiral structures have a high glass transition temperature. At the same time, they can effectively reduce molecular aggregation or the formation of excited complexes, thereby more effectively improving the light purity and stability. They are a very promising OLED electroactive layer material.

[0092] In summary, the present invention relates to a spirocyclic derivative: using a spirocyclic structure in the main molecular body gives the molecule a non-planar rigid structure, reduces molecular aggregation quenching, and ensures that the LUMO and HOMO can be effectively separated (Table 1); introducing deuterium atoms into the main molecular body, the stability and life of the device prepared from the obtained material are significantly improved (Table 1); substitution is performed at the 3 and 6 positions of the spirocyclic fluorene to ensure the triplet energy level of the material (Table 1). The spirocyclic structure involved in the present invention has the following general formula:

[0093] BRIEF DESCRIPTION OF THE DRAWINGS

[0094] The specific embodiments of the present invention are further described in detail below with reference to the accompanying drawings.

[0095] Figure 1 is the device structure diagram;

[0096] A: organic light-emitting device; 10: substrate; 09: anode; 08: hole injection layer; 07: hole transport layer; 06: electron blocking layer; 05: light-emitting layer; 04: hole blocking layer; 03: electron transport layer; 02: electron injection layer; 01: cathode. DETAILED DESCRIPTION

[0097] To specifically illustrate this specification, examples are given and described in detail. However, the examples of this specification can be modified into various different forms, and the scope of this specification should not be construed as being limited to the examples described in detail below. The examples of this specification are provided to more fully illustrate this specification to those skilled in the art.

[0098] 1. General Synthesis Route of Chemical Formula I

[0099]

[0100] Wherein, Ar1 is a deuterated aryl group, and R3 and R4 are H or Br.

[0101] 1) Compound IA

[0102] 1. Synthesis of intermediate Ia:

[0103] (1) Synthesis of intermediate 1:

[0104]

[0105] To a dry two-necked flask, bis(2-bromophenyl)methane (16.3 g, 0.05 mol) was added. The mixture was evacuated and filled with nitrogen for three cycles (so that the three-necked flask was filled with nitrogen and the reaction was carried out under nitrogen protection). Dry tetrahydrofuran (90 mL) was added to the reaction flask via a syringe, and the temperature was lowered to -80°C and stirred for 30 minutes. Subsequently, n-butyllithium (6.73 g, 0.10 mol) was added to the reaction flask via a syringe and stirred for 6 hours to obtain Intermediate 1 (8.8 g, 97%). 1 HNMR (400MHz) δ (ppm): 8.02 (d, 2H), 7.51 (dd, 2H), 7.44 (d, 2H), 7.00 (dd, 2H), 3.99 (s, 2H). HRMS(ESI,Positive)(m / z):[M]+Calcd for:C13H10Li2, 188.10, found: 188.02.

[0106] (2) Synthesis of intermediate 2:

[0107]

[0108] To a dry two-necked flask, intermediate 1 (9 g, 0.05 mol) was added, followed by dichloro(benzene d5)borane (9.83 g, 0.06 mol). The mixture was evacuated and nitrogen-filled for three cycles (so that the three-necked flask was filled with nitrogen and the reaction was carried out under nitrogen protection). Dry tetrahydrofuran (60 mL) was added to the reaction flask via a syringe, and the temperature was lowered to -80°C and stirred for 12 hours. After the reaction was completed, the mixture was returned to room temperature and filtered through a short silica gel column (containing 30 g of 100-200 mesh silica gel). The mixture was rinsed with dichloromethane (100 mL). The collected filtrate was decompressed to remove the solvent (dichloromethane and tetrahydrofuran) and separated by column chromatography (petroleum ether:dichloromethane = 5:1).

[0109] Description: Column chromatography separates substances based on their different adsorption capacities on the stationary phase. Generally, highly polar substances are more readily adsorbed by the stationary phase, while less polar substances are less readily adsorbed. The column chromatography process is a cycle of adsorption, desorption, re-adsorption, and re-desorption. The eluate containing the product was collected and spin-dried to yield Intermediate 2 (11.01 g, 85%). 1 HNMR (400MHz) δ (ppm): 7.35-7.37 (m, 2H), 7.24-7.29 (m, 4H), 7.17-7.23 (m, 2H), 4.35 (s, 2H). HRMS(ESI,Positive)(m / z):[M]+Calcd for:C 19 H 10 D5B, 259.16, found: 259.17.

