Anthryl derivative and luminescent device

Abstract

The invention belongs to the technical field of organic compounds, and particularly relates to an anthryl derivative and a light-emitting device. The structural general formula of the anthryl derivative is as shown in formula (I): # imgabs0. The anthryl derivative disclosed by the invention is good in thermal stability and high in electron mobility, and can be matched with a second-generation blue phosphorescent material luminescent system.

Description

Technical Field

[0001] The present application belongs to the technical field of organic compounds, and in particular relates to an anthracene derivative and a light-emitting device. Background Art

[0002] Organic light-emitting diodes (OLEDs) have gradually become the dominant direction of display technology due to their many advantages, such as self-luminescence, fast response speed, large viewing angle, ultra-high contrast, low power consumption, ultra-lightness, ultra-thinness, and flexibility. Electron transport materials (ETMs) are a key link in OLED devices, and their performance is crucial. Ideal ETMs should have excellent thermal stability, suitable molecular orbital energy levels, high electron mobility, and good exciton blocking ability, which can avoid luminescence quenching caused by direct contact between the cathode and the light-emitting layer, and have an important impact on the characteristics of OLEDs, including stability.

[0003] Application-oriented organic electron transport materials should have high thermal stability, high glass transition temperature (related to film morphology stability), high electron mobility, high triplet energy level, and low LUMO energy level (favorable for electron injection). Although a large number of organic electron transport materials have been reported in the prior art, it is very challenging to design and synthesize organic small molecule electron transport materials with excellent comprehensive performance, especially suitable electron transport materials with commercial application potential, with high glass transition temperature (≥150°C) and the ability to match the second-generation blue phosphorescent material luminescence system to achieve satisfactory luminescence efficiency.

[0004] Phosphorus oxygen interrupts the continuation of molecular conjugation due to its highly spatially distorted structure, thus maintaining the high triplet energy level of the molecule. Phosphorus oxygen also has a strong electron-withdrawing ability, which is beneficial to electron injection and transport. Therefore, a large number of phosphorus oxygen-containing organic electron transport materials have been reported. However, the phosphorus oxygen materials reported successively are in urgent need of optimization due to their insufficient thermal stability and electron mobility to match the second-generation blue phosphorescent material luminescence system. Summary of the invention

[0005] The present application aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present application proposes an anthracene derivative and a light-emitting device.

[0006] A first aspect of the present application provides an anthracene derivative.

[0007] In some embodiments, an anthracene derivative has a general structural formula as shown in formula (I):

[0008]

[0009] Wherein, L1 and L2 are independently selected from a single bond, a substituted or unsubstituted C6-C60 arylene group or a substituted or unsubstituted C3-C60 heteroarylene group, and when L1 is a phenyl group, The substitution position on L1 is meta-substitution;

[0010] The dotted line between L1, L2 and the anthracene group indicates that the bonding site is not limited;

[0011] Ar1, Ar2 and Ar3 are independently selected from substituted or unsubstituted C6-C36 aryl or substituted or unsubstituted C2-C36 heteroaryl;

[0012] R1 and R2 are each independently selected from hydrogen, deuterium, halogen, cyano, isocyano, substituted or unsubstituted C1-C40 alkyl, substituted or unsubstituted C1-C40 heteroalkyl, substituted or unsubstituted C3-C40 cycloalkyl, substituted or unsubstituted C3-C40 heterocycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, substituted or unsubstituted C6-C60 aryloxy, substituted or unsubstituted C1-C40 alkylamino or substituted or unsubstituted C6-C60 arylphosphinoyl;

[0013] The substitution is substituted by at least one of deuterium, halogen, cyano, isocyano, nitro, trifluoromethyl, C1-C6 alkyl, C3-C16 cycloalkyl, C1-C6 alkyl substituted amine, C1-C6 hydrocarbon substituted or unsubstituted C6-C30 aryl, C1-C6 hydrocarbon substituted or unsubstituted C3-C30 heteroaryl, C1-C6 hydrocarbon substituted or unsubstituted phosphinooxy, wherein the number of substitutions ranges from single substitution to the maximum number of substitutions;

[0014] The heteroatom in the heteroalkyl group, heterocycloalkyl group, heteroaryl group, and heteroarylene group is at least one of N, O, S, and Se;

[0015] Both x and y are natural numbers from 0 to 3;

[0016] Both m and n are natural numbers ranging from 1 to 3.

[0017] Compared with the prior art, the beneficial effects of this application are as follows:

[0018] In order to overcome the above-mentioned shortcomings and deficiencies of the prior art, the present application utilizes the thermal stability characteristics of anthracene materials, and uses anthracene-based condensed ring compound containing large π-conjugation for modification, to provide a phosphorus-containing oxyanthracene-substituted benzimidazole derivative. The anthracene-based derivative provided by the present invention has a high glass transition temperature and a high thermal decomposition temperature, and can be used as an organic small molecule electron transport material for high-efficiency and long-life OLEDs device applications. The anthracene-based derivative described in the present application has good thermal stability and high electron mobility, and can match the second-generation blue phosphorescent material luminescence system. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 This is a schematic diagram of the structure of the light emitting device in the embodiment of the present application;

[0020] Figure 2 This is an energy level diagram of the materials used in the light-emitting device of this application. DETAILED DESCRIPTION

[0021] In order to make the technical solution described in this application more clearly understood by those skilled in the art, the following examples are listed for illustration. It should be noted that the following examples do not limit the scope of protection claimed in this application.

[0022] In the description of the present application, it should be understood that the terms "upper", "lower", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present application and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be understood as a limitation on the present application.

[0023] Unless otherwise specified, the raw materials, reagents or devices used in the following examples can be obtained from conventional commercial sources or by existing known methods.

[0024] The raw materials and solvents involved in the synthesis of the compounds of the present application were purchased from suppliers well known to those skilled in the art, such as Alfa and Acros.

[0025] In the present application, aryl, aromatic, and aromatic ring system have the same meaning and can be interchanged.

[0026] In the present application, heteroaryl, heteroaromatic, and heteroaromatic ring system have the same meaning and can be interchanged.

[0027] In the present application, "substituted" means that a hydrogen atom in a substituted group is replaced by a substituent.

[0028] In the present application, aryl refers to a hydrocarbon group containing at least one aromatic ring, including a monocyclic group and a polycyclic group ring system. Heteroaryl refers to a hydrocarbon group (containing heteroatoms) containing at least one heteroaromatic ring, including a monocyclic group and a polycyclic ring system. The heteroatom can be selected from N, O, S, Se. The rings of these polycyclic groups can have two or more rings, at least one of which is an aromatic or heteroaromatic ring, which can be connected to each other via a single bond or can be fused to each other to form a fused ring, in which two carbon atoms are shared by two adjacent rings, i.e., a fused ring. At least one of these polycyclic ring species is aromatic or heteroaromatic. For the purpose of the present application, aryl or heteroaryl not only includes a system of aromatic or heteroaromatic groups, but also, wherein multiple aryl or heteroaryl groups can also be interrupted by short non-aromatic units (<10% non-H atoms, preferably less than 5% non-H atoms, such as C, N or O atoms). Thus, systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamines, diaryl ethers, etc. are also considered aromatic groups for the purposes of this application.

[0029] Specific examples of the aromatic group include benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, pyrene, benzopyrene, triphenylene, acenaphthene, fluorene, or derivatives thereof.

[0030] Specific examples of heteroaryl groups include furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furanopyrrole, furanofuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, o-naphthylidene, quinoxaline, phenanthridine, primary pyridine, quinazoline, quinazolinone, or derivatives of the above groups.

[0031] In the present application, "alkyl" refers to a straight or branched saturated hydrocarbon group. Specifically, the number of carbon atoms can be 1 to 40, 1 to 30, 1 to 20, 1 to 12, 1 to 6, or 1 to 3. Non-limiting examples of alkyl include methyl, ethyl, propyl, butyl, heptyl, decyl, etc. Each group includes various isomers, such as butyl includes isomers such as n-butyl, isobutyl, sec-butyl, tert-butyl, etc.

[0032] In the present application, cycloalkyl refers to a non-aromatic carbonyl ring consisting of at least 2 carbon atoms, and may include monocyclic, polycyclic and spiroalkyl. Different rings in polycyclic rings may be connected by single bonds, may share one carbon atom or may share two carbon atoms. Non-limiting examples of cycloalkyl include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, bicyclo [3.1.1] heptyl, spiro [4.5] decyl, spiro [5.5] undecyl, adamantyl, norbornyl.

