CN111662312B - Compound, thermal activation delay fluorescent material and application thereof - Google Patents

Compound, thermal activation delay fluorescent material and application thereof Download PDF

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CN111662312B
CN111662312B CN202010515099.4A CN202010515099A CN111662312B CN 111662312 B CN111662312 B CN 111662312B CN 202010515099 A CN202010515099 A CN 202010515099A CN 111662312 B CN111662312 B CN 111662312B
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CN111662312A (en
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汪奎
张正川
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Wuhan Tianma Microelectronics Co Ltd
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Abstract

The invention provides a compound, a thermal-activation delay fluorescent material and application thereof, in particular to a compound, a thermal-activation delay fluorescent material, a display panel and electronic equipment, wherein the compound has a structure shown in a formula I; the thermally activated delayed fluorescence material comprises any one or a combination of at least two of the compounds; the display panel includes an OLED device including an anode, a cathode, and at least one organic layer between the anode and the cathode, the organic layer including a light emitting layer including a thermally activated delayed fluorescence material; the electronic device includes a display panel; the energy difference delta Est=Es1-ET 1 between the lowest singlet state S1 and the lowest triplet state T1 of the compound is less than or equal to 0.30eV, and the compound has a thermal activation delay fluorescent material luminescence mechanism, can be used in the field of organic photoelectric devices, reduces driving voltage, improves luminescence efficiency and service life, and enables electronic equipment comprising the compound to have more excellent performance.

Description

Compound, thermal activation delay fluorescent material and application thereof
Technical Field
The invention belongs to the field of organic devices, relates to a compound, a thermal activation delay fluorescent material and application thereof, and particularly relates to a compound, a thermal activation delay fluorescent material, a display panel and electronic equipment.
Background
Optoelectronic devices based on organic materials have become increasingly popular in recent years. The inherent flexibility of organic materials makes them very suitable for fabrication on flexible substrates, which can be designed to produce aesthetically pleasing and cool optoelectronic products, as desired, with no comparable advantages over inorganic materials. Examples of such organic optoelectronic devices include Organic Light Emitting Diodes (OLEDs), organic field effect transistors, organic photovoltaic cells, organic sensors, and the like. Among them, OLED has been developed particularly rapidly, and has been commercially successful in the field of information display. OLED can provide three colors of red, green and blue with high saturation, and the full-color display device manufactured by the OLED does not need extra backlight source, and has the advantages of colorful, light, thin, soft and the like.
The OLED device core is a thin film structure containing a plurality of organic functional materials. Common functionalized organic materials are: a hole injecting material, a hole transporting material, a hole blocking material, an electron injecting material, an electron transporting material, an electron blocking material, a light emitting host material, a light emitting guest (dye), and the like. When energized, electrons and holes are injected, transported to the light emitting region, respectively, and recombined therein, thereby generating excitons and emitting light.
Various organic materials have been developed, and various peculiar device structures are combined, so that carrier mobility can be improved, carrier balance can be regulated, electroluminescent efficiency can be broken through, and device attenuation can be delayed. For quantum mechanical reasons, common fluorescent emitters emit light mainly by singlet excitons generated when electrons and air are combined, and are still widely applied to various OLED products. Some metal complexes, such as iridium complexes, can emit light using both triplet and singlet excitons, known as phosphorescent emitters, and can have energy conversion efficiencies up to four times greater than conventional fluorescent emitters. The thermal excitation delayed fluorescence (TADF) technique can achieve higher luminous efficiency by promoting transition of triplet excitons to singlet excitons, and still effectively utilizing triplet excitons without using a metal complex. The thermal excitation sensitized fluorescence (TASF) technology adopts a material with TADF property to sensitize the luminophor by means of energy transfer, and can also realize higher luminous efficiency. However, few TADF materials have been found, the performance of which is still to be improved, and new TADF materials that can be used in OLED devices are in need of development.
Therefore, a great variety of TADF materials with higher performance have been desired to be developed, so that devices including the same have higher luminous efficiency.
Disclosure of Invention
In order to develop a wider variety of TADF materials with higher performance, and devices with higher luminous efficiency, it is an object of the present invention to provide a compound having a structure represented by formula I:
in the formula I, R 1 And R is 2 Each independently selected from any one of substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C6-C30 arylamino, and R 1 And R is 2 Are all electron donating groups;
in the formula I, R 3 And R is 4 Each independently selected from any one of a substituted or unsubstituted C3-C30 electron withdrawing nitrogen heteroaryl, a substituted or unsubstituted C6-C30 cyano-containing aryl, a substituted or unsubstituted C3-C30 cyano-containing heteroaryl, a substituted or unsubstituted C6-C30 fluoro-containing aryl, a substituted or unsubstituted C3-C30 fluoro-containing heteroaryl;
in the formula I, R a 、R b And R is c Each independently selected from any one of carbonyl, cyano, amido, phosphoxy, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl;
in the formula I, m, n and p are each independently selected from integers of 0-2;
R 1 、R 2 、R 3 、R 4 、R a 、R b and R is c Wherein the substituted group is selected from any one of halogen, carbonyl, cyano, amido, phosphorus oxy, C1-C12 chain alkyl, C3-C12 cycloalkyl, C1-C6 alkoxy or thioalkoxy, C2-C20 alkenyl C6-C30 arylamino, C3-C30 heteroaryl amino, C6-C30 monocyclic or fused ring aromatic hydrocarbon groups, C3-C30 monocyclic or fused ring heteroaromatic hydrocarbon groups.
It is a second object of the present invention to provide a thermally activated delayed fluorescence material comprising any one of the compounds described in one of the objects or a combination of at least two of them.
It is a further object of the present invention to provide a display panel comprising an OLED device comprising an anode, a cathode, and at least one organic layer between the anode and the cathode, the organic layer comprising a light emitting layer comprising the two thermally activated delayed fluorescence materials of interest, and the thermally activated delayed fluorescence materials being used as any one of host materials, dopant materials or co-dopant materials.
A fourth object of the present invention is to provide an electronic apparatus including the display panel described in the third object.
Compared with the prior art, the invention has the following beneficial effects:
the compound provided by the invention forms D-A charge transfer action through chemical bond based on the design of molecular structure, and forms space charge transfer action by utilizing the space distance design of electron donor and electron acceptor, so that HOMO and LUMO can be effectively separated in the molecule, and delta E is reduced ST Enable level difference delta E ST ＝E S1 -E T1 The energy consumption is less than or equal to 0.30eV, and the physical process of efficient reverse intersystem leap is realized, so that the compound has typical TADF characteristics; the compound provided by the invention can have two D-A light-emitting subunits in one molecule, has the property of dual emission cores, effectively improves the vibrator strength and improves the light-emitting efficiency; at the same time, the bipolar nature of the compounds facilitates the transport of electrons and holes. Therefore, the compound provided by the invention is highly suitable for being used as a luminescent layer material of an OLED device, widens a luminescent layer, and improves the luminous efficiency and the service life of the OLED device.