[0110] (3) Synthesis of intermediate Ia:

[0111]

[0112] To a dry two-necked flask, intermediate 2 (13 g, 0.05 mol) was added, followed by 3-bromodibenzo[b,d]thiophene-5,5-dioxide (7.38 g, 0.075 mol) and 1,4-dioxane (150 ml). The mixture was stirred until dissolved, followed by the addition of KN(SiMe3)2 (24.94 g, 0.125 mol). The mixture was evacuated and nitrogen-filled for three cycles (so that the flask was filled with nitrogen and the reaction was carried out under nitrogen protection). The mixture was stirred at 80°C for 16 hours. After the reaction, the mixture was extracted with ethyl acetate (100 mL) and water (3 x 150 mL). The ethyl acetate phase was filtered and dried to obtain the crude product. The crude product was purified by silica gel column chromatography using petroleum ether / ethyl acetate (20 / 1) as the eluent. The organic phase was dried to obtain pure intermediate Ia (22.7 g, 93%). 1 HNMR (400MHz) δ (ppm): 8.01 (s, 1H), 7.92 (d, 2H), 7.74 (d, 2H), 7.45-7.55 (m, 2H), 7.38 (dd, 1H), 7.25-7.28 (m, 5H), 7.18 (d, 2H). HRMS(ESI,Positive)(m / z):[M]+Calcd for:C31H15D5BBr, 487.12, found: 487.10.

[0113] 2. Synthesis of Compound IA:

[0114]

[0115] To a dry three-necked flask were added intermediate Ia (0.488 g, 1.0 mmol), phenylboron ester (0.245 g, 1.2 mmol), and Pd(PPh3)4 (0.15 g, 0.1 mmol). The mixture was evacuated and nitrogen-filled for three cycles (so that the three-necked flask was filled with nitrogen and the reaction was carried out under nitrogen protection). K2CO3 (2M, 1 mL) and 1,4-dioxane (30 mL) were added to the reaction flask via a syringe. The mixture was heated to reflux in an oil bath with stirring and the reaction was continued for 12 h. After the reaction was complete, the mixture was cooled to room temperature and filtered through a short silica gel column (containing 10 g of 200-300 mesh silica gel). The mixture was rinsed with dichloromethane (100 mL), and the organic phase (i.e., the collected eluent) was spin-dried (at room temperature) to obtain a crude product. The crude product was purified by silica gel column chromatography using petroleum ether / ethyl acetate (20 / 1) as eluent, and the organic phase was spin-dried to obtain pure product IA (0.412 g, 85%). 1HNMR (400MHz) δ (ppm): 8.11 (s, 1H), 7.90 (d, 1H), 7.92 (d, 1H), 7.75-7.77 (m, 2H), 7.73 (d, 2H), 7.49 -7.50 (m, 2H), 7.41-7.42 (m, 1H), 7.45-7.55 (m, 2H), 7.38 (dd, 1H), 7.25-7.28 (m, 5H), 7.18 (d, 2H). HRMS(ESI,Positive)(m / z):[M]+Calcd for:C37H20D5B, 485.24, found: 485.23.

[0116] 2) Compound IB

[0117] 1. Synthesis of intermediate I-aa:

[0118]

[0119] The intermediate Ia was synthesized by referring to the synthetic route of intermediate Ia. Specifically, 3-bromodibenzo[b,d]thiophene-5,5-dioxide in the above "I.1.(3) Synthesis of Intermediate Ia" was replaced with 3,6-bromodibenzo[b,d]thiophene-5,5-dioxide, and KN(SiMe3)2 (24.94 g, 0.125 mol) was replaced with KN(SiMe3)2 (49.88 g, 0.25 mol). The rest of the reaction was the same as in "I.1.(3) Synthesis of Intermediate Ia", to obtain intermediate I-aa.

[0120] 1 HNMR (400MHz) δ (ppm): 8.01 (s, 2H), 7.92 (d, 2H), 7.74 (d, 2H), 7.44-7.45 (m, 4H), 7.73 (d, 2H), 7.49-7.50 (m, 2H), 7.18 (d, 2H). HRMS(ESI,Positive)(m / z):[M]+Calcd for:C31H14D5BBr2,565.03,found:565.02.

[0121] 2. Synthesis of Compound IB:

[0122]

[0123] To a dry three-necked flask, I-aa (0.488 g, 1.0 mmol), phenylboron ester (0.49 g, 2.4 mmol), and Pd(PPh3)4 (0.15 g, 0.1 mmol) were added. The mixture was evacuated and refilled with nitrogen three times. K2CO3 (2 M, 2 mL) and 1,4-dioxane (30 mL) were added to the reaction flask via syringe. The mixture was heated to reflux in an oil bath with stirring and the reaction was continued for 12 h. After the reaction was complete, the mixture was cooled to room temperature and filtered through a short silica gel column (containing 10 g of 200-300 mesh silica gel). The column was rinsed with dichloromethane (100 mL), and the organic phase was evaporated to dryness (at room temperature) to obtain the crude product. The crude product was purified by silica gel column chromatography using petroleum ether / ethyl acetate (20 / 1) as the eluent. The organic phase was evaporated to dryness to obtain pure IB (0.494 g, 88%). 1 HNMR (400MHz) δ (ppm): 8.18 (s, 2H), 7.73-7.74 (m, 4H), 7.74-7.75 (m, 4H) 7.68-7.69 (d, 2 H), 7.49(dd, 4H), 7.75-7.77(m, 2H), 7.73(d, 2H), 7.49-7.50(m, 2H), 7.40-7.41(m, 2H). HRMS(ESI,Positive)(m / z):[M]+Calcd for:C43H24D5B,561.27,found:561.25.

[0124] 3) Compound IC:

[0125] 1) Synthesis of intermediate Ib:

[0126]

[0127] Refer to the synthetic route of intermediate Ia.

