CN110903302A - Xanthene OLED material and synthetic method and application thereof - Google Patents

Xanthene OLED material and synthetic method and application thereof Download PDF

Info

Publication number
CN110903302A
CN110903302A CN201911193162.0A CN201911193162A CN110903302A CN 110903302 A CN110903302 A CN 110903302A CN 201911193162 A CN201911193162 A CN 201911193162A CN 110903302 A CN110903302 A CN 110903302A
Authority
CN
China
Prior art keywords
oled material
compound
oled
percent
iii
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
CN201911193162.0A
Other languages
Chinese (zh)
Inventor
段陆萌
范洪涛
黄春雪
杭德余
梁现丽
李仲庆
曹占广
刘阳
班全志
李继响
罗忠林
呼建军
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.)
Beijing Yanshan Gicom Photoelectric Technology Co Ltd
Original Assignee
Beijing Yanshan Gicom Photoelectric Technology Co Ltd
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 Beijing Yanshan Gicom Photoelectric Technology Co Ltd filed Critical Beijing Yanshan Gicom Photoelectric Technology Co Ltd
Priority to CN201911193162.0A priority Critical patent/CN110903302A/en
Publication of CN110903302A publication Critical patent/CN110903302A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/06—Peri-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D517/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having selenium, tellurium, or halogen atoms as ring hetero atoms
    • C07D517/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having selenium, tellurium, or halogen atoms as ring hetero atoms in which the condensed system contains two hetero rings
    • C07D517/06—Peri-condensed systems
    • 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
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • 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
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • 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
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • 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
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • 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
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • 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
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • 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
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
    • 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
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
    • 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
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • 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
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
    • 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
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1096—Heterocyclic compounds characterised by ligands containing other heteroatoms

Landscapes

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

Abstract

The invention relates to a xanthene OLED material which has any one structure shown in general formulas I-III. The OLED material and the application thereof provided by the invention take forced and xanthene as a mother nucleus, and the compound has a wider band gap, a high T1 energy level and a proper Highest Occupied Molecular Orbital (HOMO) energy level. The compound has high thermal stability and is not easy to decompose in the sublimation process. And has higher glass transition temperature, and can maintain the phase stability of the formed film. By introducing a group with larger steric hindrance, the luminescent material is further difficult to crystallize and quench and has good film-forming property. The OLED material provided by the invention is preferably used as a host material of a light-emitting layer in an organic electroluminescent device.