Drawings
FIG. 1 is a schematic view of an OLED display panel provided in one embodiment of the present invention;
FIG. 2 is a schematic representation of the HOMO distribution of compound M3 in one embodiment of the invention;
FIG. 3 is a diagram showing the LUMO distribution of Compound M3 in one embodiment of the present invention;
fig. 4 is a schematic diagram of an electronic device provided in one embodiment of the invention.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
One of the objects of the present invention is to provide a compound having the structure of formula I:
in the formula I, R 1 And R is 2 Each independently selected from any one of substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C6-C30 arylamino, and R 1 And R is 2 Are all electron donating groups, wherein the electron donating groups refer to groups capable of improving the electron cloud density on the benzene ring;
in the formula I, R 3 And R is 4 Each independently selected from any one of substituted or unsubstituted C3-C30 azaheteroaryl, substituted or unsubstituted C6-C30 cyanoheteroaryl, substituted or unsubstituted C3-C30 cyanoheteroaryl, substituted or unsubstituted C6-C30 fluoroaryl, substituted or unsubstituted C3-C30 fluoroheteroaryl, and R 1 And R is 2 All are electron withdrawing groups, wherein the electron withdrawing groups refer to groups capable of reducing electron cloud density on benzene rings;
in the formula I, R a 、R b And R is c Each independently selected from any one of carbonyl, cyano, amido, phosphoxy, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl;
in formula I, m, n and p are each independently selected from integers from 0-2 (e.g., 0,1 or 2);
R 1 、R 2 、R 3 、R 4 、R a 、R b and R is c Wherein the substituted group is selected from halogen, carbonyl, cyano, amido, phosphorus oxy, C1-C12 chain alkyl, C3-C12 cycloalkyl, C1-C6 alkoxy or thioalkoxy, C2-C20 alkenyl C6-C30 arylamino, C3-C30 heteroaryl amino, C6-C30 monocyclic aromatic hydrocarbon or polycyclic aromatic hydrocarbonAny one of a group, a C3-C30 monocyclic heteroarene or a condensed ring heteroarene group.
Use of R in formula I 1 、R 2 、R 3 、R 4 、R a 、R b And R is c In the sense that R represents a substituent 1 、R 2 、R 3 、R 4 、R a 、R b And R is c Represents a selected range of groups, not a specific group, when R a 、R b Or R is c When the number of (2) is two or more, the substituents may be the same or different, and when the parent group is substituted with two R a When the radicals are, two R a The groups may be the same or different.
C1-C20 includes C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, and the like.
C2-C20 includes C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, and the like.
C3-C30 includes C4, C6, C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, and the like.
C6-C30 includes C6, C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, and the like.
C1-C6 includes C2, C3, C4, C5, and the like.
C1-C12 includes C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, and the like.
C2-C12 includes C3, C4, C5, C6, C7, C8, C9, C10, C11, and the like.
C3-C12 includes C4, C5, C6, C7, C8, C9, C10, C11, and the like.
The compound provided by the invention takes a boron heterocyclic structure as a parent body and is matched with specific kinds of electron-withdrawing groups and electron-donating groups to ensure that R 1 -N-B-R 3 And R is 2 -N-B-R 4 Through the charge transfer function of D-A formed by chemical bond, the effective separation of HOMO and LUMO in the molecule is realized, and delta E is reduced ST Realizing the physical process of efficient reverse intersystem leap, leading the compound toWith typical TADF characteristics.
In the compound with the structure shown in the formula I, two D-A light-emitting subunits exist in the same molecule, the compound has the property of dual emission nuclei, the vibrator strength can be effectively improved, the light-emitting efficiency is improved, the compound has the bipolar characteristic, electrons and holes can be effectively transmitted, and the compound is suitable for being used as a doping material of a light-emitting layer of an OLED device, and the light-emitting efficiency and the service life of the OLED device are improved.
In the preparation process of the compound, the introduction of excessive functional group substitution is avoided, the unstable factors in the molecular electrochemical environment are increased, the service life of the device is influenced, and the compound with larger molecular weight is not easy to evaporate, so that the compound with a simple structure is designed as far as possible on the premise of not influencing the luminous efficiency of the compound.
In one embodiment, each of m, n, and p is independently selected from 0 or 1.
In one embodiment, both m and n are 1 and p is 0.
In the invention, m and n are preferably 1, p is 0, the introduction of excessive functional group substitution can be avoided, the unstable factors in the molecular electrochemical environment are increased, the service life of the device is influenced, and the compound with larger molecular weight is not easy to evaporate, so that the compound with simple structure is designed as far as possible on the premise of not influencing the luminous efficiency of the compound.
In one embodiment, the R a 、R b And R is c Each independently selected from any one of methyl, phenyl, biphenyl, terphenyl, naphthyl, fluorenyl or carbazolyl.
In one embodiment, the compound has a structure represented by formula II:
wherein R is 1 、R 2 、R 3 And R is 4 Has the same limiting scope as described above.
In the invention, the compound is selected from the structure shown in the formula II, can improve the stability of molecules, and through steric hindrance effect, distorts the molecular structure, effectively separates molecules HOMO and LUMO, and reduces delta E ST The physical process of efficient reverse intersystem leap is realized, so that the compound has typical TADF characteristics.
In one embodiment, the compound has a structure represented by formula III:
wherein R is 1 、R 2 、R 3 And R is 4 Has the same limiting scope as described above.
In one embodiment, the R 1 And R is 2 Each independently selected from any one of the following substituted or unsubstituted:
wherein the dotted line represents the attachment site of the group.
In one embodiment, R 1 And R is 2 Each independently selected from any one of the following groups:
in one embodiment, the R 1 And R is 2 The same applies.
In one embodiment, the R 3 And R is 4 Each independently selected from the group consisting of substituted or unsubstituted oxadiazoles, substituted or unsubstituted imidazoles, substituted or unsubstituted oxazoles, substituted or unsubstituted triazoles, substituted or unsubstituted quinolines, substituted or unsubstituted triazines, substituted or unsubstituted phenanthrolines, substituted or unsubstituted C6-C18 cyano-containing aryl groups, substituted or unsubstituted C3-C18 cyano-containing heteroaryl groupsAny one of a group, a substituted or unsubstituted C6-C18 fluorine-containing aryl group, and a substituted or unsubstituted C3-C18 fluorine-containing heteroaryl group.
In one embodiment, the R 3 And R is 4 Each independently selected from any one of the following groups:
wherein the dotted line represents the attachment site of the group.
In one embodiment, the R 3 And R is 4 The same applies.
In one embodiment, the compound includes any one of the following structures M1-M40:
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in one embodiment, the energy level difference Δest=e1-e1.ltoreq.0.3 eV, such as 0.30eV, 0.29eV, 0.28eV, 0.27eV, 0.26eV, 0.25eV, 0.24eV, 0.23eV, 0.22eV, 0.21eV, 0.20eV, 0.19eV, 0.18eV, 0.16eV, 0.14eV, 0.13eV, 0.12eV, 0.11eV, 0.10eV, 0.09eV, 0.08eV, 0.07eV, 0.06eV, 0.05eV, 0.04eV, 0.03eV, 0.02eV, 0.01eV, etc., between the lowest singlet S1 and the lowest triplet T1 state of the compound.
It is a second object of the present invention to provide a thermally activated delayed fluorescence material comprising any one of the compounds described in one of the objects or a combination of at least two of them.
When the compound provided by the invention is used as a thermal activation delay fluorescent material, delta Est is less than or equal to 0.30eV, so that the crossing between opposite systems is easy to occur, the triplet state exciton with long service life is easy to be up-converted into the singlet state exciton, the singlet state exciton is attenuated to a ground state S0 in a radiation manner, the high photoinduced quantum yield PLQY is caused, the roll-off effect can be effectively reduced, the device has good luminous performance, and the device can be used as a doping material, a co-doping material or a main body material of a luminous layer in an organic photoelectric device.
It is a further object of the present invention to provide a display panel comprising an OLED device comprising an anode, a cathode, and at least one organic layer between the anode and the cathode, the organic layer comprising a light emitting layer comprising the two thermally activated delayed fluorescence materials of interest, and the thermally activated delayed fluorescence materials being used as any one of host materials, dopant materials or co-dopant materials.
In the invention, the luminescent layer material comprises a host material and a guest material, wherein the guest material comprises a doping material, and when the host material of the luminescent layer is selected from the compounds, the guest material is selected from any one of a phosphorescent material, a fluorescent material or a thermally activated delayed fluorescent material.