[0128] First, the raw material in step 1.(2) was replaced from dichloro(phenyl d5) borane to 2,4,6-trimethyl(d9) borane, and the molar amount remained unchanged at 0.06 mol; the rest was referred to "1.(2) Synthesis of Intermediate 2" to obtain Intermediate 3. 1HNMR (400 MHz) δ (ppm): 7.74 (d, 2H), 7.29 (m, 2H), 7.25 (m, 2H), 7.18 (d, 2H), 6.97 (s, 2H), 4.35 (s, 2H). HRMS (ESI, Positive) (m / z): [M]+Calcd for: C22H12D9B, 305.27, found: 305.25. Intermediate 2 was replaced with intermediate 3 obtained above, with the molar amount remaining unchanged at 0.05 mol, and the rest being the same as in -1.(3), to obtain intermediate Ib.

[0129] 1 HNMR (400MHz) δ (ppm): 8.01 (s, 2H), 7.90 (d, 1H), 7.55 (d, 2H) 7.44-7.45 (m, 2H), 7.38(m, 1H), 7.28-7.29(m, 3H), 7.25(m, 2H), 7.18(d, 2H), 6.97(s, 2H). HRMS(ESI,Positive)(m / z):[M]+Calcd for:C34H17D9BBr,533.19,found:533.19.

[0130] 2. Synthesis of compound IC:

[0131]

[0132] To a dry three-necked flask, Ib (0.534 g, 1.0 mmol), p-deuterated tert-butylphenylboronate (0.323 g, 1.2 mmol), and Pd(PPh3)4 (0.15 g, 0.1 mmol) were added. The mixture was evacuated and refilled with nitrogen three times. K2CO3 (2M, 1 mL) and 1,4-dioxane (30 mL) were added to the reaction flask via syringe. The mixture was heated to reflux in an oil bath with stirring and the reaction was continued for 12 h. After the reaction was complete, the mixture was cooled to room temperature and filtered through a short silica gel column containing 10 g of 200-300 mesh silica gel. The column was rinsed with dichloromethane (100 mL). The organic phase was evaporated to dryness (at room temperature) to obtain the crude product. The crude product was purified by silica gel column chromatography using petroleum ether / ethyl acetate (20 / 1) as the eluent. The organic phase was evaporated to dryness to obtain pure IC (0.52 g, 87%). 1HNMR (400MHz) δ (ppm): 8.19 (s, 1H), 7.90-7.92 (d, 1H), 7.74-7.75 (m, 3H), 7.66-7.67 (t, 1H), 7.55 -7.56(t, 1H), 7.37-7.38(m, 3H), 7.29-7.30(m, 4H), 7.25-7.27(m, 3H), 7.17(d, 2H), 6.97(s, 2H). HRMS(ESI,Positive)(m / z):[M]+Calcd for:C44H21D18B, 596.43, found: 561.25.

[0133] 4) Compound ID

[0134] 1) Synthesis of intermediate I-bb:

[0135]

[0136] Refer to the synthetic route of intermediate Ia.

[0137] First, the raw material in step 1.(2) was replaced from dichloro(phenyl d5) borane to 2,4,6-trimethyl(d9)dichloroborane, and the molar amount remained unchanged at 0.06 mol. The rest was referred to "1.(2) Synthesis of Intermediate 2" to obtain Intermediate 3;

[0138] Relative to step 1.(3), intermediate 2 was replaced by intermediate 3 obtained above, and the molar amount remained unchanged at 0.05 mol. In addition, 3-bromodibenzo[b,d]thiophene-5,5-dioxide was changed to 3,6-dibromodibenzo[b,d]thiophene-5,5-dioxide, and the molar amount remained unchanged at 0.075 mol. KN(SiMe3)2(24.94 g, 0.125 mol) was changed to KN(SiMe3)2(49.88 g, 0.25 mol). The rest was the same as step 1.(3) to obtain intermediate I-bb.

[0139] 1 HNMR (400MHz) δ (ppm): 8.01 (s, 2H), 7.74 (d, 2H), 7.44-7.45 (m, 4H), 7.29 (dd, 2H), 7.25 (dd, 2H), 7.18 (d, 2H), 6.97 (s, 2H). HRMS(ESI,Positive)(m / z):[M]+Calcd for:C34H16D9BBr2,611.10,found:611.09.

