CN116462712A - Compound, organic electroluminescent device and electronic equipment - Google Patents

Compound, organic electroluminescent device and electronic equipment Download PDF

Info

Publication number
CN116462712A
CN116462712A CN202210028843.7A CN202210028843A CN116462712A CN 116462712 A CN116462712 A CN 116462712A CN 202210028843 A CN202210028843 A CN 202210028843A CN 116462712 A CN116462712 A CN 116462712A
Authority
CN
China
Prior art keywords
formula
compound
compound represented
independently selected
substituted
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202210028843.7A
Other languages
Chinese (zh)
Inventor
吴江
杨楚罗
张鹏飞
李凯
张友明
徐增
战鸽
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huawei Technologies Co Ltd
Shenzhen University
Original Assignee
Huawei Technologies Co Ltd
Shenzhen University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Huawei Technologies Co Ltd, Shenzhen University filed Critical Huawei Technologies Co Ltd
Priority to CN202210028843.7A priority Critical patent/CN116462712A/en
Priority to PCT/CN2023/071720 priority patent/WO2023134696A1/en
Publication of CN116462712A publication Critical patent/CN116462712A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/006—Palladium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0086—Platinum compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Inorganic Chemistry (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The application provides a compound, an organic electroluminescent device and electronic equipment, wherein the compound has a structure shown in a formula 1, and M represents Pd (II) or Pt (II); the compound contributes to the organic electroluminescent device exhibiting excellent color purity and stability.