In the present invention, when the guest material of the light emitting layer is selected from the above-mentioned compound, the host material is selected from 2, 8-bis (diphenylphosphino) dibenzothiophene, 4 '-bis (9-carbazolyl) biphenyl, 3' -bis (N-carbazolyl) -1,1 '-biphenyl, 2, 8-bis (diphenylphosphino) dibenzofuran, bis (4- (9H-carbazolyl-9-yl) phenyl) diphenylsilane, 9- (4-tert-butylphenyl) -3, 6-bis (triphenylsilyl) -9H-carbazole, bis (2-diphenylphosphino) diphenyl ether, 1, 3-bis [3, 5-bis (pyridin-3-yl) phenyl ] benzene, 4, 6-bis (3, 5-bis (3-pyridylphenyl) 2-methylpyrimidine, 9- (3H-carbazolyl-9-phenyl) -9H-carbazole-3-cyano, 9-phenyl-9- [4- (triphenylsilyl) phenyl ] -9H-fluorenyl, 1, 5-tris (3, 5-diphenyl) phenyl ] benzene, and tris (1, 5-diphenyl) phosphino 4' -tris (carbazol-9-yl) triphenylamine, 2, 6-dicarbazol-1, 5-pyridine, any one or a combination of at least two of polyvinylcarbazole and polyfluorene.
Preferably, the organic layer further includes any one or a combination of at least two of a hole transport layer, a hole injection layer, an electron blocking layer, a hole blocking layer, an electron transport layer, and an electron injection layer.
In the OLED display panel provided by the present invention, the first electrode (anode) material may be selected from metals such as copper, gold, silver, iron, chromium, nickel, manganese, palladium, platinum, etc., and alloys thereof. The first electrode material may also be selected from metal oxides such as indium oxide, zinc oxide, indium Tin Oxide (ITO), indium Zinc Oxide (IZO), and the like, and may also be selected from conductive polymers such as polyaniline, polypyrrole, poly (3-methylthiophene), and the like. Furthermore, the first electrode material may be selected from materials other than the first electrode materials listed above, which facilitate hole injection, and combinations thereof, including materials known to be suitable as the first electrode.
In the OLED display panel provided by the present invention, the second electrode (cathode) material may be selected from metals such as aluminum, magnesium, silver, indium, tin, titanium, etc., and alloys thereof. The second electrode material may also be selected from a plurality of layers of metallic materials such as LiF/Al, liO 2 /Al、BaF 2 Al, etc. In addition to the second electrode materials listed above, the second electrode materials may also be materials that facilitate electron injection and combinations thereof, including materials known to be suitable as second electrodes.
The substrate of the OLED display panel may be a rigid substrate such as borosilicate glass, float soda lime glass, high refractive index glass, stainless steel, etc., and may also be a flexible substrate such as a Polyimide (PI) plastic substrate, a polyethylene terephthalate (PET) plastic substrate, a polyethylene naphthalate (PEN) plastic substrate, a polyethersulfone resin substrate (PES), a polycarbonate plastic substrate (PC), an ultra-thin flexible glass substrate, a metal foil substrate, etc.
In the OLED display panel provided by the invention, the hole injection material, the hole transport material and the electron blocking material are respectively and independently selected from N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine, 4 '-tris (carbazole-9-yl) triphenylamine, 1, 3-dicarbazole-9-yl benzene, 4' -bis (9-carbazole) biphenyl, 3 '-bis (N-carbazolyl) -1,1' -biphenyl, 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazabenzophenanthrene and 4,4 '-cyclohexylbis [ N., any 1 or a combination of at least 2 of N-bis (4-methylphenyl) aniline, N' -diphenyl-N, N '- (1-naphthyl) -1,1' -biphenyl-4, 4 '-diamine, N' -bis (naphthalen-2-yl) -N, N '-bis (phenyl) biphenyl-4, 4' -diamine, poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid, polyvinylcarbazole, 9-phenyl-3, 9-dicarbazole, molybdenum trioxide.
In the OLED display panel provided by the invention, the hole blocking material, the electron transport material and the electron injection material are respectively and independently selected from 2, 8-bis (diphenylphosphino) dibenzothiophene, TSPO1, TPBi, 2, 8-bis (diphenylphosphino) dibenzofuran, bis (2-diphenylphosphino) diphenyl ether, lithium fluoride, 4, 6-bis (3, 5-bis (3-pyridyl) phenyl) -2-methylpyrimidine, 4, 7-diphenyl-1, 10-phenanthroline, 1,3, 5-tris [ (3-pyridyl) -3-phenyl ] benzene, tris [2,4, 6-trimethyl-3- (3-pyridyl) phenyl ] borane, 1, 3-bis (3, 5-bipyridin-3-ylphenyl) benzene, 1, 3-bis [3, 5-bis (pyridin-3-yl) phenyl ] benzene, 2,4, 6-tris (biphenyl-3-yl) -1,3, 5-triazine, diphenyl-3- (4-phenyl) quinoline, or at least one of 1, 3-hydroxy-3-phenyl ] quinoline, or at least one of 1, 8-hydroxy-3- (3-pyridyl) phenyl) quinoline, and 1, 8-hydroxy-3-phenyl) quinoline.
In the embodiment of the invention, the manufacturing process of the OLED display panel is as follows: an anode (first electrode) is formed on a transparent or opaque smooth substrate, an organic thin layer is formed on the anode, and a cathode (second electrode) is formed on the organic thin layer. The organic thin layer may be formed by a known film forming method such as vapor deposition, sputtering, spin coating, dipping, ion plating, and the like.
A fourth object of the present invention is to provide an electronic apparatus including the display panel described in the third object.
In one embodiment, the electronic device may be a cell phone, a computer, a liquid crystal television, a smart watch, a smart car, a VR or AR helmet, or the like.
The compound with the structure shown in the formula I is prepared by the following synthetic route in an exemplary way:
wherein R is 1 、R 2 、R 3 、R 4 、R a 、R b 、R c M, n and p have the same defined ranges as described above.
The present invention provides several exemplary methods for preparing compounds of the structure of formula 1. In the following preparations, the synthesis of the compounds is described exemplarily.
Preparation example 1
Synthesis of compound M3:
(1) 5.60g (20 mmol) of compound A, 7.95g (20 mmol) of compound B, 8.94g (20 mmol) of compound C, 150mL of toluene dehydrated and deoxygenated, 13.81g (30 mmol) of cesium carbonate, 0.23g (0.2 mmol) of tetrakis (triphenylphosphine) palladium were sequentially added to a 250mL three-necked flask, and then reacted at 120℃for 24 hours under a nitrogen atmosphere. Cooled to room temperature, the reaction solution was poured into 200mL of ice water, extracted three times with dichloromethane, the organic phases were combined, spun into silica gel, and purified by column chromatography (dichloromethane: n-hexane, v: v=1:1) to give compound D.
1 H NMR(400MHz,Chloroform)δ9.36(s,1H),9.08(s,1H),7.69(s,2H),7.58(s,1H),7.43(s,2H),7.36–7.29(m,5H),7.25(d,J＝11.6Hz,5H),7.08(s,2H),7.00(s,4H),2.13(s,6H).
13 C NMR(100MHz,Chloroform)δ146.93(s),140.83(s),140.21(s),134.42(s),129.38–128.87(m),127.54(s),127.38–127.04(m),125.65(s),124.67(s),122.99(s),122.20(s),121.16(s),119.25(s),95.28(s),13.27(s).
(2) In a 250mL three-necked flask, 17.51g (20 mmol) of the substrate D and 80mL of THF were added and dissolved, and the mixture was replaced with nitrogen three times. Cooling to-78deg.C, controlling the temperature below-65deg.C, slowly adding n-BuLi 20mL (50 mmol) dropwise, and stirring for 30min. TMS-Cl 4.35g (40 mmol) was then slowly added dropwise and the reaction was carried out at 0℃for 4h. And adding ice water to quench after the completion. DCM (80 ml x 2) was added for extraction. The organic phase was collected by rotary evaporation and crystallized from Tol/EtOH to give a solid. A200 mL jar was charged with 16.97g (20 mmol) of solid, a solution of anhydrous toluene (70 mL) and 3.04mL (40 mmol) of boron tribromide in this order. Stirring for 12h at 120 ℃. H after the reaction is finished 2 O (100 mL) quench. The reaction was extracted with DCM (100 ml x 3), the organic phase was collected, dried and filtered and the solvent was removed by rotary evaporation. Crystallization using DCM/EtOH gives solid E.