[0140] 2) Synthesis of compound ID:

[0141]

[0142] To a dry three-necked flask, I-bb (0.613 g, 1.0 mmol), I-1 (2-naphthylthiophene trimethyltin salt) (0.784 g, 2.1 mmol) and Pd(dba)2 (0.029 g, 0.05 mmol) were added. The mixture was vacuumed and nitrogen-filled for three cycles. Anhydrous tetrahydrofuran (30 mL) was added to the reaction flask using a syringe. The mixture was heated to reflux in an oil bath under stirring and the reaction was continued for 12 h. After the reaction was complete, the mixture was cooled to room temperature, filtered through diatomaceous earth, rinsed with dichloromethane (100 mL), and the organic phase was dried (at room temperature) to obtain a crude product. The crude product was purified by silica gel column chromatography using petroleum ether / ethyl acetate (20 / 1) as the eluent. The obtained organic phase was dried to obtain pure product ID (0.81 g, 93%). 1 HNMR (400MHz) δ (ppm): 8.97 (d, 2H), 8.25 (d, 2H), 8.18 (s, 2H) 8.15 (d, 2H), 8.10 (d, 2H), 8.00-8.01 (m, 2H), 7. 74(m, 4H), 7.68-7.69(d, 2H), 7.52-7.59(m, 4H), 7.29-7.30(m, 6H), 7.25(dd, 2H), 7.18(d, 2H), 6.97(s, 2H). HRMS(ESI,Positive)(m / z):[M]+Calcd for:C62H34D9BS2,871.35,found:871.35.

[0143] V) Synthesis of Compound IE

[0144]

[0145] Weigh I-bb (3.07 g, 5 mmol), di(4-tert-butylphenyl)amine (3.378 g, 12 mmol) and sodium tert-butoxide (1.44 g, 15 mmol) in a 250 mL two-necked flask and dissolve thoroughly with 100 mL of anhydrous toluene. Weigh PdCl2(Amphos)2 (0.106 g, 0.15 mmol) and quickly add it to the flask and seal it with a rubber stopper. Pass nitrogen into the bottle for 30 minutes, stir and heat, and reflux for 18 hours. After the reaction is completed, cool to room temperature, filter with diatomaceous earth, rinse with dichloromethane (100 mL), and the organic phase is spin-dried (room temperature) to obtain a crude product. The crude product obtained is purified by silica gel column chromatography using petroleum ether / dichloromethane (10 / 1) as eluent, and the obtained organic phase is spin-dried to obtain pure IE (7.3 g, 72%). 1HNMR (400MHz) δ (ppm): 7.74 (d, 2H), 7.62 (s, 2H), 7.51 (d, 2H), 7.28-7.29 (m, 2H), 7.24- 7.25 (m, 2H), 7.18 (d, 2H), 7.09-7.10 (m, 16H), 7.06 (m, 2H), 6.97 (s, 2H), 1.33 (s, 36H). HRMS(ESI,Positive)(m / z):[M]+Calcd for:C74H68D9BN2,1013.67,found:1013.66.

[0146] VI) Synthesis of Compound IF:

[0147]

[0148] Weigh I-bb (3.07 g, 5 mmol), 3,6-dimethoxy (d6) -9H- carbazole (2.57 g, 11 mmol), CuI (0.095 g, 0.5 mmol) K2CO3 (1.73 g, 12.5 mmol) in a 250 mL two-necked flask, add DMPU (60 mL) to dissolve, pass nitrogen into the flask for 30 min, stir and heat to 180 ° C overnight. After the reaction is completed, cool to room temperature, filter through silica gel, and the organic phase is spin-dried (room temperature) to obtain a crude product. The crude product is purified by silica gel column chromatography using petroleum ether / dichloromethane (9 / 1) as eluent. The obtained organic phase is spin-dried to obtain pure IF (4.1 g, 89%). 1 HNMR (400MHz) δ (ppm): 8.24 (s, 2H), 7.96 (s, 2H), 7.74 (d, 2H), 7.72 (s, 2H), 7.69 (d, 2H), 7.58 (d , 2H), 7.40(m, 2H), 7.33(d, 2H), 7.25-7.29(m, 4H), 7.18-7.20(m, 4H), 6.97(s, 2H), 6.60(d, 2H). HRMS(ESI,Positive)(m / z):[M]+Calcd for:C62H28D21BN2O4,917.51,found:917.30.

[0149] VII) Synthesis of compound IG:

[0150]

[0151] Ib (2.67 g, 5 mmol), 3,6-dicyanoacridine (1.56 g, 6 mmol), CuI (0.095 g, 0.5 mmol) and potassium tert-butoxide (0.89 g, 8 mmol) were weighed into a 250 mL two-necked flask and fully dissolved with 100 mL of anhydrous DMF. Nitrogen was passed through the flask for 30 min, stirred and heated, and refluxed for 12 h. After the reaction was completed, it was cooled to room temperature and filtered through silica gel. The organic phase was spin-dried (room temperature) to obtain a crude product. The crude product was purified by silica gel column chromatography using petroleum ether / dichloromethane (9 / 1) as eluent. The obtained organic phase was spin-dried to obtain pure IG (2.81 g, 82%). 1 HNMR (400MHz) δ (ppm): 7.90 (s, 1H), 7.74 (d, 2H), 7.65 (s, 2H), 7.62 (s, 1H), 7.50-7.55 (m, 2H ), 7.35-7.38(m, 5H), 7.25-7.29(m, 5H), 7.18(d, 2H), 7.06(d, 1H), 6.97(s, 2H), 1.69(s, 6H). HRMS(ESI,Positive)(m / z):[M]+Calcdfor:C51H29D9BN3,712.75,found:712.75.