Description

Xanthene OLED material and synthetic method and application thereof
Technical Field
The invention relates to the technical field of organic electroluminescence display, in particular to a xanthene OLED material and a synthetic method and application thereof.
Background
The application of the organic electroluminescent (OLED) material in the fields of information display materials, organic optoelectronic materials and the like has great research value and good application prospect. With the development of multimedia information technology, the requirements for the performance of flat panel display devices are higher and higher. The main display technologies at present are plasma display devices, field emission display devices, and organic electroluminescent display devices (OLEDs). The OLED has a series of advantages of self luminescence, low-voltage direct current driving, full curing, wide viewing angle, rich colors and the like, and compared with a liquid crystal display device, the OLED does not need a backlight source, has a wider viewing angle and low power consumption, has the response speed 1000 times that of the liquid crystal display device, and has a wider application prospect.
The Peri-xanthenoxanthene (Peri-xP1nthenoxP1nthene, PXX) is a condensed ring aromatic compound, which has 22 pi electrons in the divalent cation and its conjugated system of 22 atoms (20 carbon atoms and 2 oxygen atoms) and is very stable. The xanthenoxanthene is often used as an electron donor in charge transfer complexes and therefore has potential as a hole transport material. The merck company invents the related compounds to increase the efficiency and the service life of electronic devices, but the structure invented by the merck company is unstable, easy to quench and crystallize and poor in film forming property. At present, a fluorescent host material with high efficiency, long service life, difficult quenching and crystallization and good film forming property is urgently needed to be provided.
Disclosure of Invention
The invention aims to provide an OLED host material which is not easy to quench, crystallize and has good film-forming property, and an OLED element using the compound.
Specifically, the invention provides an OLED material, which has any one of the structures shown in general formulas I-III:
Figure BDA0002294084610000011
in the general formulas I to III, X, Y each independently represents an S atom or a Se atom, and X, Y may be the same or different.
X, Y each represents an S atom as one embodiment of the present invention.
X, Y each represents a Se atom as one embodiment of the present invention.
In the general formulas I to III, R1By substitution of H atoms at any one or two positions on the phenyl ring in which it is located, R2By substitution of H atoms in any one, two or three positions of the phenyl ring in which they are located, R3By substitution of H atoms in any one, two or three positions of the phenyl ring in which they are located, R4Substituted with H atoms at any one, two or three positions on the phenyl ring on which it is located.
The R is1、R2、R3、R4Each independently represents-H, -F, -Cl, -Br and-I、-N(Ar)、-C(＝O)Ar、-P(＝O)Ar、-S(＝O)Ar、-S(＝O)2Ar、-OAr、-SAr、-CN、-NO2An alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms or a sulfoalkoxy group having 1 to 40 carbon atoms.
The alkyl group having 1 to 40 carbon atoms may be a straight-chain alkyl group having 1 to 40 carbon atoms, a branched-chain alkyl group having 3 to 40 carbon atoms, or a cyclic alkyl group having 3 to 40 carbon atoms.
The alkoxy group having 1 to 40 carbon atoms may be a linear alkoxy group having 1 to 40 carbon atoms, a branched alkoxy group having 3 to 40 carbon atoms, or a cyclic alkoxy group having 3 to 40 carbon atoms.
The thioalkoxy group having 1 to 40 carbon atoms may be a linear thioalkoxy group having 1 to 40 carbon atoms, a branched thioalkoxy group having 3 to 40 carbon atoms, or a cyclic thioalkoxy group having 3 to 40 carbon atoms.
The R is1、R2、R3、R4The groups represented by each may be different, any two of them may be the same and different from the remaining two, any three of them may be the same and different from the remaining one, or four of them may be the same.
As a specific embodiment of the present invention, R is1、R2、R3、R4All represent H atoms.
In the general formulas I to III of the present invention for Ar1、Ar2The respective substitution positions are preferably selected to enhance the overall performance of the compound.
Specifically, the method comprises the following steps:
in the general formula II, Ar1、Ar2The respective specific substitution positions are preferably as shown in the general formulae II-1 to II-3.
Figure BDA0002294084610000021
In the general formula III, Ar1、Ar2Each specific substitution positionPreferably represented by the general formulae III-1 to III-6.
Figure BDA0002294084610000031
As a specific embodiment of the invention, the OLED material has a structure shown as a general formula II-1.
As a specific embodiment of the present invention, the OLED material has a structure represented by the general formula II-1':
Figure BDA0002294084610000032
as a specific embodiment of the present invention, the OLED material has a structure represented by the general formula II-1':
Figure BDA0002294084610000033
ar of the invention1、Ar2Each independently represents an aromatic group having an electron-withdrawing property and having a benzene ring and/or an aromatic heterocyclic ring or represents an H atom, Ar1、Ar2May be the same or different, and Ar1、Ar2Not H atoms at the same time.
Preferably, Ar is1、Ar2Each independently selected from the group consisting of:
Figure BDA0002294084610000041
more preferably, Ar is1、Ar2Each independently selected from the group consisting of:
Figure BDA0002294084610000042
Figure BDA0002294084610000051
ar is1、Ar2The substituents represented by each may be the same or different.
In each of the above-mentioned substituent groups,
Figure BDA0002294084610000052
or "- - -" represents a substituted position.
As a particular embodiment of the present invention, the OLED material is selected from compounds of the following specific structures:
Figure BDA0002294084610000053
Figure BDA0002294084610000061
Figure BDA0002294084610000071
Figure BDA0002294084610000081
Figure BDA0002294084610000091
Figure BDA0002294084610000101
Figure BDA0002294084610000111
Figure BDA0002294084610000121
Figure BDA0002294084610000131
Figure BDA0002294084610000141
the invention also provides a preparation method of the OLED material.
When in formula I Ar1、Ar2The radicals being identical, i.e. Ar1、Ar2When all Ar is contained, the method for synthesizing the compound shown in the general formula I comprises the following steps: taking a compound P-I as a raw material, and carrying out a coupling reaction with Ar to obtain a compound I;
the reaction process is as follows:
Figure BDA0002294084610000142
when in formula I Ar1、Ar2When the groups are different, the method for synthesizing the compound shown in the general formula I comprises the following steps: taking a compound P-I' as a raw material, and sequentially reacting with Ar1、Ar2Carrying out coupling reaction to obtain a compound I;
the reaction process is as follows:
Figure BDA0002294084610000151
when in formula II Ar1、Ar2The radicals being identical, i.e. Ar1、Ar2When both are Ar, the method for synthesizing the compound shown in the general formula II comprises the following steps: taking a compound P-II as a raw material, and carrying out a coupling reaction with Ar to obtain a compound II;
the reaction process is as follows:
Figure BDA0002294084610000152
when in formula II Ar1、Ar2When the groups are different, the method for synthesizing the compound shown in the general formula II comprises the following steps: taking a compound P-II 'as a raw material, and reacting the compound P-II' with Ar in sequence1、Ar2Carrying out coupling reaction to obtain a compound II;
the reaction process is as follows:
Figure BDA0002294084610000153
when in formula III Ar1、Ar2The radicals being identical, i.e. Ar1、Ar2When both are Ar, the method for synthesizing the compound shown in the general formula III comprises the following steps: taking a compound P-III as a raw material, and carrying out a coupling reaction with Ar to obtain a compound III;
the reaction process is as follows:
Figure BDA0002294084610000154
Figure BDA0002294084610000161
when in formula III Ar1、Ar2When the groups are different, the method for synthesizing the compound shown in the general formula III comprises the following steps: taking a compound P-III 'as a raw material, and reacting the compound P-III' with Ar in sequence1、Ar2Carrying out coupling reaction to obtain a compound III;
the reaction process is as follows:
Figure BDA0002294084610000162
the above steps can be carried out by a person skilled in the art by known and conventional means, such as selecting a suitable catalyst, solvent, determining a suitable reaction temperature, time, etc.
In the above process for preparing a compound represented by any one of the general formulae I to III, when Ar is Ar1、Ar2The radicals being identical, i.e. Ar1、Ar2When both are Ar, as a preferred embodiment of the present invention, the method comprises: and (2) taking xylene as a reaction solvent, cuprous chloride as a catalyst, potassium hydroxide as an alkali, controlling the temperature to be 75-85 ℃ under the protection of nitrogen, and performing a coupling reaction on the raw materials and Ar to obtain the target compound.
The above preparation has the general formula I-IIIn the process for preparing a compound represented by any one of I, when Ar is1、Ar2When the groups are different, as a preferred embodiment of the present invention, the method comprises: firstly, dimethylbenzene is used as a reaction solvent, cuprous chloride is used as a catalyst, potassium hydroxide is used as alkali, nitrogen is used for protection, the temperature is controlled to be 75-85 ℃, and the raw material and Ar are mixed1Coupling reaction is carried out to obtain an intermediate product; and then taking toluene as a solvent, palladium acetate and tri-tert-butylphosphine as catalysts, potassium tert-butoxide as an alkali, protecting with nitrogen, controlling the temperature to be 90-120 ℃, and reacting the intermediate product and Ar2Coupling reaction is carried out to obtain the target compound.
The starting materials for the solvents, catalysts, bases, etc., used in the present invention can be synthesized by published commercial routes or methods known in the art.
The invention also protects the application of the OLED material in an organic electroluminescent device. Preferably, the OLED material is used as a host material in the light emitting layer.
The invention also provides an organic electroluminescent device, wherein a luminescent layer of the organic electroluminescent device contains the OLED material. Specifically, the organic electroluminescent device protected by the invention sequentially comprises a transparent substrate, an anode layer, a hole transport layer, a light emitting layer with the OLED material as a main material, an electron transport layer, an electron injection layer and a cathode layer from bottom to top.
The OLED material provided by the invention is a novel compound which takes tonne-to-tonne as a center and has a high T1 energy level, a narrow band gap and a shallow Highest Occupied Molecular Orbital (HOMO) energy level. The perixanthenoxanthene is easily sublimable, stable in air, and does not undergo oxidative decomposition. Has high thermal stability and high glass transition temperature in air. By introducing a group with larger steric hindrance, the luminescent material is not easy to crystallize and quench and has good film-forming property.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
According to some embodiments of the present invention, the preferred solvent for preparing the organic electroluminescent device according to the present invention is selected from toluene, DMF or a mixture of these solvents. The reagents are analytically pure reagents, and the intermediate is purchased from an online shopping mall or is custom-synthesized from outsourcing companies.
Example 1
Figure BDA0002294084610000171
Synthesis of (Compound II-1-7)
The synthetic route is as follows:
Figure BDA0002294084610000172
synthesis of Compound II-1-7
A1L three-necked flask was stirred with magnetic stirring and then replaced with nitrogen, and 40.07g (0.378mol) of sodium carbonate, 58.59g (purity 99%, 0.21mol) of phenanthro [9,10-d ] thiazol-2-ylboronic acid and 100ml of toluene were sequentially added. After nitrogen replacement, 0.5g of Pd132 was added in this order. After the addition, the temperature was raised to 80 ℃. Dropwise addition was started in a solution consisting of 47.2g of compound P1 (purity 99%, 0.1mol) and 100ml of toluene, the temperature being controlled at 75-90 ℃. Cooling to room temperature, adding 100ml deionized water for hydrolysis, stirring for 10 min, filtering, repeatedly boiling and washing filter cake with DMF for several times, and filtering to obtain 62.4g of light yellow solid with purity of 99% and yield of 80%.
Product MS (m/e): 780, a water-soluble polymer; elemental analysis (C)50H24N2S4): theoretical value C: 76.89 percent; h: 3.10 percent; n: 3.59 percent; s: 16.42 percent; found value C: 76.88 percent; h: 3.11 percent; n: 3.59 percent; s: 16.42 percent.
Example 2
Figure BDA0002294084610000181
Synthesis of (Compound II-1-12)
The synthetic route is as follows:
Figure BDA0002294084610000182
synthesis of Compound II-1-12
A1 liter three-necked flask was equipped with magnetic stirring, and after nitrogen substitution, 40.07g (0.378mol) of sodium carbonate, 65.94g (purity 99%, 0.21mol) of 4- (1-phenyl-1H-benzo [ d ] imidazol-2-yl) phenyl) boronic acid and 100ml of toluene were added in this order. After nitrogen replacement, 0.5g of Pd132 was added in this order. After the addition, the temperature was raised to 80 ℃. Dropwise addition was started in a solution consisting of 56.6g of compound P1 (purity 99%, 0.1mol) and 100ml of toluene, the temperature being controlled at 75-90 ℃. Cooling to room temperature, adding 100ml deionized water for hydrolysis, stirring for 10 min, filtering, repeatedly boiling and washing the filter cake with DMF for several times, and filtering to obtain 76.63g of light yellow solid with purity of 99% and yield of 81%.
Product MS (m/e): 946; elemental analysis (C)58H34N4Se2): theoretical value C: 73.73 percent; h: 3.63 percent; n: 5.93 percent; se: 16.71 percent; found value C: 73.72 percent; h: 3.64 percent; n: 5.93 percent; se: 16.71 percent.
Example 3
Figure BDA0002294084610000183
Synthesis of (Compound II-1-21)
The synthetic route is as follows:
Figure BDA0002294084610000184
Figure BDA0002294084610000191
synthesis of Compound II-1-21
A1 liter three-necked flask was charged with magnetic stirring, and after nitrogen substitution, 40.07g (0.378mol) of sodium carbonate, 17.93g (purity: 99%, 0.11mol) of benzo [ d ] oxazol-2-ylboronic acid and 100ml of toluene were added in this order. After nitrogen replacement, 0.5g of Pd132 was added in this order. After the addition, the temperature was raised to 80 ℃. Dropwise addition was started in a solution consisting of 39.1g of compound P1 (purity 99%, 0.1mol) and 100ml of toluene, the temperature being controlled at 75-90 ℃. Cooling to room temperature, adding 100ml deionized water for hydrolysis, stirring for 10 min, filtering, repeatedly boiling and washing filter cake with DMF for several times, and filtering to obtain 33.62g of light yellow solid with purity of 99% and yield of 78%.
Product MS (m/e): 431; elemental analysis (C)27H13NOS2): theoretical value C: 75.15 percent; h: 3.04 percent; n: 3.25 percent; o: 3.71 percent; s: 14.86 percent; found value C: 75.14 percent; h: 3.05 percent; n: 3.25 percent; o: 3.71 percent; s: 14.86 percent.
Example 4
Figure BDA0002294084610000192
Synthesis of (Compound II-1-26)
The synthetic route is as follows:
Figure BDA0002294084610000193
synthesis of Compound II-1-26
A1 liter three-necked flask was equipped with magnetic stirring, and after nitrogen substitution, 40.07g (0.378mol) of sodium carbonate, 60.27g (purity 99%, 0.21mol) of 6-phenylpyridin-3-yl) boronic acid and 100ml of toluene were added in this order. After nitrogen replacement, 0.5g of Pd132 was added in this order. After the addition, the temperature was raised to 80 ℃. Dropwise addition was started in a solution consisting of 56.6g of compound P1 (purity 99%, 0.1mol) and 100ml of toluene, the temperature being controlled at 75-90 ℃. Cooling to room temperature, adding 100ml deionized water for hydrolysis, stirring for 10 min, filtering, repeatedly boiling and washing the filter cake with DMF for several times, and filtering to obtain 47.04g of light yellow solid with purity of 99% and yield of 80%.
Product MS (m/e): 716; elemental analysis (C)42H24N2Se2): theoretical value C: 70.59 percent; h: 3.39 percent; n: 3.92 percent; se: 22.10 percent; found value C: 70.58 percent; h: 3.40 percent; n: 3.92 percent; se: 22.10 percent.
Example 5
Figure BDA0002294084610000201
Synthesis of (Compound II-1-49)
The synthetic route is as follows:
Figure BDA0002294084610000202
synthesis of Compound II-1-49
A1 liter three-necked flask was equipped with magnetic stirring, and after nitrogen substitution, 40.07g (0.378mol) of sodium carbonate, 30.36g (purity 99%, 0.11mol) of 3, 5-bis (pyridin-3-yl) phenyl) boronic acid and 100ml of toluene were added in this order. After nitrogen replacement, 0.5g of Pd132 was added in this order. After the addition, the temperature was raised to 80 ℃. Dropwise addition was started in a solution consisting of 39.1g of compound P1 (purity 99%, 0.1mol) and 100ml of toluene, the temperature being controlled at 75-90 ℃. Cooling to room temperature, adding 100ml deionized water for hydrolysis, stirring for 10 min, filtering, and repeatedly boiling and washing the filter cake with DMF for several times to obtain 44.61g of light yellow solid with purity of 99% and yield of 82%.
Product MS (m/e): 544; elemental analysis (C)36H20N2S2): theoretical value C: 79.38%, H: 3.70 percent; n: 5.14 percent; s: 11.77 percent; found value C: 79.37 percent; h: 3.71 percent; n: 5.14 percent; s: 11.77 percent.
Example 6
Figure BDA0002294084610000203
Synthesis of (Compound II-1-65)
The synthetic route is as follows:
Figure BDA0002294084610000211
synthesis of Compound II-1-65-1
A1 liter three-necked flask was equipped with magnetic stirring, and after nitrogen substitution, 20.03g (0.19mol) of sodium carbonate, 19.69g (purity 99%, 0.11mol) of benzo [ d ] thiazol-2-ylboronic acid and 100ml of toluene were sequentially added. After nitrogen replacement, 0.25g of Pd132 was added in this order. After the addition, the temperature was raised to 80 ℃. Dropwise addition was started in a solution consisting of 47.2g of compound P1 (purity 99%, 0.1mol) and 100ml of toluene, the temperature being controlled at 75-90 ℃. Cooling to room temperature, adding 100ml deionized water for hydrolysis, stirring for 10 min, filtering, repeatedly boiling and washing the filter cake with DMF for several times, and filtering to obtain 26.2g of light yellow solid with purity of 99% and yield of 50%.
Synthesis of Compound II-1-65
A1 liter three-necked flask was equipped with magnetic stirring, and after nitrogen substitution, 20.03g (0.19mol) of sodium carbonate, 26.18g (purity 99%, 0.11mol) of (1-phenyl-1H-benzo [ d ] imidazol-2-yl) boronic acid and 100ml of toluene were sequentially added. After nitrogen replacement again, 0.25g of Pd132 was added in this order. After the addition, the temperature was raised to 80 ℃. A solution consisting of 52.4g of Compound II-1-65-1 (purity 99%, 0.1mol) and 100ml of toluene was initially added dropwise, the temperature being controlled at 75-90 ℃. Cooling to room temperature, adding 100ml deionized water for hydrolysis, stirring for 10 min, filtering, repeatedly boiling and washing the filter cake with DMF for several times, and filtering to obtain 53.04g of light yellow solid with purity of 99% and yield of 83%.
Product MS (m/e): 639; elemental analysis (C)40H21N3S3): theoretical value C: 75.09 percent; h: 3.31 percent; n: 6.57 percent; s: 15.03 percent; found value C: 75.08 percent; h: 3.32 percent; n: 6.57 percent; s: 15.03 percent.
According to the technical schemes of examples 1 to 6, the compounds shown in II-1-1 to II-1-122 above can be synthesized by simply replacing the corresponding raw materials without changing any substantial operation.
Preparing devices OLED-1-OLED-6
(1) Carrying out ultrasonic treatment on the glass plate coated with the ITO transparent conductive layer in a commercial cleaning agent, washing the glass plate in deionized water, ultrasonically removing oil in an acetone-ethanol mixed solvent (the volume ratio is 1: 1), baking the glass plate in a clean environment until the water is completely removed, cleaning the glass plate by using ultraviolet light and ozone, and bombarding the surface by using low-energy cationic beams;
(2) placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to 1 × 10-5～9×10-3PP1, evaporating HATCN as a first hole injection layer on the anode layer film in vacuum, wherein the evaporation rate is 0.1nm/s, and the total evaporation film thickness is 1 nm; then evaporating a second hole injection layer HT01 at the evaporation rate of 0.1nm/s and the thickness of 40 nm;
Figure BDA0002294084610000221
(3) evaporating and plating a layer of NPB (nitrogen-phosphorus) on the hole injection layer film to form a hole transport layer, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 20 nm;
Figure BDA0002294084610000222
(4) the compound II-1-7 provided in example 1 was further vapor-deposited as a host material on the hole transport layer at a rate of 0.1nm/s, Ir (piq)2acac is used as a doping material (namely a luminescent material), the doping concentration is 10%, an organic luminescent layer of the device is formed, and the total film thickness of the organic luminescent layer obtained by evaporation is 30 nm;
Figure BDA0002294084610000223
(5) continuously evaporating a layer of compound BCP on the organic light-emitting layer to be used as an electron transport layer of the device, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 30 nm;
Figure BDA0002294084610000224
(6) continuously evaporating a layer of LiF on the electron transport layer to be used as an electron injection layer of the device, wherein the thickness of the evaporated film is 0.5 nm;
(7) continuously evaporating a layer of Al on the electron injection layer to be used as a cathode of the device, wherein the thickness of the evaporated film is 150 nm; the OLED device provided by the invention is obtained and is marked as a device OLED-1.
According to the same steps, replacing the compounds II-1-7 in the step (4) with the compounds prepared in the embodiments 2-6 of the invention to obtain the devices OLED-2-OLED-6 provided by the invention.
According to the same procedure as above, compound II-1-7 in step (4) was replaced with comparative compound 1 (structure shown below), to give comparative device OLED-7.
Figure BDA0002294084610000231
Comparative Compound 1
The results of performance tests of the obtained devices, examples 1 to 7, are shown in table 1.
Table 1: performance test results of OLED-1 to OLED-7
Figure BDA0002294084610000232
From the above results, the current efficiency of the devices OLED-1 to OLED-6 prepared by using the OLED material provided by the invention is higher, and the working voltage is obviously lower than that of the device OLED-7 with the comparative compound 1 as the organic light-emitting main material under the condition of the same brightness.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (10)

1. The xanthene OLED material is characterized by having any one of the structures shown in general formulas I-III:
Figure FDA0002294084600000011
in the general formulas I to III, X, Y independently represent an S atom or a Se atom, and X, Y may be the same or different;
the R is1、R2、R3、R4Each independently represents-H, -F, -Cl, -Br, -I, -n (Ar), -C (═ O) Ar, -P (═ O) Ar, -S (═ O)2Ar、-OAr、-SAr、-CN、-NO2An alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms or a sulfoalkoxy group having 1 to 40 carbon atoms;
ar is1、Ar2Each independently represents an aromatic group having an electron-withdrawing property having a benzene ring and/or an aromatic heterocyclic ring orRepresents a H atom, Ar1、Ar2May be the same or different, and Ar1、Ar2Not H atoms at the same time.
2. The OLED material of claim 1, having any one of the structures of formulas II-1-II-3 and III-1-III-6:
Figure FDA0002294084600000012
Figure FDA0002294084600000021
3. OLED material according to claim 1 or 2, characterized in that R is1、R2、R3、R4All represent H atoms.
4. An OLED material as claimed in any one of claims 1 to 3 wherein X, Y each represents an S atom or X, Y each represents a Se atom.
5. The OLED material of claim 1, having a structure according to formula II-1' or formula II-1 ":
Figure FDA0002294084600000022
6. the OLED material according to any one of claims 1 to 5, wherein Ar is Ar1、Ar2Each independently selected from the group consisting of:
Figure FDA0002294084600000023
Figure FDA0002294084600000031
preferably, Ar is1、Ar2Each independently selected from the group consisting of:
Figure FDA0002294084600000032
Figure FDA0002294084600000041
7. the OLED material of claim 1, wherein the compound is selected from the following specific structures:
Figure FDA0002294084600000042
Figure FDA0002294084600000051
Figure FDA0002294084600000061
Figure FDA0002294084600000071
Figure FDA0002294084600000081
Figure FDA0002294084600000091
Figure FDA0002294084600000101
Figure FDA0002294084600000111
Figure FDA0002294084600000121
Figure FDA0002294084600000131
8. use of the OLED material of any one of claims 1 to 7 in an organic electroluminescent device; preferably, the OLED material is used as a host material in the light emitting layer.
9. An organic electroluminescent device, characterized in that the light-emitting layer contains the OLED material according to any one of claims 1 to 7.
10. An organic electroluminescent device, characterized in that the organic electroluminescent device comprises a transparent substrate, an anode layer, a hole transport layer, a luminescent layer using the OLED material of any one of claims 1 to 7 as a main material, an electron transport layer, an electron injection layer and a cathode layer in sequence from bottom to top.
CN201911193162.0A 2019-11-28 2019-11-28 Xanthene OLED material and synthetic method and application thereof Pending CN110903302A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911193162.0A CN110903302A (en) 2019-11-28 2019-11-28 Xanthene OLED material and synthetic method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911193162.0A CN110903302A (en) 2019-11-28 2019-11-28 Xanthene OLED material and synthetic method and application thereof

Publications (1)

Publication Number Publication Date
CN110903302A true CN110903302A (en) 2020-03-24

Family

ID=69820230

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911193162.0A Pending CN110903302A (en) 2019-11-28 2019-11-28 Xanthene OLED material and synthetic method and application thereof

Country Status (1)

Country Link
CN (1) CN110903302A (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101490208A (en) * 2006-07-28 2009-07-22 默克专利有限公司 Novel materials for organic electroluminescent devices
CN103087065A (en) * 2011-11-03 2013-05-08 三星显示有限公司 Ovel Heterocyclic Compound, Organic Light-emitting Device Including The Same And Flat Panel Display Device
JP2018039777A (en) * 2016-08-31 2018-03-15 共栄社化学株式会社 Peri-xanthenoxanthene bisimide compound, method for producing the same, organic el element, and organic thin film solar cell
CN109503457A (en) * 2018-11-03 2019-03-22 浙江大学 Dinaphtho heterocycle small molecule hole transport material, synthetic method and its application
CN110218212A (en) * 2019-06-28 2019-09-10 武汉天马微电子有限公司 Nitrogen heterocyclic, display panel and display device

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101490208A (en) * 2006-07-28 2009-07-22 默克专利有限公司 Novel materials for organic electroluminescent devices
CN103087065A (en) * 2011-11-03 2013-05-08 三星显示有限公司 Ovel Heterocyclic Compound, Organic Light-emitting Device Including The Same And Flat Panel Display Device
JP2018039777A (en) * 2016-08-31 2018-03-15 共栄社化学株式会社 Peri-xanthenoxanthene bisimide compound, method for producing the same, organic el element, and organic thin film solar cell
CN109503457A (en) * 2018-11-03 2019-03-22 浙江大学 Dinaphtho heterocycle small molecule hole transport material, synthetic method and its application
CN110218212A (en) * 2019-06-28 2019-09-10 武汉天马微电子有限公司 Nitrogen heterocyclic, display panel and display device

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JOSEPH A. CHRISTENSEN ET AL.: "Near-Infrared Excitation of the peri-Xanthenoxanthene Radical Cation Drives Energy-Demanding Hole Transfer Reactions", 《THE JOURNAL OF PHYSICAL CHEMISTRY C》 *

Similar Documents

Publication Publication Date Title
CN111039954A (en) Novel organic material and application thereof in device
EP1499624B1 (en) Electroluminescent materials
JP4068461B2 (en) Spiro compounds based on boron or aluminum and methods of using those spiro compounds in the electronics industry
CN110563746B (en) Novel SO2 spiro-structure-containing compound and application thereof in OLED (organic light emitting diode) device
CN110467626B (en) Novel spiro-structure compound and application thereof in OLED (organic light emitting diode) device
CN110551132A (en) ketone-containing compound and application thereof in organic electroluminescent device
JP5943467B2 (en) Diphenylsulfone derivative, host material comprising the same, and organic electroluminescence device using the same
CN111825671A (en) Compound containing carbazole ring and application thereof
WO2012081541A1 (en) 1, 2, 4, 5-substituted phenyl derivative, production method for same, and organic electroluminescent element
CN114560870B (en) Sulfur-containing polycyclic aromatic compound and application thereof
CN111004248B (en) Novel organic material and application thereof
CN110003020A (en) A kind of electroluminescent organic material and the preparation method and application thereof fluorene structured with spiral shell two
CN109970578A (en) A kind of organic compound and the preparation method and application thereof fluorene structured with 9,9 '-spiral shells two
CN109776396A (en) A kind of organic compound and the preparation method and application thereof fluorene structured with spiral shell two
CN109776395A (en) A kind of cavitation material and the preparation method and application thereof that fluorine-containing spiral shell two is fluorene structured
CN111004253B (en) OLED material and application thereof
CN110903296B (en) OLED material and application thereof in device
CN110903302A (en) Xanthene OLED material and synthetic method and application thereof
CN111116602B (en) OLED material and application thereof in organic electroluminescent device
CN110511234B (en) Novel heterocyclic spiro-structure compound and application thereof in OLED (organic light emitting diode) device
CN111004249B (en) OLED material and application thereof
CN111039953A (en) Xanthene organic material and application thereof in devices
CN111087407A (en) OLED material and application thereof
CN110511232B (en) Electron transport material and application thereof in device
CN110467625B (en) OLED bipolar main body material and application thereof in device

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
RJ01 Rejection of invention patent application after publication

Application publication date: 20200324

RJ01 Rejection of invention patent application after publication