1 H NMR(400MHz,Chloroform)δ9.36(s,1H),9.08(s,1H),δ7.69(s,2H),7.60(d,J＝16.0Hz,3H),7.50(s,2H),7.32(s,2H),7.24(s,4H),7.08(s,4H),7.00(s,2H),6.55(s,1H),6.50(s,1H),2.13(s,6H).
13 C NMR(100MHz,Chloroform)δ146.93(s),142.85(s),140.54(s),134.71(s),129.48(s),129.27(s),128.58–128.29(m),126.84(s),125.89(s),124.67(s),122.99(s),122.24(s),119.94(s),119.32(s),113.19(s),14.23(s).
(3) Into a reaction flask, 14.74g (20 mmol) of compound E was added, diethyl ether (50 mL) was added for dissolution, and nitrogen was substituted three times. Cooling to-78deg.C, controlling the temperature below-65deg.C, slowly adding n-BuLi 16.08mL (2.5M, 40 mmol) dropwise, and stirring for 30min. Then, 10.56g (40 mmol) of the compound F was slowly added dropwise to the reaction mixture, and the mixture was allowed to react at room temperature for 6 hours after completion of the dropwise addition. After the completion of the reaction, ice water (100 mL) was added to quench the reaction. DCM (80 ml x 2) was added for extraction and finally extracted once with saturated brine. The organic phase was collected and distilled to give a pale yellow oil. The product was purified by column chromatography (mobile phase n-hexane: dichloromethane=3:1) to give compound M3.
1 H NMR(400MHz,Chloroform)δ8.25(s,4H),7.69(s,2H),7.60(d,J＝16.0Hz,4H),7.50(s,2H),7.32(s,2H),7.24(s,4H),7.08(s,4H),7.00(s,2H),6.65(s,1H),6.52(s,1H),2.13(s,6H).
13 C NMR(100MHz,Chloroform)δ172.45(s),169.25(s),166.72(s),153.94(s),146.93(s),142.85(s),140.54(s),134.71(s),134.34(s),130.26(s),129.48(s),129.27(s),128.46(d,J＝3.7Hz),127.46(s),126.84(s),124.70(d,J＝5.7Hz),122.99(s),122.24(s),114.39(s),112.01(s),14.23(s).
Preparation example 2
Synthesis of Compound M1
(1) In a 250mL three-necked flask, 8.94g (20 mmol) of Compound A, 3.98g (10 mmol) of Compound B, 150mL of toluene dehydrated and deoxygenated, 13.81g (30 mmol) of cesium carbonate, 0.23g (0.2 mmol) of tetrakis (triphenylphosphine) palladium were successively added, and then reacted at 120℃for 24 hours under nitrogen atmosphere. Cooled to room temperature, the reaction solution was poured into 200mL of ice water, extracted three times with dichloromethane, the organic phases were combined, spun into silica gel, and purified by column chromatography (dichloromethane: n-hexane, v: v=1:1) to give compound D.
1 H NMR(400MHz,Chloroform)δ7.50–7.44(m,6H),7.32–7.24(m,8H),7.22–7.17(m,6H),7.14–7.07(m,10H),6.67(s,2H),2.29(s,6H).
13 C NMR(100MHz,Chloroform)δ146.34,144.20,137.71,134.55,134.13,133.53,130.17,129.22,127.64,126.89,125.87,123.63,122.29,96.94,14.03.
(2) In a 250mL three-necked flask, 10.43g (10 mmol) of the substrate D and 80mL of THF were added and dissolved, and the mixture was replaced with nitrogen three times. Cooling to-78deg.C, controlling the temperature below-65deg.C, slowly adding n-BuLi 20mL (50 mmol) dropwise, and stirring for 30min. TMS-Cl 4.35g (40 mmol) was then slowly added dropwise and the reaction was carried out at 0℃for 4h. And adding ice water to quench after the completion. DCM (80 ml x 2) was added for extraction. The organic phase was collected by rotary evaporation and crystallized from Tol/EtOH to give a solid. Sequentially adding the solid into a 200mL jar20.32g (20 mmol), anhydrous toluene solution (70 mL) and 3.04mL (40 mmol) of boron tribromide. Stirring for 12h at 120 ℃. H after the reaction is finished 2 O (100 mL) quench. The reaction was extracted with DCM (100 ml x 3), the organic phase was collected, dried and filtered and the solvent was removed by rotary evaporation. Crystallization using DCM/EtOH gives solid E.
1 H NMR(400MHz,Chloroform)δ7.51–7.43(m,6H),7.31–7.25(m,8H),7.23–7.14(m,6H),7.14–7.07(m,12H),2.24(d,J＝0.7Hz,6H).
13 C NMR(100MHz,Chloroform)δ146.34,144.61,138.34,137.75,132.52,129.22,127.64,126.89,123.66,123.46,123.27,122.16,119.93,15.51,-7.68.
(3) To a reaction flask was added 18.08g (20 mmol) of compound E, and diethyl ether (50 mL) was added for dissolution, and nitrogen was substituted three times. Cooling to-78deg.C, controlling the temperature below-65deg.C, slowly adding n-BuLi 16.08mL (2.5M, 40 mmol) dropwise, and stirring for 30min. Then, 9.52g (40 mmol) of the compound F was slowly added dropwise to the reaction mixture, and the mixture was allowed to react at room temperature for 6 hours after completion of the dropwise addition. After the completion of the reaction, ice water (100 mL) was added to quench the reaction. DCM (80 ml x 2) was added for extraction and finally extracted once with saturated brine. The organic phase was collected and distilled to give a pale yellow oil. The product was purified by column chromatography (mobile phase n-hexane: dichloromethane=3:1) to give compound M1.
1 H NMR(400MHz,Chloroform)δ9.71(s,3H),8.31(s,3H),7.44–7.35(m,6H),7.31–7.24(m,10H),7.20–7.15(m,3H),7.13–7.05(m,15H),2.23(d,J＝0.7Hz,6H).
13 C NMR(100MHz,Chloroform)δ161.08,156.89,146.34,145.99,144.25,141.92,138.02,133.53,130.99,129.98,129.43,127.84,126.89,125.11,124.05,123.27,122.11,119.27,52.33,15.28.
Preparation example 3
Synthesis of Compound M2
(1) 9.22g (20 mmol) of compound A, 3.98g (10 mmol) of compound B, 150mL of toluene dehydrated and deoxygenated, 13.81g (30 mmol) of cesium carbonate, 0.23g (0.2 mmol) of tetrakis (triphenylphosphine) palladium were sequentially added to a 250mL three-necked flask, and then reacted at 120℃for 24 hours under a nitrogen atmosphere. Cooled to room temperature, the reaction solution was poured into 200mL of ice water, extracted three times with dichloromethane, the organic phases were combined, spun into silica gel, and purified by column chromatography (dichloromethane: n-hexane, v: v=1:1) to give compound D.
1 H NMR(400MHz,Chloroform)δ7.52–7.46(m,4H),7.34–7.28(m,4H),7.15(dd,J＝7.3,1.8Hz,6H),7.11(td,J＝7.2,1.5Hz,6H),7.07(td,J＝7.3,1.8Hz,2H),6.78(dd,J＝7.4,1.6Hz,4H),6.67(s,2H),2.29(s,6H).
13 C NMR(100MHz,Chloroform)δ146.45,139.72,137.77,134.55,134.13,133.40,133.34,130.17,126.28,126.22,125.77,123.92,122.95,120.19,116.50,96.94,14.03.