Description

Compound, organic electroluminescent device and electronic equipment
Technical Field
The application relates to a compound, an organic electroluminescent device and electronic equipment, and belongs to the technical field of organic electroluminescence.
Background
In the 60 s of the 20 th century, 400V applied to an anthracene single crystal plate was observed by Pope et al, new york university in the united states, which was the first report of the phenomenon of organic electroluminescence. After 20 years, researchers invented a vacuum evaporation technique to prepare an anthracene film, and observed blue light with an External Quantum Efficiency (EQE) of 0.03% at a drive voltage of 30V. The organic electroluminescent device studied in the early stage has the defects of low carrier injection efficiency, poor film quality, large device working voltage and the like, and has low practical application value. Until 1987, C.W.Tang et al utilized octahydroxyquinoline aluminum as the light-emitting layer, aromatic amine compounds as the hole-transporting layer, and aluminum magnesium alloy as the cathode to obtain a sandwich-type green light device with high luminous efficiency. Organic light emitting diodes (Organic Light Emitting Diode, abbreviated to OLEDs) have been a research focus in the field of organic photovoltaics as a device that emits light by current driving. The power for promoting the final popularization and application of the OLED technology is characterized by simple process, low energy consumption, low cost, high response speed, capability of realizing flexible display, large-area display and the like.
In the field of OLED materials, the phosphorescent OLED luminescent layer doped material is developed rapidly and mature, and particularly, the energy use efficiency of 100% can be achieved by introducing heavy metal atoms such as iridium or platinum to realize the transition from singlet excitons to triplet excitons, so that the phosphorescent luminescent material is a luminescent material which is researched in relatively large quantity in the industry and academia.
In recent years, phosphorescent OLED materials based on platinum (II) are gradually developed and have achieved better research results. However, the phosphorescent material of platinum (II) still has certain drawbacks such as an excessively broad light emission spectrum and poor stability.
Disclosure of Invention
The embodiment provides a compound, an organic electroluminescent device and an electronic device, wherein the compound has a special structure so as to be used as a phosphorescent light-emitting material and has excellent color purity and stability.
A first aspect of the present embodiments provides a compound having a structure represented by formula 1,
in the formula 1, M represents Pd (II) or Pt (II);
Q 1 、Q 2 、Q 3 q and 4 independently selected from O, S or a single bond;
Ar 1 selected from substituted or unsubstituted first cyclic groups, ar 2 A second cyclic group selected from substituted or unsubstituted; the first cyclic group comprises N substituted or unsubstituted cyclic groups, the second cyclic group comprises M substituted or unsubstituted cyclic groups, N is more than or equal to 1, and M is more than or equal to 1; (n+m) cyclic groups are each independently selected from 3 to 50 membered substituted or unsubstituted cyclic groups;
When N is more than 1, N cyclic groups are connected in a pair-by-pair fused mode or connected in a single bond mode; when M is more than 1, M cyclic groups are connected in a pair-by-pair fused mode or connected in a single bond mode;
L 1 l and 2 independently selected from substituted or unsubstituted cyclic groups, or L 1 L and 2 one of which is a substituted or unsubstituted cyclic group and the other is absent.
As can be seen from the above formula 1, the compound provided in the present application is a metal complex, specifically, a tetradentate coordination compound of metal Pt (II) and metal Pd (II). According to the method, the carbon-carbon double bond is introduced between two ligands, on one hand, the introduction of the carbon-carbon double bond is beneficial to realizing improvement of color purity through narrowing of a luminescence spectrum, on the other hand, the introduction of the carbon-carbon double bond is beneficial to improving coordination rigidity of the ligands and a central coordination atom, unnecessary vibration energy loss is restrained to a certain extent, and stability improvement is further shown.
In one possible implementation, the compound has a structure represented by formula 2,
ar in formula 2 3 Selected from substituted or unsubstituted third cyclic groups, ar 4 A fourth cyclic group selected from substituted or unsubstituted; the third cyclic group comprises N substituted or unsubstituted cyclic groups, and the fourth cyclic group comprises M substituted or unsubstituted cyclic groups, N is more than or equal to 1 and less than N, and M is more than or equal to 1 and less than M; (n+m) cyclic groups are each independently selected from 3-50 membered substituted or unsubstituted cyclic groups;
When n is more than 1, n cyclic groups are connected in a pair-by-pair fused mode or connected in a single bond mode; when m is more than 1, m cyclic groups are connected in a condensed mode or connected in a single bond mode;
a 1 ～a 6 b 1 ～b 6 Each independently selected from C or N;
R 1 、R 2 independently selected from hydrogen, deuterium, halogen, hydroxy, thiol, nitro, cyano, isocyano, sulfone, hydroxylamine, carboxyl, carbonyl, or one of the following substituted or unsubstituted groups: C6-C48 monocyclic aromatic hydrocarbon or polycyclic aromatic hydrocarbon, C3-C48 monocyclic heteroaromatic hydrocarbon or polycyclic heteroaromatic hydrocarbon, C1-C36 alkyl, C2-C36 heterocycloalkyl, C2-C36 alkenyl, C2-C36 alkynyl, amino, C1-C36 alkoxy, C1-C36 alkylthio, amido, silicon base and boron base.
In one possible implementation, the compound has a structure represented by formula 3,
in formula 3, ya, yb, yc and Yd are each independently selected from C or N;
Y 1 、Y 2 independently selected from N, P, as, B, al, bi, -CR 3 ,-SiR 3 ,-GeR 3 、-Bi＝O、-PR 3 R 4 、-P＝O、-As＝O、-AsR 3 R 4 A single bond or absence;
Y 3 、Y 4 、Y 5 y is as follows 6 Independently selected from O, S, se, -CR 3 R 4 ,-C＝O、-SiR 3 R 4 ,-GeR 3 R 4 、-NR 3 、-BR 3 、-AlR 3 、-PR 3 、-AsR 3 ,-S＝O,-SO 2 ,-Se＝O,-SeO 2 、-BiR 3 A single bond or absence;
A 1 a is a 2 Independently selected from C5-C30 cyclic groups;
A 3 a is a 4 Independently selected from C5-C30 cyclic groups or are absent;
R 1 、R 2 、R 3 r is as follows 4 Independently selected from hydrogen, deuterium, halogen, hydroxy, thiol, nitro, cyano, isocyano, sulfone, hydroxylamine, carboxyl, carbonyl, or one of the following substituted or unsubstituted groups: C6-C48 monocyclic aromatic hydrocarbon or polycyclic aromatic hydrocarbon, C3-C48 monocyclic heteroaromatic hydrocarbon or polycyclic heteroaromatic hydrocarbon, C1-C36 alkyl, C2-C36 heterocycloalkyl, C2-C36 alkenyl, C2-C36 alkynyl, amino, C1-C36 alkoxy, C1-C36 alkylthio, amido, silicon base and boron base.
In one possible implementation, the compound has a structure as shown in 1-1, 1-2, 1-3, or 1-4.
Wherein Ye, yf, yg and Yh are each independently selected from C or N; x, X 1 X is as follows 2 Independently selected from O, S, se, -CR 3 R 4 ,C＝O、-SiR 3 R 4 、-GeR 3 R 4 、-NR 3 、-BR 3 、-AlR 3 、-PR 3 、-AsR 3 、-S＝O、-SO 2 、-Se＝O、-SeO 2 、-BiR 3 。
In one possible implementation, the compounds have a structure shown in 2-1 to 2-16.
Wherein Yi, yj, yk, yl, ym, yn, yo, yp, yq and Yr are each independently selected from C or N; A. b, C, E and F are each independently selected from C, N, si, O, S, ge, P, as, se, B, al, -BiCR 5 、-SiR 5 、-GeR 5 、-NR 5 、-P＝O、-As＝O、-BR 5 、-AlR 5 、-Bi＝O、-CR 5 R 6 、-C＝O、-SiR 5 R 6 、-GeR 5 R 6 、-PR 5 、-PR 5 R 6 、-NR 5 R 6 、-AsR 5 、-S＝O、-SO 2 、-Se＝O、-SeO 2 、-BR 5 R 6 、-AlR 5 、-AlR 5 R 6 Or BiR 5 One of, or not present; r is R 5 、R 6 R is as follows 7 Independently selected from hydrogen, deuterium, halogen, hydroxy, thiol, nitro, cyano, isocyano, sulfone, hydroxylamine, carboxyl, carbonyl, or one of the following substituted or unsubstituted groups: C6-C48 monocyclic aromatic hydrocarbon or polycyclic aromatic hydrocarbon, C3-C48 monocyclic heteroaromatic hydrocarbon or polycyclic heteroaromatic hydrocarbon, C1-C36 alkyl, C2-C36 heterocycloalkyl, C2-C36 alkenyl, C2-C36 alkynyl, amino, C1-C36 alkoxy, C1-C36 alkylthio, amido, silicon base and boron base.
In one possible implementation, the compounds have the structure shown as P1-P96. Wherein Y is t Y is as follows u Each independently selected from C or N; r is R 8 R is as follows 9 Independently selected from hydrogen, deuterium, halogen, hydroxy, thiol, nitro, cyano, isocyano, sulfone, hydroxylamine, carboxyl, carbonyl, or one of the following substituted or unsubstituted groups: C6-C48 monocyclic aromatic hydrocarbon or polycyclic aromatic hydrocarbon, C3-C48 monocyclic heteroaromatic hydrocarbon or polycyclic heteroaromatic hydrocarbon, C1-C36 alkyl group, C2-C36 heterocycloalkyl group, C2-C36 alkenyl group, C2-C36 alkynyl group, amino group, C1-C36 alkoxy group, C1-C36 alkylthio group, acyl groupAmino, silicon, boron.
In one possible implementation, the compounds have the structure shown in C1-C693 and structures S1-S684.
In one possible implementation, the compound is obtained by a process comprising reacting a compound represented by formula a with a halide of metal M.
Further, the compound represented by the formula a is obtained by a method comprising the following process:
reacting a compound shown in a formula a-1 with pinacol diboronate to obtain a compound shown in a formula a-2;
reacting a compound represented by formula a-2 with a compound represented by formula A1 to obtain a compound represented by formula a, wherein L 2 Absence of;
or,
Reacting a compound represented by formula a-3 with a compound represented by formula a-4 to obtain a compound represented by formula a-5;
cyclizing the compound represented by a-5 to obtain a compound represented by formula a, wherein L 2 Is absent and L 1 A cyclic group including Z as a ring-forming atom.
In one possible implementation, the compound is obtained by a process comprising reacting a compound represented by formula b with a halide of metal M.
Further, the compound represented by the formula b is obtained by a method comprising the following process:
carrying out dehydrogenation reaction on the compound shown in the formula b-1 to obtain a compound shown in the formula b-2;
reacting a compound shown in a formula b-2 with pinacol diboronate to obtain a compound shown in a formula b-3;
reacting a compound represented by the formula B-3 with a compound represented by the formula B1 to obtain a compound represented by the formula B-4,
reacting the compound represented by the formula B-4 with the compound represented by the formula B2 to obtain the compound represented by the formula B.
A second aspect of embodiments of the present application provides a method for preparing a compound of the first aspect, comprising the steps of:
the compound shown in the formula a is reacted with a halide of metal M to obtain the compound.
Further, the compound represented by the formula a is obtained by a method comprising the following process:
Reacting a compound shown in a formula a-1 with pinacol diboronate to obtain a compound shown in a formula a-2;
reacting a compound represented by formula a-2 with a compound represented by formula A1 to obtain a compound represented by formula a, wherein L 2 Absence of;
or,
reacting a compound represented by formula a-3 with a compound represented by formula a-4 to obtain a compound represented by formula a-5;
cyclizing the compound represented by a-5 to obtain a compound represented by formula a, wherein L 2 Is absent and L 1 A cyclic group including Z as a ring-forming atom.
A third aspect of embodiments of the present application provides a method for preparing a compound of the first aspect, comprising the steps of: the compound represented by the formula b is reacted with a halide of a metal M.
Further, the compound represented by the formula b is obtained by a method comprising the following process:
carrying out dehydrogenation reaction on the compound shown in the formula b-1 to obtain a compound shown in the formula b-2;
reacting a compound shown in a formula b-2 with pinacol diboronate to obtain a compound shown in a formula b-3;
reacting a compound represented by the formula B-3 with a compound represented by the formula B1 to obtain a compound represented by the formula B-4,
reacting the compound represented by the formula B-4 with the compound represented by the formula B2 to obtain the compound represented by the formula B.
A fourth aspect of embodiments of the present application provides a functional layer comprising a compound of the foregoing first aspect.
A fifth aspect of embodiments of the present application provides a mixture comprising at least one compound of the first aspect described above.
The specific composition of the mixture is not limited to this application, and the mixture referred to in this application is any compound including the aforementioned first aspect. Since the mixture has the aforementioned compounds, the mixture has advantages of improving color purity and stability in the field of organic electroluminescence.
A sixth aspect of embodiments of the present application also provides an organic electroluminescent device comprising a light-emitting layer comprising a compound according to any one of the preceding first aspects.
The organic electroluminescent device of the embodiment of the present application exhibits excellent color purity and device stability because the above-described compound is used as a phosphorescent material.
It is understood that the organic electroluminescent device in the embodiments of the present application further includes other functional layers, such as a cathode layer, an anode layer, an electron transport layer, a hole transport layer, etc., in addition to the above-described light emitting layer.
In one possible implementation manner, the light-emitting layer of the organic electroluminescent device according to the embodiments of the present application is composed of only the compound of the foregoing first aspect.
In one possible implementation manner, the light-emitting layer of the organic electroluminescent device according to the embodiment of the present application includes a host material and a dye, where the dye is a compound of the foregoing first aspect.
In this implementation, the dye receives excitons from the host material and itself undergoes transition from singlet excitons to triplet excitons, thereby emitting phosphorescence to achieve efficient use of energy.
In one possible implementation manner, the light-emitting layer of the organic electroluminescent device of the embodiments of the present application includes a host material, a sensitizer, and a dye, and one of the sensitizer and the dye is a compound of the foregoing first aspect.
Specifically, when the aforementioned compound is used as a sensitizer, it receives excitons from the host material and passes throughEnergy transfer and Dexter energy transfer singlet excitons and triplet excitons to the dye, sensitizing the dye to phosphorescence emission.
When the compound is used as a dye, the compound receives excitons from a sensitizer and generates transition from singlet excitons to triplet excitons by itself, and phosphorescence is emitted to realize efficient energy utilization.
The organic electroluminescent device according to the embodiment of the present application, because the compound of the first aspect is included in the light-emitting layer, the characteristics of narrow spectrum and high stability of the compound are beneficial to improving the color purity and stability of the organic electroluminescent device, and in particular, the stability is mainly represented by prolonging the service life of the organic electroluminescent device, regardless of the specific composition mode of the light-emitting layer.
In one possible implementation, the dye is present in the light-emitting layer in an amount of 0.1 to 20% by mass.
In one possible implementation, the mass percentage of the host material in the light-emitting layer is 50-95%, the mass percentage of the sensitizer in the light-emitting layer is 1-30%, and the mass percentage of the dye in the light-emitting layer is 0.1-20%.
In one possible implementation, the host material is selected from at least one of carbazole, triphenylene, benzothiophene, benzofuran, dibenzothiophene, dibenzofuran, azacarbazole, azatriphenylene, azabenzothiophene, azabenzofuran, azadibenzothiophene, azadibenzofuran.
A seventh aspect of embodiments of the present application provides an electronic device, including the organic electroluminescent device of the sixth aspect. The electronic device has excellent color purity and stability.
Drawings
FIG. 1 is an electroluminescence spectrum of an organic electroluminescent device of example 1;
FIG. 2 is an electroluminescence spectrum of the organic electroluminescent device of example 2;
FIG. 3 is an electroluminescence spectrum of the organic electroluminescent device of example 3;
FIG. 4 is an electroluminescence spectrum of the organic electroluminescent device of example 4;
fig. 5 is an electroluminescence spectrum of the organic electroluminescent device of example 5.
Detailed Description
The terminology used in the description of the embodiments of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application, as will be described in detail with reference to the accompanying drawings.
Currently, mainstream tetradentate platinum (II) complex phosphorescent materials and tetradentate palladium (II) complex phosphorescent materials mainly adopt carbon, nitrogen, oxygen, sulfur, phosphorus and other atoms capable of providing lone pair electrons or atoms capable of forming covalent bonds with platinum (II) atoms and palladium (II) atoms for coordination. At present, the arrangement and combination of coordination atoms and the ligand constitution modes of the phosphorescent light emitting materials are different, and the main bonding modes comprise single bond bonding, nitrogen atom bonding, oxygen atom bonding and the like, and the conjugation mode is limited to a certain extent. In application, although the OLED devices comprising the phosphorescent materials have higher luminous efficiency, the defects of half-width and poor stability of the OLED devices also lead to a certain limit on the commercial application of the phosphorescent materials.
Based on this, the first aspect of the present embodiment provides a compound having a structure represented by formula 1,
in the formula 1, M represents Pd (II) or Pt (II);
Q 1 、Q 2 、Q 3 q and 4 independently selected from O, S or a single bond;
Ar 1 selected from substituted or unsubstituted first cyclic groups, ar 2 A second cyclic group selected from substituted or unsubstituted; the first cyclic group comprises N substituted or unsubstituted cyclic groups, the second cyclic group comprises M substituted or unsubstituted cyclic groups, and N is more than or equal to 1M is more than or equal to 1; (n+m) cyclic groups are each independently selected from 3 to 50 membered substituted or unsubstituted cyclic groups;
when N is more than 1, N cyclic groups are connected in a pair-by-pair fused mode or connected in a single bond mode; when M is more than 1, M cyclic groups are connected in a pair-by-pair fused mode or connected in a single bond mode;
L 1 l and 2 independently selected from substituted or unsubstituted cyclic groups, or L 1 L and 2 one of which is a substituted or unsubstituted cyclic group and the other is absent.
As can be seen from formula 1, the above compounds in the embodiments of the present application are metal tetradentate complexes, wherein the metal coordination atom M is Pt (II) or Pd (II).
Ar in formula 1 1 Selected from a substituted or unsubstituted first cyclic group, which may be a 3-to 50-membered substituted or unsubstituted cyclic group, or a plurality of 3-to 50-membered substituted or unsubstituted cyclic groups, and the cyclic groups may be linked by a single bond or by a condensed bond. When the first cyclic group has a substituent, the present invention is not limited in the number, position and specific kind of the substituent, and the substituent may be, for example, a hydroxyl group, an amino group, an alkoxy group, a nitro group, a cyano group, a hydrocarbon group, an aryl group, a heteroaryl group or the like.