[0033] In some embodiments, an anthracene derivative has a general structural formula as shown in formula (I):

[0034]

[0035] Wherein, L1 and L2 are independently selected from a single bond, a substituted or unsubstituted C6-C60 arylene group or a substituted or unsubstituted C3-C60 heteroarylene group, and when L1 is a phenyl group, The substitution position on L1 is meta-substitution;

[0036] The dotted line between L1, L2 and the anthracene group indicates that the bonding site is not limited;

[0037] Ar1, Ar2 and Ar3 are independently selected from substituted or unsubstituted C6-C36 aryl or substituted or unsubstituted C2-C36 heteroaryl;

[0038] R1 and R2 are each independently selected from hydrogen, deuterium, halogen, cyano, isocyano, substituted or unsubstituted C1-C40 alkyl, substituted or unsubstituted C1-C40 heteroalkyl, substituted or unsubstituted C3-C40 cycloalkyl, substituted or unsubstituted C3-C40 heterocycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, substituted or unsubstituted C6-C60 aryloxy, substituted or unsubstituted C1-C40 alkylamino or substituted or unsubstituted C6-C60 arylphosphinoyl;

[0039] The substitution is substituted by at least one of deuterium, halogen, cyano, isocyano, nitro, trifluoromethyl, C1-C6 alkyl, C3-C16 cycloalkyl, C1-C6 alkyl substituted amine, C1-C6 hydrocarbon substituted or unsubstituted C6-C30 aryl, C1-C6 hydrocarbon substituted or unsubstituted C3-C30 heteroaryl, C1-C6 hydrocarbon substituted or unsubstituted phosphinooxy, wherein the number of substitutions ranges from single substitution to the maximum number of substitutions;

[0040] The heteroatom in the heteroalkyl group, heterocycloalkyl group, heteroaryl group, and heteroarylene group is at least one of N, O, S, and Se;

[0041] Both x and y are natural numbers from 0 to 3;

[0042] Both m and n are natural numbers of 1 to 3, and preferably both m and n are 1.

[0043] In some embodiments of the present application, the anthracene derivative has a general structural formula as shown in formula (II):

[0044]

[0045] In some embodiments of the present application, m and n are both 1.

[0046] In some embodiments of the present application, L1 and L2 may be the same or different.

[0047] In some embodiments of the present application, Ar1 and Ar2 are independent aromatic groups or heteroaromatic groups, and may also be connected to form a ring, and the ring may be a five-membered ring, a six-membered ring, or a seven-membered ring.

[0048] x and y are the number of substituents, and m and n are the number of repeating units.

[0049] In some embodiments of the present application, L1 and L2 are independently selected from a single bond, a substituted or unsubstituted C6-C40 arylene group, or a substituted or unsubstituted C3-C40 heteroarylene group.

[0050] In some embodiments of the present application, L1 and L2 are each independently selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, or a substituted or unsubstituted C3-C30 heteroarylene group.

[0051] In some embodiments of the present application, Ar1, Ar2 and Ar3 are independently selected from substituted or unsubstituted C6-C30 aryl or substituted or unsubstituted C2-C30 heteroaryl.

[0052] In some embodiments of the present application, Ar1, Ar2 and Ar3 are independently selected from substituted or unsubstituted C6-C20 aryl or substituted or unsubstituted C2-C20 heteroaryl.

[0053] In some embodiments of the present application, R1 and R2 are independently selected from hydrogen, deuterium, halogen, cyano, isocyano, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 heteroalkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C3-C40 heteroaryl, substituted or unsubstituted C6-C40 aryloxy, substituted or unsubstituted C1-C30 alkylamino or substituted or unsubstituted C6-C40 arylphosphinoyl.

[0054] In some embodiments of the present application, R1 and R2 are independently selected from hydrogen, deuterium, halogen, cyano, isocyano, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 heteroalkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C3-C20 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C1-C20 alkylamino or substituted or unsubstituted C6-C30 arylphosphinoyl.

[0055] In some embodiments of the present application, the substitution is by at least one of deuterium, halogen, cyano, isocyano, nitro, C1-C6 alkyl, C3-C10 cycloalkyl, C1-C6 alkyl substituted amine, C1-C6 hydrocarbon substituted or unsubstituted C6-C20 aryl, C1-C6 hydrocarbon substituted or unsubstituted C3-C20 heteroaryl, C1-C6 hydrocarbon substituted or unsubstituted phosphinoyl, wherein the number of substitutions is from a single substitution to a maximum number of substitutions.

[0056] In some embodiments of the present application, L1 and L2 are selected from any of the following structures:

[0057]

[0058] Among them, R, R a or R b Each of them is independently selected from hydrogen, deuterium, halogen, cyano, isocyano, substituted or unsubstituted C1-C40 alkyl, substituted or unsubstituted C1-C40 heteroalkyl, substituted or unsubstituted C3-C40 cycloalkyl, substituted or unsubstituted C3-C40 heterocycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, substituted or unsubstituted C6-C60 aryloxy or substituted or unsubstituted C1-C40 alkylamino. The number of substituents R is from a single to the maximum number;

[0059] Ar is selected from substituted or unsubstituted C6-C36 aryl, substituted or unsubstituted C2-C36 heteroaryl;

[0060] Ring A is a substituted or unsubstituted C3-C40 cycloalkyl group, preferably a substituted or unsubstituted C3-C7 cycloalkyl group;

[0061] R, R a or R b , Ar, and the substitution in ring A is substitution by at least one of deuterium, halogen, cyano, isocyano, C1-C6 alkyl, and C3-C16 cycloalkyl, wherein the number of substitutions ranges from single substitution to the maximum number of substitutions; "*" indicates the bond connection position. R, R a , R b There is only 1.

[0062] In some embodiments of the present application, L1 and L2 are selected from any of the following structures:

[0063]

[0064] In some embodiments of the present application, the structural formula of the anthracene derivative is any one of the following:

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071] In some embodiments, a method for preparing an anthracene derivative comprises the following steps:

[0072]

[0073] In some embodiments, a light-emitting device comprises an anode, a cathode, and one or more organic layers between the anode and the cathode, wherein at least one of the one or more organic layers comprises the anthracene derivative described in the present application.

[0074] In some embodiments, the anthracene derivative described herein and the N-type dopant Liq are used together as components of the electron transport layer.

[0075] Synthesis of anthracene derivative E1:

[0076] The structural formula of the anthracene derivative E1 is:

[0077]

[0078] The specific synthetic route of anthracene derivative E1 is as follows:

[0079]

[0080] Step 1.1: Synthesis of compound 1-c

[0081] Compound 1-a (7.5 g, 18.9 mmol, 1.0 eq), compound 1-b (6.7 g, 19.8 mmol, 1.05 eq), Pd(PPh3)4 (tetrakis(triphenylphosphine)palladium, 1.2 g, 0.94 mmol, 0.05 eq), K3PO4 (10.0 g, 47.2 mmol, 2.5 eq) and THF / H2O (200 mL / 40 mL, THF represents tetrahydrofuran) were put into a reaction bottle, heated to 80 °C under nitrogen protection, and reacted for 4 h. The reaction solution was cooled to room temperature, quenched with water (200 mL), extracted with EA (ethyl acetate 250 mL x 2), the organic phases were combined, concentrated, and separated by column chromatography using Hex (cyclohexane): EA (ethyl acetate): DCM (dichloromethane) = 10:1:0.5 (V / V / V) as eluent to obtain a yellow solid, which was then further purified by recrystallization using DCM / Hex to obtain 6.3 g of a light yellow solid compound 1-c with a yield of 63.4% and a HPLC (high performance liquid chromatography) purity of 99.90%.

[0082] The NMR characterization results of compound 1-c are as follows: 1 H NMR(400MHz, CDCl3, δ)8.65(d,J=8.7Hz,2H),7.96(d,J=7.2Hz,1H),7.75–7.71(m,2H),7.64(t,J =8.1Hz,4H),7.54(s,4H),7.53–7.48(m,2H),7.47(s,1H),7.46–7.41(m,4H),7.40–7.37(m,1H).