(2) In a 250mL three-necked flask, 10.71g (10 mmol) of the substrate D and 80mL of THF were added and dissolved, and the mixture was replaced with nitrogen three times. Cooling to-78deg.C, controlling the temperature below-65deg.C, slowly adding n-BuLi 20mL (50 mmol) dropwise, and stirring for 30min. TMS-Cl 4.35g (40 mmol) was then slowly added dropwise and the reaction was carried out at 0℃for 4h. And adding ice water to quench after the completion. DCM (80 ml x 2) was added for extraction. The organic phase was collected by rotary evaporation and crystallized from Tol/EtOH to give a solid. To a 200mL jar was added, in order, 20.87g (20 mmol) of solid, a solution of anhydrous toluene (70 mL) and 3.04mL (40 mmol) of boron tribromide. Stirring for 12h at 120 ℃. H after the reaction is finished 2 O (100 mL) quench. The reaction was extracted with DCM (100 ml x 3), the organic phase was collected, dried and filtered and the solvent was removed by rotary evaporation. Crystallization using DCM/EtOH gives solid E.
1 H NMR(400MHz,Chloroform)δ7.51–7.44(m,6H),7.38–7.32(m,4H),7.21(s,2H),7.18–7.04(m,12H),6.78(dd,J＝7.3,1.7Hz,4H),2.24(d,J＝0.7Hz,6H).
13 C NMR(100MHz,Chloroform)δ146.45,139.72,138.34,137.30,133.40,132.22,126.28,126.22,123.66,123.51,123.46,122.68,120.17,119.76,116.41,15.51,-7.68.
(3) Compound E18.64g (20 mmol) was added to a reaction flask, dissolved in diethyl ether (50 mL) and replaced with nitrogen three times. Cooling to-78deg.C, controlling the temperature below-65deg.C, slowly adding n-BuLi 16.08mL (2.5M, 40 mmol) dropwise, and stirring for 30min. Then, 9.56g (40 mmol) of the compound F was slowly added dropwise to the reaction mixture, and the mixture was allowed to react at room temperature for 6 hours after completion of the dropwise addition. After the completion of the reaction, ice water (100 mL) was added to quench the reaction. DCM (80 ml x 2) was added for extraction and finally extracted once with saturated brine. The organic phase was collected and distilled to give a pale yellow oil. The product was purified by column chromatography (mobile phase n-hexane: dichloromethane=3:1) to give compound M2.
1 H NMR(400MHz,Chloroform)δ8.35(d,J＝14.8Hz,6H),7.50–7.44(m,4H),7.39–7.32(m,6H),7.18–7.03(m,14H),6.78(dd,J＝7.4,1.6Hz,4H),2.22(d,J＝0.7Hz,6H).
13 C NMR(100MHz,Chloroform)δ171.33,168.23,165.31,159.25,157.16,145.20,141.92,139.84,138.04,133.44,130.99,129.98,126.42,126.41,125.11,124.06,124.05,122.68,120.19,119.27,115.80,52.33,15.28.
Preparation example 4
Synthesis of Compound M4
(1) To a 250mL three-necked flask, 3.71g (10 mmol) of Compound A, 3.98g (10 mmol) of Compound B, 4.87g (10 mmol) of Compound C, 150mL of toluene dehydrated and deoxygenated, 13.81g (30 mmol) of cesium carbonate, 0.23g (0.2 mmol) of tetrakis (triphenylphosphine) palladium were successively added, and then reacted at 120℃for 24 hours under a nitrogen atmosphere. Cooled to room temperature, the reaction solution was poured into 200mL of ice water, extracted three times with dichloromethane, the organic phases were combined, spun into silica gel, and purified by column chromatography (dichloromethane: n-hexane, v: v=1:1) to give compound D.
1 H NMR(400MHz,Chloroform)δ7.99(dd,J＝7.3,1.6Hz,1H),7.57–7.44(m,6H),7.41–7.31(m,2H),7.25–7.17(m,4H),7.17(dd,J＝7.5,1.5Hz,2H),7.09–6.99(m,6H),6.72–6.66(m,2H),2.31–2.27(m,6H),1.56(s,6H).
13 C NMR(100MHz,Chloroform)δ156.30,154.65,142.47,140.25,139.22,138.36,136.73,134.45,134.36,134.17,134.08,133.42,133.33,130.26,130.17,129.44,128.69,127.21,125.96,125.87,125.08,124.43,123.99,123.92,123.64,122.90,121.79,117.85,117.80,111.70,111.27,97.02,96.94,37.50,27.89,14.09,14.03.
(2) In a 250mL three-necked flask, 10.05g (10 mmol) of the substrate D and 80mL of THF were added and dissolved, and the mixture was replaced with nitrogen three times. Cooling to-78deg.C, controlling the temperature below-65deg.C, slowly adding n-BuLi 20mL (50 mmol) dropwise, and stirring for 30min. TMS-Cl 4.35g (40 mmol) was then slowly added dropwise and the reaction was carried out at 0℃for 4h. And adding ice water to quench after the completion. DCM (80 ml x 2) was added for extraction. The organic phase was collected by rotary evaporation and crystallized from Tol/EtOH to give a solid. To a 200mL jar was added 19.84g (20 mmol) of solid, a solution of anhydrous toluene (70 mL) and 3.04mL (40 mmol) of boron tribromide in this order. Stirring for 12h at 120 ℃. H after the reaction is finished 2 O (100 mL) quench. The reaction was extracted with DCM (100 ml x 3), the organic phase was collected, dried and filtered and the solvent was removed by rotary evaporation. Crystallization using DCM/EtOH gives solid E.
1 H NMR(400MHz,Chloroform)δ8.03–7.98(m,1H),7.69–7.65(m,1H),7.57–7.44(m,7H),7.41–7.32(m,2H),7.30(dd,J＝7.5,1.5Hz,1H),7.26–7.17(m,5H),7.17(dd,J＝7.4,1.6Hz,2H),7.09–7.02(m,4H),2.27–2.23(m,6H),1.56(s,6H).
13 C NMR(100MHz,Chloroform)δ156.30,154.58,142.47,139.22,139.02,138.42,138.34,137.30,136.59,132.60,132.52,129.44,128.69,126.56,124.73,124.17,124.09,124.05,123.99,123.64,123.54,123.46,123.09,122.71,122.17,119.84,119.76,117.71,117.53,111.70,110.97,37.50,27.89,16.04,15.97,-7.59,-7.68.
(3) Into a reaction flask, 17.34g (20 mmol) of compound E was added, diethyl ether (50 mL) was added for dissolution, and nitrogen was substituted three times. Cooling to-78deg.C, controlling the temperature below-65deg.C, slowly adding n-BuLi 16.08mL (2.5M, 40 mmol) dropwise, and stirring for 30min. Then, 9.56g (40 mmol) of the compound F was slowly added dropwise to the reaction mixture, and the mixture was allowed to react at room temperature for 6 hours after completion of the dropwise addition. After the completion of the reaction, ice water (100 mL) was added to quench the reaction. DCM (80 ml x 2) was added for extraction and finally extracted once with saturated brine. The organic phase was collected and distilled to give a pale yellow oil. The product was purified by column chromatography (mobile phase n-hexane: dichloromethane=3:1) to give compound M4.
1 H NMR(400MHz,Chloroform)δ8.89(s,3H),8.23–8.16(m,3H),8.10(s,1H),7.99(dd,J＝7.3,1.6Hz,1H),7.74(d,J＝7.5Hz,2H),7.69–7.65(m,1H),7.54(dd,J＝7.5,1.6Hz,2H),7.48(td,J＝7.5,1.4Hz,2H),7.44–7.39(m,2H),7.42–7.34(m,3H),7.37–7.29(m,1H),7.26–7.18(m,4H),7.17(dd,J＝7.6,1.6Hz,2H),7.10–7.01(m,4H),2.22(dd,J＝3.1,0.7Hz,6H),1.56(s,6H).