Ar 2 Selected from a substituted or unsubstituted second cyclic group, which may be a 3-to 50-membered substituted or unsubstituted cyclic group, or a plurality of 3-to 50-membered substituted or unsubstituted cyclic groups, and the cyclic groups may be linked by a single bond or by a condensed bond. When the second cyclic group has a substituent, the present invention is not limited in the number, position and specific kind of the substituent, and the substituent may be, for example, a hydroxyl group, an amino group, an alkoxy group, a nitro group, a cyano group, a hydrocarbon group, an aryl group, a heteroaryl group or the like.
The 3-to 50-membered substituted or unsubstituted cyclic group mentioned in the present application means a substituted or unsubstituted cyclic group composed of 3 to 50 ring-forming atoms, and is not limited to the kind of the ring-forming atoms, and may be a carbon atom or a hetero atom.
Ar of the present invention 1 And L1 may be fused or linked by a single bond, and when N > 1, the invention is not limited to the number of cyclic groups linked to L1; and Ar of the present invention 2 And L2 may be fused or linked by a single bond, and when M > 1, the present invention is not limited to the number of cyclic groups linked to L2.
According to the technical scheme provided by the invention, the compound with the composition is used as a phosphorescence luminescent material, so that the color purity and stability of the organic electroluminescent device can be obviously improved. The inventors analyzed based on this phenomenon, and considered that it is possible to: in the compound, two ligands are connected through a carbon-carbon double bond, and the connection mode is favorable for improving the plane conjugation performance of the compound and reducing the charge transfer in molecules, so that the improvement of the color purity is realized by narrowing the half-peak width; meanwhile, the introduction of the high bond energy carbon-carbon double bond is beneficial to the increase of the rigidity of the molecule, and the vibration loss in the molecule caused by the excessively low bond energy is avoided, so that the stability is improved.
Further, the compounds of the present application have the structure shown in formula 2:
ar in formula 2 3 Selected from substituted or unsubstituted third cyclic groups, ar 4 A fourth cyclic group selected from substituted or unsubstituted; the third cyclic group comprises N substituted or unsubstituted cyclic groups, and the fourth cyclic group comprises M substituted or unsubstituted cyclic groups, N is more than or equal to 1 and less than N, and M is more than or equal to 1 and less than M; (n+m) cyclic groups are each independently selected from 3-50 membered substituted or unsubstituted cyclic groups;
when n is more than 1, n cyclic groups are connected in a pair-by-pair fused mode or connected in a single bond mode; when m is more than 1, m cyclic groups are connected in a condensed mode or connected in a single bond mode;
a 1 ～a 6 b 1 ～b 6 Each independently selected from C or N;
R 1 、R 2 independently selected from the group consisting of hydrogen, deuterium,halogen, hydroxy, thiol, nitro, cyano, isocyano, sulfone, hydroxylamine, carboxyl, carbonyl, or one of the following substituted or unsubstituted groups: C6-C48 monocyclic aromatic hydrocarbon or polycyclic aromatic hydrocarbon, C3-C48 monocyclic heteroaromatic hydrocarbon or polycyclic heteroaromatic hydrocarbon, C1-C36 alkyl, C2-C36 heterocycloalkyl, C2-C36 alkenyl, C2-C36 alkynyl, amino, C1-C36 alkoxy, C1-C36 alkylthio, amido, silicon base and boron base.
In the compound represented by formula 2, the six-membered ring in which the cyclic group L1 and a1 to a6 are located is condensed and connected, and the ring-forming atom of the six-membered ring is not limited to this application and may be a carbon atom or a nitrogen atom; similarly, the six-membered ring in which the cyclic group L2 and b1 to b6 are located is condensed and connected, and the present application is not limited to the ring-forming atom of the six-membered ring, and may be a carbon atom or a nitrogen atom.
Further, the compound has a structure represented by the following formula 3,
in formula 3, ya, yb, yc and Yd are each independently selected from C or N;
Y 1 、Y 2 independently selected from N, P, as, B, al, bi, -CR 3 ,-SiR 3 ,-GeR 3 、-Bi＝O、-PR 3 R 4 、-BR 3 R 4 、-P＝O、-As＝O、-AsR 3 R 4 A single bond or absence;
Y 3 、Y 4 、Y 5 y is as follows 6 Independently selected from O, S, se, -CR 3 R 4 ,-C＝O、-SiR 3 R 4 ,-GeR 3 R 4 、-NR 3 、-BR 3 、-AlR 3 、-PR 3 、-AsR 3 ,-S＝O,-SO 2 ,-Se＝O,-SeO 2 、-BiR 3 A single bond or absence;
A 1 a is a 2 Independently selected from C5-C30 cyclic groups;
A 3 a is a 4 Independently selected from C5-C30 cyclic groups are either absent;
R 1 、R 2 、R 3 r is as follows 4 Independently selected from hydrogen, deuterium, halogen, hydroxy, thiol, nitro, cyano, isocyano, sulfone, hydroxylamine, carboxyl, carbonyl, or one of the following substituted or unsubstituted groups: C6-C48 monocyclic aromatic hydrocarbon or polycyclic aromatic hydrocarbon, C3-C48 monocyclic heteroaromatic hydrocarbon or polycyclic heteroaromatic hydrocarbon, C1-C36 alkyl, C2-C36 heterocycloalkyl, C2-C36 alkenyl, C2-C36 alkynyl, amino, C1-C36 alkoxy, C1-C36 alkylthio, amido, silicon base and boron base.
It should be noted that "-" in the above groups is a compound bond and is used to represent a bonding atom. In Y form 3 is-CR 3 R 4 For example, CR is shown 3 R 4 And carbon atoms of A respectively 3 A is a 1 Connection (when A) 3 A is a 1 All present).
Specifically, Y 1 、Y 2 In addition to the above-mentioned limitations of the specific groups, when Y 1 When representing a single bond, it means A 1 The ring shown is directly bonded to the ring where Ya, yc are located; when Y is 2 When representing a single bond, it means A 2 The ring is directly bonded with the ring where Yb and Yd are positioned; when Y is 1 In the absence, refer to A 1 The ring and the rings where Ya and Yc are located have no bonding relationship; when Y is 2 In the absence, refer to A 2 The ring and the rings where Yb and Yd are located have no bonding relationship.
Y 3 、Y 4 、Y 5 、Y 6 In addition to the above-mentioned definition of specific groups, it may be selected from single bonds or may be absent. In Y form 3 For example, when a single bond is represented, it means A 1 Shown ring sum A 3 The rings shown are directly bonded; when not present, means A 1 Shown ring sum A 3 The rings shown have no bonding relationship.
A 1 、A 2 、A 3 、A 4 The C5-C30 cyclic group referred to specifically includes a C5-C30 aromatic (hetero) ring or (hetero) cycloalkyl group.
L 1 L and 2 independently selected from a substituted or unsubstituted cyclic group, the specific form of the cyclic group is not limited herein, and may be, for example, a substituted or unsubstituted aromatic (hetero) ring, (hetero) cycloalkyl group. Notably, when L 1 L and 2 when one of them is a substituted or unsubstituted cyclic group, the other is not cyclic and is absent. Specifically, when L 1 And L 2 L is a substituted or unsubstituted cyclic group 1 And L 2 A carbon-carbon double bond is shared between the two; when L 1 Is a substituted or unsubstituted cyclic group and L 2 L in the absence of 1 Is bound to Y by a single bond only b 、Y d The ring is bonded; when L 2 Is a substituted or unsubstituted cyclic group and L 1 L in the absence of 2 Is bound to Y by a single bond only a 、Y c The ring where it is located is bonded.
In addition, when R 1 As substituents of the ring in which Ya, yc are located or R 2 When the substituents on the ring where Yb and Yd are located, the specific number and substitution positions of the substituents are not limited in the present application. By R 1 For example, when cyclic group L 1 Exists and Y is 6 When present, the ring in which Ya, yc are located has only one substitution position, in which case R 1 The number of substituents is 1; when cyclic group L 1 Exists and Y is 6 In the absence, the ring in which Ya, yc are located has two substituents, R being 1 The substituent may be substituted at each of the two substitution positions or may be substituted at any one substitution position (when each of the two substitution positions is substituted, the two substituents may be the same or different); when cyclic group L 1 Is absent and Y 6 When present, the ring in which Ya, yc are located has two substituents, R being 1 The substituent may be substituted at each of the two substitution positions or may be substituted at any one substitution position (when each of the two substitution positions is substituted, the two substituents may be the same or different); when cyclic group L 1 And Y 6 When none of them exists, the ring where Ya and Yc are located has three substitution positions, R 1 The substituents may be substituted at three substituents or may be substituted at any one or two substituents (when two or three substituents are substituted, the substituents may be identical, different or different from each other).
In addition, when R 1 、R 2 、R 3 R is as follows 4 When the substituent is provided, the substituent is selected from at least one of deuterium, cyano, amino, nitro, halogen, carbonyl, C2-C6 alkenyl, C1-C6 alkoxy or thioalkoxy, carboxyl, ester group and C6-C30 (hetero) aryl.
Further, this can achieve a greater improvement in the planar conjugation performance of the compound by limiting the substituents of the ligand in the compound represented by formula 1, thereby further narrowing the emission spectrum.
For example, L 1 And L 2 And when the two are all substituted or unsubstituted cyclic groups, the compound is more favorable for having good plane conjugation performance.
In one embodiment, the compound has a structure shown as 1-1, 1-2, 1-3, or 1-4.
Wherein,,
ye, yf, yg and Yh are each independently selected from C or N;
X、X 1 x is as follows 2 Independently selected from O, S, se, -CR 3 R 4 、C＝O、-SiR 3 R 4 ,-GeR 3 R 4 、-NR 3 、-BR 3 、-AlR 3 、-PR 3 、-AsR 3 、-S＝O、-SO 2 、-Se＝O、-SeO 2 、-BiR 3 。
Wherein when R is 1 ～R 4 When the substituent is a cyclic group, the present application is not limited to a specific number and specific substitution positions thereof.
In another embodiment, the compound has the structure shown.
/>
Wherein Yi, yj, yk, yl, ym, yn, yo, yp, yq and Yr are each independently selected from C or N;
A. b, C, E and F are each independently selected from C, N, si, O, S, ge, P, as, se, B, al, -BiCR 5 、-SiR 5 、-GeR 5 、-NR 5 、-P＝O、-As＝O、-BR 5 、-AlR 5 、-Bi＝O、-CR 5 R 6 、-C＝O、-SiR 5 R 6 、-GeR 5 R 6 、-PR 5 、-PR 5 R 6 、-NR 5 R 6 、-AsR 5 、-S＝O、-SO 2 、-Se＝O、-SeO 2 、-BR 5 R 6 、-AlR 5 、-AlR 5 R 6 Or BiR 5 One of, or not present;
R 5 、R 6 r is as follows 7 Independently selected from hydrogen, deuterium, halogen, hydroxy, thiol, nitro, cyano, isocyano, sulfone, hydroxylamine, carboxyl, carbonyl, or one of the following substituted or unsubstituted groups: C6-C48 monocyclic aromatic hydrocarbon or polycyclic aromatic hydrocarbon, C3-C48 monocyclic heteroaromatic hydrocarbon or polycyclic heteroaromatic hydrocarbon, C1-C36 alkyl, C2-C36 heterocycloalkyl, C2-C36 alkenyl, C2-C36 alkynyl, amino, C1-C36 alkoxy, C1-C36 alkylthio, amido, silicon base and boron base.
Wherein when R is 1 ～R 7 When the substituent is a cyclic group, the present application is not limited to a specific number and specific substitution positions thereof.
Further, the compounds have the structures shown below as P1 to P96.
/>
/>
/>
/>
/>
/>
/>
Wherein Yt and Yu are each independently selected from C or N;
R 8 r is as follows 9 Independently selected from hydrogen, deuterium, halogen, hydroxy, thiol, nitro, cyano, isocyano, sulfone, hydroxylamine, carboxyl, carbonyl, or one of the following substituted or unsubstituted groups: C6-C48 monocyclic aromatic hydrocarbon or polycyclic aromatic hydrocarbon, C3-C48 monocyclic heteroaromatic hydrocarbon or polycyclic heteroaromatic hydrocarbon, C1-C36 alkyl, C2-C36 heterocycloalkyl, C2-C36 alkenyl, C2-C36 alkynyl, amino, C1-C36 alkoxy, C1-C36 alkylthio, amido, silicon base and boron base.
Wherein when R is 1 ～R 9 When the substituent is a cyclic group, the present application is not limited to a specific number and specific substitution positions thereof.
The definition of substituents shown in the same symbol in the present application is uniform in any compound shown in the structural formula in the present application. For example, the substituents R of the cyclic groups represented by L1 and L2 in formulas 1 to 4 3 And R is 4 R in formula 3 as described above 3 And R is 4 Is the same as defined in the following.
More specifically, the compound represented by formula 1 of the present application is specifically a compound having one of the following structures represented by C1 to C693 and structures S1 to S684.
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
The inventors have found that when a compound has a larger substituent such as t-butyl or the like, it is advantageous to further improve the color purity of the light emission spectrum.
The present application is not limited to the synthesis method of the compound having the above structure.
In one embodiment, the above compound comprises a compound represented by formula a reacted with a halide of a metal M;
in formula a, G 1 ～G 4 Each independently selected from hydroxy, alkoxy, mercapto, alkylthio, or absent. Examples of the halogenides of the metal M in the present application include potassium tetrachloroplatinate, potassium hexachloroplatinate, potassium tetrachloropalladate, and potassium hexachloropalladate, which are raw materials for producing an organometallic compound.
The present invention is not limited to the preparation method of the compound represented by formula a, for example,
reacting a compound shown in a formula a-1 with pinacol diboronate to obtain a compound shown in a formula a-2;
reacting a compound represented by formula a-2 with a compound represented by formula A1 to obtain a compound represented by formula a, wherein L 2 Is not present.
The specific preparation equation is as follows:
in the above compound, X is halogen.
Taking the compound shown as 1-1 as an example, the compound is obtained by the preparation method as follows.
Synthesis path 1:
wherein the product I is a compound shown as 1-1, and X in 1-1 is S.
Synthesis path 2:
wherein the product II is a compound shown as 1-1, X in 1-1 is NR, R is selected from R and R 3 Identical, i.e. X is-NR 3 。
As another example of this, and as another example,
reacting a compound represented by formula a-3 with a compound represented by formula a-4 to obtain a compound represented by formula a-5;
cyclizing the compound represented by a-5 to obtain a compound represented by formula a, wherein L 2 Is absent and L 1 A cyclic group including Z as a ring-forming atom;
wherein t is more than or equal to 1, X is halogen, rz is selected from one of hydroxyl, amino and sulfhydryl, and Z is selected from O, N or S.
Taking the compound shown as 1-1 as an example, the compound is obtained by the preparation method as follows.
Wherein the product III is a compound shown as 1-1, and X in 1-1 is O.
In another embodiment, the above compound comprises a compound represented by formula b reacted with a halide of metal M;
in formula b, G 1 ～G 4 Each independently selected from hydroxy, alkoxy, mercapto, alkylthio, or absent.
The present invention is not limited to the preparation method of the compound represented by formula b, for example,
Carrying out dehydrogenation reaction on the compound shown in the formula b-1 to obtain a compound shown in the formula b-2;
reacting a compound shown in a formula b-2 with pinacol diboronate to obtain a compound shown in a formula b-3;
reacting a compound represented by the formula B-3 with a compound represented by the formula B1 to obtain a compound represented by the formula B-4,
reacting a compound shown in a formula B-4 with a compound shown in a formula B2 to obtain a compound shown in a formula B;
taking the compounds shown in 1-4 as examples, the preparation method is adopted to obtain the compound.
Wherein IV is a compound shown as 1-4, wherein Ya-Yh in 1-4 are all C, and R1-R4 are all H.
In all the above synthetic routes, ar1 and ar2 are the remaining fragments of the target compound and vary depending on the target compound, and the groups included in ar1 and ar2 all meet the requirements of formula 1.
In a second aspect, an embodiment of the present application provides a method for preparing the foregoing compound, including the steps of:
reacting a compound represented by formula a with a halide of a metal M;
in formula a, G 1 ～G 4 Each independently selected from hydroxy, alkoxy, mercapto, alkylthio, or absent.
Further, the compound represented by the formula a is obtained by a method comprising the following process:
Reacting a compound shown in a formula a-1 with pinacol diboronate to obtain a compound shown in a formula a-2;
reacting a compound represented by formula a-2 with a compound represented by formula A1 to obtain a compound represented by formula a, wherein L 2 Absence of;
wherein X is halogen;
or,
reacting a compound represented by formula a-3 with a compound represented by formula a-4 to obtain a compound represented by formula a-5;
cyclizing the compound represented by a-5 to obtain a compound represented by formula a, wherein L 2 Is absent and L 1 A cyclic group including Z as a ring-forming atom;
wherein t is more than or equal to 1, X is halogen, rz is selected from one of hydroxyl, amino and sulfhydryl, and Z is selected from O, N or S.
A third aspect of embodiments of the present application provides a method for preparing the foregoing compound, including the steps of:
reacting a compound represented by formula b with a halide of a metal M;
in formula b, G 1 ～G 4 Each independently selected from hydroxy, alkoxy, mercapto, alkylthio, or absent.
Further, the compound represented by the formula b is obtained by a method comprising the following process:
carrying out dehydrogenation reaction on the compound shown in the formula b-1 to obtain a compound shown in the formula b-2;
reacting a compound shown in a formula b-2 with pinacol diboronate to obtain a compound shown in a formula b-3;
Reacting a compound represented by the formula B-3 with a compound represented by the formula B1 to obtain a compound represented by the formula B-4,
reacting a compound shown in a formula B-4 with a compound shown in a formula B2 to obtain a compound shown in a formula B;
a fourth aspect of embodiments of the present application provides a functional layer comprising a compound of the foregoing first aspect. The functional layer has a layered or film-like structure, and can be used as a device of the aggregate to improve the color purity and stability of the aggregate.
In a fifth aspect, embodiments of the present application provide a mixture comprising at least one compound of the first aspect. The mixture has the advantages of narrow spectrum and high stability in the field of organic electroluminescence due to the inclusion of the compound.
The present application is not limited to the mass percentage of the compound in the mixture and the kind and mass percentage of other components, and all compounds as long as the compound of the first aspect of the present application is included in the mixture are included in the protection scope of the present application.
A sixth aspect of embodiments of the present application provides an organic electroluminescent device, wherein the light-emitting layer of the organic electroluminescent device comprises the compound of the first aspect.
The organic electroluminescent device of the present application includes other functional layers common in the art in addition to the light emitting layer.
In one embodiment, an organic electroluminescent device of the present application includes a cathode layer and an anode layer, and a light emitting layer is located between the anode layer and the cathode layer.
Further, the organic electroluminescent device further comprises a hole injection layer and/or an electron injection layer, wherein the hole injection layer is positioned between the anode layer and the light emitting layer, and the electron injection layer is positioned between the cathode layer and the light emitting layer.