[0152] Eight), Synthesis of Compound IH:

[0153]

[0154] To a dry three-necked flask were added I-bb (3.07 g, 5 mmol), I-2 (4.79 g, 11 mmol), and Pd(dppf)2Cl2 (0.11 g, 0.15 mmol). The mixture was evacuated and filled with nitrogen for three cycles. K2CO3 (4 M, 3.75 mL) was then added via syringe to the reaction flask. Aliquat 336 (0.02 g, 0.05 mmol) and anhydrous toluene (150 mL) were then added. The mixture was heated to reflux in an oil bath with stirring and the reaction was continued for 12 h. After the reaction was complete, the mixture was cooled to room temperature and filtered through silica gel. The organic phase was then dried (at room temperature) to afford the crude product. The crude product was purified by silica gel column chromatography using petroleum ether / dichloromethane (9 / 1) as the eluent. The organic phase was then dried to afford pure IH (4.34 g, 81%). 1HNMR (400MHz) δ (ppm): 8.24 (s, 2H), 8.18 (s, 2H), 7.91-7.92 (m, 8H), 7.72-7.74 (m, 6H), 7.20-7.25 (m, 4H), 7.29-7.33 (m, 4H), 7.18-7.20 (m, 6H), 6.97 (s, 4H). HRMS(ESI,Positive)(m / z):[M]+Calcd for:C74H36D21BN2O4, 1069.57, found: 1069.57.

[0155] IX) Synthesis of Compound II:

[0156]

[0157] The synthesis steps were similar to those in "IV.2. Synthesis of Compound ID." Compound II was obtained by replacing the starting material I-bb in "IV.2. Synthesis of Compound ID" with I-aa (the molar amounts remained unchanged) and the starting material 2-naphthylthiophenetrimethyltin salt with 2-naphthyl(d7)furantrimethyltin salt (the molar amounts remained unchanged). The remaining steps were identical to those in "IV.2. Synthesis of Compound ID."

[0158] 1 HNMR (400MHz) δ (ppm): 8.18 (s, 2H), 7.74 (m, 4H), 7.68 (m, 2H), 7.25-7.29 (m, 4H), 7.18-7.20 (m, 2H), 7.07 (m, 4H). HRMS(ESI,Positive)(m / z):[M]+Calcd for:C59H18D19BO2,807.41,found:807.41.

[0159] 10), Synthesis of Compound IJ:

[0160]

[0161] The synthesis steps were similar to those of Compound IE. Specifically, the di(4-tert-butylphenyl)amine in "V. Synthesis of Compound IE" was replaced with di(4-dimethoxyphosphinophenyl)amine, with the molar amounts remaining unchanged. The remaining steps were identical to those of "V. Synthesis of Compound IE," yielding Compound IJ.

[0162] 1HNMR (400MHz) δ (ppm): 7.74 (d, 2H), 7.62-7.66 (m, 10H), 7.51 (d, 2H), 7.29-7.32 (m, 10H), 7.25 (m, 2H), 7.07 (m, 2H), 6.97 (s, 4H), 3.78 (s, 24H). HRMS(ESI,Positive)(m / z):[M]+Calcd for:C66H56D9BN2O12P4, 1221.41, found: 1221.40.

[0163] XI), Synthesis of Compound IK:

[0164]

[0165] (1) Synthesis of intermediate I-cc:

[0166]

[0167] The synthesis was carried out according to the route of intermediate Ia.

[0168] Right now:

[0169] First, the raw material in step 1. (2) was replaced from dichloro(phenyl d5) borane to dichloro-2,6-di(propylene (d6))phenyl borane, and the molar amount remained unchanged at 0.06 mol. 3-bromodibenzo[b,d]thiophene-5,5-dioxide was replaced with 3,6-bromodibenzo[b,d]thiophene-5,5-dioxide, and the molar amount remained unchanged at 0.075 mol. The rest was referred to "1. (2) Synthesis of Intermediate 2" to obtain intermediate 4. 1 HNMR (400MHz) δ (ppm): 7.74 (m, 2H), 7.29 (m, 2H), 7.25 (m, 2H), 7.24-7.22 (m, 3H), 7.18 (d, 2H), 5.16-5.25 (s, 4H), 4.35 (s, 2H). HRMS(ESI,Positive)(m / z):[M] + Calcd for:C25H17D6B, 340.31, found: 340.26.

[0170] The intermediate 2 was replaced by the intermediate 4 obtained above, and the molar amount remained unchanged at 0.05 mol. 3-bromodibenzo[b,d]thiophene-5,5-dioxide was changed to 3,6-dibromodibenzo[b,d]thiophene-5,5-dioxide, and the molar amount remained unchanged at 0.075 mol. The rest was the same as "Step 1.1(3) Synthesis of Intermediate Ia" to obtain Intermediate I-cc.

[0171] 1 HNMR (400MHz) δ (ppm): 7.79 (s, 2H), 7.72-7.74 (m, 4H), 7.55 (d, 2H), 7.29 (m, 2H), 7.22-7.25 (m, 5H), 7.18 (d, 2H), 5.16 (s, 2H), 5.12 (s, 2H). HRMS(ESI,Positive)(m / z):[M] + Calcd for:C37H21D6BBr2, 646.09, found: 611.09.