13 C NMR(100MHz,Chloroform)δ161.08,160.99,156.05,154.23,148.97,148.92,148.88,144.24,143.50,143.42,141.33,141.25,139.86,139.72,139.21,139.18,139.13,139.09,138.54,138.05,137.99,136.68,133.00,132.93,132.45,131.89,131.80,131.73,129.44,128.48,128.00,127.94,126.01,125.52,125.47,125.38,124.93,124.33,124.24,124.13,124.09,123.60,123.42,122.75,122.51,120.07,119.99,119.44,118.28,116.70,116.64,116.58,111.75,111.13,109.44,109.36,37.50,27.89,15.35,15.28,6.01,5.91.
Preparation example 5
Synthesis of Compound M21
(1) 9.22g (20 mmol) of compound A, 3.98g (10 mmol) of compound B, 150mL of toluene dehydrated and deoxygenated, 13.81g (30 mmol) of cesium carbonate, 0.23g (0.2 mmol) of tetrakis (triphenylphosphine) palladium were sequentially added to a 250mL three-necked flask, and then reacted at 120℃for 24 hours under a nitrogen atmosphere. Cooled to room temperature, the reaction solution was poured into 200mL of ice water, extracted three times with dichloromethane, the organic phases were combined, spun into silica gel, and purified by column chromatography (dichloromethane: n-hexane, v: v=1:1) to give compound D.
1 H NMR(400MHz,Chloroform)δ7.47–7.41(m,4H),7.32–7.24(m,8H),7.19–7.14(m,4H),7.17–7.07(m,14H),2.39(s,6H),2.26(s,6H).
13 C NMR(100MHz,Chloroform)δ146.34,143.99,140.82,137.16,135.48,133.61,131.41,130.31,129.22,127.84,126.89,123.30,122.08,100.28,12.54,11.75.
(2) In a 250mL three-necked flask, 10.71g (10 mmol) of the substrate D and 80mL of THF were added and dissolved, and the mixture was replaced with nitrogen three times. Cooling to-78deg.C, controlling the temperature below-65deg.C, slowly adding n-BuLi 20mL (50 mmol) dropwise, and stirring for 30min. TMS-Cl 4.35g (40 mmol) was then slowly added dropwise and the reaction was carried out at 0℃for 4h. And adding ice water to quench after the completion. DCM (80 ml x 2) was added for extraction. The organic phase was collected by rotary evaporation and crystallized from Tol/EtOH to give a solid. To a 200mL jar was added, in order, 20.87g (20 mmol) of solid, a solution of anhydrous toluene (70 mL) and 3.04mL (40 mmol) of boron tribromide. Stirring for 12h at 120 ℃. H after the reaction is finished 2 O (100 mL) quench. The reaction was extracted with DCM (100 ml x 3), the organic phase was collected, dried and filtered and the solvent was removed by rotary evaporation. Crystallization using DCM/EtOH gives solid E.
1 H NMR(400MHz,Chloroform)δ7.49–7.43(m,4H),7.31–7.21(m,8H),7.19–7.14(m,4H),7.17–7.06(m,14H),2.41(s,6H),2.22(s,6H).
13 C NMR(100MHz,Chloroform)δ146.34,144.44,139.53,137.03,133.33,132.38,129.82,129.22,127.64,126.89,124.61,122.03,120.47,13.45,12.57.
(3) Compound E18.65g (20 mmol) was added to a reaction flask, dissolved in diethyl ether (50 mL) and replaced with nitrogen three times. Cooling to-78deg.C, controlling the temperature below-65deg.C, slowly adding n-BuLi 16.08mL (2.5M, 40 mmol) dropwise, and stirring for 30min. Then, 9.52g (40 mmol) of the compound F was slowly added dropwise to the reaction mixture, and the mixture was allowed to react at room temperature for 6 hours after completion of the dropwise addition. After the completion of the reaction, ice water (100 mL) was added to quench the reaction. DCM (80 ml x 2) was added for extraction and finally extracted once with saturated brine. The organic phase was collected and distilled to give a pale yellow oil. The product was purified by column chromatography (mobile phase n-hexane: dichloromethane=3:1) to give compound M21.
1 H NMR(400MHz,Chloroform)δ9.71(s,4H),8.31(s,4H),7.42–7.37(m,4H),7.31–7.24(m,8H),7.19–7.13(m,4H),7.13–7.08(m,8H),7.09(dd,J＝3.5,1.9Hz,6H),2.41(s,6H),2.22(s,6H).
13 C NMR(100MHz,Chloroform)δ161.08,156.89,148.33,146.34,146.25,144.45,140.55,138.01,137.63,133.53,129.89,129.49,129.43,128.89,127.81,126.89,124.34,121.98,119.69,32.05,13.45,12.57.
Preparation example 6
Synthesis of Compound M22
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(1) 9.22g (20 mmol) of compound A, 3.98g (10 mmol) of compound B, 150mL of toluene dehydrated and deoxygenated, 13.81g (30 mmol) of cesium carbonate, 0.23g (0.2 mmol) of tetrakis (triphenylphosphine) palladium were sequentially added to a 250mL three-necked flask, and then reacted at 120℃for 24 hours under a nitrogen atmosphere. Cooled to room temperature, the reaction solution was poured into 200mL of ice water, extracted three times with dichloromethane, the organic phases were combined, spun into silica gel, and purified by column chromatography (dichloromethane: n-hexane, v: v=1:1) to give compound D.
1 H NMR(400MHz,Chloroform)δ7.48–7.43(m,4H),7.35–7.29(m,4H),7.15(dd,J＝7.3,1.8Hz,8H),7.11(td,J＝7.2,1.5Hz,4H),7.07(td,J＝7.3,1.8Hz,4H),6.78(dd,J＝7.4,1.6Hz,4H),5.78(s,2H),2.33(s,6H).
13 C NMR(100MHz,Chloroform)δ146.45,139.73,137.88,136.15,136.00,133.40,129.08,128.85,126.28,126.22,123.66,122.79,120.23,120.19,116.50,95.90,13.82.
(2) In a 250mL three-necked flask, 10.71g (10 mmol) of the substrate D and 80mL of THF were added and dissolved, and the mixture was replaced with nitrogen three times. Cooling to-78deg.C, controlling the temperature below-65deg.C, slowly adding n-BuLi 20mL (50 mmol) dropwise, and stirring for 30min. TMS-Cl 4.35g (40 mmol) was then slowly added dropwise and the reaction was carried out at 0℃for 4h. And adding ice water to quench after the completion. DCM (80 ml x 2) was added for extraction. The organic phase was collected by rotary evaporation and crystallized from Tol/EtOH to give a solid. Sequentially adding into 200mL stuffiness tank20.87g (20 mmol) of solid, an anhydrous toluene solution (70 mL) and 3.04mL (40 mmol) of boron tribromide were added. Stirring for 12h at 120 ℃. H after the reaction is finished 2 O (100 mL) quench. The reaction was extracted with DCM (100 ml x 3), the organic phase was collected, dried and filtered and the solvent was removed by rotary evaporation. Crystallization using DCM/EtOH gives solid E.
1 H NMR(400MHz,Chloroform)δ7.50–7.44(m,4H),7.40–7.34(m,4H),7.33(s,2H),7.18–7.04(m,12H),6.78(dd,J＝7.3,1.7Hz,4H),5.96(s,2H),2.31(s,6H).
13 C NMR(100MHz,Chloroform)δ146.45,139.76,137.36,133.40,131.72,131.17,130.67,130.50,126.28,126.22,122.82,122.61,120.34,120.17,116.41,114.31,14.06.
(3) Compound E18.65g (20 mmol) was added to a reaction flask, dissolved in diethyl ether (50 mL) and replaced with nitrogen three times. Cooling to-78deg.C, controlling the temperature below-65deg.C, slowly adding n-BuLi 16.08mL (2.5M, 40 mmol) dropwise, and stirring for 30min. Then, 9.52g (40 mmol) of the compound F was slowly added dropwise to the reaction mixture, and the mixture was allowed to react at room temperature for 6 hours after completion of the dropwise addition. After the completion of the reaction, ice water (100 mL) was added to quench the reaction. DCM (80 ml x 2) was added for extraction and finally extracted once with saturated brine. The organic phase was collected and distilled to give a pale yellow oil. The product was purified by column chromatography (mobile phase n-hexane: dichloromethane=3:1) to give compound M22.