[0083] Step 1.2: Synthesis of anthracene derivative E1

[0084] Compound 1-c (5.3 g, 10.1 mmol, 1.0 eq), compound 1-d (4.5 g, 11.1 mmol, 1.05 eq, synthesized with reference to patent CN116332991A), Pd(dppf)Cl2 ([1,1′-bis(diphenylphosphino)ferrocene]palladium dichloride, 0.368 g, 0.5 mmol, 0.05 eq), K3PO4 (5.3 g, 25.5 mmol, 2.5 eq) and Tol(toluene) / EtO H(ethanol) / H2O (80mL / 20mL / 20mL) was put into a reaction flask, heated to 85°C under nitrogen protection, reacted for 6h, the reaction solution was cooled to room temperature, water (50mL) was added to the reaction solution, and EA (200mLx2) was added for extraction. The organic phases were combined, spin-dried, and separated by column chromatography (Hex:EA:DCM=1:1:0.5 (V / V / V)) to obtain a light yellow oil. Hex was heated to 60°C to dissolve, and crystallized at room temperature for 16h to obtain 7.0g of a white solid anthracene derivative E1, HPLC=99.93%, yield 79.51%.

[0085] The NMR characterization results of anthracene derivative E1 are as follows: 1 H NMR (400MHz, CDCl3) δ7.95(t,J=9.4Hz,2H),7.82–7.71(m,8H),7.68(d,J=8.7Hz,3H),7.62(t,J=7.7H z,3H),7.60–7.55(m,4H),7.53(d,J=5.7Hz,3H),7.48(d,J=5.3Hz,3H),7.41(dd,J=17.1,7.7Hz,9H).

[0086] HR-MS (high resolution mass spectrometry) determined the molecular weight to be 723.2478 [M+1]. Elemental analysis test: 84.96% C, 4.84% H, 3.80% N, 2.23% O corresponding to C 51 H 35 N2OP.

[0087] Synthesis of anthracene derivative E3:

[0088] The structural formula of the anthracene derivative E3 is:

[0089]

[0090] The specific synthetic route of anthracene derivative E3 is as follows:

[0091]

[0092] The synthesis steps are similar to those of the anthracene derivative E1, and 2.1 g is finally obtained, HPLC = 99.96%; HR-MS determines the molecular weight to be 773.2644 [M+1]. Elemental analysis test: 85.49% C, 4.79% H, 3.60% N, 2.07% O corresponding to C 55 H 37 N2OP.

[0093] Synthesis of anthracene derivative E4:

[0094] The structural formula of the anthracene derivative E4 is:

[0095]

[0096] The specific synthetic route of anthracene derivative E4 is as follows:

[0097]

[0098] Step 1: Synthesis of compound 2-c

[0099] Compound 2-a (15 g) was added and dissolved in 300 mL DCM (dichloromethane), and the mixture was cooled to -78 °C under nitrogen protection. Then n-BuLi (n-butyl lithium) solution (25 mL) was added dropwise. After the addition was complete, stirring was continued for 30 min. Then compound 2-b (10 mL) was slowly added dropwise. After the addition was complete, stirring was continued at -78 °C for 15 min. TLC (thin layer chromatography) monitored the complete reaction of the raw materials. After the reaction was completed, the temperature was lowered to room temperature, 200 mL of water was added to quench, and DCM was extracted (100 mL*2). The organic phase was washed with water (200 mL), concentrated and directly used in the next step. 100 mL of DCM was used to dissolve the product of the previous step, and 30% mass fraction hydrogen peroxide solution (20 mL) was slowly added dropwise thereto. After the addition was complete, stirring was continued for 10 min. TLC monitored the complete reaction of the raw materials. After the reaction was completed, the temperature was restored to room temperature, 150 mL of water and 50 mL DCM, liquid separation, organic phase washed with water (100mL*2), concentrated at 55°C, separated by silica gel column chromatography (10g, 200-300 mesh) (eluent Hex:EA=2:1, 2:1 is volume ratio), crude product was obtained, 50mL of n-hexane was added, a little EA was added, solid was precipitated after ultrasonication, filtered to obtain 14g of white solid compound 2-c. Yield: 61.72%, purity: 99%.

[0100] The NMR characterization results of compound 2-c are as follows: 1H NMR (400MHz, CDCl3) δ8.29–8.24(m,1H),7.90(dd,J=11.9,7.8Hz,4H),7.68(td,J=7.7,3.2Hz,1H),7.56–7.49(m,3H),7.49–7.42(m,4H).

[0101] Step 2: Synthesis of anthracene derivative E4

[0102] Compound 2-c (2.19 g, 6.11 mmol, 1.0 eq.), compound 2-d (3.5 g, 6.11 mmol, 1.0 eq.), Pd(PPh3)4 (tetrakis(triphenylphosphine)palladium, 0.35 g, 0.3 mmol, 5% eq.), K3PO4 (3.89 g, 18.34 mmol, 3.0 eq.) were dissolved in Tol / EtOH / H2O (200 mL / 50 mL / 50 mL) and the mixture was stirred at room temperature under nitrogen atmosphere. The reaction mixture was changed 3 times, and the temperature was raised to 80°C and stirred to react overnight. The reaction of the raw materials was completed by TLC monitoring. The developing solvent polarity was pure EA. After the reaction, the mixture was cooled to room temperature and poured into 500 mL of deionized water. The mixture was extracted with EA. The organic phase was spin-dried at 60°C and separated by silica gel column chromatography (eluent was DCM:MeOH=50:1, 50:1 by volume) to obtain a solid. The solid was recrystallized from DCM / MeOH at room temperature to obtain 4.5 g of anthracene derivative E4 with a yield of 79.10% and a purity of 99.95%.

[0103] The NMR characterization results of anthracene derivative E4 are as follows: 1 H NMR (400MHz, CDCl3) δ8.60–8.52(m,1H),8.10(td,J=7.7,3.8Hz,1H),7.98(dd,J=12.0,7.4Hz,4H),7.74(d,J=9.4Hz,2H),7.71–7.66(m,2H) ,7.65(d,J=8.0Hz,2H),7.62–7.57(m,2H),7.53(dd,J=17.1,8.6Hz,6H),7.47–7.41(m,8H),7.37(dd,J=9.9,6.8Hz,4H),7.33–7.28(m,2H).

[0104] HR-MS determined the molecular weight to be 724.2445 as [M+1]. Elemental analysis test: 82.96% C, 4.84% H, 5.80% N, 2.23% O corresponding to C 51 H 35 N2OP.

[0105] Synthesis of anthracene derivative E5:

[0106] The structural formula of the anthracene derivative E5 is:

[0107]

[0108] The specific synthetic route of anthracene derivative E5 is as follows:

[0109]

[0110] Step 1: Synthesis of compound 5-c

[0111] Compound 5-a (15 g, 63 mmol, 1.0 eq) was added and dissolved in 300 mL of anhydrous toluene, and the temperature was cooled to -78 °C under nitrogen protection, and then 2.5 M n-BuLi solution (26 mL, 66 mmol, 1.05 eq) was added dropwise. After the addition was completed, stirring was continued for 30 min, and then compound 2-b (15 g, 69 mmol, 1.1 eq.) was slowly added dropwise. After the addition was completed, stirring was continued at -78 °C for 20 min. TLC monitored the complete reaction of the raw materials; after the reaction was completed, the temperature was cooled to room temperature, 200 mL of water was added to quench, and DCM was extracted (100 mL*2). The organic phase was washed with water (200 mL), concentrated and used directly in the next step, and washed with DCM 100mL of the product from the previous step was dissolved, and 30% mass fraction of hydrogen peroxide solution (20mL) was slowly added dropwise thereto. After the addition was completed, stirring was continued for 10min. TLC monitored the complete reaction of the raw materials. After the reaction was completed, the temperature was restored to room temperature, and water and DCM were added for extraction and separation. The organic phase was washed with water (100mL*2), concentrated at 55°C, and separated by silica gel column chromatography (eluent: Hex:EA=2:1) ​​to obtain a crude product. 50mL of n-hexane was added, and a small amount of EA was dropped. After ultrasonication, solids were precipitated and filtered to obtain 13.5g of white solid compound 5-c with a yield of 60% and a purity of 98.8%.

[0112] The NMR characterization results of compound 5-c are: 1 H NMR (400MHz, CDCl3) δ9.68 (s, 1H), 8.88 (s, 1H), 7.78 (dd, J = 11.9, 7.8Hz, 4H), 7.51-7.42 (m, 6H).

[0113] Step 2: Synthesis of anthracene derivative E5

[0114] Compound 5-c (2.18 g, 6.11 mmol, 1.0 eq.), compound 2-d (3.5 g, 6.11 mmol, 1.0 eq.), dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine palladium (II) (0.21 g, 0.3 mmol, 5% eq.), and Cs2CO3 (5.96 g, 18.34 mmol, 3.0 eq.) were dissolved in Tol / EtOH / H2O (200 mL / 50 mL / 50mL), nitrogen replaced 3 times, heated to 80℃, stirred and reacted overnight, TLC monitored the complete reaction of the raw materials, the developing solvent polarity: pure EA, cooled to room temperature after the reaction, poured into 500mL deionized water, extracted with EA, the organic phase was spin-dried at 60℃, and separated by silica gel column chromatography (eluent: DCM:MeOH=50:1) to obtain a solid, and recrystallized from DCM / MeOH at room temperature to obtain 3.6g of anthracene derivative E5, with a yield of 82% and a purity of 99.98%.