[0172] (2) Synthesis of Compound IK:

[0173]

[0174] The synthesis steps were similar to those for Compound IE. Specifically, the di(4-tert-butylphenyl)amine in "V. Synthesis of Compound IE" was replaced with 4,4-dimethylphenothiazine, with the molar amounts remaining unchanged. The remaining steps were identical to those in "V. Synthesis of Compound IE," yielding Compound IK.

[0175] 1 HNMR (400MHz) δ (ppm): 7.86 (d, 2H), 7.74 (d, 2H), 7.33 (s, 2H), 7.22-7.24 (m, 3H), 7.25 -7.29(m, 4H), 7.15-7.18(m, 8H), 6.79-6.87(m, 8H), 5.12-5.16(m, 4H), 2.36(s, 12H). HRMS(ESI,Positive)(m / z):[M] + Calcd for:C65H45D6BN2S2,940.40,found:940.40.

[0176] 12), Synthesis of Compound IL:

[0177]

[0178] (1) Synthesis of intermediate I-dd:

[0179]

[0180] Refer to the route of intermediate Ia for synthesis.

[0181] First, the raw material in step 1.(2) was replaced with dichloro(benzene d5)borane by dichlorocarbazole borane, and the molar amount remained unchanged at 0.06 mol. The rest was referred to "1.(2) Synthesis of Intermediate 2" to obtain Intermediate 5;1 HNMR (400MHz) δ (ppm): 8.55 (d, 2H), 7.94 (s, 2H), 7.74 (d, 2H), 7.50 (m, 2H), 7.29 (m, 2H), 7.25 (m, 2H), 7.20-7.18 (m, 4H) 4.35 (s, 2H). HRMS(ESI,Positive)(m / z):[M]+Calcd for: C25H18BN, 343.24, found: 343.23.

[0182] Relative to step 1.1.(3), intermediate 2 is replaced by intermediate 5 obtained above, and the molar amount remains unchanged at 0.05 mol. In addition, 3-bromodibenzo[b,d]thiophene-5,5-dioxide is changed to 3,6-dibromodibenzo[b,d]thiophene-5,5-dioxide, and the molar amount remains unchanged at 0.075 mol. The rest is the same as step 1.(3) to obtain intermediate I-dd.

[0183] 1 HNMR (400MHz) δ (ppm): 8.55 (d, 2H), 8.01 (s, 2H), 7.74 (d, 2H), 7.58 (d, 2H), 7.50 (m, 2H), 7.44-7.45 (m, 4H), 7.25-7.29 (m, 4H), 7.19-7.20 (m, 4H). HRMS(ESI,Positive)(m / z):[M] + Calcd for:C37H22BBr2N, 649.02, found: 649.01.

[0184] (2) Synthesis of compound IL:

[0185]

[0186] The synthesis steps were similar to those for Compound IB. Specifically, in "II.2. Synthesis of Compound IB," I-aa was replaced with I-dd, and phenylboron ester was replaced with naphthaleneboron ester, while the molar amounts remained unchanged. The remaining steps were identical to those in "II.2. Synthesis of Compound IB," yielding Compound IL.

[0187] 1HNMR (400MHz) δ (ppm): 8.95 (d, 2H), 8.50-8.55 (m, 4H), 8.20-8.18 (m, 4H), 8.09 (d, 2H), 7.77 (s, 2H) , 7.74-7.75(m, 4H), 7.68(dd, 2H), 7.50-7.58(m, 6H), 7.39(d, 2H), 7.25-7.29(m, 4H), 7.18(d, 4H). HRMS(ESI,Positive)(m / z):[M] + Calcd for:C57H36BN,745.29,found:745.29.

[0188] 13) Synthesis of compound IM:

[0189]

[0190] The synthesis steps were similar to those of Compound IE. Specifically, the di(4-tert-butylphenyl)amine in "V. Synthesis of Compound IE" was replaced with 1-phenyl-(3-dibenzofuranyl)amine, with the molar amounts remaining unchanged. The remaining steps were identical to those of "V. Synthesis of Compound IE," yielding Compound IM.

[0191] 1 HNMR (400MHz) δ (ppm): 8.22 (s, 1H), 7.90-7.98 (m, 2H), 7.74 (d, 2H), 7.62 (s, 1H), 7.58 (d, 1H), 7.51-7.55 (m, 3H), 7 .38-9.39(dd, 2H), 7.31(s, 1H), 7.28-7.29(m, 3H), 7.24-7.25(m, 3H), 7.18(m, 2H), 7.01-7.06(m, 4H), 6.97(s, 4H). HRMS(ESI,Positive)(m / z):[M] + Calcd for:C52H29D9BNO, 712.36, found: 712.29.

[0192] 14), Synthesis of Compound IN:

[0193]

[0194] (1) Synthesis of intermediate Ie:

[0195]

[0196] Refer to the route of intermediate Ia for synthesis.