Still further, the organic electroluminescent layer further comprises a hole functional layer and/or an electron functional layer, wherein the hole functional layer is located between the hole injection layer and the light emitting layer, and the electron functional layer is located between the electron injection layer and the light emitting layer. It should be noted that, the hole functional layer in the present application includes a hole transport layer and/or an electron blocking layer, and when the hole transport layer and the electron blocking layer exist at the same time, the electron blocking layer is located between the hole transport layer and the light emitting layer; the electron functional layer of the present application includes an electron transport layer and/or a hole blocking layer, and when the electron transport layer and the hole blocking layer are present at the same time, the hole blocking layer is located between the electron transport layer and the light emitting layer.
The materials of the functional layers are not particularly limited, and materials commonly used in the art can be used. It will be appreciated that the thickness of each functional layer may also be consistent with the thickness of the corresponding functional layer of a device commonly known in the art.
As described above, since the light emitting layer of the organic electroluminescent device includes the aforementioned compound, the organic electroluminescent device has characteristics of excellent color purity and stability.
In one embodiment, the light emitting layer consists of the aforementioned compounds.
In another embodiment, the light emitting layer includes a host material and the aforementioned compound present in the light emitting layer as a dye.
In another embodiment, the light emitting layer includes a host material, a sensitizer, and a dye. Wherein, the compound can be used as a sensitizer to sensitize dye to emit phosphorescence, and the dye can be a phosphorescence dye commonly used in the field; alternatively, the above-mentioned compound may be sensitized as a dye to emit phosphorescence, and the sensitizer may be selected from sensitizer materials commonly used in the art.
The host material of the light-emitting layer is not particularly limited, and may be at least one of carbazole, triphenylene, benzothiophene, benzofuran, dibenzothiophene, dibenzofuran, azacarbazole, azatriphenylene, azabenzothiophene, azabenzofuran, azadibenzothiophene, and azadibenzofuran, for example.
In addition, the performance of the device can be further optimized by controlling the specific mass percent of the material in the light emitting layer.
In the implementation process of the application, the mass ratio of the compound in the light-emitting layer is generally controlled to be more than 0.1%. The doping amount of the compound in the light-emitting layer is reasonably controlled, so that the stability and the color purity of the device are further improved.
Specifically, when the light-emitting layer includes a host material and a dye, the foregoing compound is present as the dye in an amount of 0.1 to 20% by mass in the light-emitting layer, and further, the foregoing compound is present as the dye in an amount of 3 to 12% by mass in the light-emitting layer.
When the light-emitting layer comprises a main body material, a sensitizer and a dye, the mass percentage of the main body material in the light-emitting layer is 50-95%, the mass percentage of the sensitizer in the light-emitting layer is 1-30%, and the mass percentage of the dye in the light-emitting layer is 0.1-20%. Further, the mass percentage of the main material in the light-emitting layer is 70-95%, the mass percentage of the sensitizer in the light-emitting layer is 4.9-25%, and the mass percentage of the dye in the light-emitting layer is 0.1-10%
In addition, the thickness of the light-emitting layer in the electroluminescent device is not particularly limited, and is, for example, 10 to 100nm.
A seventh aspect of the embodiments of the present application further provides an electronic device, which includes the organic electroluminescent device shown in the sixth aspect. The electronic device provided by the embodiment of the application includes, but is not limited to, a display device, and any product or component with a display function, such as a television, a digital camera, a mobile phone, a tablet computer, a video wall or screen, an illuminating lamp, a transmitting lamp, a wearable device, a video camera, a sign board and the like, which include the display device. The display device can be an OLED flat-panel display, an OLED vehicle-mounted display, an OLED flexible display, a full-transparent or semitransparent display, a virtual reality display or an augmented reality display and other display devices. The electronic device and the organic electroluminescent device have the same advantages as those of the prior art, and are not described herein.
Synthetic examples
Synthesis example 1: synthesis of Compound C690
1. Synthesis of intermediate 1
5-Chlorobenzo [ b ] thiophene (6.0 g,36.0 mmol) was placed in a 100mL Schlenk flask containing 20mL chloroform and 20mL acetic acid mixed solvent, and then 30mL chloroform solution containing NBS (8.0 g,45.0 mmol) was slowly added to the system, and the reaction was quenched by adding 10mL acetone after reacting at room temperature for 12 hours. After the solvent was removed in vacuo, the mixture was washed 3 times with 40mL of dichloromethane solution, followed by saturated aqueous sodium chloride solution, the organic phase was separated, dried over anhydrous magnesium sulfate (MgSO 4), and the solvent was dried. Finally, purification by column chromatography on silica gel (eluent: dichloromethane) gave 7.3g of a white solid in 96% yield.
2. Synthesis of intermediate 2
Intermediate 1 (2.9 g,11.7 mmol), pd (dppf) Cl 2 (840mg,8mol％)，B 2 pin 2 (3.3 g,13.4 mmol) KOAc (3.3 g,330 mol) was placed in a 50mL Shi Laike bottle and the system was evacuated to replace nitrogen 3 times. The system was reacted at 100℃for 4 hours after 10mL of 1, 4-dioxane solution was added under a nitrogen atmosphere, 20mL of DCM was added to the system, the above mixture was washed 3 times with saturated aqueous sodium chloride solution, the organic phase was separated, and the mixture was washed with anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by column chromatography on silica gel (eluent: petroleum ether/ethyl acetate=15/1) gave 2.3g of a white solid with a yield of 56%.
3. Synthesis of intermediate 3
Intermediate 2 (360 mg,1.2 mmol), 2-bromo-9- (2-pyridine) -9H-carbazole (310 mg,0.95 mmol), pd (PPh 3 ) 4 (80mg,7mol％)，K 2 CO 3 (400.0 mg,3.3 mol) was placed in a 50mL Shi Laike bottle, and the system was evacuated to replace nitrogen 3 times. The system was reacted at 100℃for 4 hours after adding a mixed solution of 10mL of 1, 4-dioxane and 2mL of water under a nitrogen ball atmosphere, 20mL of DCM was added to the system, the mixed solution was washed 3 times with a saturated aqueous sodium chloride solution, the organic phase was separated, and the mixture was washed with anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by silica gel column chromatography (eluent: petroleum ether) gave 273mg of a white solid in 87% yield.
4. Synthesis of intermediate 4
Intermediate 3 (400.0 g,0.9 mmol), pd (dba) 2 (10mg,10mol％)，Xphos(15mg,20mol％)，B 2 pin 2 (300.0 mg,1.2 mmol) KOAc (180 mg,1.3 mol) was placed in a 50mL Shi Laike bottle and the system was evacuated to displace nitrogen 3 times. The system was reacted at 100℃for 12 hours after 5mL of 1, 4-dioxane solution was added under nitrogen atmosphere, 20mL of DCM was added to the system, the above mixture was washed 3 times with saturated aqueous sodium chloride solution, the organic phase was separated, and the mixture was washed with anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by column chromatography on silica gel (eluent: petroleum ether/ethyl acetate=8/1) gave 400mg of white solid in 86% yield.
5. Synthesis of intermediate 5
Intermediate 4 (600 mg,1.2 mmol), 2-chloro-4 tert-butylpyridine (300 mg,1.5 mmol), pd (PPh) 3 ) 4 (90mg,7mol％)，K 2 CO 3 (420.0 mg,3.5 mol) was placed in a 50mL Shi Laike bottle, and the system was evacuated to replace nitrogen 3 times. The system was reacted at 100℃for 4 hours after 10mL of a mixed solution of 1, 4-dioxane and 2mL of water was added under a nitrogen ball atmosphere, 20mL of DCM was added to the system, the above mixed solution was washed 3 times with a saturated aqueous sodium chloride solution, the organic phase was separated, and the mixture was washed with anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by column chromatography on silica gel (eluent: petroleum ether/ethyl acetate=6/1) gave 450mg of a white solid with a yield of 67%.
6. Synthesis of C690
Intermediate 5 (61 mg,0.1 mmol), K 2 PtCl 4 (42 mg,0.11 mmol) was placed in a 50mL Shi Laike bottle, and the system was evacuated to replace nitrogen 3 times. The system is added with 10mL of deoxidized acetic acid solution under the atmosphere of nitrogen ballsThe reaction was then carried out at 125℃for 24h, after which the acetic acid solvent was removed in vacuo and purified by column chromatography on silica gel (eluent: dichloromethane) to give 45mg of yellow solid in 61% yield.
1 H NMR(400MHz,CDCl 3 )δ8.98(dd,1H),8.35(d,1H),8.10(d,1H),8.05(m,2H),7.88(d,2H),7.78(m,2H),7.65(d,2H),7.42(t,1H),7.35(t,1H),7.24(d,1H),7.10(t,1H),1.43(s,9H).
Synthesis example 2: synthesis of Compound C93
1. Synthesis of intermediate 1
5-Bromobenzo [ b ]]Thiophene (1.3 g,6.0 mmol), 2-pyridineboronic acid (1.3 g,10.0 mmol), pd (OAc) 2 (67mg,5mol％)，Cs 2 CO 3 (4.8 g,15.3 mol), cuCl (490 mg,5 mol), dppf (322.0 mg,0.5 mol) were placed in a 50mL Shi Laike bottle, and the system was evacuated to replace nitrogen 3 times. The system was reacted at 100℃for 4h after adding 10mL of DMF under nitrogen atmosphere, after which 20mL of DCM was added to the system, the above mixture was washed 3 times with saturated aqueous sodium chloride solution, the organic phase was separated, and the mixture was washed with anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by silica gel column chromatography (eluent: petroleum ether) gave 750mg of a white solid with a yield of 60%.
2. Synthesis of intermediate 2
Intermediate 1 (3.0 g,14.2 mmol) was placed in a 100mL Schlenk flask containing 10mL chloroform and 10mL acetic acid mixed solvent, and then 30mL chloroform solution containing NBS (3.8 g,21.0 mmol) was slowly added to the system, and the reaction was quenched by adding 10mL acetone after reacting at room temperature for 12 h. After the solvent was removed in vacuo, the mixture was washed 3 times with 40mL of dichloromethane solution and then with saturated aqueous sodium chloride, the organic phase was separated, and dried over anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by column chromatography on silica gel (eluent: dichloromethane) gave 4.3g of a white solid in 76% yield.
3. Synthesis of intermediate 3
Intermediate 2 (130.9 mg,0.47 mmol), pd (dppf) Cl 2 (40mg,8mol％)，B 2 pin 2 (130.3 mg,0.6 mmol) KOAc (150.0 mg,1.1 mmol) was placed in a 50mL Shi Laike bottle and the system was evacuated to displace nitrogen 3 times. The system was reacted at 100℃for 4 hours after 10mL of 1, 4-dioxane solution was added under a nitrogen atmosphere, 20mL of DCM was added to the system, the above mixture was washed 3 times with saturated aqueous sodium chloride solution, the organic phase was separated, and the mixture was washed with anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by column chromatography on silica gel (eluent: petroleum ether/ethyl acetate=15/1) gave 100mg of white solid in 88% yield.
4. Synthesis of intermediate 4
Intermediate 3 (700 mg,2.43 mmol), 2- (3-bromophenyl) pyridine (780 mg,2.7 mmol), pd (PPh) 3 ) 4 (312mg,7mol％)，K 2 CO 3 (1.0 g,7.25 mmol) was placed in a 50mL Shi Laike bottle and the system was evacuated to replace nitrogen 3 times. The system was reacted at 100℃for 4 hours after 10mL of a mixed solution of 1, 4-dioxane and 2mL of water was added under a nitrogen ball atmosphere, 20mL of DCM was added to the system, the above mixed solution was washed 3 times with a saturated aqueous sodium chloride solution, the organic phase was separated, and the mixture was washed with anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by column chromatography on silica gel (eluent: petroleum ether/ethyl acetate=6/1) gave 650mg of white solid in 68% yield.
5. Synthesis of C93
Intermediate 4 (50 mg,0.14 mmol), K 2 PtCl 4 (60 mg,0.15 mmol) was placed in a 50mL Shi Laike bottle and the system was evacuated to displace nitrogen 3 times. The system was reacted at 125℃for 24 hours after adding 10mL of an oxygen-scavenging acetic acid solution under nitrogen sphere atmosphere, followed by spin-removal of the acetic acid solvent in vacuo, and purification by suction filtration gave 45mg of yellow solid with a yield of 70%. 1 H NMR(400MHz,DMF)δ9.60(dd,1H),9.42(d,1H),8.88(d,1H),8.35(m,3H),8.2-8.3(m,6H),7.78(m,1H),7.35(m,1H).
Synthesis example 3: synthesis of Compound C95
1. Synthesis of intermediate 1
5-Bromobenzo [ b ]]Thiophene (1.3 g,6.0 mmol), 2-pyridineboronic acid (1.3 g,10.0 mmol), pd (OAc) 2 (67mg,5mol％)，Cs 2 CO 3 (4.8 g,15.3 mol), cuCl (490 mg,5 mol), dppf (322.0 mg,0.5 mol) were placed in a 50mL Shi Laike bottle, and the system was evacuated to replace nitrogen 3 times. The system was reacted at 100℃for 4h after adding 10mL of DMF under nitrogen atmosphere, after which 20mL of DCM was added to the system, the above mixture was washed 3 times with saturated aqueous sodium chloride solution, the organic phase was separated, and the mixture was washed with anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by silica gel column chromatography (eluent: petroleum ether) gave 750mg of a white solid with a yield of 60%.
2. Synthesis of intermediate 2
Intermediate 1 (3.0 g,14.2 mmol) was placed in a 100mL Schlenk flask containing 10mL of chloroform and 10mL of acetic acid, and 30mL of chloroform solution containing NBS (3.8 g,21.0 mmol) was slowly added to the system, and after 12h of reaction at room temperature, 10mL of propylene was addedThe ketone quench reaction. After the solvent was removed in vacuo, the mixture was washed 3 times with 40mL of dichloromethane solution and then with saturated aqueous sodium chloride, the organic phase was separated, and dried over anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by silica gel column chromatography (eluent: dichloromethane) gave 4.3 as a white solid in 76% yield.
3. Synthesis of intermediate 3
Intermediate 2 (130.9 mg,0.47 mmol), pd (dppf) Cl 2 (40mg,8mol％)，B 2 pin 2 (130.3 mg,0.6 mmol) KOAc (150.0 mg,1.1 mmol) was placed in a 50mL Shi Laike bottle and the system was evacuated to displace nitrogen 3 times. The system was reacted at 100℃for 4 hours after 10mL of 1, 4-dioxane solution was added under a nitrogen atmosphere, 20mL of DCM was added to the system, the above mixture was washed 3 times with saturated aqueous sodium chloride solution, the organic phase was separated, and the mixture was washed with anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by column chromatography on silica gel (eluent: petroleum ether/ethyl acetate=15/1) gave 100mg of white solid in 88% yield.
4. Synthesis of intermediate 4
Intermediate 3 (700 mg,2.43 mmol), 2- (3-bromophenyl) phenol (630 mg,2.7 mmol), pd (PPh) 3 ) 4 (312mg,7mol％)，K 2 CO 3 (1.0 g,7.25 mmol) was placed in a 50mL Shi Laike bottle and the system was evacuated to replace nitrogen 3 times. The system was reacted at 100℃for 4 hours after 10mL of a mixed solution of 1, 4-dioxane and 2mL of water was added under a nitrogen ball atmosphere, 20mL of DCM was added to the system, the above mixed solution was washed 3 times with a saturated aqueous sodium chloride solution, the organic phase was separated, and the mixture was washed with anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, subjecting the mixture to silica gel column chromatography (eluent: petroleum ether/ethyl acetate)=6/1) purification gave 510mg of a white solid in 43% yield.
5. Synthesis of C95
Intermediate 4 (50 mg,0.12 mmol), K 2 PtCl 4 (54 mg,0.13 mmol) was placed in a 50mL Shi Laike bottle and the system was evacuated to displace nitrogen 3 times. The system was reacted at 125℃for 24 hours after adding 10mL of an oxygen-scavenging acetic acid solution under nitrogen sphere atmosphere, followed by spin-removal of the acetic acid solvent in vacuo, and purification by suction filtration gave 30mg of a yellow solid with a yield of 45%. 1 H NMR(400MHz,DMF)δ10.20(dd,1H),9.82(d,1H),8.48(d,1H),8.25(d,1H),8.0-8.15(m,2H),7.80(m,3H),7.60(m,1H),7.30(m,2H),6.9-7.0(m,2H).
Synthesis example 4: synthesis of Compound C691
1. Synthesis of intermediate 1
5-Chlorobenzo [ b ]]Thiophene (6.0 g,36.0 mmol) was placed in a 100mL Schlenk flask containing 20mL chloroform and 20mL acetic acid mixed solvent, and then 30mL chloroform solution containing NBS (8.0 g,45.0 mmol) was slowly added to the system, and the reaction was quenched by adding 10mL acetone after reacting at room temperature for 12 h. After the solvent was removed in vacuo, the mixture was washed 3 times with 40mL of dichloromethane solution and then with saturated aqueous sodium chloride, the organic phase was separated, and dried over anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by silica gel column chromatography (eluent: dichloromethane) gave 7.3 as a white solid in 96% yield.
2. Synthesis of intermediate 2
Intermediate 1 (2.9 g,11.7 mmol), pd (dppf) Cl 2 (840mg,8mol％)，B 2 pin 2 (3.3 g,13.4 mmol) KOAc (3.3 g,330 mol) was placed in a 50mL Shi Laike bottle and the system was evacuated to replace nitrogen 3 times. The system was reacted at 100℃for 4 hours after 10mL of 1, 4-dioxane solution was added under a nitrogen atmosphere, 20mL of DCM was added to the system, the above mixture was washed 3 times with saturated aqueous sodium chloride solution, the organic phase was separated, and the mixture was washed with anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by column chromatography on silica gel (eluent: petroleum ether/ethyl acetate=15/1) gave 2.3g of a white solid with a yield of 56%.
3. Synthesis of intermediate 3
Intermediate 2 (360 mg,1.2 mmol), 2-bromo-6- (2-pyridinyl) pyridine (307 mg,0.9 mmol), pd (PPh 3 ) 4 (80mg,7mol％)，K 2 CO 3 (400.0 mg,3.3 mol) was placed in a 50mL Shi Laike bottle, and the system was evacuated to replace nitrogen 3 times. The system was reacted at 100℃for 4 hours after adding a mixed solution of 10mL of 1, 4-dioxane and 2mL of water under a nitrogen ball atmosphere, 20mL of DCM was added to the system, the mixed solution was washed 3 times with a saturated aqueous sodium chloride solution, the organic phase was separated, and the mixture was washed with anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by column chromatography on silica gel (eluent: petroleum ether/ethyl acetate=8/1) gave 240mg of a white solid in 75% yield.
4. Synthesis of intermediate 4
Intermediate 3 (413 mg,1.1 mmol), 2-hydroxyphenylboronic acid (276 mg,1.9 mmol), pd (PPh 3 ) 4 (80mg,7mol％)，K 2 CO 3 (400.0 mg,3.3 mol) was placed in a 50mL Shi Laike bottle, and the system was evacuated to replace nitrogen 3 times. The system is added with 10mL of mixed solution of 1, 4-dioxane and 2mL of water under the atmosphere of nitrogen ball and then reacts for 4 hours at 100 ℃,after 20mL of DCM was added to the system, the above mixture was washed 3 times with saturated aqueous sodium chloride, the organic phase was separated, and the mixture was washed with anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by column chromatography on silica gel (eluent: petroleum ether/ethyl acetate=6/1) gave 420mg of white solid in 85% yield.
5. Synthesis of C691
Intermediate 4 (50 mg,0.13 mmol), K 2 PtCl 4 (35 mg,0.15 mmol) was placed in a 50mL Shi Laike bottle and the system was evacuated to displace nitrogen 3 times. The system was reacted at 125℃for 24 hours after adding 10mL of an oxygen-scavenging acetic acid solution under nitrogen sphere atmosphere, followed by spin-removal of the acetic acid solvent in vacuo, and purification by suction filtration gave 37mg of a red solid with a yield of 64%. 1 H NMR(400MHz,DMSO)δ9.58(s,1H),8.90(d,1H),8.52(d,1H),8.40(d,1H),7.91-8.22(m,4H),7.42(d,1H),7.40(d,1H),7.20(t,2H),7.00(d,1H),6.92(d,1H).