[0115] The NMR characterization results of anthracene derivative E5 are as follows: 1 H NMR (400MHz, CDCl3) δ8.79 (s, 1H), 8.56 (s, 1H), 8.28 (s, 2H), 8.20 (d, J = 15.0Hz, 4H), 7.79 (q, J = 5.0Hz, 9H), 7.56-7.44 (m, 14H), 7.28 (s, 1H).

[0116] HR-MS determined the molecular weight to be 725.2392 [M+1]. Elemental analysis test: 81.21% C, 4.55% H, 7.70% N, 2.23% O corresponding to C 49 H 33 N4OP.

[0117] Synthesis of anthracene derivative E7:

[0118] The structural formula of the anthracene derivative E7 is:

[0119]

[0120] The specific synthetic route of anthracene derivative E7 is as follows:

[0121]

[0122] Step 1: Synthesis of compound 7-b

[0123] Compound 7-a (10 g, 27.64 mmol) was dissolved in DCM (200 mL) at room temperature, replaced with nitrogen three times, cooled to -78°C, and 2.5 M n-BuLi solution (12 mL, 30.4 mmol) was added dropwise thereto. The mixture was stirred for 30 min after the addition was completed. The mixture was stirred for 30 min, and then a DCM (20 mL) solution of compound 2-b (6.71 g, 30.4 mmol) was added dropwise thereto. The mixture was stirred for 30 min after the addition was completed. The mixture was stirred at room temperature overnight. After the reaction was completed, 300 mL of water was added for washing. The organic phases were separated, combined and spin-dried, and separated by silica gel column chromatography (200-300 mesh) (eluent: Hex) to obtain 7.4 g of colorless solid with a yield of 57.32% and a purity of 98.61%. Continue to the next step of reaction, dissolve with DCM, cool to 0°C and stir, then add 30% mass fraction hydrogen peroxide aqueous solution (5.91g, 52.73mmol) dropwise, drip for 10min, stir at 0°C for 1h, return to room temperature after the reaction, pour in 500mL water to wash the reaction solution, extract the organic phase with DCM and spin dry, perform silica gel column chromatography (eluent is DCM: EtOH = 20:1) to obtain 6.85g white solid compound 7-b. Yield: 90.39%, purity: 99.81%.

[0124] The NMR characterization results of compound 7-b are: 1 H NMR (400MHz, CDCl3) δ7.82(s,1H),7.72(d,J=1.3Hz,1H),7.69(d,J=1.3Hz,1H),7.66(s ,1H),7.64(d,J=5.0Hz,2H),7.59(dd,J=13.7,4.1Hz,3H),7.50(dt,J=7.2,3.6Hz,4H).

[0125] Step 2: Synthesis of compound 7-c

[0126] Compound 7-b (2.51 g, 5.76 mmol), compound 2-d (3.3 g, 5.76 mmol), Pd(PPh3)4 (0.33 g, 0.29 mmol), K3PO4 (3.67 g, 17.29 mmol) were dissolved in dioxane / H2O (200 mL / 50 mL) in two parallel pots, replaced with nitrogen 3 times, heated to 100 ° C and stirred for 5 h. After the reaction, 500 mL of water was poured in, extracted with EA (300 mL*2), the organic phase was spin-dried, and separated by silica gel column chromatography (eluent: Hex:DCM:EA=2:2:1), and 5.29 g of light yellow foam solid compound 7-c was obtained. Yield: 63.4%, purity: 99.41%.

[0127] The NMR characterization results of compound 7-c are as follows: 1 H NMR (400MHz, CDCl3) δ8.10(d,J=11.6Hz,1H),7.95(d,J=7.1Hz,1H),7.84(s,1H),7.80–7.71(m,5H),7.66(dd ,J=16.6,9.8Hz,6H),7.57(d,J=12.8Hz,7H),7.52–7.47(m,6H),7.43(d,J=6.9Hz,6H),7.35(d,J=7.8Hz,1H).

[0128] Step 3: Synthesis of anthracene derivative E7

[0129] Two pots were added in parallel, compound 7-c (2.8 g, 3.49 mmol), Zn(CN)2 (0.61 g, 5.24 mmol), Pd2(dba)3 (0.16 g, 0.17 mmol), dppf (1,1'-bis(diphenylphosphino)ferrocene, 0.39 g, 0.69 mmol) were dissolved in DMAc (dimethylacetamide, 150 mL), nitrogen was replaced 3 times, the temperature was raised to 160 ° C, stirred and reacted overnight, and the temperature was lowered to room temperature after the reaction was completed. The mixture was combined, 500 mL of water was poured into it, and it was extracted with EA (200 mL*3). The organic phase was spin-dried and separated by silica gel column chromatography (50 g, 200-300 mesh) (eluent was Hex:EA=1:1, volume ratio) to obtain 3.4 g of white solid anthracene derivative E7. The yield was 65.09%, and the purity was: 99.98%.

[0130] The NMR characterization results of anthracene derivative E7 are as follows: 1 H NMR (400MHz, CDCl3) δ8.16(d,J=11.4Hz,1H),8.07(d,J=11.4Hz,1H),7.96(d,J=8.0Hz,2H),7.77(d,J=7.1H z,2H),7.76–7.71(m,5H),7.70(s,1H),7.55(ddd,J=28.9,17.5,9.2Hz,14H),7.41(dd,J=14.0,7.0Hz,8H).

[0131] HR-MS determined the molecular weight to be 748.2440 [M+1]. Elemental analysis test: 83.53% C, 4.54% H, 6.60% N, 2.13% O corresponding to C 52 H 34 N3OP.

[0132] Synthesis of anthracene derivative E12:

[0133] The structural formula of the anthracene derivative E12 is:

[0134]

[0135] The specific synthetic route of anthracene derivative E12 is as follows:

[0136]

[0137] The synthesis steps are similar to those of the anthracene derivative E1, and finally 1.3 g of anthracene derivative E12 is obtained, HPLC = 99.94%; HR-MS determines the molecular weight to be 833.3583 [M+1]. Elemental analysis test: 85.09% C, 5.88% H, 3.36% N, 1.92% O corresponding to C 59 H 49 N2OP.

[0138] Synthesis of anthracene derivative E16:

[0139] The structural formula of anthracene derivative E16 is:

[0140]

[0141] The specific synthetic route of anthracene derivative E16 is as follows:

[0142]

[0143] The synthesis steps are similar to those of the anthracene derivative E1, and finally 1.5 g of anthracene derivative E16 is obtained, HPLC = 99.98%; HR-MS determines the molecular weight to be 773.2644 [M+1]. Elemental analysis test: 85.38% C, 4.79% H, 3.62% N, 2.07% O corresponding to C 55 H 37 N2OP.

[0144] Synthesis of anthracene derivative E35:

[0145] The structural formula of anthracene derivative E35 is:

[0146]

[0147] The specific synthetic route of anthracene derivative E35 is as follows:

[0148]

[0149] Step 1: Synthesis of compound 35-b

[0150] Compound 1-d (4.0 g, 10 mmol, 1.0 eq), compound 35-a (2.5 g, 10 mmol, 1.0 eq.), Pd132 (0.35 g, 0.5 mmol, 5% eq.), Cs2CO3 (9.75 g, 30 mmol, 3.0 eq.) were dissolved in Tol / EtOH / H2O (200 mL / 50 mL / 50 mL), replaced with nitrogen three times, heated to 100 ° C, stirred and refluxed (reflux means reflux) for overnight reaction, cooled to room temperature after the reaction, poured into 500 mL of deionized water, extracted with EA, concentrated the organic phase at 60 ° C, separated by silica gel column chromatography (eluent DCM: MeOH = 100: 1) to obtain a solid, and recrystallized from DCM / MeOH at room temperature to obtain 3.76 g of compound 35-b, with a yield of 83% and a purity of 99%. HR-MS determined the molecular weight of 455.1487 as [M+1];