[0197] First, the raw material in step 1.(2) was replaced from dichloro(benzene d5) borane to dichlorocarbazole (d8) borane, and the molar amount remained unchanged at 0.06 mol. The rest was referred to "1.(2) Synthesis of Intermediate 2" to obtain Intermediate 6; 1 HNMR (400MHz) δ (ppm): 7.74 (d, 2H), 7.29 (m, 2H), 7.25 (m, 2H), 7.18 (d, 2H), 4.35 (s, 2H). HRMS(ESI,Positive)(m / z):[M]+Calcd for: C25H10D8BN, 351.28, found: 351.24.

[0198] Relative to step 1.1.(3), intermediate 2 was replaced by intermediate 6 obtained above, and the molar amount remained unchanged at 0.05 mol. The rest was the same as step 1.(3) to obtain intermediate Ie.

[0199] 1 HNMR (400MHz) δ (ppm): 8.01 (s, 1H), 7.90 (s, 1H), 7.74 (d, 2H), 7.55 (d, 1H), 7 .44-7.45 (m, 2H), 7.38 (dd, 1H), 7.28-7.29 (m, 3H), 7.25 (m, 2H), 7.18 (d, 2H). HRMS(ESI,Positive)(m / z):[M] + Calcd for: C37H15D8BBrN, 579.16, found: 579.15.

[0200] (2) Synthesis of compound IN:

[0201]

[0202] The synthesis steps were similar to those of Compound IE. Specifically, I-bb in "V. Synthesis of Compound IE" was replaced with I-dd, and the di(4-tert-butylphenyl)amine starting material was replaced with 1-phenyl-(3-dibenzofuran)amine, with the molar amounts remaining unchanged. The remaining steps were identical to those of "V. Synthesis of Compound IE," yielding Compound IN.

[0203] 1HNMR (400MHz) δ (ppm): 8.22 (s, 1H), 7.98 (s, 1H), 7.90 (s, 1H), 7.62 (s, 1H), 7.54-7.56 (m, 4H), 7.38-7.39 (d, 2H) , 7.31 (dd, 1H), 7.28-7.29 (m, 3H), 7.24-7.25 (m, 4H), 7.18 (m, 2H), 7.08 (d, 2H), 6.97-7.00 (m, 2H), 6.87 (d, 3H). HRMS(ESI,Positive)(m / z):[M] + Calcd for: C55H27D8BN2O, 758.33, found: 758.33.

[0204] 15) Synthesis of compound IO: The synthesis method of this compound refers to compound IB.

[0205]

[0206] (1) Synthesis of intermediate I-ee:

[0207]

[0208] Refer to the route of intermediate Ia for synthesis.

[0209] First, the raw material in step 1.(2) was replaced from dichloro(benzene d5) borane to dichlorocarbazole (d8) borane, and the molar amount remained unchanged at 0.06 mol. The rest was referred to "1.(2) Synthesis of Intermediate 2" to obtain Intermediate 6.

[0210] Relative to step 1.1.(3), intermediate 2 is replaced by intermediate 6 obtained above, and 3-bromodibenzo[b,d]thiophene-5,5-dioxide is changed to 3,6-dibromodibenzo[b,d]thiophene-5,5-dioxide, the molar amounts remain unchanged, and the rest are the same as step 1.(3), to obtain intermediate I-ee.

[0211] 1 HNMR (400MHz) δ (ppm): 8.01 (s, 2H), 7.74 (d, 2H), 7.44-7.45 (m, 4H), 7.29 (m, 2H), 7.25 (m, 2H), 7.18 (d, 2H). HRMS(ESI,Positive)(m / z):[M] + Calcd for: C37H14D8BBr2N, 657.07, found: 657.07.

[0212] (2) Synthesis of Compound IO:

[0213]

[0214] The synthesis steps were the same as those in "II.2. Synthesis of Compound IB," except that I-aa in "II.2. Synthesis of Compound IB" was replaced with I-dd, 3-bromodibenzo[b,d]thiophene-5,5-dioxide was replaced with 3,6-dibromodibenzo[b,d]thiophene-5,5-dioxide, and the phenylboron ester starting material was replaced with naphthaleneboron ester (d7). All other molar amounts remained unchanged, and the remaining steps were identical to those in "II.2. Synthesis of Compound IB," to yield Compound IO.

[0215] 1 HNMR (400MHz) δ (ppm): 7.54-7.56 (m, 2H), 7.38-7.39 (d, 2H), 7.31 (dd, 2H), 7.28-7.29 (m, 2H), 7.24 (m, 2H), 7.18 (m, 2H), 7.08 (d, 2H). HRMS(ESI,Positive)(m / z):[M] + Calcdfor: C57H14D22BN, 767.43, found: 767.42.

[0216] The other compounds in this specification are referred to Table 1 below, and their synthesis methods are all synthesized according to the above methods.

[0217] Table 1

[0218]

[0219]

[0220]

[0221]

[0222] Hereinafter, a method for preparing an OLED device including the compound according to the present disclosure and its characteristics will be explained in detail. However, the following examples only illustrate the characteristics of the OLED according to the present disclosure in detail, but the present disclosure is not limited to the following examples.

[0223] Based on the same inventive concept, embodiments of the present invention further provide an organic light-emitting device comprising the compounds of the above embodiments. An OLED is used as an example of an organic light-emitting device for illustration below. However, it should be understood that the following detailed description is not intended to limit the present invention, and those skilled in the art may extend the following detailed description to other organic light-emitting devices.