Synthesis example 5: synthesis of Compound C97
1. Synthesis of intermediate 1:
5-Chlorobenzo [ b ]]Thiophene (6.0 g,36.0 mmol) was placed in a 100mL Schlenk flask containing 20mL chloroform and 20mL acetic acid mixed solvent, and then 30mL chloroform solution containing NBS (8.0 g,45.0 mmol) was slowly added to the system, and the reaction was quenched by adding 10mL acetone after reacting at room temperature for 12 h. After the solvent was removed in vacuo, the mixture was washed 3 times with 40mL of dichloromethane solution and then with saturated aqueous sodium chloride, the organic phase was separated, and dried over anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by silica gel column chromatography (eluent: dichloromethane) gave 7.3 as a white solid in 96% yield.
2. Synthesis of intermediate 2
Intermediate 1 (2.9 g,11.7 mmol), pd (dppf) Cl 2 (840mg,8mol％)，B 2 pin 2 (3.3 g,13.4 mmol) KOAc (3.3 g,330 mol) was placed in a 50mL Shi Laike bottle and the system was evacuated to replace nitrogen 3 times. The system was reacted at 100℃for 4 hours after 10mL of 1, 4-dioxane solution was added under a nitrogen atmosphere, 20mL of DCM was added to the system, the above mixture was washed 3 times with saturated aqueous sodium chloride solution, the organic phase was separated, and the mixture was washed with anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by column chromatography on silica gel (eluent: petroleum ether/ethyl acetate=15/1) gave 2.3g of a white solid with a yield of 56%.
3. Synthesis of intermediate 3
Intermediate 2 (2.0 g,6.8 mmol), 2- (3-bromophenyl) pyridine (1.33 g,5.67 mmol), pd (PPh 3 ) 4 (650mg,7mol％)，K 2 CO 3 (1.58 mg,11.4 mol) was placed in a 50mL Shi Laike bottle, and the system was evacuated to replace nitrogen 3 times. The system was reacted at 100℃for 4 hours after adding a mixed solution of 20mL of 1, 4-dioxane and 4mL of water under a nitrogen ball atmosphere, after which 20mL of DCM was added to the system, the above mixed solution was washed 3 times with a saturated aqueous sodium chloride solution, the organic phase was separated, and the mixture was washed with anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by column chromatography on silica gel (eluent: petroleum ether/ethyl acetate=10/1) gave 2.8g of a white solid in 78% yield.
4. Synthesis of intermediate 4
Intermediate 3 (400.0 g,0.9 mmol), pd (dba) 2 (10mg,10mol％)，Xphos(15mg,20mol％)，B 2 pin 2 (300.0 mg,1.2 mmol) KOAc (180 mg,1.3 mol) was placed in a 50mL Shi Laike bottle and the system was evacuated to displace nitrogen 3 times. The system was reacted at 100℃for 12 hours after 5mL of 1, 4-dioxane solution was added under nitrogen atmosphere, 20mL of DCM was added to the system, the above mixture was washed 3 times with saturated aqueous sodium chloride solution, the organic phase was separated, and the mixture was washed with anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by column chromatography on silica gel (eluent: petroleum ether/ethyl acetate=10/1) gave 400mg of white solid in 86% yield.
5. Synthesis of intermediate 5
Intermediate 4 (3.9 g,10.0 mmol), 1-bromoisoquinoline (2.7 g,13 mmol), pd (PPh 3 ) 4 (580mg,7mol％)，K 2 CO 3 (4.14 g,30.1 mol) was placed in a 50mL Shi Laike bottle and the system was evacuated to replace nitrogen 3 times. The system was reacted at 100℃for 4 hours after adding a mixed solution of 20mL of 1, 4-dioxane and 4mL of water under a nitrogen ball atmosphere, after which 20mL of DCM was added to the system, the above mixed solution was washed 3 times with a saturated aqueous sodium chloride solution, the organic phase was separated, and the mixture was washed with anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by column chromatography on silica gel (eluent: petroleum ether/ethyl acetate=8/1) gave 3.4g of a white solid with a yield of 64%.
6. Synthesis of C97
Intermediate 5 (50 mg,0.12 mmol), K 2 PtCl 4 (53 mg,0.13 mmol) was placed in a 50mL Shi Laike bottle and the system was evacuated to displace nitrogen 3 times. Adding 10mL of deoxidized acetic acid solution into the system under nitrogen sphere atmosphere, reacting at 125 ℃ for 24 hours, removing acetic acid solvent in vacuum, and purifying by silica gel column chromatography (eluting solution: dichloromethane) to obtain 20mg of red solid, thereby producingThe rate was 40%. 1 H NMR(400MHz,DMF)δ8.30(dd,2H),8.15(d,2H),7.95(d,2H),7.60-7.45(m,4H),6.90-7.05(m,3H),6.75-6.60(m,3H).
Synthesis example 6: synthesis of Compound C693
1. Synthesis of intermediate 1
5-Chlorobenzo [ b ]]Thiophene (6.0 g,36.0 mmol) was placed in a 100mL Schlenk flask containing 20mL chloroform and 20mL acetic acid mixed solvent, and then 30mL chloroform solution containing NBS (8.0 g,45.0 mmol) was slowly added to the system, and the reaction was quenched by adding 10mL acetone after reacting at room temperature for 12 h. After the solvent was removed in vacuo, the mixture was washed 3 times with 40mL of dichloromethane solution and then with saturated aqueous sodium chloride, the organic phase was separated, and dried over anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by column chromatography on silica gel (eluent: dichloromethane) gave 7.3g of a white solid in 96% yield.
2. Synthesis of intermediate 2:
intermediate 1 (2.9 g,11.7 mmol), pd (dppf) Cl 2 (840mg,8mol％)，B 2 pin 2 (3.3 g,13.4 mmol) KOAc (3.3 g,330 mol) was placed in a 50mL Shi Laike bottle and the system was evacuated to replace nitrogen 3 times. The system was reacted at 100℃for 4 hours after 10mL of 1, 4-dioxane solution was added under a nitrogen atmosphere, 20mL of DCM was added to the system, the above mixture was washed 3 times with saturated aqueous sodium chloride solution, the organic phase was separated, and the mixture was washed with anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by column chromatography on silica gel (eluent: petroleum ether/ethyl acetate=15/1) gave 2.3g of a white solid with a yield of 56%.
3. Synthesis of intermediate 3:
intermediate 2 (2.0 g,6.8 mmol), 2- (3-bromophenyl) pyridine (1.33 g,5.67 mmol), pd (PPh 3 ) 4 (650mg,7mol％)，K 2 CO 3 (1.58 mg,11.4 mol) was placed in a 50mL Shi Laike bottle, and the system was evacuated to replace nitrogen 3 times. The system was reacted at 100℃for 4 hours after adding a mixed solution of 20mL of 1, 4-dioxane and 4mL of water under a nitrogen ball atmosphere, after which 20mL of DCM was added to the system, the above mixed solution was washed 3 times with a saturated aqueous sodium chloride solution, the organic phase was separated, and the mixture was washed with anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by column chromatography on silica gel (eluent: petroleum ether/ethyl acetate=10/1) gave 2.8g of a white solid in 78% yield.
4. Synthesis of intermediate 4:
/>
intermediate 3 (400.0 mg,0.9 mmol), pd (dba) 2 (10mg,10mol％)，Xphos(15mg,20mol％)，B 2 pin 2 (300.0 mg,1.2 mmol) KOAc (180 mg,1.3 mol) was placed in a 50mL Shi Laike bottle and the system was evacuated to displace nitrogen 3 times. The system was reacted at 100℃for 12 hours after 5mL of 1, 4-dioxane solution was added under nitrogen atmosphere, 20mL of DCM was added to the system, the above mixture was washed 3 times with saturated aqueous sodium chloride solution, the organic phase was separated, and the mixture was washed with anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by column chromatography on silica gel (eluent: petroleum ether/ethyl acetate=10/1) gave 400mg of white solid in 86% yield.
5. Synthesis of intermediate 5
Intermediate 4 (413 mg,1.0 mmol), 2-bromo-4- (2, 4, 6-trimethylphenyl) pyridine (300 mg,1.2 mmol),Pd(PPh 3 ) 4 (80mg,7mol％)，K 2 CO 3 (400.0 mg,3.1 mol) was placed in a 50mL Shi Laike bottle, and the system was evacuated to replace nitrogen 3 times. The system was reacted at 100℃for 4 hours after adding a mixed solution of 20mL of 1, 4-dioxane and 4mL of water under a nitrogen ball atmosphere, after which 20mL of DCM was added to the system, the above mixed solution was washed 3 times with a saturated aqueous sodium chloride solution, the organic phase was separated, and the mixture was washed with anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by column chromatography on silica gel (eluent: petroleum ether/ethyl acetate=8/1) gave 600mg of white solid in 74% yield.
6. Synthesis of C693
Intermediate 5 (50 mg,0.12 mmol), K 2 PtCl 4 (43 mg,0.13 mmol) was placed in a 50mL Shi Laike bottle, and the system was evacuated to replace nitrogen 3 times. The system was reacted at 125℃for 24h after adding 10mL of an oxygen-scavenging acetic acid solution under nitrogen sphere atmosphere, followed by spin-removal of the acetic acid solvent in vacuo, and finally purification by silica gel column chromatography (eluent: dichloromethane) to give 20mg of a reddish brown solid with a yield of 40%. 1 H NMR(400MHz,CDCl 3 )δ9.30(dd,1H),9.10(dd,1H),8.35(d,1H),7.26-8.25(m,10H),7.04(s,2H),2.4(s,3H),2.14(s,6H).
Synthesis example 7: synthesis of Compound C1
1. Synthesis of intermediate 1
5-Chlorobenzo [ b ]]Thiophene (6.0 g,36.0 mmol) was placed in a 100mL Schlenk flask containing 20mL chloroform and 20mL acetic acid mixed solvent, and then 30mL chloroform solution containing NBS (8.0 g,45.0 mmol) was slowly added to the system, and the reaction was quenched by adding 10mL acetone after reacting at room temperature for 12 h. After spin-drying the solvent under vacuum, the solvent was dissolved in 40mL of methylene chloride and the solution was washed with saturated aqueous sodium chlorideThe mixture was 3 times, the organic phase was separated and washed with anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by silica gel column chromatography (eluent: dichloromethane) gave 7.3 as a white solid in 96% yield.
2. Synthesis of intermediate 2
Intermediate 1 (2.9 g,11.7 mmol), pd (dppf) Cl 2 (840mg,8mol％)，B 2 pin 2 (3.3 g,13.4 mmol) KOAc (3.3 g,330 mol) was placed in a 50mL Shi Laike bottle and the system was evacuated to replace nitrogen 3 times. The system was reacted at 100℃for 4 hours after 10mL of 1, 4-dioxane solution was added under a nitrogen atmosphere, 20mL of DCM was added to the system, the above mixture was washed 3 times with saturated aqueous sodium chloride solution, the organic phase was separated, and the mixture was washed with anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by column chromatography on silica gel (eluent: petroleum ether/ethyl acetate=15/1) gave 2.3g of a white solid with a yield of 56%.
3. Synthesis of intermediate 3
Intermediate 2 (2.0 g,6.8 mmol), 2-bromo-9- (2-pyridine) -9H-carbazole (1.8 g,5.67 mmol), pd (PPh 3 ) 4 (650mg,7mol％)，K 2 CO 3 (1.58 mg,11.4 mol) was placed in a 50mL Shi Laike bottle, and the system was evacuated to replace nitrogen 3 times. The system was reacted at 100℃for 4 hours after adding a mixed solution of 20mL of 1, 4-dioxane and 4mL of water under a nitrogen ball atmosphere, after which 20mL of DCM was added to the system, the above mixed solution was washed 3 times with a saturated aqueous sodium chloride solution, the organic phase was separated, and the mixture was washed with anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by column chromatography on silica gel (eluent: petroleum ether/ethyl acetate=10/1) gave 3.4g of a white solid in 78% yield.
4. Synthesis of intermediate 4
Intermediate 3 (560.0 mg,0.9 mmol), pd (dba) 2 (10mg,10mol％)，Xphos(15mg,20mol％)，B 2 pin 2 (300.0 mg,1.2 mmol) KOAc (180 mg,1.3 mol) was placed in a 50mL Shi Laike bottle and the system was evacuated to displace nitrogen 3 times. The system was reacted at 100℃for 12 hours after 5mL of 1, 4-dioxane solution was added under nitrogen atmosphere, 20mL of DCM was added to the system, the above mixture was washed 3 times with saturated aqueous sodium chloride solution, the organic phase was separated, and the mixture was washed with anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by column chromatography on silica gel (eluent: petroleum ether/ethyl acetate=10/1) gave 500mg of white solid in 76% yield.
5. Synthesis of intermediate 5
Intermediate 4 (503 mg,1.0 mmol), 1-bromoisoquinoline (300 mg,1.2 mmol), pd (PPh 3 ) 4 (80mg,7mol％)，K 2 CO 3 (400.0 mg,3.1 mol) was placed in a 50mL Shi Laike bottle, and the system was evacuated to replace nitrogen 3 times. The system was reacted at 100℃for 4 hours after adding a mixed solution of 20mL of 1, 4-dioxane and 4mL of water under a nitrogen ball atmosphere, after which 20mL of DCM was added to the system, the above mixed solution was washed 3 times with a saturated aqueous sodium chloride solution, the organic phase was separated, and the mixture was washed with anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by column chromatography on silica gel (eluent: petroleum ether/ethyl acetate=8/1) gave 640mg of white solid in 54% yield.
6. Synthesis of C1
Intermediate 5 (50 mg,0.12 mmol), K 2 PtCl 4 (37 mg,0.13 mmol) was placed in a 50mL Shi Laike bottle and the system was evacuated to displace nitrogen 3 times. The system was reacted at 125℃for 24h after adding 10mL of an oxygen-scavenging acetic acid solution under nitrogen sphere atmosphere, followed by spin-removal of the acetic acid solvent in vacuo, and finally purification by silica gel column chromatography (eluent: dichloromethane) to give 29mg of a reddish brown solid in 40% yield. 1 H NMR(400MHz,CDCl 3 )δ8.93(dd,1H),8.69(dd,1H),8.45(d,1H),8.29(s,1H)8.05(d,2H),7.91(dd,1H),7.85(dd,1H),7.73(d,1H),7.61(dd,1H),7.50(dd,1H),7.43(d,1H),7.31(dd,2H),7.25(dd,1H),7.18(d,2H),7.10-7.00(m,2H).
Synthesis example 8: synthesis of Compound C7
1. Synthesis of intermediate 1
5-Chlorobenzo [ b ]]Thiophene (6.0 g,36.0 mmol) was placed in a 100mL Schlenk flask containing 20mL chloroform and 20mL acetic acid mixed solvent, and then 30mL chloroform solution containing NBS (8.0 g,45.0 mmol) was slowly added to the system, and the reaction was quenched by adding 10mL acetone after reacting at room temperature for 12 h. After the solvent was removed in vacuo, the mixture was washed 3 times with 40mL of dichloromethane solution and then with saturated aqueous sodium chloride, the organic phase was separated, and dried over anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by silica gel column chromatography (eluent: dichloromethane) gave 7.3 as a white solid in 96% yield.
2. Synthesis of intermediate 2
Intermediate 1 (2.9 g,11.7 mmol), pd (dppf) Cl 2 (840mg,8mol％)，B 2 pin 2 (3.3 g,13.4 mmol) KOAc (3.3 g,330 mol) was placed in a 50mL Shi Laike bottle and the system was evacuated to replace nitrogen 3 times. The system is reacted for 4 hours at 100 ℃ after 10mL of 1, 4-dioxane solution is added under the atmosphere of nitrogen ball, and the reaction is backward20mL of DCM was added to the system, the above mixture was washed 3 times with saturated aqueous sodium chloride, the organic phase was separated, and the mixture was washed with anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by column chromatography on silica gel (eluent: petroleum ether/ethyl acetate=15/1) gave 2.3g of a white solid with a yield of 56%.
3. Synthesis of intermediate 3
/>
Intermediate 2 (2.0 g,6.8 mmol), 2-bromo-9- (3-tert-butyl-2-pyridinyl) -9H-carbazole (1.9 g,5.67 mmol), pd (PPh 3 ) 4 (650mg,7mol％)，K 2 CO 3 (1.58 mg,11.4 mol) was placed in a 50mL Shi Laike bottle, and the system was evacuated to replace nitrogen 3 times. The system was reacted at 100℃for 4 hours after adding a mixed solution of 20mL of 1, 4-dioxane and 4mL of water under a nitrogen ball atmosphere, after which 20mL of DCM was added to the system, the above mixed solution was washed 3 times with a saturated aqueous sodium chloride solution, the organic phase was separated, and the mixture was washed with anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by column chromatography on silica gel (eluent: petroleum ether/ethyl acetate=10/1) gave 3.7g of a white solid with a yield of 78%.
4. Synthesis of intermediate 4
Intermediate 3 (580.0 mg,0.9 mmol), pd (dba) 2 (10mg,10mol％)，Xphos(15mg,20mol％)，B 2 pin 2 (300.0 mg,1.2 mmol) KOAc (180 mg,1.3 mol) was placed in a 50mL Shi Laike bottle and the system was evacuated to displace nitrogen 3 times. The system was reacted at 100℃for 12 hours after 5mL of 1, 4-dioxane solution was added under nitrogen atmosphere, 20mL of DCM was added to the system, the above mixture was washed 3 times with saturated aqueous sodium chloride solution, the organic phase was separated, and the mixture was washed with anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, subjecting the mixture to silica gel column chromatography (eluent: petroleum ether/ethyl acetate)=10/1) to give 550mg of a white solid with a yield of 78%.
5. Synthesis of intermediate 5
Intermediate 4 (530 mg,1.0 mmol), 1-bromo-6- (2-methylbutyl) isoquinoline (390 mg,1.2 mmol), pd (PPh 3 ) 4 (80mg,7mol％)，K 2 CO 3 (400.0 mg,3.1 mol) was placed in a 50mL Shi Laike bottle, and the system was evacuated to replace nitrogen 3 times. The system was reacted at 100℃for 4 hours after adding a mixed solution of 20mL of 1, 4-dioxane and 4mL of water under a nitrogen ball atmosphere, after which 20mL of DCM was added to the system, the above mixed solution was washed 3 times with a saturated aqueous sodium chloride solution, the organic phase was separated, and the mixture was washed with anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by column chromatography on silica gel (eluent: petroleum ether/ethyl acetate=8/1) gave 720mg of white solid in 69% yield.
6. Synthesis of C7
Intermediate 5 (50 mg,0.12 mmol), K 2 PtCl 4 (33 mg,0.13 mmol) was placed in a 50mL Shi Laike bottle, and the system was evacuated to replace nitrogen 3 times. The system was reacted at 125℃for 24h after adding 10mL of an oxygen-scavenging acetic acid solution under nitrogen sphere atmosphere, followed by spin-removal of the acetic acid solvent in vacuo, and finally purification by silica gel column chromatography (eluent: dichloromethane) to give 29mg of a reddish brown solid in 62% yield. 1 H NMR(400MHz,CDCl 3 )δ9.01(dd,1H),8.80(dd,1H),8.43(d,1H),8.05(d,2H),7.91(dd,1H),7.85(dd,1H),7.73(d,1H),7.61(dd,1H),7.50(dd,1H),7.43(d,1H),7.31(dd,2H),7.25(dd,1H),7.18(d,2H),7.10-7.00(m,2H),2.78(m,1H),2.54(m,1H),1.85(m,1H),1.43(m,2H),1.43(s,9H),0.98(d,3H),0.93(t,3H).
Synthesis example 9: synthesis of Compound C188
1. Synthesis of intermediate 1
4-chloroindole (5 g,33.12 mmol), iodobenzene (10 g,50.13 mmol), cu powder (500 mg) were placed in a 50mL Shi Laike bottle and the system was evacuated to replace nitrogen 3 times. The system was reacted at 105℃for 12h with the addition of 100mL of deoxygenated DMF solution under nitrogen atmosphere, followed by spin-removal of the solvent in vacuo and finally purification by silica gel column chromatography (eluent: dichloromethane) to give 7g of white solid with a yield of 49%.
2. Synthesis of intermediate 2
Intermediate 1 (6.0 g,12.0 mmol) was placed in a 100mL Schlenk flask containing 20mL chloroform and 20mL acetic acid mixed solvent, and then 30mL chloroform solution containing NBS (8.0 g,45.0 mmol) was slowly added to the system, and the reaction was quenched by adding 10mL acetone after reacting at room temperature for 12 h. After the solvent was removed in vacuo, the mixture was washed 3 times with 40mL of dichloromethane solution and then with saturated aqueous sodium chloride, the organic phase was separated, and dried over anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by silica gel column chromatography (eluent: dichloromethane) gave 6.8 of a white solid in 92% yield.
3. Synthesis of intermediate 3
Intermediate 2 (2.9 g,7.7 mmol), pd (dppf) Cl 2 (840mg,8mol％)，B 2 pin 2 (3.3 g,13.4 mmol) KOAc (3.3 g,330 mol) was placed in a 50mL Shi Laike bottle and the system was evacuated to replace nitrogen 3 times. The system was reacted at 100℃for 4 hours after 10mL of 1, 4-dioxane solution was added under a nitrogen balloon atmosphere, and then 20mL of DCM was added to the system, and the above was washed with a saturated aqueous sodium chloride solutionThe mixture was 3 times, the organic phase was separated and washed with anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by column chromatography on silica gel (eluent: petroleum ether/ethyl acetate=15/1) gave 0.9g of a white solid with a yield of 30%.
4. Synthesis of intermediate 4