[0151] Step 2: Synthesis of compound 35-c

[0152] Compound 35-b (2.27 g, 5 mmol, 1.0 eq), CuBr2 (1.11 g, 5 mmol, 1.0 eq.), 30 mL of chloroform, nitrogen replacement 3 times, heated to 80 ° C, stirred and reacted overnight, cooled to room temperature after the reaction, poured into 500 mL of deionized water, extracted with EA, the organic phase was concentrated at 60 ° C, and separated by silica gel column chromatography (eluent DCM: MeOH = 100: 1) to obtain a solid, and DCM / MeOH was recrystallized at room temperature to obtain 2.4 g of compound 35-c, with a yield of 90% and a purity of 99.84%. HR-MS determined the molecular weight of 533.0592 as [M+1];

[0153] Step 5.2: Synthesis of anthracene derivative E35

[0154] Compound 35-c (1.6 g, 3 mmol, 1.0 eq), compound 1-a (1.3 g, 3.3 mmol, 1.1 eq), Pd132 (0.16 g, 0.15 mmol, 5% eq.), and Cs2CO3 (3.00 g, 9 mmol, 3.0 eq.) were dissolved in Tol / EtOH / H2O (200 mL / 50 mL / 50 mL), replaced with nitrogen three times, heated to 90°C and stirred to react overnight. After the reaction, cooled to room temperature, poured into 500 mL of deionized water, extracted with EA, and the organic phase was concentrated at 60°C. The solid was separated by silica gel column chromatography (eluent: DCM:MeOH=50:1) and recrystallized from DCM / HEX at room temperature to obtain 1.86 g of anthracene derivative E35 with a yield of 86% and a purity of 99.97%.

[0155] The NMR characterization results of anthracene derivative E35 are as follows: 1H NMR (400MHz, CDCl3) δ8.56-8.51(m,8H),8.44-8.26(m,6H),8.18(t,J=9.4Hz ,2H),7.95-7.77(m,7H),7.48(d,J=5.3Hz,3H),7.41(dd,J=17.1,7.7Hz,9H).

[0156] HR-MS determined the molecular weight to be 723.2478 [M+1]. Elemental analysis test: 84.96% C, 4.84% H, 3.80% N, 2.23% O corresponding to C 51 H 35 N2OP.

[0157] Synthesis of anthracene derivative E48:

[0158] The structural formula of anthracene derivative E48 is:

[0159]

[0160] The specific synthetic route of anthracene derivative E48 is as follows:

[0161]

[0162] Compound 1-d (4.0 g, 10 mmol, 1.0 eq), compound 48-a (6.8 g, 10 mmol, 1.0 eq.), Pd2(dba)3 (0.91 g, 1 mmol, 10% eq.), X-phos (0.95 g, 2 mmol, 20% eq.), and Cs2CO3 (9.75 g, 30 mmol, 3.0 eq.) were dissolved in THF / H2O (200 mL / 40 mL), replaced with nitrogen three times, heated to 90°C and stirred to react overnight. After the reaction, the temperature was cooled to room temperature, 100 mL of methanol was added, and a yellow solid was precipitated. The solid was separated by two silica gel column chromatography (eluent was DCM:MeOH=20:1) to obtain a solid, and recrystallized from DCM / HEX at room temperature to obtain 5.7 g of anthracene derivative E48 with a yield of 65% and a purity of 99.98%.

[0163] The NMR characterization results of anthracene derivative E48 are as follows: 1H NMR(500MHz,Chloroform,δ)9.36(s,1H),8.71(s,1H),8.56(s,1H),8.24(d,J=35.0Hz,6H),8.09(s,1H),7.89(d,J=10.0Hz ,3H),7.84–7.66(m,8H),7.51(t,J=7.5Hz,10H),7.43(s,4H),7.28(s,1H),1.77(d,J=92.0Hz,5H),1.29(d,J=97.0Hz,5H).

[0164] HR-MS determined the molecular weight to be 879.3426 [M+1]. Elemental analysis test: 86.10% C, 5.35% H, 3.19% N, 1.82% O corresponding to C 63 H 47 N2OP.

[0165] Synthesis of anthracene derivative E50:

[0166] The structural formula of anthracene derivative E50 is:

[0167]

[0168] The specific synthetic route of anthracene derivative E50 is as follows:

[0169]

[0170] Compound 1-d (4.00 g, 10 mmol, 1.0 eq), compound 50-a (7.32 g, 10 mmol, 1.0 eq.), Pd2(dba)3 (0.91 g, 1 mmol, 10% eq.), X-phos (0.95 g, 2 mmol, 20% eq.), and Cs2CO3 (9.75 g, 30 mmol, 3.0 eq.) were dissolved in THF / H2O (200 mL / 40 mL), replaced with nitrogen three times, heated to 90°C and stirred to react overnight. After the reaction, the temperature was cooled to room temperature, 100 mL of methanol was added, and a yellow solid was precipitated. The solid was separated by two silica gel column chromatography (eluent was DCM:MeOH=20:1) to obtain a solid, and recrystallized from DCM / HEX at room temperature to obtain 6.5 g of anthracene derivative E50 with a yield of 71% and a purity of 99.92%.

[0171] The NMR characterization results of anthracene derivative E50 are as follows: 1HNMR(500MHz,Chloroformδ)8.56(s,1H),8.28(s,2H),8.21(s,5H),8.13(s,1H),8.09(s,1H),7.89(d,J=10.0Hz,2H),7.84–

[0172] 7.67(m,9H),7.55–

[0173] 7.47(m,12H),7.42(d,J=11.7Hz,6H),7.28(s,1H),2.40(s,2H),2.06(s,2H),1.72(s,6H),1.07(s,6H).

[0174] HR-MS determined the molecular weight to be 931.3739 [M+1]. Elemental analysis test: 86.45% C, 5.48% H, 3.01% N, 1.72% O corresponding to C 67 H 51 N2OP.

[0175] Synthesis of anthracene derivative E82:

[0176] The structural formula of anthracene derivative E82 is:

[0177]

[0178] The specific synthetic route of anthracene derivative E82 is as follows:

[0179]

[0180] Step 1: Synthesis of compound 82-b

[0181] Compound 1-d (8.0 g, 20 mmol, 2.0 eq), compound 82-a (2.5 g, 10 mmol, 1.0 eq.), Pd2(dba)3 (tridibenzylideneacetone dipalladium, 0.91 g, 1 mmol, 10% eq.), X-phos (2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl, 0.95 g, 2 mmol, 20% eq.), and Cs2CO3 (9.75 g, 30 mmol, 3.0 eq.) were dissolved in THF / H2O (200 mL / 40 mL), replaced with nitrogen three times, heated to 90°C and stirred to react overnight. After the reaction, the temperature was cooled to room temperature, 100 mL of methanol was added, and a yellow solid was precipitated. The solid was slurried in toluene (60°C) twice to obtain 4.38 g of compound 82-b with a yield of 60% and a purity of 98%. The molecular weight determined by HR-MS was 731.2191 as [M+1];

[0182] Step 2: Synthesis of compound 82-c

[0183] Compound 82-b (2.19 g, 5 mmol, 1.0 eq), tetrabutylammonium tribromide (TBAB-Br2, 3.6 g, 7.5 mmol, 1.5 eq.), 30 mL of acetic acid, nitrogen replacement 3 times, heated to 125 ° C, stirred and reacted overnight, cooled to room temperature after the reaction, poured into 500 mL of deionized water, extracted with EA, the organic phase was concentrated at 60 ° C, and separated by silica gel column chromatography (eluent DCM: MeOH = 20: 1) to obtain a solid, and DCM / MeOH was recrystallized at room temperature to obtain 3.27 g of compound 82-c, with a yield of 81% and a purity of 99.83%. HR-MS determined the molecular weight to be 809.1296 [M+1];

[0184] Step 3: Synthesis of anthracene derivative E82

[0185] Compound 82-c (2.4 g, 3 mmol, 1.0 eq), compound 1-a (1.3 g, 3.3 mmol, 1.1 eq), Pd2(dba)3 (0.27 g, 0.3 mmol, 10% eq.), X-phos (0.28 g, 0.6 mmol, 20% eq.), Cs2CO3 (3.00 g, 9 mmol, 3.0 eq.) and CsF (0.45 g, 3 mmol, 1.0 eq.) was dissolved in THF / H2O (200mL / 50mL), replaced with nitrogen three times, heated to 90°C with stirring for reaction overnight, cooled to room temperature after the reaction, poured into 500mL of deionized water, extracted with DCM, the organic phase was concentrated at 60°C, separated by silica gel column chromatography (eluent: DCM:MeOH=60:1) to obtain a solid, and recrystallized from THF / EA at room temperature to obtain 2.27g of anthracene derivative E82 with a yield of 76% and a purity of 99.98%.