1 H NMR(400MHz,Chloroform)δ8.41(s,2H),8.33(s,4H),7.50–7.43(m,6H),7.40–7.34(m,4H),7.18–7.03(m,14H),6.78(dd,J＝7.4,1.6Hz,4H),2.31(s,6H).
13 C NMR(100MHz,Chloroform)δ176.77,168.39,165.31,159.25,157.37,145.20,139.88,138.73,136.22,133.44,132.97,128.16,127.17,126.42,126.41,122.78,122.61,120.19,120.16,117.56,115.80,78.65,14.06.
Preparation example 7
Synthesis of Compound M30
(1) To a 250mL three-necked flask, 4.47g (10 mmol) of Compound A, 3.98g (10 mmol) of Compound B, 4.77g (10 mmol) of Compound C, 150mL of toluene dehydrated and deoxygenated, 13.81g (30 mmol) of cesium carbonate, 0.23g (0.2 mmol) of tetrakis (triphenylphosphine) palladium were successively added, and then reacted at 120℃for 24 hours under a nitrogen atmosphere. Cooled to room temperature, the reaction solution was poured into 200mL of ice water, extracted three times with dichloromethane, the organic phases were combined, spun into silica gel, and purified by column chromatography (dichloromethane: n-hexane, v: v=1:1) to give compound D.
1 H NMR(400MHz,Chloroform)δ7.48–7.43(m,4H),7.35–7.29(m,4H),7.15(dd,J＝7.3,1.8Hz,8H),7.11(td,J＝7.2,1.5Hz,4H),7.07(td,J＝7.3,1.8Hz,4H),6.78(dd,J＝7.4,1.6Hz,4H),5.78(s,2H),2.33(s,6H).
13 C NMR(100MHz,Chloroform)δ146.45,139.73,137.88,136.15,136.00,133.40,129.08,128.85,126.28,126.22,123.66,122.79,120.23,120.19,116.50,95.90,13.82.
(2) In a 250mL three-necked flask, 10.73g (10 mmol) of the substrate D and 80mL of THF were added and dissolved, and the mixture was replaced with nitrogen three times. Cooling to-78deg.C, controlling the temperature below-65deg.C, slowly adding n-BuLi 20mL (50 mmol) dropwise, and stirring for 30min. TMS-Cl 4.35g (40 mmol) was then slowly added dropwise and the reaction was carried out at 0℃for 4h. And adding ice water to quench after the completion. DCM (80 ml x 2) was added for extraction. The organic phase was collected by rotary evaporation and crystallized from Tol/EtOH to give a solid. To a 200mL jar was added, in order, 20.88g (20 mmol) of solid, a solution of anhydrous toluene (70 mL) and 3.04mL (40 mmol) of boron tribromide. Stirring for 12h at 120 ℃. H after the reaction is finished 2 O (100 mL) quench. The reaction was extracted with DCM (100 ml x 3), the organic phase was collected, dried and filtered and the solvent was removed by rotary evaporation. Crystallization using DCM/EtOH gives solid E.
1 H NMR(400MHz,Chloroform)δ7.50–7.44(m,4H),7.40–7.34(m,4H),7.33(s,2H),7.18–7.04(m,12H),6.78(dd,J＝7.3,1.7Hz,4H),5.96(s,2H),2.31(s,6H).
13 C NMR(100MHz,Chloroform)δ146.45,139.76,137.36,133.40,131.72,131.17,130.67,130.50,126.28,126.22,122.82,122.61,120.34,120.17,116.41,114.31,14.06.
(3) Compound E18.68g (20 mmol) was added to a reaction flask, dissolved in diethyl ether (50 mL) and replaced with nitrogen three times. Cooling to-78deg.C, controlling the temperature below-65deg.C, slowly adding n-BuLi 16.08mL (2.5M, 40 mmol) dropwise, and stirring for 30min. Then, a toluene solution of 4.78g (20 mmol) of compound F and 3.51g (20 mmol) of compound E was slowly added dropwise to the reaction mixture, and the mixture was allowed to react at room temperature for 6 hours after completion of the dropwise addition. After the completion of the reaction, ice water (100 mL) was added to quench the reaction. DCM (80 ml x 2) was added for extraction and finally extracted once with saturated brine. The organic phase was collected and distilled to give a pale yellow oil. The product was purified by column chromatography (mobile phase n-hexane: dichloromethane=3:1) to give compound M30.
1 H NMR(400MHz,Chloroform)δ8.35(d,J＝15.6Hz,3H),8.10(s,1H),7.66–7.59(m,2H),7.51–7.44(m,4H),7.39–7.31(m,4H),7.31–6.98(m,16H),6.78(dd,J＝7.4,1.6Hz,2H),6.42(d,J＝7.5Hz,1H),2.22(d,J＝0.7Hz,6H).
13 C NMR(100MHz,Chloroform)δ171.02,168.23,164.53,159.25,157.16,146.03,144.50,143.22,142.47,141.92,139.84,139.83,138.62,138.04,134.09,134.02,133.46,130.99,129.38,128.08,127.17,126.97,126.42,126.41,126.01,125.31,124.05,123.99,123.67,123.34,122.68,122.55,120.19,119.35,119.27,119.16,118.21,116.94,115.80,115.19,115.03,52.33,50.76,15.28.
Example 1
The application example provides an OLED device, as shown in fig. 1, where the OLED device sequentially includes: the light emitting device comprises a substrate 1, an ITO anode 2, a hole injection layer 3, a first hole transport layer 4, a second hole transport layer 5, a light emitting layer 6, a first electron transport layer 7, a second electron transport layer 8, an electron injection layer 9, a cathode 10 (aluminum electrode) and a cap layer (CBP) 11, wherein the thickness of the ITO anode is 15nm, the thickness of the hole injection layer is 10nm, the thickness of the hole transport layer is 110nm, the thickness of the light emitting layer is 30nm, the thickness of the first electron transport layer is 30nm, the thickness of the second electron transport layer is 5nm, the thickness of the cathode is 15nm (magnesium silver electrode, magnesium silver mass ratio is 1:9), and the thickness of the cap layer is 100nm, wherein an arrow in the figure indicates the light direction.
The OLED device was prepared as follows:
(1) Cutting a glass substrate into a size of 50mm multiplied by 0.7mm, respectively carrying out ultrasonic treatment in isopropanol and deionized water for 30min, and then exposing the glass substrate to ozone for cleaning for 10min to obtain a substrate; mounting the obtained glass substrate with the ITO anode having a thickness of 15nm on a vacuum deposition apparatus;
(2) Vacuum evaporating compound HAT-CN with thickness of 10nm on ITO anode layer under vacuum degree of 2×10-6Pa to obtain hole injection layer;
(3) Vacuum evaporating a compound TAPC on the hole injection layer to serve as a hole transport layer, wherein the thickness of the hole transport layer is 110nm;
(4) Co-depositing a light-emitting layer on the hole-transporting layer, wherein the organic compound M1 provided in the embodiment 1 of the invention is used as a doping material of the light-emitting layer, the compound mCBP is used as a main material of the light-emitting layer, the mass ratio of M1 to mCBP is 1:9, and the thickness is 30nm;
(5) Vacuum evaporating a compound TPBi on the light-emitting layer as a first electron transport layer, wherein the thickness of the compound TPBi is 30nm;
(6) Vacuum evaporating a compound Alq3 on the first electron transport layer to form a second electron transport layer with the thickness of 5nm;
(7) Vacuum evaporating a magnesium silver electrode on the second electron transport layer to serve as a cathode, wherein the thickness of the cathode is 15nm;
(8) CBP was vacuum evaporated on the cathode as a cathode coating (capping layer) with a thickness of 100nm.