Intermediate 3 (2.0 g,4.3 mmol), 2-bromo-9- (2-pyridine) -9H-carbazole (2.3 g,5.9 mmol), pd (PPh 3 ) 4 (650mg,7mol％)，K 2 CO 3 (1.58 mg,11.4 mol) was placed in a 50mL Shi Laike bottle, and the system was evacuated to replace nitrogen 3 times. The system was reacted at 100℃for 4 hours after adding a mixed solution of 20mL of 1, 4-dioxane and 4mL of water under a nitrogen ball atmosphere, after which 20mL of DCM was added to the system, the above mixed solution was washed 3 times with a saturated aqueous sodium chloride solution, the organic phase was separated, and the mixture was washed with anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by column chromatography on silica gel (eluent: petroleum ether/ethyl acetate=10/1) gave 2.9g of a white solid with a yield of 66%.
5. Synthesis of intermediate 5
Intermediate 4 (580.0 mg,0.9 mmol), pd (dba) 2 (10mg,10mol％)，Xphos(15mg,20mol％)，B 2 pin 2 (300.0 mg,1.2 mmol) KOAc (180 mg,1.3 mol) was placed in a 50mL Shi Laike bottle and the system was evacuated to displace nitrogen 3 times. The system was reacted at 100℃for 12 hours after 5mL of 1, 4-dioxane solution was added under nitrogen atmosphere, 20mL of DCM was added to the system, the above mixture was washed 3 times with saturated aqueous sodium chloride solution, the organic phase was separated, and the mixture was washed with anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by column chromatography on silica gel (eluent: petroleum ether/ethyl acetate=10/1) gave 550mg of white solid in 78% yield.
6. Synthesis of intermediate 6
Intermediate 5 (433 mg,1.0 mmol), 1-bromoisoquinoline (230 mg,1.2 mmol), pd (PPh 3 ) 4 (80mg,7mol％)，K 2 CO 3 (400.0 mg,3.1 mol) was placed in a 50mL Shi Laike bottle, and the system was evacuated to replace nitrogen 3 times. The system was reacted at 100℃for 4 hours after adding a mixed solution of 20mL of 1, 4-dioxane and 4mL of water under a nitrogen ball atmosphere, after which 20mL of DCM was added to the system, the above mixed solution was washed 3 times with a saturated aqueous sodium chloride solution, the organic phase was separated, and the mixture was washed with anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by column chromatography on silica gel (eluent: petroleum ether/ethyl acetate=8/1) gave 520mg of white solid in 76% yield.
7. Synthesis of C188
Intermediate 6 (50 mg,0.12 mmol), K 2 PtCl 4 (43 mg,0.13 mmol) was placed in a 50mL Shi Laike bottle, and the system was evacuated to replace nitrogen 3 times. The system was reacted at 125℃for 24h after adding 10mL of an oxygen-scavenging acetic acid solution under nitrogen sphere atmosphere, followed by spin-removal of the acetic acid solvent in vacuo, and finally purification by silica gel column chromatography (eluent: dichloromethane) to give 42mg of a reddish brown solid with a yield of 72%. 1 H NMR(400MHz,CDCl 3 )δ8.93(dd,1H),8.69(dd,1H),8.45(d,1H),8.29(s,1H)8.05(d,2H),7.91(dd,1H),7.85(dd,1H),7.73(d,1H),7.64(m,2H),7.61(dd,1H),7.58(m,1H),7.50(m,3H),7.43(d,1H),7.31(dd,2H),7.25(dd,1H),7.18(d,2H),7.10-7.00(m,2H).
Synthesis example 10: synthesis of Compound C109
1. Synthesis of intermediate 1
4-chloroindole (5 g,33.12 mmol), iodobenzene (10 g,50.13 mmol), cu powder (500 mg) were placed in a 50mL Shi Laike bottle and the system was evacuated to replace nitrogen 3 times. The system was reacted at 105℃for 12h with the addition of 100mL of deoxygenated DMF solution under nitrogen atmosphere, followed by spin-removal of the solvent in vacuo and finally purification by silica gel column chromatography (eluent: dichloromethane) to give 7g of white solid with a yield of 49%.
2. Synthesis of intermediate 2
Intermediate 1 (6.0 g,12.0 mmol) was placed in a 100mL Schlenk flask containing 20mL chloroform and 20mL acetic acid mixed solvent, and then 30mL chloroform solution containing NBS (8.0 g,45.0 mmol) was slowly added to the system, and the reaction was quenched by adding 10mL acetone after reacting at room temperature for 12 h. After the solvent was removed in vacuo, the mixture was washed 3 times with 40mL of dichloromethane solution and then with saturated aqueous sodium chloride, the organic phase was separated, and dried over anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by silica gel column chromatography (eluent: dichloromethane) gave 6.8 of a white solid in 92% yield.
3. Synthesis of intermediate 3
/>
Intermediate 2 (2.9 g,7.7 mmol), pd (dppf) Cl 2 (840mg,8mol％)，B 2 pin 2 (3.3 g,13.4 mmol) KOAc (3.3 g,330 mol) was placed in a 50mL Shi Laike bottle and the system was evacuated to replace nitrogen 3 times. The system was reacted at 100℃for 4 hours after 10mL of 1, 4-dioxane solution was added under a nitrogen atmosphere, 20mL of DCM was added to the system, the above mixture was washed 3 times with saturated aqueous sodium chloride solution, the organic phase was separated, and the mixture was washed with anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, the mixture is subjected to silica gel column chromatography (eluting solution): petroleum ether/ethyl acetate=15/1) to yield 0.9g of white solid with a yield of 30%.
4. Synthesis of intermediate 4
Intermediate 3 (2.0 g,8.8 mmol), 2- (3-bromophenyl) pyridine (2.0 g,9.0 mmol), pd (PPh 3 ) 4 (650mg,7mol％)，K 2 CO 3 (1.58 mg,11.4 mol) was placed in a 50mL Shi Laike bottle, and the system was evacuated to replace nitrogen 3 times. The system was reacted at 100℃for 4 hours after adding a mixed solution of 20mL of 1, 4-dioxane and 4mL of water under a nitrogen ball atmosphere, after which 20mL of DCM was added to the system, the above mixed solution was washed 3 times with a saturated aqueous sodium chloride solution, the organic phase was separated, and the mixture was washed with anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by column chromatography on silica gel (eluent: petroleum ether/ethyl acetate=10/1) gave 2.5g of a white solid in 76% yield.
5. Synthesis of intermediate 5
Intermediate 4 (580.0 mg,2.3 mmol), pd (dba) 2 (10mg,10mol％)，Xphos(15mg,20mol％)，B 2 pin 2 (900.0 mg,3.6 mmol) KOAc (180 mg,1.3 mol) was placed in a 50mL Shi Laike bottle and the system was evacuated to replace nitrogen 3 times. The system was reacted at 100℃for 12 hours after 5mL of 1, 4-dioxane solution was added under nitrogen atmosphere, 20mL of DCM was added to the system, the above mixture was washed 3 times with saturated aqueous sodium chloride solution, the organic phase was separated, and the mixture was washed with anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by column chromatography on silica gel (eluent: petroleum ether/ethyl acetate=10/1) gave 590mg of white solid in 48% yield.
6. Synthesis of intermediate 6
/>
Intermediate 5 (284 mg,2.0 mmol), 1-bromoisoquinoline (450 mg,2.3 mmol), pd (PPh 3 ) 4 (80mg,7mol％)，K 2 CO 3 (800.0 mg,6.2 mol) was placed in a 50mL Shi Laike bottle, and the system was evacuated to replace nitrogen 3 times. The system was reacted at 100℃for 4 hours after adding a mixed solution of 20mL of 1, 4-dioxane and 4mL of water under a nitrogen ball atmosphere, after which 20mL of DCM was added to the system, the above mixed solution was washed 3 times with a saturated aqueous sodium chloride solution, the organic phase was separated, and the mixture was washed with anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by column chromatography on silica gel (eluent: petroleum ether/ethyl acetate=8/1) gave 820mg of white solid in 74% yield.
7. Synthesis of C109
Intermediate 6 (50 mg,0.12 mmol), K 2 PtCl 4 (43 mg,0.13 mmol) was placed in a 50mL Shi Laike bottle, and the system was evacuated to replace nitrogen 3 times. The system was reacted at 125℃for 24h after adding 10mL of an oxygen-scavenging acetic acid solution under nitrogen sphere atmosphere, followed by spin-removal of the acetic acid solvent in vacuo, and finally purification by silica gel column chromatography (eluent: dichloromethane) to give 42mg of a reddish brown solid with a yield of 72%. 1 H NMR(400MHz,CDCl 3 )δ8.78(dd,1H),8.58(dd,1H),8.56(d,1H),8.26(dd,1H),7.90(dd,1H),7.85(dd,1H),7.73(d,1H),7.64(m,2H),7.61(dd,1H),7.58(m,1H),7.50(m,1H),7.43(d,1H),7.31(dd,2H),7.25(dd,1H),7.18(d,2H),7.10-7.00(m,3H).
Synthesis example 11: synthesis of Compound C197
1. Synthesis of intermediate 1
1-bromoisoquinoline (206 mg,1.0 mmol), 4-methoxyphenylboronic acid (160 mg,1.1 m)mol)，Pd(PPh 3 ) 4 (80mg,7mol％)，K 2 CO 3 (800.0 mg,6.2 mol) was placed in a 50mL Shi Laike bottle, and the system was evacuated to replace nitrogen 3 times. The system was reacted at 100℃for 4 hours after adding a mixed solution of 20mL of 1, 4-dioxane and 4mL of water under a nitrogen ball atmosphere, after which 20mL of DCM was added to the system, the above mixed solution was washed 3 times with a saturated aqueous sodium chloride solution, the organic phase was separated, and the mixture was washed with anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by column chromatography on silica gel (eluent: petroleum ether/ethyl acetate=8/1) gave 200mg of white solid in 94% yield.
2. Synthesis of intermediate 2
Intermediate 1 (50 mg,0.21 mmol) was placed in a 50mL Shi Laike bottle and the system was evacuated to displace nitrogen 3 times. 1mL BBr is added into the system under the atmosphere of nitrogen balls 3 The solution was reacted with 5mL of methylene chloride at 0℃for 12 hours, followed by spin-drying of the acetic acid solvent in vacuo, and finally purification by silica gel column chromatography (eluent: methylene chloride) to give 42mg of a white solid in 92% yield.
3. Synthesis of intermediate 3
2-bromo-9- (2-pyridine) -9H-carbazole (700 mg,2.21 mmol) was placed in a 50mL Shi Laike bottle, and the system was evacuated to replace nitrogen 3 times. 5mL of anhydrous THF was added. The system was slowly added with 1mL of n-butyllithium (2.5M) solution at-78deg.C under nitrogen sphere, and after 1h reaction at-78deg.C, 3mL of anhydrous DMAc solvent was added. After 1h of reaction, the solvent was removed by vacuum spin and finally purified by column chromatography on silica gel (eluent: petroleum ether/ethyl acetate=9/1) to give 550mg of yellow solid in 78% yield.
4. Synthesis of intermediate 4
Intermediate 3 (700 mg,2.44 mmol) was placed in a 50mL Shi Laike bottle and the system was evacuated to displace nitrogen 3 times. 5mL of anhydrous THF was added. The system was slowly added with 0.1mL of liquid bromine at 0deg.C under nitrogen sphere atmosphere, and after 1h reaction at 0deg.C, 3mL of saturated sodium thiosulfate solvent was added. After 1h of reaction, the solvent was removed by vacuum spin and finally purified by column chromatography on silica gel (eluent: petroleum ether/ethyl acetate=9/1) to give 600mg of yellow solid in 60% yield.
5. Synthesis of intermediate 5
Intermediate 2 (450 mg,2.0 mmol), intermediate 4 (750 mg,2.3 mmol), naOH (200.0 mg,5.0 mol) were placed in a 50mL Shi Laike bottle and the system was evacuated to displace nitrogen 3 times. The system was reacted at 100℃for 1 hour after adding 20mL of methanol solution under nitrogen sphere atmosphere, and the solvent was dried by spin-drying. Finally, purification by column chromatography on silica gel (eluent: petroleum ether/ethyl acetate=7/1) gave 900mg of white solid in 92% yield.
6. Synthesis of C197
Intermediate 5 (500 mg,1.0 mmol) TiCl 4 (43 mg) was placed in a 50mL Shi Laike bottle, and the system was evacuated to replace nitrogen 3 times. The system was reacted at 65℃for 4h after adding 10mL of an oxygen-scavenging dichloromethane solution under nitrogen sphere atmosphere, followed by spin-removal of the acetic acid solvent in vacuo, and finally purification by silica gel column chromatography (eluent: dichloromethane) to give 300mg of a reddish brown solid with a yield of 52%.
The product obtained above (100 mg,0.6 mmol), K 2 PtCl 4 (85 mg,0.13 mmol) was placed in a 50mL Shi Laike bottle and the system was evacuated to displace nitrogen 3 times. After the system is added with 10mL of deoxidized acetic acid solution under the atmosphere of nitrogen ballsThe mixture was reacted at 125℃for 24 hours, then the acetic acid solvent was removed by vacuum spin-drying, and finally purified by silica gel column chromatography (eluent: dichloromethane) to give 133mg of a reddish brown solid with a yield of 64%. 1 H NMR(400MHz,CDCl 3 )δ8.99(dd,1H),8.72(dd,1H),8.54(d,1H),8.29(s,1H),8.03(d,2H),7.99(dd,1H),7.87(dd,1H),7.75(d,1H),7.63(dd,1H),7.50(dd,1H),7.43(d,1H),7.31(dd,2H),7.25(dd,1H),7.18(d,2H),7.10-7.00(m,2H).
Synthesis example 12: synthesis of Compound C692
1. Synthesis of intermediate 1
1, 5-bis (4-bromophenyl) -3-pentanone (4 g,10.0 mmol), trimethylsulfoxide iodide (4.5 g,20.0 mmol), potassium t-butoxide (2.5 g,20.0 mmol) were placed in a 50mL Shi Laike bottle, and the system was evacuated to displace nitrogen 3 times. The system was reacted at room temperature for 24 hours after adding 20mL of DMSO solution under nitrogen sphere atmosphere, after which 20mL of DCM was added to the system, the above mixture was washed 3 times with saturated aqueous sodium chloride solution, the organic phase was separated, and the mixture was washed with anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by column chromatography on silica gel (eluent: petroleum ether/ethyl acetate=20/1) gave 3g of a white solid in 75% yield.
2. Synthesis of intermediate 2
Intermediate 1 (2 g,5.21 mmol) was placed in a 50mL Shi Laike bottle and the system was evacuated to displace nitrogen 3 times. The system was charged with 1mL TiCl under nitrogen sphere atmosphere 4 The solution and 30mL of chlorobenzene are reacted for 48 hours at room temperature, the chlorobenzene solvent is removed in vacuum, and finally, the white solid is obtained by purifying by silica gel column chromatography (eluent: petroleum ether) with the yield of 34 percent.
3. Synthesis of intermediate 3
Intermediate 2 (300 mg,0.8 mmol) was placed in a 50mL Shi Laike bottle and the system was evacuated to displace nitrogen 3 times. 500mg of DDQ and 30mL of toluene solution are added into the system under the atmosphere of nitrogen balls, then the reaction is carried out for 48 hours at 125 ℃, the chlorobenzene solvent is removed in a rotary way under vacuum, and finally, 150mg of white solid is obtained through pulping and purification of methanol solution, and the yield is 45%.
4. Synthesis of intermediate 4
Intermediate 3 (100 mg,0.28 mmol), pd (dppf) Cl 2 (84mg,8mol％)，B 2 pin 2 (250 mg,1 mmol), KOAc (100 mg,1 mol) was placed in a 10mL Shi Laike bottle and the system was evacuated to displace nitrogen 3 times. The system was reacted at 100℃for 4 hours after 10mL of 1, 4-dioxane solution was added under a nitrogen atmosphere, 20mL of DCM was added to the system, the above mixture was washed 3 times with saturated aqueous sodium chloride solution, the organic phase was separated, and the mixture was washed with anhydrous magnesium sulfate (MgSO 4 ) Drying and spin-drying the solvent. Finally, purification by column chromatography on silica gel (eluent: petroleum ether/ethyl acetate=15/1) gave 70mg of white solid in 60% yield.
5. Synthesis of intermediate 5
Intermediate 4 (480 mg,1.0 mmol), 1-bromo-4-tert-butylpyridine (600 mg,2.8 mmol), pd (PPh 3 ) 4 (80mg,7mol％)，K 2 CO 3 (800.0 mg,6.2 mol) was placed in a 50mL Shi Laike bottle, and the system was evacuated to replace nitrogen 3 times. The system was reacted at 100℃for 4 hours after adding a mixed solution of 20mL of 1, 4-dioxane and 4mL of water under a nitrogen ball atmosphere, and then 20mL of DCM was added to the system, the above mixed solution was washed 3 times with a saturated aqueous sodium chloride solution, the organic phase was separated, and the mixture was washed with anhydrousMagnesium sulfate (MgSO) 4 ) Drying and spin-drying the solvent. Finally, purification by column chromatography on silica gel (eluent: petroleum ether/ethyl acetate=8/1) gave 300mg of white solid in 60% yield.
6. Synthesis of C692
Intermediate 5 (100 mg,0.2 mmol), K 2 PtCl 4 (91 mg,0.22 mmol) was placed in a 50mL Shi Laike bottle and the system was evacuated to displace nitrogen 3 times. The system was reacted at 125℃for 24h after adding 10mL of an oxygen-scavenging acetic acid solution under nitrogen sphere atmosphere, followed by spin-removal of the acetic acid solvent in vacuo, and finally purification by silica gel column chromatography (eluent: dichloromethane) to give 83mg of a reddish brown solid with a yield of 68%. 1 H NMR(400MHz,CDCl 3 )δ8.57(dd,2H),8.54(dd,2H),8.52(d,1H),8.28(s,2H),7.97(d,2H),7.84(dd,2H),7.05(dd,2H),1.32(s,18H).
The various chemicals in the above synthesis examples are all commercially available.
Hereinafter, the organic electroluminescent device comprising the organic compound according to the present invention will be described in more detail by way of specific examples.
Example 1
The organic electroluminescent device of this embodiment is a double-main-body structure, and the dye is C693, and the device structure is:
ITO/HATCN(5nm)/TAPC(30nm)/TCTA(10nm)/mCBP(5nm)/TAPC:POT2T:C693(48.5％:48.5％:3％,20nm)/POT2T(10nm)/TPBi(30nm)/Liq(2nm)/Al(100nm)
example 2
The organic electroluminescent device of this embodiment is a double-main structure, and the dye is C690, and the device structure is:
ITO/HATCN(5nm)/TAPC(30nm)/TCTA(10nm)/mCBP(5nm)/TAPC:POT2T:C690(48.5％:48.5％:3％,20nm)/POT2T(10nm)/TPBi(30nm)/Liq(2nm)/Al(100nm)
example 3
The organic electroluminescent device of this embodiment is a double-main-body structure, and the dye is C95, and the device structure is:
ITO/HATCN(5nm)/TAPC(30nm)/TCTA(10nm)/mCBP(5nm)/TAPC:POT2T:C95(48.5％:48.5％:3％,20nm)/POT2T(10nm)/TPBi(30nm)/Liq(2nm)/Al(100nm)
example 4
The organic electroluminescent device of this embodiment is a double-main-body structure, and the dye is C691, and the device structure is:
ITO/HATCN(5nm)/TAPC(30nm)/TCTA(10nm)/mCBP(5nm)/TAPC:POT2T:C691(48.5％:48.5％:3％,20nm)/POT2T(10nm)/TPBi(30nm)/Liq(2nm)/Al(100nm)
example 5
The organic electroluminescent device of this embodiment is a double-main-body structure, and the dye is C197, and the device structure is:
ITO/HATCN(5nm)/TAPC(30nm)/TCTA(10nm)/mCBP(5nm)/TAPC:POT2T:C197(48.5％:48.5％:3％,20nm)/POT2T(10nm)/TPBi(30nm)/Liq(2nm)/Al(100nm)
Example 6
The device structure of this example is substantially identical to that of example 1, with the only difference being the proportions of host material and dye. The composition of the luminescent layer of the device of this example was TAPC:POTO2T:C690 (47%: 47%:6%,20 nm)
Example 7
The device structure of this example is substantially identical to that of example 1, with the only difference being the proportions of host material and dye. The composition of the luminescent layer of the device of this example was TAPC:POTO2T:C690 (44%: 44%:12%,20 nm)
Comparative example 1-comparative example 5
The device structures of comparative examples 1-5 were substantially identical to example 1, except that the dye of example 1 was replaced with another dye.
Wherein the dye of comparative example 1 is D1, the dye of comparative example 2 is D2, the dye of comparative example 3 is D3, the dye of comparative example 4 is D4, and the dye of comparative example 5 is D5.
The electroluminescence spectra of the devices of the examples and comparative examples were characterized, and the maximum emission wavelength λmax and the full width at half maximum FWHM of the devices are shown in table 1. Fig. 1 is an electroluminescence spectrum of the organic electroluminescent device of example 1, fig. 2 is an electroluminescence spectrum of the organic electroluminescent device of example 2, fig. 3 is an electroluminescence spectrum of the organic electroluminescent device of example 3, fig. 4 is an electroluminescence spectrum of the organic electroluminescent device of example 4, and fig. 5 is an electroluminescence spectrum of the organic electroluminescent device of example 5. The maximum emission wavelength of the device of the various embodiments can be seen from fig. 1-5.
TABLE 1
As can be seen from table 1: the half-width FWHM of examples 1 to 7 was significantly reduced compared to comparative examples, and thus the compound of the present invention was able to effectively improve the color purity of the device.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the embodiments of the present application, and are not limited thereto; although embodiments of the present application have been described in detail with reference to the foregoing embodiments, it will be appreciated by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the essence of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present application.