[0186] The NMR characterization results of anthracene derivative E82 are as follows: 1 H NMR (400MHz, CDCl3) δ8.95 (s, 2H), 8.57 (d, J = 5.0Hz, 2H), 8.39 (s, 2H), 8.28 (s, 2H), 8.1 5(s,2H),7.88(s,2H),7.83–7.74(m,16H),7.52(dd,J=17.5,7.5Hz,19H),7.28(s,1H).

[0187] HR-MS determined the molecular weight to be 999.3191 as [M+1]. Elemental analysis test: 82.96% C, 4.84% H, 2.80% N, 3.20% O corresponding to C 69 H 48 N2O2P2.

[0188] Synthesis of anthracene derivative E88:

[0189] The structural formula of anthracene derivative E88 is:

[0190]

[0191] The specific synthetic route of anthracene derivative E88 is as follows:

[0192]

[0193] Step 1: Synthesis of compound 88-a

[0194] Compound 1-a (7.9 g, 20 mmol, 1.0 eq), compound 88-a (5.0 g, 20 mmol, 1.0 eq.), Pd132 (0.70 g, 1 mmol, 5% eq.), Cs2CO3 (20 g, 60 mmol, 3.0 eq.) were dissolved in Tol / EtOH / H2O (350 mL / 50 mL / 50 mL), replaced with nitrogen 3 times, heated to 100 ° C, stirred and reacted overnight, cooled to room temperature after the reaction, poured into 500 mL of deionized water, extracted with EA, concentrated the organic phase at 60 ° C, separated by silica gel column chromatography (eluent DCM:HEX = 3:1) to obtain a solid, and recrystallized from DCM / HEX at room temperature to obtain 7.40 g of compound 88-a, with a yield of 83% and a purity of 99.2%. HR-MS determined the molecular weight of 447.1783 as [M+1];

[0195] Step 2: Synthesis of compound 88-b

[0196] Compound 88-a (2.23 g, 5 mmol, 1.0 eq), tetrabutylammonium tribromide (7.9 g, 16.5 mmol, 3.3 eq.), 60 mL of acetic acid, nitrogen replacement 3 times, heated to 120 ° C, stirred for 48 h, cooled to room temperature after the reaction, poured into 500 mL of deionized water, extracted with EA, the organic phase was concentrated at 60 ° C, and separated by silica gel column chromatography twice (eluent HEX: DCM: EA = 5: 2: 1) to obtain a solid, DCM / HEX room temperature recrystallization to obtain 2.14 g of compound 88-b, yield 71%, purity: 99.90%. HR-MS determined the molecular weight of 604.9973 [M + 1];

[0197] Step 3: Synthesis of anthracene derivative E88

[0198] Compound 88-b (1.8 g, 3 mmol, 1.0 eq), compound 1-d (1.3 g, 3.3 mmol, 1.1 eq), Pd132 (0.16 g, 0.15 mmol, 5% eq.), and Cs2CO3 (3.00 g, 9 mmol, 3.0 eq.) were dissolved in Tol / EtOH / H2O (200 mL / 50 mL / 50 mL), replaced with nitrogen three times, heated to 90 °C and stirred to react overnight. After the reaction, the temperature was cooled to room temperature, poured into 500 mL of deionized water, extracted with EA, and the organic phase was concentrated at 60 °C. The solid was separated by silica gel column chromatography (eluent: DCM:MeOH=20:1) and recrystallized from DCM / HEX at room temperature to obtain 2.2 g of anthracene derivative E88 with a yield of 76% and a purity of 99.96%.

[0199] The NMR characterization results of anthracene derivative E88 are as follows: 1 H NMR (400MHz, CDCl3) δ8.96(s,1H),8.56(s,1H),8.41(s,1H),8.34(s,1H),8.29(d,J=11.9Hz,3H),8.23(s,2H),7.88(s,2H ),7.83–7.73(m,17H),7.71(s,1H),7.62(s,1H),7.51(t,J=7.5Hz,16H),7.33(s,2H),7.28(s,1H),7.25(d,J=2.9Hz,1H).

[0200] HR-MS determined the molecular weight to be 999.3191 [M+1]. Elemental analysis test: 82.96% C, 4.84% H, 2.80% N, 3.20% O corresponding to C 69 H 48 N2O2P2.

[0201] Synthesis of anthracene derivative E93:

[0202] The structural formula of the anthracene derivative E93 is:

[0203]

[0204] The specific synthetic route of anthracene derivative E93 is as follows:

[0205]

[0206] Step 1: Synthesis of compound 93-a

[0207] Compound 35-b (2.27 g, 5 mmol, 1.0 eq), tetrabutylammonium tribromide (7.9 g, 16.5 mmol, 3.3 eq.), and 60 mL of acetic acid were replaced with nitrogen three times, heated to 120°C and stirred for reaction for 48 h. After the reaction, the temperature was cooled to room temperature and poured into 500 mL of deionized water. The mixture was extracted with EA, and the organic phase was concentrated at 60°C. The solid was separated by two silica gel column chromatography (eluent: DCM:EtOH=50:1). The solid was recrystallized from DCM / HEX at room temperature to obtain 2.04 g of compound 93-a with a yield of 67% and a purity of 99.89%.

[0208] The NMR characterization results of compound 17-a are: 1 H NMR (400MHz, CDCl3) δ8.47 (s, 2H), 8.37–8.30 (m, 3H), 7.88 (s, 1H), 7.77 (d, J = 10.0Hz, 5H), 7.68 (s, 2H), 7.62 (s, 1H), 7.51 (s, 6H).

[0209] The molecular weight determined by HR-MS was 612.9697 as [M+1];

[0210] Step 11.2: Synthesis of anthracene derivative E93

[0211] Compound 93-a (1.8 g, 3 mmol, 1.0 eq), compound 1-a (1.3 g, 3.3 mmol, 1.1 eq), dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine palladium (II) (0.16 g, 0.15 mmol, 5% eq.), and Cs2CO3 (3.00 g, 9 mmol, 3.0 eq.) were dissolved in Tol / EtOH / H2O (200 mL / 50 mL / 50 mL), replaced with nitrogen three times, heated to 90°C and stirred to react overnight. After the reaction, the temperature was cooled to room temperature, poured into 500 mL of deionized water, extracted with EA, and the organic phase was concentrated at 60°C. The solid was separated by two silica gel column chromatography (eluent: DCM:MeOH=50:1) and recrystallized from DCM / HEX at room temperature to obtain 2.0 g of anthracene derivative E93 with a yield of 69% and a purity of 99.94%.

[0212] The NMR characterization results of anthracene derivative E93 are as follows: 1H NMR (400MHz, CDCl3) δ8.95 (s, 1H), 8.55 (s, 2H), 8.32 (d, J = 4.4Hz, 2H), 8.27 (s, 4H), 8.22 (s, 2H) ,7.87(s,1H),7.83–7.71(m,16H),7.61(s,1H),7.50(t,J=7.5Hz,14H),7.29(d,J=25.0Hz,4H).

[0213] HR-MS determined the molecular weight to be 991.3487 [M+1]. Elemental analysis test: 84.84% C, 4.74% H, 5.65% N, 1.61% O corresponding to C 70 H 47 N4OP.

[0214] Synthesis of anthracene derivative E94:

[0215] The structural formula of anthracene derivative E94 is:

[0216]

[0217] The specific synthetic route of anthracene derivative E94 is as follows:

[0218]

[0219] Step 1: Synthesis of compound 94-a

[0220] Compound 82-b (3.65 g, 5 mmol, 1.0 eq), tetrabutylammonium tribromide (7.9 g, 16.5 mmol, 3.3 eq.), 60 mL of acetic acid, nitrogen replacement 3 times, heated to 120 ° C, stirred for 48 h, cooled to room temperature after the reaction, poured into 500 mL of deionized water, extracted with EA, concentrated the organic phase at 60 ° C, and separated by silica gel column chromatography twice (eluent DCM: EtOH = 50: 1) to obtain a solid, and recrystallized from DCM / HEX at room temperature to obtain 2.9 g of compound 93-a, with a yield of 67% and a purity of 99.81%. HR-MS determined the molecular weight to be 889.0380 [M+1];

[0221] Step 2: Synthesis of anthracene derivative E94

[0222] Compound 94-a (2.6 g, 3 mmol, 1.0 eq), compound 1-a (1.3 g, 3.3 mmol, 1.1 eq), Pd132 (0.16 g, 0.15 mmol, 5% eq.), and Cs2CO3 (3.00 g, 9 mmol, 3.0 eq.) were dissolved in Tol / EtOH / H2O (200 mL / 50 mL / 50 mL), replaced with nitrogen three times, heated to 90°C and stirred to react overnight. After the reaction, cooled to room temperature, poured into 500 mL of deionized water, extracted with EA, and the organic phase was concentrated at 60°C. The solid was separated by two silica gel column chromatography (eluent: DCM:MeOH=50:1), and recrystallized from DCM / HEX at room temperature to obtain 3.0 g of anthracene derivative E94 with a yield of 79% and a purity of 99.95%.