The structure of the compound used in the OLED device is as follows:
examples 2 to 7
The only difference from example 1 is that M1 in example 1 was replaced with M2, M3, M4, M21, M22 and M30, resulting in examples 2 to 7.
Comparative example 1
The only difference from example 1 is that M1 in example 1 is replaced with DCJTB.
Performance test:
(1) Analog calculation of compounds
The energy level difference between the singlet state and the triplet state of the organic material can be achieved by a Guassian 09 software (Guassian inc. Specific simulation method of the energy level difference deltaest is referred to j.chem. Technical company, 2013, doi:10.1021/ct400415r, molecular structure optimization and excitation can be achieved by a TD-DFT method "B3LYP" and a group "6-31g (d)", tg is measured by differential scanning calorimetry, and the results of the compounds prepared for preparation examples 1-7 and the compound DCJTB selected for comparative example are shown in table 1.
TABLE 1
As can be seen from the data in table 1, the Δest of all the compounds prepared in the preparation examples provided by the invention is smaller than 0.3eV, so that smaller singlet and triplet energy level differences are realized, and the reverse intersystem crossing is facilitated.
The HOMO and LUMO energy levels of the compound provided by the invention are calculated through Gaussian simulation, wherein the HOMO and LUMO distribution diagrams of the compound M3 provided by the invention are shown in figures 2 and 3 respectively. It can be seen from FIGS. 2 and 3 that the HOMO and LUMO of M3 are spatially well separated, helping to reduce ΔEST.
(2) Evaluation of the Performance of OLED devices
The efficiency, voltage and efficiency of the devices were measured at a current density of 10mA/cm2 using a Spectroscan PR 705 spectrometer and a Keithley 236 current-voltage source measurement system, and the lifetime of LT95 was tested as follows: using a luminance meter at 10000cd/m 2 Under the condition of brightness, constant current is kept, and the brightness of the organic electroluminescent device is measured to be reduced to 9500cd/m 2 The results in hours are shown in table 2.
TABLE 2
As can be seen from Table 2, the OLED display panel provided by the invention has lower driving voltage, higher luminous efficiency and service life, wherein the driving voltage is less than 3.85V, the current efficiency is more than 27.5Cd/A, and the service life is more than 89h. Compared with comparative example 1, the compound is mainly beneficial to TADF characteristics of the compound, has lower delta EST (less than 0.3 eV), has an efficient photophysical process of reverse intersystem channeling between a singlet state and a triplet state, and can emit light by utilizing triplet state excitons forbidden by traditional fluorescence molecular transition, thereby improving the efficiency of the device and further prolonging the service life of the device to a certain extent.
In still another aspect, an embodiment of the present invention provides an electronic device, including the above-mentioned organic optoelectronic device, where the electronic device may be any electronic device with a display function, such as a touch display screen, a mobile phone, a tablet computer, a notebook computer, an electronic paper book, a television, a VR or AR helmet, or a smart watch. Fig. 4 is a schematic diagram of an electronic device according to an embodiment of the present invention. Wherein 100 is a mobile phone display screen.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.

Claims (15)

1. A compound, characterized in that the compound has the structure of formula I:
in the formula I, R 1 And R is 2 Each independently selected from any one of the following groups:
in the formula I, R 3 And R is 4 Each independently selected from any one of a substituted or unsubstituted oxadiazolyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted oxazolyl group, a substituted or unsubstituted triazolyl group, a substituted or unsubstituted quinolinyl group, and a substituted or unsubstituted triazinyl group;
in the formula I, R a 、R b And R is c Each independently selected from any one of cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C20 heteroaryl;
in the formula I, m, n and p are each independently selected from integers of 0-2;
R 3 、R 4 、R a 、R b and R is c Wherein the substituted group is selected from any one of halogen, cyano, C1-C12 chain alkyl, C6-C20 monocyclic aromatic hydrocarbon or condensed ring aromatic hydrocarbon group, and C3-C20 monocyclic heteroaromatic hydrocarbon or condensed ring heteroaromatic hydrocarbon group.
2. The compound of claim 1, wherein m, n and p are each independently selected from 0 or 1.
3. The compound of claim 1, wherein m and n are both 1 and p is 0.
4. The compound of claim 1, wherein R a 、R b And R is c Each independently selected from any one of methyl, phenyl, biphenyl, terphenyl, naphthyl, fluorenyl or carbazolyl.
5. The compound of claim 1, wherein the compound has a structure represented by formula II:
wherein R is 1 、R 2 、R 3 And R is 4 Has the same limitations as claim 1.
6. The compound of claim 5, wherein the compound has a structure represented by formula III:
wherein R is 1 、R 2 、R 3 And R is 4 Has the same limitations as claim 5.
7. The compound of claim 1, wherein R 1 And R is 2 The same applies.
8. The compound of claim 1, wherein R 3 And R is 4 Each independently selected from any one of the following groups:
wherein the dotted line represents the attachment site of the group.
9. The compound of claim 1, wherein R 3 And R is 4 The same applies.
10. The compound of claim 1, wherein the compound is any one of the following structures:
11. the compound of claim 1, wherein the energy difference Δest = ES1-ET1 between the lowest singlet S1 and the lowest triplet T1 of the compound is less than or equal to 0.3eV.
12. A thermally activated delayed fluorescence material, characterized in that it comprises any one of the compounds of any one of claims 1-11 or a combination of at least two.
13. A display panel comprising an OLED device comprising an anode, a cathode, and at least one organic layer between the anode and the cathode, the organic layer comprising a light-emitting layer comprising the thermally activated delayed fluorescence material of claim 12, and the thermally activated delayed fluorescence material being used as any one of a host material, a dopant material, or a co-dopant material.
14. The display panel according to claim 13, wherein the organic layer further comprises any one or a combination of at least two of a hole transport layer, a hole injection layer, an electron blocking layer, a hole blocking layer, an electron transport layer, and an electron injection layer.
15. An electronic device comprising the display panel of claim 13 or 14.
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CN113321677B (en) * 2021-06-30 2023-05-05 京东方科技集团股份有限公司 Thermal-activation delay fluorescent material, organic light-emitting device and display device
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102899027A (en) * 2012-04-12 2013-01-30 杭州师范大学 Boron-containing luminescent material and its preparation method and use
JP2016092280A (en) * 2014-11-07 2016-05-23 コニカミノルタ株式会社 Luminescent thin film, organic electroluminescent element, illuminating device and display device
EP3038181A1 (en) * 2014-12-22 2016-06-29 Solvay SA Organic electronic devices comprising acridine derivatives in an emissive layer free of heavy atom compounds
CN106887444A (en) * 2015-12-15 2017-06-23 昆山工研院新型平板显示技术中心有限公司 Organic light emitting display and display device
CN109417131A (en) * 2016-07-08 2019-03-01 柯尼卡美能达株式会社 Organic electroluminescent device, display device, lighting device
CN110305150A (en) * 2019-06-29 2019-10-08 武汉天马微电子有限公司 A kind of hot activation delayed fluorescence material and its application

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102899027A (en) * 2012-04-12 2013-01-30 杭州师范大学 Boron-containing luminescent material and its preparation method and use
JP2016092280A (en) * 2014-11-07 2016-05-23 コニカミノルタ株式会社 Luminescent thin film, organic electroluminescent element, illuminating device and display device
EP3038181A1 (en) * 2014-12-22 2016-06-29 Solvay SA Organic electronic devices comprising acridine derivatives in an emissive layer free of heavy atom compounds
CN106887444A (en) * 2015-12-15 2017-06-23 昆山工研院新型平板显示技术中心有限公司 Organic light emitting display and display device
CN109417131A (en) * 2016-07-08 2019-03-01 柯尼卡美能达株式会社 Organic electroluminescent device, display device, lighting device
CN110305150A (en) * 2019-06-29 2019-10-08 武汉天马微电子有限公司 A kind of hot activation delayed fluorescence material and its application

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