[0224] Device Examples

[0225] The OLED device includes a first electrode (anode) and a second electrode (cathode), and several organic material layers between the electrodes. The organic material layer can be divided into multiple regions. For example, the organic material layer can include a hole injection layer, a hole transport region, a light-emitting layer, an electron injection layer, and an electron transport region. In a specific embodiment, a substrate can be used below the first electrode or above the second electrode. The substrates are all glass or polymer materials with excellent mechanical strength, thermal stability, water resistance, and transparency.

[0226] Device Example Device 1: An OLED device is prepared using the heteroatom-containing spiro derivatives (hereinafter referred to as spiro derivatives) prepared according to the present invention, and can be prepared by referring to the method of the published patent CN 106831745 A.

[0227] The OLED device (ie, device A) is as follows Figure 1 The substrate 10, anode 09, hole injection layer 08, hole transport layer 07, electron blocking layer 06, light-emitting layer 05, hole blocking layer 04, electron transport layer 03, electron injection layer 02, and cathode 01 are stacked in sequence from bottom to top; the substrate 10 and anode 09 are prepared as an integrated whole.

[0228] The material of the hole injection layer 08 is HI; the material of the hole transport layer 07 is HT; the material of the electron blocking layer 06 is EB; the light-emitting layer 05 is composed of a host and a guest in a specific ratio, the host material is a spiro derivative prepared by the present invention, and the guest material is BD; the material of the hole blocking layer 04 is HB; the material of the electron transport layer 03 is ET; the material of the electron injection layer 02 is EI.

[0229]

[0230] The OLED device prepared has an anode 09 (ITO) with a thickness of 50 nm; a hole injection layer 08 (HI) with a thickness of 10 nm, a hole transport layer 07 (HT) with a thickness of 65 nm, an electron blocking layer 06 (EB) with a thickness of 25 nm, and a light-emitting layer 05 with a thickness of 20 nm. The material of the light-emitting layer 05 is a mixture of compound IA (as a host material): BD (as a guest material) in a mass ratio of 90:10; the sum of the thicknesses of the hole blocking layer 04 and the electron transport layer 03 is 40 nm, and the weight ratio of HB:ET is 1:1; the thickness of the electron injection layer 02 (EI) is 2 nm; and the thickness of the cathode 01 (Al) is 80 nm.

[0231] Device Example Device 2-13,

[0232] Compared with the device example device 1, only the host material used in the light-emitting layer 05 is changed (as described in Table 3), and the weight ratio of the host material to the guest material remains unchanged; the rest is the same as the device example device 1.

[0233] The test was performed according to the method described in CN 106831745 A. The results are shown in Table 2 below:

[0234] Table 2

[0235] Compound HOMO (eV) LUMO (eV) T1 (eV) I-A -5.2 -1.57 3.27 I-B -5.17 -1.63 3.23 I-D -5.27 -1.59 3.31 I-G -5.29 -1.58 3.33 I-M -5.31 -1.46 3.51 I-L -5.30 -1.43 3.32 I-Q -5.24 -1.75 3.29 I-S -5.32 -1.56 3.41 I-C-A -5.2 -1.57 3.03 I-C-B -5.04 -2.59 3.31 I-C-C -4.31 -1.46 3.01 I-C-D -4.17 -2.53 2.91 SiBSTPA -5.30 -1.77 2.75

[0236] Table 3

[0237]

[0238]

[0239] T95 is the time (in hours) to reach 95% of the initial brightness at 50° C. and a current density of 16.5 mA / cm 2 .

[0240] It can be seen from the results of the embodiment that compared with device 9, device 2 has a longer life (LT95) than device 9. This is because the CD bond and the CH bond have significantly smaller stretching vibration and bending vibration. These factors significantly improve the stability and service life of the deuterated material. Compared with device 12, device 5 has a significantly higher external quantum efficiency (EQE) and life (LT95). This is mainly because the introduction of the spirocyclic structure makes the molecule present a cross-shaped configuration, which improves the rigidity of the material. In addition, the rigid spirocyclic structure weakens the fluorescence quenching caused by molecular aggregation under the film, thereby obtaining a very high solid-state luminescence efficiency. Compared with device 1 and device 2, device 1 has a longer life. This is mainly because the asymmetric structure can effectively inhibit molecular accumulation, thereby alleviating the fluorescence quenching caused by molecular aggregation.

[0241] Obviously, the present invention is not limited to the above embodiments, and many variations are possible. All variations that can be directly derived or associated with the contents disclosed by a person skilled in the art should be considered to be within the scope of protection of the present invention.

Claims

1. A spirocyclic derivative containing a heteroatom, characterized in that Any of the following structural formulas: 、 、 、 、 、 、 、 。 2. The use of the heteroatom-containing spiro derivative according to claim 1, characterized in that: Preparation of organic optoelectronic devices.

3. The use of the heteroatom-containing spiro derivative according to claim 2, characterized in that: As a material for the light-emitting layer of organic optoelectronic devices.

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