[0223] The NMR characterization results of anthracene derivative E94 are as follows: 1 H NMR (400 MHz, CDCl3) δ8.97 (s, 2H), 8.56 (s, 2H), 8.35 (s, 2H), 8.28 (s, 4H), 7.88 (s, 2H), 7.85–7.69 (m, 24H), 7.52 (dd, J=10.0, 5.0 Hz, 22H), 7.28 (s, 2H). HR-MS determined the molecular weight to be 1267.4192 [M+1].

[0224] For compounds of anthracene derivatives E1-E95 for which no specific preparation process is given, they can be prepared by referring to the method for anthracene derivative E1.

[0225] For example, compared with the anthracene derivative E1, in the synthesis process of the anthracene derivative E20, the triphenylphosphine oxide unit in the synthesis process of the anthracene derivative E1 is replaced by a dibenzofuran-substituted phosphorus oxide unit; in the synthesis process of the anthracene derivative E26, the triphenylphosphine oxide unit in the synthesis process of the anthracene derivative E1 is replaced by a bispyridine-substituted phosphorus oxide unit; in the synthesis process of the anthracene derivative E28, the anthracene unit in the synthesis process of the anthracene derivative E1 is replaced by a bipyridine-substituted anthracene unit; in the synthesis process of the anthracene derivative E36, 3- The anthracene unit in the synthesis process of anthracene derivative E1 is replaced by a triphenylphosphine oxide unit and an anthracene derivative modified with 9-(pyridyl)phenyl; in the synthesis process of anthracene derivative E37, the triphenylphosphine oxide unit in the synthesis process of anthracene derivative E1 is replaced by a cyclotriphenylphosphine oxide unit; in the synthesis process of anthracene derivative E55, the benzimidazole unit in the synthesis process of anthracene derivative E1 is replaced by a carbazole-modified benzimidazole unit; in the synthesis process of anthracene derivative E61, the anthracene unit substituted with a diphosphine oxide is replaced by a cyclotriphenylphosphine oxide unit anthracene unit; in the synthesis of anthracene derivative E62, an anthracene unit substituted with a bisbenzimidazole is substituted for the anthracene unit in the synthesis of anthracene derivative E1; in the synthesis of anthracene derivative E65, a naphthalene-modified benzimidazole unit is substituted for the benzimidazole unit in the synthesis of anthracene derivative E1; in the synthesis of anthracene derivative E67, a cyclohexane-modified benzimidazole unit is substituted for the benzimidazole unit in the synthesis of anthracene derivative E1; in the synthesis of anthracene derivative E68, a cyclohexane-modified benzimidazole unit is substituted for the benzimidazole unit in the synthesis of anthracene derivative E1. The imidazole unit replaces the benzimidazole unit in the synthesis process of the anthracene derivative E1; in the synthesis process of the anthracene derivative E71, the pyrimidine-modified benzimidazole unit is used to replace the benzimidazole unit in the synthesis process of the anthracene derivative E1; in the synthesis process of the anthracene derivative E80, the anthracene unit modified with benzimidazole at different positions and pyridine is used to replace the anthracene unit in the synthesis process of the anthracene derivative E1; in the synthesis process of the anthracene derivative E87, the anthracene unit modified with a diphosphine oxide unit and a naphthyl unit is used to replace the anthracene unit in the synthesis process of the anthracene derivative E1.

[0226] The anthracene derivative of the present application is used as a doped electron transport material to prepare a light-emitting device.

[0227] The anthracene derivative of the present application is doped with N-type dopant Liq and used as an electron transport layer to prepare a blue light phosphorescent device. The structure of the prepared device is as follows:

[0228] As attached Figure 1 As shown, a blue light phosphorescent device includes a stacked glass substrate with an ITO transparent electrode (anode 1), a hole injection layer 2, a hole transport layer 3 (HTL), an electron blocking layer 4 (EBL), an auxiliary layer 5, a light-emitting layer 6, an electron transport layer 7, an electron injection layer 8, and a cathode 9.

[0229] Providing a glass substrate (anode 1) having an ITO transparent electrode on the surface, wherein the thickness of the ITO transparent electrode is 100 nm;

[0230] The glass substrate 1 was ultrasonically cleaned with deionized water, acetone, deconex 12basic detergent, deionized water and isopropanol for 20 minutes respectively, then dried at 150° C., and then treated with N2 plasma for 30 minutes;

[0231] Compounds HATCN and HTL are evaporated on the surface of one side of the glass substrate (anode 1) having an ITO transparent electrode, and the weight ratio of the compounds HATCN and HTL is 3%:97%, to form a hole injection layer 2, and the thickness of the hole injection layer 2 is 100A;

[0232] Compound HTL is evaporated on the surface of one side of the hole injection layer 2 to form a hole transport layer 3, and the thickness of the hole transport layer 3 is 300 Å;

[0233] The compound EBL is evaporated on the surface of one side of the hole transport layer 3 to form an electron blocking layer 4, and the thickness of the electron blocking layer 4 is 50A;

[0234] SiCzCz is co-evaporated on the surface of one side of the electron blocking layer 4 to form an auxiliary layer 5, and the thickness of the auxiliary layer 5 is 50A;

[0235] SiCzCz, SiTrzCz and PtON-TBBI are evaporated on the surface of one side of the auxiliary layer 5 to form a light-emitting layer 6, the thickness of the light-emitting layer 6 is 300A; wherein the mass ratio of SiCzCz, SiTrzCz and PtON-TBBI is 45.5%_45.5%:9%;

[0236] An electron transport material is evaporated on the surface of one side of the light-emitting layer 6 to form an electron transport layer 7, the thickness of the electron transport layer is 350 Å, and the electron transport material is a mixture of compound ETL, one of the anthracene derivatives or comparative compounds of the present application and Liq, and the weight ratio of one of the anthracene derivatives or comparative compounds of the present application to Liq is 50%:50%;

[0237] Metal Yb is evaporated on the surface of one side of the electron transport layer 7 to form an electron injection layer 8, and the thickness of the electron injection layer 8 is 10A;

[0238] Metal Ag was evaporated on the surface of the electron injection layer 8 to form a cathode 9. The thickness of the cathode 9 was 1000 Å.

[0239] The constant current is 20mA / cm -2Under the condition of 1000 cd·m -2 , test the performance of the light emitting device, the specific values ​​are shown in Table 2 below.

[0240] The preparation and testing methods of the light-emitting devices in other embodiments and comparative examples are the same as the above methods, the only difference being that different anthracene derivatives or comparative compounds of the present application are used.

[0241] The structural formulas of the comparative compounds 1, 2, 3, 4, 5, 6 and the materials used in the above-mentioned light-emitting devices are as follows:

[0242] Comparison of compound structures:

[0243]

[0244] The structural formula of the material used in the above-mentioned light-emitting device is as follows:

[0245]

[0246] The energy levels of the materials used in the above-mentioned light-emitting devices are as follows: Figure 2 shown. Figure 2 The "Emitter" in the figure represents the emission area.

[0247] The electron transport layer material was made into DMF (N,N-dimethylformamide) solution and the HOMO and LUMO values ​​were measured by cyclic voltammetry (scanning range: -2 to +2 V) as shown in Table 1 (E g =LUMO-HOMO).

[0248] Table 1

[0249]

[0250]

[0251] As can be seen from Table 1 above, compared with the commonly used electron transport layer materials (Comparative Compound 1 and Comparative Compound 2), the HOMO / LUMO energy levels of the anthracene derivatives of the present application as electron transport layer materials have a tendency to rise, and have better energy level matching with the light-emitting layer in the light-emitting device. Compared with the HOMO / LUMO energy levels between the electron transport layer materials of the present application, HOMO is basically between -5.59 and -5.64eV, and LUMO is basically between -2.90 and -2.70eV, with little change; combined with the DFT (density functional theory) calculation results, it can be seen that the HOMO / LUMO of the electron transport layer material of the present application with the three-unit structure of combined phosphorus oxygen, anthracene, and benzimidazole is mainly distributed on the anthracene ring, and the phosphorus oxygen unit (except for the addition of a strong electron-withdrawing group) and the benzimidazole unit have little effect on the HOMO / LUMO of the material; however, the addition or change of the phosphorus oxygen unit and the benzimidazole unit mainly changes the stability and electron transport capacity of the material, which is directly fed back to the subsequent OLED device performance, which is also the main advantage of the present application.

[0252] The anthracene derivative of the present application, which combines phosphorus oxygen, anthracene and benzimidazole, is doped with Liq (the mass ratio of anthracene derivative to Liq is 50%:50%) as an electron transport material, which can match the second-generation blue phosphorescent material luminescence system and has high commercial value. The above electron transport material is made into a light-emitting device, and the above light-emitting device is measured at 20mA / cm 2 The voltage, current efficiency and life of the light-emitting device at 1000 nits are measured, and the results are shown in Table 2 (in Table 2, the voltage, current efficiency and LT95h@1000nits corresponding to device embodiment 1 are used as a benchmark to record the relative levels of voltage, current efficiency and LT95h@1000nits of other device embodiments and device comparison examples. Taking device embodiment 2 as an example, the voltage corresponding to device embodiment 2 is 97.7%, the current efficiency is 98.9%, and the LT95h@1000nits is 101.5%, indicating that the voltage corresponding to device embodiment 2 is 97.7%, the current efficiency is 98.9%, and the LT95h@1000nits is 101.5% of that of device embodiment 1).

[0253] Table 2

[0254]

[0255]

[0256] As can be seen from Table 2, compared with the commonly used electron transport layer materials (Comparative Compound 1 and Comparative Compound 2), the light-emitting devices using the anthracene derivatives of the present application as electron transport materials show more superior performance in terms of operating voltage, luminous efficiency, and device life, among which preferred embodiments 14 and 15 of the present application have obvious advantages in device life. Compared with Comparative Example 4, the main difference in molecular structure of Example 1 of the present application is anthracene and naphthyl derivatives. Example 1 of the present application shows more superior performance in terms of operating voltage, luminous efficiency, and device life. Compared with Comparative Example 6, the main difference in molecular structure is benzimidazole derivatives and pyrrolo[2,3-B:4,5-B']bipyridine derivatives. Example 1 of the present application performs better in device life.

[0257] In general: the anthracene derivatives of the present application are used in light-emitting devices as electron transport layer materials, and show more superior performance in terms of operating voltage, luminous efficiency, and device life compared to the comparative compounds. The benzimidazole derivatives substituted with phosphorus oxygen and anthracene used in the present application have good optical, electrical, and thermal stability (for example, the Tg of the anthracene derivatives E48 and the anthracene derivatives E50 of the present application is greater than 150°C, and 5% Td is greater than 520°C, where Tg represents the glass transition temperature and Td represents the decomposition temperature), high luminous efficiency, low voltage, and long life, and can be used in organic light-emitting devices, and have better application prospects in the AMOLED industry.

[0258] The above-mentioned various embodiments are only used as examples and are not intended to limit the scope of the invention. Without departing from the spirit of the invention, the various materials and structures in this application can be replaced with other materials and structures. It should be understood that those skilled in the art can make many modifications and changes according to the thinking of this application without creative work.

Claims

1. An anthracene derivative, characterized in that: Its general structural formula is shown in formula (I): Wherein, L1 and L2 are independently selected from a single bond, a substituted or unsubstituted C6-C60 arylene group or a substituted or unsubstituted C3-C60 heteroarylene group, and when L1 is a phenyl group, The substitution position on L1 is meta-substitution; The dotted line between L1, L2 and the anthracene group indicates that the bonding site is not limited; Ar1, Ar2 and Ar3 are independently selected from substituted or unsubstituted C6-C36 aryl or substituted or unsubstituted C2-C36 heteroaryl; R1 and R2 are each independently selected from hydrogen, deuterium, halogen, cyano, isocyano, substituted or unsubstituted C1-C40 alkyl, substituted or unsubstituted C1-C40 heteroalkyl, substituted or unsubstituted C3-C40 cycloalkyl, substituted or unsubstituted C3-C40 heterocycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, substituted or unsubstituted C6-C60 aryloxy, substituted or unsubstituted C1-C40 alkylamino or substituted or unsubstituted C6-C60 arylphosphinoyl; The substitution is substituted by at least one of deuterium, halogen, cyano, isocyano, nitro, trifluoromethyl, C1-C6 alkyl, C3-C16 cycloalkyl, C1-C6 alkyl substituted amine, C1-C6 hydrocarbon substituted or unsubstituted C6-C30 aryl, C1-C6 hydrocarbon substituted or unsubstituted C3-C30 heteroaryl, C1-C6 hydrocarbon substituted or unsubstituted phosphinooxy, wherein the number of substitutions ranges from single substitution to the maximum number of substitutions; The heteroatom in the heteroalkyl group, heterocycloalkyl group, heteroaryl group, and heteroarylene group is at least one of Si, N, O, and S; Both x and y are natural numbers from 0 to 3; Both m and n are natural numbers ranging from 1 to 3.

2. The anthracene derivative according to claim 1, characterized in that The anthracene derivative has a general structural formula as shown in formula (II):

3. The anthracene derivative according to claim 2, characterized in that Both m and n are 1.

4. The anthracene derivative according to claim 1, characterized in that Ar1 and Ar2 may be linked to form a ring.

5. The anthracene derivative according to claim 1, characterized in that L1 and L2 are each independently selected from a single bond, a substituted or unsubstituted C6-C40 arylene group or a substituted or unsubstituted C3-C40 heteroarylene group; and / or Ar1, Ar2 and Ar3 are each independently selected from a substituted or unsubstituted C6-C30 aryl group or a substituted or unsubstituted C2-C30 heteroaryl group; and / or R1 and R2 are each independently selected from hydrogen, deuterium, halogen, cyano, isocyano, substituted or unsubstituted C1-C30 alkyl group, substituted or unsubstituted C1-C30 heteroalkyl group, substituted or unsubstituted C3-C30 cycloalkyl group, substituted or unsubstituted C3-C30 heterocycloalkyl group, substituted or unsubstituted C6-C40 aryl group, substituted or unsubstituted C3-C40 heteroaryl group, substituted or unsubstituted C6-C40 aryloxy group, substituted or unsubstituted C1-C30 alkylamino group or substituted or unsubstituted C6-C40 arylphosphinoyl group.

6. The anthracene derivative according to claim 1, characterized in that The substitution is substituted by at least one of deuterium, halogen, cyano, isocyano, nitro, C1-C6 alkyl, C3-C10 cycloalkyl, C1-C6 alkyl substituted amine, C1-C6 hydrocarbon substituted or unsubstituted C6-C20 aryl, C1-C6 hydrocarbon substituted or unsubstituted C3-C20 heteroaryl, C1-C6 hydrocarbon substituted or unsubstituted phosphinooxy, wherein the number of substitutions is from a single substitution to a maximum number of substitutions.

7. The anthracene derivative according to claim 1, characterized in that L1 and L2 are independently selected from any of the following structures: Among them, R, R a or R b Each of the following is independently selected from hydrogen, deuterium, halogen, cyano, isocyano, substituted or unsubstituted C1-C40 alkyl, substituted or unsubstituted C1-C40 heteroalkyl, substituted or unsubstituted C3-C40 cycloalkyl, substituted or unsubstituted C3-C40 heterocycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, substituted or unsubstituted C6-C60 aryloxy or substituted or unsubstituted C1-C40 alkylamino; Ar is selected from substituted or unsubstituted C6-C36 aryl, substituted or unsubstituted C2-C36 heteroaryl; Ring A is a substituted or unsubstituted C3-C40 cycloalkyl group; R, R a or R b , Ar, and the substitution in ring A is substitution by at least one of deuterium, halogen, cyano, isocyano, C1-C6 alkyl, and C3-C16 cycloalkyl, wherein the number of substitutions ranges from single substitution to the maximum number of substitutions; "*" indicates the key connection position.

8. The anthracene derivative according to claim 6, characterized in that L1 and L2 are selected from any of the following structures:

9. The anthracene derivative according to claim 1, characterized in that The structural formula of the anthracene derivative is any one of the following:

10. A light emitting device, characterized in that: The invention comprises an anode, a cathode and one or more organic layers between the anode and the cathode, wherein at least one of the one or more organic layers comprises the anthracene derivative according to any one of claims 1 to 9.

Images