Claims (25)

1. A compound characterized in that the compound has a structure represented by formula 1,
in the formula 1, M represents Pd (II) or Pt (II);
Q 1 、Q 2 、Q 3 q and 4 independently selected from O, S or a single bond;
Ar 1 selected from substituted or unsubstituted first cyclic groups, ar 2 A second cyclic group selected from substituted or unsubstituted; the first cyclic group comprises N substituted or unsubstituted cyclic groups, the second cyclic group comprises M substituted or unsubstituted cyclic groups, N is more than or equal to 1, and M is more than or equal to 1; (n+m) cyclic groups are each independently selected from 3 to 50 membered substituted or unsubstituted cyclic groups;
When N is more than 1, N cyclic groups are connected in a pair-by-pair fused mode or connected in a single bond mode; when M is more than 1, M cyclic groups are connected in a pair-by-pair fused mode or connected in a single bond mode;
L 1 l and 2 independently selected from substituted or unsubstituted cyclic groups, or L 1 L and 2 one of which is a substituted or unsubstituted cyclic group and the other is absent.
2. The compound according to claim 1, wherein the compound has a structure represented by formula 2,
ar in formula 2 3 Selected from substituted or unsubstituted third cyclic groups, ar 4 A fourth cyclic group selected from substituted or unsubstituted; the third cyclic group comprises N substituted or unsubstituted cyclic groups, and the fourth cyclic group comprises M substituted or unsubstituted cyclic groups, N is more than or equal to 1 and less than N, and M is more than or equal to 1 and less than M; (n+m) cyclic groups are each independently selected from 3-50 membered substituted or unsubstituted cyclic groups;
when n is more than 1, n cyclic groups are connected in a pair-by-pair fused mode or connected in a single bond mode; when m is more than 1, m cyclic groups are connected in a condensed mode or connected in a single bond mode;
a 1 ～a 6 b 1 ～b 6 Each independently selected from C or N;
R 1 、R 2 independently selected from hydrogen, deuterium, halogen, hydroxy, thiol, nitro, cyanoA group, isocyano, sulfone, hydroxylamine, carboxyl, carbonyl, or one of the following substituted or unsubstituted groups: C6-C48 monocyclic aromatic hydrocarbon or polycyclic aromatic hydrocarbon, C3-C48 monocyclic heteroaromatic hydrocarbon or polycyclic heteroaromatic hydrocarbon, C1-C36 alkyl, C2-C36 heterocycloalkyl, C2-C36 alkenyl, C2-C36 alkynyl, amino, C1-C36 alkoxy, C1-C36 alkylthio, amido, silicon base and boron base.
3. A compound according to claim 1 or 2, wherein the compound has a structure represented by formula 3,
in formula 3, ya, yb, yc and Yd are each independently selected from C or N;
Y 1 、Y 2 independently selected from N, P, as, B, al, bi, -CR 3 ,-SiR 3 ,-GeR 3 、-Bi＝O、-PR 3 R 4 、-P＝O、-As＝O、-AsR 3 R 4 A single bond or absence;
Y 3 、Y 4 、Y 5 y is as follows 6 Independently selected from O, S, se, -CR 3 R 4 ,-C＝O、-SiR 3 R 4 ,-GeR 3 R 4 、-NR 3 、-BR 3 、-AlR 3 、-PR 3 、-AsR 3 ,-S＝O,-SO 2 ,-Se＝O,-SeO 2 、-BiR 3 A single bond or absence;
A 1 a is a 2 Independently selected from C5-C30 cyclic groups;
A 3 a is a 4 Independently selected from C5-C30 cyclic groups or are absent;
R 1 、R 2 、R 3 r is as follows 4 Independently selected from hydrogen, deuterium, halogen, hydroxy, thiol, nitro, cyano, isocyano, sulfone, hydroxylamine, carboxyl, carbonyl, or one of the following substituted or unsubstituted groups: C6-C48 monocyclic ringAromatic hydrocarbon or polycyclic aromatic hydrocarbon, C3-C48 monocyclic heteroaromatic hydrocarbon or polycyclic heteroaromatic hydrocarbon, C1-C36 alkyl, C2-C36 heterocycloalkyl, C2-C36 alkenyl, C2-C36 alkynyl, amino, C1-C36 alkoxy, C1-C36 alkylthio, amido, silicon base and boron base.
4. A compound according to claim 3, wherein the compound has a structure shown as 1-1, 1-2, 1-3 or 1-4,
wherein,,
ye, yf, yg and Yh are each independently selected from C or N;
X、X 1 X is as follows 2 Independently selected from O, S, se, -CR 3 R 4 ,C＝O、-SiR 3 R 4 、-GeR 3 R 4 、-NR 3 、-BR 3 、-AlR 3 、-PR 3 、-AsR 3 、-S＝O、-SO 2 、-Se＝O、-SeO 2 、-BiR 3 。
5. A compound according to claim 4, wherein the compound has a structure shown in any one of the following 2-1 to 2-16,
wherein Yi, yj, yk, yl, ym, yn, yo, yp, yq and Yr are each independently selected from C or N;
A. b, C, E and F are each independently selected from C, N, si, O, S, ge, P, as, se, B, al, -BiCR 5 、-SiR 5 、-GeR 5 、-NR 5 、-P＝O、-As＝O、-BR 5 、-AlR 5 、-Bi＝O、-CR 5 R 6 、-C＝O、-SiR 5 R 6 、-GeR 5 R 6 、-PR 5 、-PR 5 R 6 、-NR 5 R 6 、-AsR 5 、-S＝O、-SO 2 、-Se＝O、-SeO 2 、-BR 5 R 6 、-AlR 5 、-AlR 5 R 6 Or BiR 5 One of, or not present;
R 5 、R 6 r is as follows 7 Independently selected from hydrogen, deuterium, halogen, hydroxy, thiol, nitro, cyano, isocyano, sulfone, hydroxylamine, carboxyl, carbonyl, or one of the following substituted or unsubstituted groups: C6-C48 monocyclic aromatic hydrocarbon or polycyclic aromatic hydrocarbon, C3-C48 monocyclic heteroaromatic hydrocarbon or polycyclic heteroaromatic hydrocarbon, C1-C36 alkyl, C2-C36 heterocycloalkyl, C2-C36 alkenyl, C2-C36 alkynyl, amino, C1-C36 alkoxy, C1-C36 alkylthio, amido, silicon base and boron base.
6. A compound according to any one of claims 4 to 5, wherein the compound has a structure as shown in any one of P1 to P96,
/>
/>
wherein Yt and Yu are each independently selected from C or N;
R 8 r is as follows 9 Independently selected from hydrogen, deuterium, halogen, hydroxy, thiol, nitro, cyano, isocyano, sulfone, hydroxylamine, carboxyl, carbonyl, or one of the following substituted or unsubstituted groups: C6-C48 monocyclic aromatic hydrocarbon or polycyclic aromatic hydrocarbon, C3-C48 monocyclic heteroaromatic hydrocarbon or polycyclic heteroaromatic hydrocarbon, C1-C36 alkyl, C2-C36 heterocycloalkyl, C2-C36 alkenyl, C2-C36 alkynyl, amino, C1-C36 alkoxy, C1-C36 alkylthio, amido, silicon base and boron base.
7. A compound according to any one of claims 1 to 6, wherein the compound has any one of the following structures:
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
8. the compound according to any one of claims 1 to 7, wherein the compound is obtained by reacting a compound represented by formula a with a halide of a metal M;
in formula a, G 1 ～G 4 Each independently selected from hydroxy, alkoxy, mercapto, alkylthio, or absent.
9. The compound of claim 8, wherein the compound of formula a is obtained by a process comprising:
reacting a compound shown in a formula a-1 with pinacol diboronate to obtain a compound shown in a formula a-2;
reacting a compound represented by formula a-2 with a compound represented by formula A1 to obtain a compound represented by formula a, wherein L 2 Absence of;
wherein X is halogen;
or,
reacting a compound represented by formula a-3 with a compound represented by formula a-4 to obtain a compound represented by formula a-5;
cyclizing the compound represented by a-5 to obtain a compound represented by formula a, wherein L 2 Is absent and L 1 A cyclic group including Z as a ring-forming atom;
wherein t is more than or equal to 1, X is halogen, rz is selected from one of hydroxyl, amino and sulfhydryl, and Z is selected from O, N or S.
10. The compound according to any one of claims 1 to 7, wherein the compound is obtained by reacting a compound represented by formula b with a halide of a metal M;
in formula b, G 1 ～G 4 Each independently selected from hydroxy, alkoxy, mercapto, alkylthio, or absent.
11. The compound of claim 10, wherein the compound of formula b is obtained by a process comprising:
carrying out dehydrogenation reaction on the compound shown in the formula b-1 to obtain a compound shown in the formula b-2;
reacting a compound shown in a formula b-2 with pinacol diboronate to obtain a compound shown in a formula b-3;
reacting a compound represented by the formula B-3 with a compound represented by the formula B1 to obtain a compound represented by the formula B-4,
reacting a compound shown in a formula B-4 with a compound shown in a formula B2 to obtain a compound shown in a formula B;
12. a process for the preparation of a compound according to any one of claims 1 to 11, comprising the steps of:
reacting a compound represented by formula a with a halide of a metal M;
in formula a, G 1 ～G 4 Each independently selected from hydroxy, alkoxy, mercapto, alkylthio, or absent.
13. The preparation method according to claim 12, wherein the compound represented by formula a is obtained by a method comprising:
reacting a compound shown in a formula a-1 with pinacol diboronate to obtain a compound shown in a formula a-2;
reacting a compound represented by formula a-2 with a compound represented by formula A1 to obtain a compound represented by formula a, wherein L 2 Absence of;
wherein X is halogen;
or,
reacting a compound represented by formula a-3 with a compound represented by formula a-4 to obtain a compound represented by formula a-5;
cyclizing the compound represented by a-5 to obtain a compound represented by formula a, wherein L 2 Is absent and L 1 A cyclic group including Z as a ring-forming atom;
wherein t is more than or equal to 1, X is halogen, rz is selected from one of hydroxyl, amino and sulfhydryl, and Z is selected from O, N or S.
14. A process for the preparation of a compound according to any one of claims 1 to 11, comprising the steps of:
reacting a compound represented by formula b with a halide of a metal M;
in formula b, G 1 ～G 4 Each independently selected from hydroxy, alkoxy, mercapto, alkylthio, or absent.
15. The preparation method according to claim 14, wherein the compound represented by formula b is obtained by a method comprising:
Carrying out dehydrogenation reaction on the compound shown in the formula b-1 to obtain a compound shown in the formula b-2;
reacting a compound shown in a formula b-2 with pinacol diboronate to obtain a compound shown in a formula b-3;
reacting a compound represented by the formula B-3 with a compound represented by the formula B1 to obtain a compound represented by the formula B-4,
reacting a compound shown in a formula B-4 with a compound shown in a formula B2 to obtain a compound shown in a formula B;
16. a functional layer, characterized in that it comprises a compound according to any one of claims 1 to 11.
17. A mixture, characterized in that it comprises at least one compound according to any one of claims 1 to 11.
18. An organic electroluminescent device, characterized in that it comprises a light-emitting layer comprising the compound according to any one of claims 1 to 11.
19. The organic electroluminescent device of claim 18, wherein the light-emitting layer consists of the compound.
20. The organic electroluminescent device of claim 18, wherein the light-emitting layer comprises a host material and a dye, the dye being the compound.
21. The organic electroluminescent device of claim 18, wherein the light-emitting layer comprises a host material, a sensitizer, and a dye, and one of the sensitizer and the dye is the compound.
22. The organic electroluminescent device according to claim 20, wherein the mass percentage of the dye in the light-emitting layer is 0.1 to 20%.
23. The organic electroluminescent device according to claim 21, wherein the mass percentage of the host material in the light-emitting layer is 50-95%, the mass percentage of the sensitizer in the light-emitting layer is 1-30%, and the mass percentage of the dye in the light-emitting layer is 0.1-20%.
24. The organic electroluminescent device of any one of claims 20-23, wherein the host material is selected from at least one of carbazole, triphenylene, benzothiophene, benzofuran, dibenzothiophene, dibenzofuran, azacarbazole, azatriphenylene, azabenzothiophene, azabenzofuran, azadibenzothiophene, azadibenzofuran.
25. An electronic device, characterized in that it comprises an organic electroluminescent device as claimed in any one of claims 18-24.
CN202210028843.7A 2022-01-11 2022-01-11 Compound, organic electroluminescent device and electronic equipment Pending CN116462712A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN202210028843.7A CN116462712A (en) 2022-01-11 2022-01-11 Compound, organic electroluminescent device and electronic equipment
PCT/CN2023/071720 WO2023134696A1 (en) 2022-01-11 2023-01-10 Compound, organic light emitting device, and electronic device

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210028843.7A CN116462712A (en) 2022-01-11 2022-01-11 Compound, organic electroluminescent device and electronic equipment

Publications (1)

Publication Number Publication Date
CN116462712A true CN116462712A (en) 2023-07-21

Family

ID=87172196

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210028843.7A Pending CN116462712A (en) 2022-01-11 2022-01-11 Compound, organic electroluminescent device and electronic equipment

Country Status (2)

Country Link
CN (1) CN116462712A (en)
WO (1) WO2023134696A1 (en)

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009267170A (en) * 2008-04-25 2009-11-12 Fujifilm Corp Organic electroluminescent device
JP2009267176A (en) * 2008-04-25 2009-11-12 Fujifilm Corp Organic electroluminescent element
JP2009267244A (en) * 2008-04-28 2009-11-12 Fujifilm Corp Organic electroluminescent element
KR102654864B1 (en) * 2016-11-18 2024-04-05 삼성전자주식회사 Organometallic compound, organic light emitting device including the same and a composition for diagnosing including the same
KR20180098011A (en) * 2017-02-24 2018-09-03 삼성전자주식회사 Organometallic compound, organic light emitting device including the same and a composition for diagnosing including the same
US20190081252A1 (en) * 2017-09-13 2019-03-14 Samsung Display Co., Ltd. Organometallic compound, organic light-emitting device including the organometallic compound, and organic light-emitting apparatus including the organic light-emitting device

Also Published As

Publication number Publication date
WO2023134696A1 (en) 2023-07-20

Similar Documents

Publication Publication Date Title
JP7278631B2 (en) Emissive materials with polycyclic ligands
CN103936653A (en) Benzo carbazoles OLED material, its preparation method and its application
CN115197184A (en) Luminescent auxiliary material and preparation method and application thereof
CN111004270A (en) Organic compound, electron transport material and application thereof
CN114773399B (en) Metal organic luminescent material and application thereof
CN115304566A (en) Luminescent auxiliary material and preparation method and application thereof
CN113416175B (en) Compound with anthracene benzofuran as core framework and application thereof
CN113563325A (en) ESIPT luminescent material with high exciton utilization rate and preparation method and application thereof
WO2023207992A1 (en) Indole derivative, organic electroluminescent element, display device, and lighting device
CN116332933A (en) Condensed ring organic compound, luminous composition and organic electroluminescent device
JP5653179B2 (en) Phenanthrene compound and organic light emitting device using the same
CN116462712A (en) Compound, organic electroluminescent device and electronic equipment
CN117263893A (en) Organic compound containing dimethylfluorene structure and organic electroluminescent device containing same
CN110105231B (en) Compound containing azulene ring, application thereof and organic photoelectric device containing compound
CN114106028A (en) Indolocarbazole diboron derivative, and preparation and application thereof
CN112480092A (en) Compound with diphenylacridine as core and application thereof in organic electroluminescent device
CN114507224B (en) Ketone-containing organic compound and application thereof
CN114685465B (en) Ketone-containing organic compound and organic electroluminescent device comprising same
CN114507249B (en) B/N-containing organic compound and electroluminescent application thereof
CN117486817B (en) Organic electroluminescent material and preparation method and application thereof
CN116217605B (en) Polycyclic compound and light-emitting device thereof
CN116496311B (en) Luminescent layer doping material, preparation method thereof and electroluminescent device
CN113861118B (en) Condensed ring compound and organic electroluminescent device thereof
CN114315695B (en) Thermal activity delayed fluorescence molecular material based on indole condensed ring unit and application thereof
CN115093335B (en) Luminescent auxiliary material and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination