CN112479987B - Fluorene phosphorescent compound, preparation method thereof and organic electroluminescent device - Google Patents

Fluorene phosphorescent compound, preparation method thereof and organic electroluminescent device Download PDF

Info

Publication number
CN112479987B
CN112479987B CN202011527964.3A CN202011527964A CN112479987B CN 112479987 B CN112479987 B CN 112479987B CN 202011527964 A CN202011527964 A CN 202011527964A CN 112479987 B CN112479987 B CN 112479987B
Authority
CN
China
Prior art keywords
phosphorescent compound
fluorene
preparation
substituted
unsubstituted
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.)
Active
Application number
CN202011527964.3A
Other languages
Chinese (zh)
Other versions
CN112479987A (en
Inventor
王永光
汪康
张鹤
王进政
黄悦
张雪
马晓宇
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.)
Jilin Optical and Electronic Materials Co Ltd
Original Assignee
Jilin Optical and Electronic Materials 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 Jilin Optical and Electronic Materials Co Ltd filed Critical Jilin Optical and Electronic Materials Co Ltd
Priority to CN202011527964.3A priority Critical patent/CN112479987B/en
Publication of CN112479987A publication Critical patent/CN112479987A/en
Application granted granted Critical
Publication of CN112479987B publication Critical patent/CN112479987B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
    • C07C13/62—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with more than three condensed rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
    • C07C211/61—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton with at least one of the condensed ring systems formed by three or more rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
    • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
    • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
    • C07D235/06—Benzimidazoles; Hydrogenated benzimidazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
    • C07D235/08—Radicals containing only hydrogen and carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
    • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
    • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
    • C07D235/18—Benzimidazoles; Hydrogenated benzimidazoles with aryl radicals directly attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/26—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/24—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/76—Dibenzothiophenes
    • 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
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
    • 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
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
    • 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
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • 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
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
    • 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
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
    • 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
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • 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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/54—Ortho- or ortho- and peri-condensed systems containing more than five condensed rings
    • 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
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—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
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
    • 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
    • C09K2211/1044—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
    • C09K2211/1059—Heterocyclic compounds characterised by ligands containing three 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
    • C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen 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
    • C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom

Landscapes

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

Abstract

The invention discloses a fluorene phosphorescent compound, a preparation method thereof and an organic electroluminescent device, belonging to the technical field of chemistry and organic luminescent materials, wherein the phosphorescent compound has a general structural formula as follows:
Figure DDA0002851385430000011
in the formula, L1、L2Each independently is at least one of a linkage, a substituted or unsubstituted C6-C30 aryl, a substituted or unsubstituted C6-C30 heteroaryl. The organic electroluminescent device containing the phosphorescent compound has lower driving voltage, longer service life and higher efficiency. The phosphorescent compound provided by the invention can adjust the wavelength of the compound by selecting the ligand combination of a specific heterocyclic ring, so that the luminous efficiency and the service life of a device can be improved after the phosphorescent compound is used for an organic electroluminescent device.

Description

Fluorene phosphorescent compound, preparation method thereof and organic electroluminescent device
Technical Field
The invention relates to the technical field of chemistry and organic luminescent materials, in particular to a fluorene phosphorescent compound, a preparation method thereof and an organic electroluminescent device.
Background
The OLED is a hole and electron dual injection type light emitting device, and directly converts electric energy into light energy of organic semiconductor material molecules. Compared with traditional display devices such as a CRT (cathode ray tube), an LCD (liquid crystal display), a PDP (plasma display panel) and the like, the OLED has all the advantages of the existing display, has unique advantages, not only has high brightness, high contrast, high definition, wide visual angle, wide color gamut and the like to realize high-quality images, but also has the characteristics of ultra-thinness, ultra-lightness, low driving voltage, low power consumption, wide temperature and the like to meet the requirements of portable equipment on portability, power saving and outdoor operation; the OLED display has the unique characteristics of self-luminescence, high luminous efficiency, short response time, transparency, flexibility and the like.
The noble metal complex is used as a phosphorescent material, fully utilizes singlet excitons and triplet excitons, only utilizes the singlet excitons compared with a fluorescent material, and effectively utilizes the triplet excitons with the proportion up to 75 percent, so that the PhOLED based on the phosphorescent material realizes 100 percent of internal quantum efficiency. In recent three years, phosphorescent materials gradually replace traditional fluorescent materials, and become hot spots for research on OLED luminescent materials. However, since the synthesis process of the phosphorescent material is complicated, takes a long time, and has a short lifetime, further development of the phosphorescent material is urgently needed.
Disclosure of Invention
An object of an embodiment of the present invention is to provide a fluorene phosphorescent compound to solve the above problems in the background art.
In order to achieve the above purpose, the embodiments of the present invention provide the following technical solutions:
a fluorene phosphorescent compound has a structural general formula as formula I:
Figure BDA0002851385420000021
wherein m is 0 or 1, n is 0 or 1, and m and n cannot be 0 simultaneously;
R1、R2each independently is at least one of substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 cycloalkenyl, substituted or unsubstituted 3-to 7-membered heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-to 30-membered heteroaryl, C3-C30 aliphatic or aromatic ring joined to adjacent substituents to form a substituted or unsubstituted mono-or polycyclic ring;
L1、L2each independently is at least one of a linkage, a substituted or unsubstituted C6-C30 aryl, a substituted or unsubstituted C6-C30 heteroaryl;
Ar1、Ar2、Ar3、Ar4each independently is at least one of C1-C1 alkyl, C1-C1 aryl, C1-C1 heteroaryl, C1-C1 cycloalkyl, C1-C1 alkylamino, C1-C1 arylamino, C1-C1 aryloxy, 5-6 membered heterocycloalkyl containing one or more heteroatoms selected from 1 and S, tri (C1-C1) alkylsilyl, di (C1-C1) alkyl, C1-C1 arylsilyl, tri (C1-C1) arylsilyl, adamantyl, C1-C1 cycloalkyl, C1-C1 alkenyl, C1-C1 alkynyl, C1-C1 alkylcarbonyl, C1-C1 arylcarbonyl.
Preferably, the carbon atoms in the C3-C30 aliphatic or aromatic ring that are linked to adjacent substituents to form a substituted or unsubstituted mono-or polycyclic ring are replaced with at least one heteroatom selected from nitrogen, oxygen and sulfur.
Preferably, Ar is1、Ar2、Ar3、Ar4Each independently is an alkyl group unsubstituted or substituted with at least one substituent, an alkenyl group unsubstituted or substituted with at least one substituent, an alkynyl group unsubstituted or substituted with at least one substituent, an unsubstitutedAt least one of cycloalkyl which is substituted or substituted with at least one substituent, heterocycloalkyl which is unsubstituted or substituted with at least one substituent, aryl which is unsubstituted or substituted with at least one substituent, heteroaryl which is unsubstituted or substituted with at least one substituent, arylsilyl which is unsubstituted or substituted with at least one substituent, alkylsilyl which is unsubstituted or substituted with at least one substituent, alkylamino which is unsubstituted or substituted with at least one substituent, arylamino which is unsubstituted or substituted with at least one substituent.
Preferably, the substituents are independently deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, C1-C60 alkyl, C6-C60 aryl, C3-C60 heteroaryl, C3-C60 cycloalkyl, C1-C60 alkoxy, C1-C60 alkylamino, C6-C60 arylamino, C6-C60 aryloxy, at least one of C6-C60 arylthio, 5-6 membered heterocycloalkyl containing one or more heteroatoms selected from N, O and S, tri (C1-C60) alkylsilyl, di (C1-C60) alkyl, (C6-C60) arylsilyl, tri (C6-C60) arylsilyl, adamantyl, C7-C60 bicycloalkyl, C2-C60 alkenyl, C2-C60 alkynyl, C1-C60 alkoxycarbonyl, C1-C60 alkylcarbonyl, C1-C60 arylcarbonyl.
Preferably, the chemical structural formula of the phosphorescent compound is any one of formula 1 to formula 114:
Figure BDA0002851385420000031
Figure BDA0002851385420000041
Figure BDA0002851385420000051
Figure BDA0002851385420000061
Figure BDA0002851385420000071
Figure BDA0002851385420000081
Figure BDA0002851385420000091
Figure BDA0002851385420000101
it is noted that, in the above technical solutions, the term "substituted or unsubstituted" means substituted with one, two or more substituents selected from the group consisting of: deuterium; a halogen group; a nitrile group; a hydroxyl group; a carbonyl group; an ester group; a silyl group; a boron group; substituted or unsubstituted alkyl; substituted or unsubstituted cycloalkyl; substituted or unsubstituted alkoxy; substituted or unsubstituted alkenyl; substituted or unsubstituted alkylamino; substituted or unsubstituted heterocyclylamino; substituted or unsubstituted arylamine; substituted or unsubstituted aryl; and a substituted or unsubstituted heterocyclic group, or a substituent in which two or more substituents among the above-shown substituents are connected, or no substituent. For example, "a substituent in which two or more substituents are linked" may include a biphenyl group. In other words, biphenyl can be an aryl group, or can be interpreted as a substituent with two phenyl groups attached.
Another objective of the embodiments of the present invention is to provide a method for preparing the fluorene phosphorescent compound, which comprises the following steps:
under a protective atmosphere, reactant A, reactant B, Pd (pph)3)4Reacting potassium carbonate in a solvent, and purifying to obtain an intermediate C;
under the protection atmosphere, dissolving the intermediate C in anhydrous Tetrahydrofuran (THF), adding MgBr Me to react, then dropwise adding an ammonium chloride solution to carry out liquid separation, and purifying to obtain an intermediate D;
adding the intermediate D into Tetrahydrofuran (THF), adding methanesulfonic acid (MSA), polyphosphoric acid and ethanol for reaction, and purifying to obtain an intermediate E;
adding the intermediate E into dichloromethane, then adding N-chlorosuccinimide (NCS) for reaction, and purifying to obtain an intermediate F;
pd (pph) under a protective atmosphere3)4The potassium carbonate, the reactant H, the reactant I and the intermediate F are placed in a solvent for reaction to obtain the phosphorescent compound;
the structural formula of the reactant A is shown as a formula A, the structural formula of the reactant B is shown as a formula B, the structural formula of the intermediate C is shown as a formula C, the structural formula of the intermediate D is shown as a formula D, the structural formula of the intermediate E is shown as a formula E, the structural formula of the intermediate F is shown as a formula F, the structural formula of the reactant H is shown as a formula H, and the structural formula of the reactant I is shown as a formula I:
Figure BDA0002851385420000121
preferably, the solvent is a mixture of toluene, ethanol and water.
Specifically, the synthetic route of the preparation method is as follows:
Figure BDA0002851385420000122
the method specifically comprises the following steps:
1) preparation of intermediate C: after adding reactant A and reactant B to the reaction vessel, Pd (pph) was added3)4Potassium carbonate, and a mixed solution of solvents toluene, ethanol and water, and fully replacing air with nitrogen for three times; heating to 85-95 deg.c for 16-20 hr. Cooling and separating liquid after the reaction is finished, spin-drying the toluene layer to obtain a dark solid, and using dichloroDissolved through a silica gel column, dichloromethane: petroleum ether is 1: (3.5-4.5) most of the product is washed out, and the white solid intermediate C is obtained by spin drying.
2) Preparation of intermediate D: dissolving the product C in anhydrous THF, and stirring at 0 ℃ for 20-40 minutes under the protection of nitrogen. Then adding the compound MgBrMe, reacting for 1-3 hours, gradually heating to room temperature, and reacting for 10-14 hours. And (3) dropwise adding saturated ammonium chloride solution into the reaction solution, separating, extracting a primary water layer by THF, combining organic layers, drying for 5-15 minutes by anhydrous magnesium sulfate, and carrying out rotary drying to obtain the compound shown as the intermediate D.
3) Preparation of intermediate E: adding the intermediate D into THF, cooling at 0 deg.C for 20-40 min, and adding MSA (20-40mL), polyphosphoric acid and ethanol respectively. After reacting for 2-4 hours, heating to room temperature, stirring for 12-16 hours, separating out solids, directly filtering, washing filter cakes by water, ethanol and petroleum ether respectively, and drying to obtain an intermediate E.
4) Preparation of intermediate F: intermediate E was added to dichloromethane, stirred at room temperature for 20-40 minutes, and NCS was added slowly. And after the reaction is finished for 14-18 hours, spin-drying the organic layer to obtain a light yellow solid, adding petroleum ether, a proper amount of ethanol and water, stirring overnight, directly performing suction filtration, washing filter cakes by using water, ethanol and petroleum ether respectively, and drying to obtain an intermediate F.
5) Preparation of phosphorescent compound: pd (pph)3)4Adding potassium carbonate, raw material H, I and intermediate F into a reaction bottle, adding a mixed solution of toluene, ethanol and water, heating to 80-100 ℃ under the protection of nitrogen, and reacting for 22-26 hours. Cooling, performing suction filtration to obtain a dark filtrate, spin-drying the filtrate to obtain a solid, adding dichloromethane to dissolve the solid, and passing through a silica gel funnel to obtain the phosphorescent compound shown in the chemical formula I.
In the above preparation method, the preferred solvent for the synthesis of formula I is toluene, ethanol and water in a volume ratio of 2: 0.5-1: 0.5-1, the catalyst and base are each Pd (pph)3)4And potassium carbonate in a molar ratio of 1: 100-300, the dosage is not more than 5% (mol) of the main reactant, the reaction temperature is not more than 100 ℃, and the reaction time is not more than 24 hours. The final product is large according to the reaction reagentMolar ratio (based on composition).
Another object of the embodiments of the present invention is to provide a use of the above phosphorescent compound in the preparation of an organic electroluminescent device.
It is another object of an embodiment of the present invention to provide an organic electroluminescent device, which includes an anode, a cathode, and at least one organic layer disposed between the anode and the cathode, wherein the organic layer includes the phosphorescent compound described above.
Preferably, the organic layer includes a light emitting layer; the light-emitting layer comprises a host material and a doping material; the host material partially or completely contains the phosphorescent compound.
The kind of the anode is not particularly limited, and may be a conventional anode known to those skilled in the art, and is more preferably one of ITO (indium tin oxide), tin oxide, zinc oxide, and indium oxide. The thickness of the anode is preferably set to
Figure BDA0002851385420000141
The kind of the cathode is not particularly limited, and may be a conventional cathode well known to those skilled in the art, and more preferably one of Al, Li, Na, K, Mg, Ca, Au, Ag, and Pb. The cathode preferably has a thickness
Figure BDA0002851385420000142
Preferably, the organic layer includes a light emitting layer; the light-emitting layer comprises a host material and a doping material; the doping material partially or completely contains the phosphorescent compound.
The doping material is preferably Ir (ppy)3And iridium metal complexes.
In addition, the organic layer may further include other functional layers, and the other functional layers may be specifically selected from one or more of the following functional layers: a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), a hole injection-hole transport functional layer (i.e., having both hole injection and hole transport functions), an Electron Blocking Layer (EBL), a Hole Blocking Layer (HBL), an Electron Transport Layer (ETL), an Electron Injection Layer (EIL), and an electron transport-electron injection functional layer (i.e., having both electron transport and electron injection functions).
The kind of each functional layer is not particularly limited, and may be a conventional functional layer known to those skilled in the art. Preferably: the hole injection layer is one of 2-TNATA (namely N1- (2-naphthyl) -N4, N4-di (4- (2-naphthyl (phenyl) amino) phenyl) -N1-phenyl benzene-1, 4-diamine), phthalocyanine and porphyrin compounds, starburst triarylamine, conductive polymer, N-type semiconductive organic complex and metal organic complex; the thickness of the hole injection layer is preferably set to be
Figure BDA0002851385420000151
The hole transport layer is one of NPB (namely N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine), TPD (namely N, N '-diphenyl-N, N' - (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine), PAPB (namely N, N '-bis (phenanthrene-9-yl) -N, N' -diphenyl benzidine) arylamine carbazole compound and indolocarbazole compound; the thickness of the hole transport layer is preferably set to
Figure BDA0002851385420000152
The electron transport layer is one of Alq3, coumarin No. 6, triazole derivatives, azole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives and anthrone derivatives; the thickness of the electron transport layer is preferably set to
Figure BDA0002851385420000153
Figure BDA0002851385420000154
The electron injection layer is LiF, CsF or Li2O、Al2O3MgO; the thickness of the electron injection layer is preferably 0.1-10 nm.
In the embodiment of the present invention, the various functional layers described above may be formed by a solution coating method and a vacuum deposition method. The solution coating method means spin coating, dip coating, inkjet printing, screen printing, spraying method, etc., but is not limited thereto.
In addition, the organic electroluminescent device may be applied to an Organic Light Emitting Device (OLED), an Organic Solar Cell (OSC), electronic paper (e-paper), an Organic Photoreceptor (OPC), an organic thin film transistor (OTF T), or the like, according to the same principle, but is not limited thereto.
Compared with the prior art, the embodiment of the invention has the beneficial effects that:
according to the fluorene phosphorescent compound provided by the embodiment of the invention, the specific heterocyclic ligand combination is selected, and the wavelength of the compound is adjusted, so that the fluorene phosphorescent compound can improve the luminous efficiency and the service life of an organic electroluminescent device after being used in the organic electroluminescent device. In addition, the preparation method of the fluorene phosphorescent compound provided by the embodiment of the invention has the advantages of easily available raw materials, simple synthesis process and higher product yield.
Detailed Description
The following are examples of the present invention, which are provided to aid understanding of the present invention and are not intended to limit the scope of the present invention. In addition, the preparation methods of the compounds which are not specifically listed in the embodiments of the present invention are methods generally applied in the related industries, and the methods described in the embodiments can be referred to when preparing other compounds.
Example 1
This example provides a fluorene phosphorescent compound, which is prepared by the following steps:
Figure BDA0002851385420000161
1) preparation of intermediate C1: after addition of reactants A-1(73.5mmo) l and B1-1(80.85mmol) to the reaction vessel, additional Pd (pph)3)4(7.35mmol), potassium carbonate (14.7mmol), and 600mL of a mixture of solvents toluene, ethanol, and water, the air was sufficiently replaced with nitrogen three times; the temperature was raised to 90 ℃ and the reaction was carried out for about 18 hours. And after the reaction is finished, cooling, separating liquid, spin-drying a toluene layer to obtain a dark solid, dissolving the dark solid by using about 30mL of dichloromethane, and then passing through a silica gel column, wherein dichloromethane: petroleum ether is 1: 4 most of the product is washed out and spin-dried to obtain a white solid product C1-1(61.7 mmol).
2) Preparation of intermediate D1-1: product C1-1(61.7mmol) was dissolved in anhydrous 400mL THF under nitrogen and stirred at 0 deg.C for 30 min. About 185.1mmol of MgBrMe compound is added, and after 2 hours of reaction, the temperature is gradually raised to room temperature and the reaction is carried out for 12 hours. The saturated ammonium chloride solution was added dropwise to the reaction solution, followed by liquid separation, extraction of the primary aqueous layer with THF, combination of the organic layers, and drying over anhydrous magnesium sulfate for 10 minutes to obtain about 55mmol of the compound represented by intermediate D1-1.
3) Preparation of intermediate E1-1: intermediate D1-1(55mmol) was added to THF (200mL), cooled at 0 deg.C for 30 minutes, and then separately added MSA (60mL), 52g polyphosphoric acid, and 100mL ethanol. After reacting for 3 hours, heating to room temperature, stirring for 14 hours, separating out solids, directly filtering, washing filter cakes by water, ethanol and petroleum ether respectively, and drying to obtain an intermediate E1-1.
4) Preparation of intermediate F1-1: intermediate E1-1(55mmol) was added to dichloromethane, stirred at room temperature for 30 min and NCS (60mmol) was added slowly. And after the reaction is finished for 16 hours, spin-drying the organic layer to obtain a light yellow solid, adding petroleum ether, a proper amount of ethanol and water, stirring overnight, directly performing suction filtration, washing filter cakes with water, ethanol and petroleum ether respectively, and drying to obtain an intermediate F1-1.
5) Preparation of fluorene phosphorescent compound 1: pd (pph)3)4(0.5mmol), potassium carbonate (100mmol), raw material H1-1(60mmol) and intermediate F1-1(50mmol) are added into a reaction bottle, 300mL of mixed solution of toluene, ethanol and water is added, nitrogen is used for protection, and the temperature is raised to 90 ℃ for reaction for 24 hours. Cooling, suction filtering to obtain light yellow filtrate, spin drying the filtrate to obtain solid, adding dichloromethane to dissolve, and passing through silica gel funnel to obtain fluorene phosphorescent compound 1(18.6g, 91%).
The HPLC purity of the fluorene phosphorescent compound is more than 99.9%. Mass spectrum with a theoretical value of 420.56; the test value was 420.13.
Example 2
This example provides a fluorene phosphorescent compound, which is prepared by the following steps:
Figure BDA0002851385420000171
1) preparation of intermediate C1-1: after addition of reactants A-1(73.5mmo) l and B1-1(80.85mmol) to the reaction vessel, additional Pd (pph)3)4(7.35mmol), potassium carbonate (14.7mmol), and 600mL of a mixture of solvents toluene, ethanol, and water, the air was sufficiently replaced with nitrogen three times; the temperature was raised to 90 ℃ and the reaction was carried out for about 18 hours. And after the reaction is finished, cooling, separating liquid, spin-drying a toluene layer to obtain a dark solid, dissolving the dark solid by using about 30mL of dichloromethane, and then passing through a silica gel column, wherein dichloromethane: petroleum ether is 1: 4 most of the product is washed out and spin-dried to obtain a white solid product C1-1(61.7 mmol).
2) Preparation of intermediate D1-1: product C1-1(61.7mmol) was dissolved in anhydrous 400mL THF under nitrogen and stirred at 0 deg.C for 30 min. About 185.1mmol of MgBrMe compound is added, and after 2 hours of reaction, the temperature is gradually raised to room temperature and the reaction is carried out for 12 hours. The saturated ammonium chloride solution was added dropwise to the reaction solution, followed by liquid separation, extraction of the primary aqueous layer with THF, combination of the organic layers, and drying over anhydrous magnesium sulfate for 10 minutes to obtain about 55mmol of the compound represented by intermediate D1-1.
3) Preparation of intermediate E1-1: intermediate D1-1(55mmol) was added to THF (200mL), cooled at 0 deg.C for 30 minutes, and then separately added MSA (60mL), 52g polyphosphoric acid, and 100mL ethanol. After reacting for 3 hours, heating to room temperature, stirring for 14 hours, separating out solids, directly filtering, washing filter cakes by water, ethanol and petroleum ether respectively, and drying to obtain an intermediate E1-1.
4) Preparation of intermediate F1-1: intermediate E1-1(55mmol) was added to dichloromethane, stirred at room temperature for 30 min and NCS (60mmol) was added slowly. And after the reaction is finished for 16 hours, spin-drying the organic layer to obtain a light yellow solid, adding petroleum ether, a proper amount of ethanol and water, stirring overnight, directly performing suction filtration, washing filter cakes with water, ethanol and petroleum ether respectively, and drying to obtain an intermediate F1-1.
5) Preparation of the fluorene-based phosphorescent compound 10: pd (pph)3)4(0.5mmol), potassium carbonate (100mmol), raw material H1-10(60mmol) and intermediate F1-1(50mmol) are added into a reaction bottle, 300mL of mixed solution of toluene, ethanol and water is added, nitrogen is used for protection, the temperature is raised to 90 ℃, and the reaction is carried outShould be 24 hours. Cooling, suction filtering to obtain light yellow filtrate, spin drying the filtrate to obtain solid, adding dichloromethane to dissolve, and passing through silica gel funnel to obtain fluorene phosphorescent compound 10(20.8g, yield 84%).
The HPLC purity of the fluorene phosphorescent compound is more than 99.9%. Mass spectrum with a theoretical value of 456.77; the test value was 456.67.
Example 3
This example provides a fluorene phosphorescent compound, which is prepared by the following steps:
Figure BDA0002851385420000191
1) preparation of intermediate C1-62: after addition of reactants A-62(73.5mmo) l and B1-62(80.85mmol) to the reaction vessel, additional Pd (pph)3)4(7.35mmol), potassium carbonate (14.7mmol), and 600mL of a mixture of solvents toluene, ethanol, and water, the air was sufficiently replaced with nitrogen three times; the temperature was raised to 90 ℃ and the reaction was carried out for about 18 hours. And after the reaction is finished, cooling, separating liquid, spin-drying a toluene layer to obtain a dark solid, dissolving the dark solid by using about 30mL of dichloromethane, and then passing through a silica gel column, wherein dichloromethane: petroleum ether is 1: 4 most of the product is washed out and spin-dried to obtain a white solid product C1-62(61.7 mmol).
2) Preparation of intermediate D1-62: product C1-62(61.7mmol) was dissolved in anhydrous 400mL THF under nitrogen and stirred at 0 deg.C for 30 min. About 185.1mmol of MgBrMe compound is added, and after 2 hours of reaction, the temperature is gradually raised to room temperature and the reaction is carried out for 12 hours. The saturated ammonium chloride solution was added dropwise to the reaction solution, followed by liquid separation, extraction of the once aqueous layer with THF, combination of the organic layers, and drying over anhydrous magnesium sulfate for 10 minutes to obtain about 55mmol of the compound represented by intermediate D1-62.
3) Preparation of intermediate E1-62: intermediate D1-62(55mmol) was added to THF (200mL), cooled at 0 deg.C for 30 minutes, and then separately added MSA (60mL), 52g polyphosphoric acid, and 100mL ethanol. After reacting for 3 hours, heating to room temperature, stirring for 14 hours, separating out solids, directly filtering, washing filter cakes by water, ethanol and petroleum ether respectively, and drying to obtain an intermediate E1-1.
4) Preparation of intermediate F1-62: intermediate E1-1(55mmol) was added to dichloromethane, stirred at room temperature for 30 min and NCS (60mmol) was added slowly. And after the reaction is finished for 16 hours, spin-drying the organic layer to obtain a light yellow solid, adding petroleum ether, a proper amount of ethanol and water, stirring overnight, directly performing suction filtration, washing filter cakes with water, ethanol and petroleum ether respectively, and drying to obtain an intermediate F1-62.
5) Preparation of fluorene-based phosphorescent compound 62: pd (pph)3)4(0.5mmol), potassium carbonate (100mmol), raw material H1-10(60mmol) and intermediate F1-1(50mmol) are added into a reaction bottle, 300mL of mixed solution of toluene, ethanol and water is added, nitrogen is used for protection, and the temperature is raised to 90 ℃ for reaction for 24 hours. Cooling, suction filtering to obtain light yellow filtrate, spin drying the filtrate to obtain solid, dissolving with dichloromethane, and passing through silica gel funnel to obtain fluorene phosphorescent compound 62(20.8g, yield 84%).
The HPLC purity of the fluorene phosphorescent compound is more than 99.9%. Mass spectrum with a theoretical value of 560.74; the test value was 560.18.
Example 4
This example provides a fluorene phosphorescent compound, which is prepared by the following steps:
Figure BDA0002851385420000201
1) preparation of intermediate C1-76: after the reactants A-76(73.5mmo) l and B2-76(80.85mmol) were added to the reaction vessel, Pd (pph) was added3)4(7.35mmol), potassium carbonate (14.7mmol), and 600mL of a mixture of solvents toluene, ethanol, and water, the air was sufficiently replaced with nitrogen three times; the temperature was raised to 90 ℃ and the reaction was carried out for about 18 hours. And after the reaction is finished, cooling, separating liquid, spin-drying a toluene layer to obtain a dark solid, dissolving the dark solid by using about 30mL of dichloromethane, and then passing through a silica gel column, wherein dichloromethane: petroleum ether is 1: 4 most of the product is washed out and spin-dried to obtain a white solid product C2-76(61.7 mmol).
2) Preparation of intermediate D2-76: product C2-76(61.7mmol) was dissolved in anhydrous 400mL THF under nitrogen and stirred at 0 deg.C for 30 min. About 185.1mmol of MgBrMe compound is added, and after 2 hours of reaction, the temperature is gradually raised to room temperature and the reaction is carried out for 12 hours. The saturated ammonium chloride solution was added dropwise to the reaction solution, followed by liquid separation, extraction of the primary aqueous layer with THF, combination of the organic layers, and drying over anhydrous magnesium sulfate for 10 minutes to obtain about 55mmol of the compound represented by intermediate D2-76.
3) Preparation of intermediate E2-76: intermediate D2-76(55mmol) was added to THF (200mL), cooled at 0 deg.C for 30 minutes, and then separately added MSA (60mL), 52g polyphosphoric acid, and 100mL ethanol. After reacting for 3 hours, heating to room temperature, stirring for 14 hours, separating out solids, directly filtering, washing filter cakes by water, ethanol and petroleum ether respectively, and drying to obtain an intermediate E2-76.
4) Preparation of fluorene-based phosphorescent compound 76: preparation of compound 76: pd is added2(dba)3(0.6mmol) and sodium tert-butoxide (66mmol) were added to dry toluene and stirred at room temperature for 30 minutes under nitrogen. Then the intermediate D-76(30mmol) and the reactant E-76(36mmol) are added, finally P (t-bu)3(6mmol), and the reaction was carried out at 100 ℃ for 24 hours. The temperature was reduced, the mixture was filtered through a silica gel funnel, and the fluorene phosphorescent compound 76(13.6g, 84% yield) was obtained.
The HPLC purity of the fluorene phosphorescent compound is more than 99.9%. Mass spectrum calculated 539.72; the test value was 539.84.
Example 5
This example provides a fluorene phosphorescent compound, which is prepared by the following steps:
Figure BDA0002851385420000221
1) the preparation method of the intermediate F3-103 is the same as that of the intermediate F1-10.
2) Preparation of the fluorene-based phosphorescent compound 102: preparation of compound 102: pd (pph)3)4(0.5mmol), potassium carbonate (100mmol), raw material H3-102(60mmol) and intermediate F3-102(50mmol) are added into a reaction bottle, 300mL of mixed solution of toluene, ethanol and water is added, nitrogen is used for protection, and the temperature is raised to 90 ℃ for reaction for 24 hours. Cooling, vacuum filtering to obtain light yellow filtrate, spin drying the filtrate to obtain solid,the mixture was dissolved in dichloromethane and filtered through a silica gel funnel to obtain the fluorene phosphorescent compound 102(20.8g, 84% yield).
The HPLC purity of the fluorene phosphorescent compound is more than 99.9%. Mass spectrum calculated 587.77; the test value was 587.93.
Examples 6 to 15
The synthetic routes and principles of the preparation methods of other phosphorescent compounds having the general structural formula of formula I in the summary of the invention are the same as those of the above-listed example 1, and the corresponding phosphorescent compounds can be obtained only by replacing the raw materials with the raw materials corresponding to the corresponding ligand structures in the target product and adjusting the material amounts according to the corresponding stoichiometric ratios, so that the embodiments of the present invention are not exhaustive, and the synthesis of the phosphorescent compounds 2, 10, 15, 36, 39, 42, 43, 58, 62, 67 is completed with reference to the preparation methods of examples 1 to 5, and the mass spectra, the molecular formulae and the yields are shown in table 1.
TABLE 1
Figure BDA0002851385420000222
Figure BDA0002851385420000231
Device example 1
The embodiment of the device provides an organic electroluminescent device, and the specific preparation method comprises the following steps:
coating with a thickness of
Figure BDA0002851385420000232
The ITO glass substrate of (1) was washed in distilled water for 2 times, ultrasonically for 30 minutes, repeatedly washed in distilled water for 2 times, ultrasonically for 10 minutes, and after the washing with distilled water was completed, solvents such as isopropyl alcohol, acetone, and methanol were ultrasonically washed in this order, dried, transferred to a plasma cleaning machine, and the substrate was washed for 5 minutes and sent to an evaporation coater. First, vapor deposition is carried out on the ITO (anode)
Figure BDA0002851385420000233
Followed by evaporation
Figure BDA0002851385420000234
The fluorene phosphorescent compound 1 and the dopant Ir (ppy)395:5 weight ratio hybrid evaporation
Figure BDA0002851385420000235
Vapor deposition electron transport layer
Figure BDA0002851385420000236
Vapor deposition of electron injection layer
Figure BDA0002851385420000237
Evaporation cathode
Figure BDA0002851385420000238
And (4) preparing the organic electroluminescent device.
Device example 2-device example 14
By referring to the preparation method provided in device example 1 above, the fluorene-based phosphorescent compound 1 used in device example 1 was replaced with the fluorene-based phosphorescent compounds 2, 5, 10, 15, 17, 36, 39, 42, 43, 58, 62, 67, 76 provided in the above examples, respectively, as host materials, and the corresponding organic electroluminescent devices were prepared.
Comparative device example 1
The device comparative example produced an organic electroluminescent device. Specifically, according to the preparation method of the device example 1, the host material fluorene phosphorescent compound 1 in the light-emitting layer is replaced by the compound CBP, and the other methods are the same, so as to prepare the organic electroluminescent device. Wherein, the structural formula of CBP is as follows:
Figure BDA0002851385420000241
for the performance luminescence property test of the device obtained above, a KEITHLEY 2400 type source measuring unit and a CS-2000 spectral radiance luminance meter are used for the measurement to evaluate the driving voltage, the luminescence efficiency and the device lifetime, and the evaluation results are shown in table 2 below.
TABLE 2
Figure BDA0002851385420000242
Figure BDA0002851385420000251
In table 2, the device performance test results are based on device comparative example 1, i.e., the performance index of device comparative example 1 is set to 1.0, and the performance index of the device example is a multiple of that of device comparative example 1. The results in table 2 show that the fluorene phosphorescent compound provided by the present invention can be applied to an organic electroluminescent device, and compared with an organic electroluminescent device containing a conventional host material, the organic electroluminescent device containing the fluorene phosphorescent compound provided by the present invention has improved voltage, efficiency and lifetime.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.

Claims (3)

1. A fluorene phosphorescent compound, wherein the chemical structural formula of the phosphorescent compound is any one of formulas 1, 2, 5, 10, 15, 17, 36, 39, 42, 43, 58, 62, 67, and 76:
Figure FDA0003463132960000011
2. an organic electroluminescent device comprising an anode, a cathode and at least one organic layer disposed between said anode and said cathode, wherein said organic layer comprises the phosphorescent compound of claim 1.
3. An organic electroluminescent device according to claim 2, wherein the organic layer comprises a light-emitting layer; the light-emitting layer comprises a host material and a doping material; the host material partially or completely contains the phosphorescent compound.
CN202011527964.3A 2020-12-22 2020-12-22 Fluorene phosphorescent compound, preparation method thereof and organic electroluminescent device Active CN112479987B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011527964.3A CN112479987B (en) 2020-12-22 2020-12-22 Fluorene phosphorescent compound, preparation method thereof and organic electroluminescent device

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011527964.3A CN112479987B (en) 2020-12-22 2020-12-22 Fluorene phosphorescent compound, preparation method thereof and organic electroluminescent device

Publications (2)

Publication Number Publication Date
CN112479987A CN112479987A (en) 2021-03-12
CN112479987B true CN112479987B (en) 2022-04-01

Family

ID=74915318

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011527964.3A Active CN112479987B (en) 2020-12-22 2020-12-22 Fluorene phosphorescent compound, preparation method thereof and organic electroluminescent device

Country Status (1)

Country Link
CN (1) CN112479987B (en)

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008054141A1 (en) * 2008-10-31 2010-05-06 Merck Patent Gmbh New materials for organic electroluminescent devices
KR102180763B1 (en) * 2015-08-31 2020-11-19 엘티소재주식회사 Hetero-cyclic compound and organic light emitting device using the same
WO2018099433A1 (en) * 2016-11-30 2018-06-07 广州华睿光电材料有限公司 Fused ring compound and use thereof, mixture and organic electronic device
EP3679024B1 (en) * 2017-09-08 2022-11-02 Merck Patent GmbH Materials for electronic devices
US11557743B2 (en) * 2018-01-17 2023-01-17 Konica Minolta, Inc. Luminescent film, organic electroluminescent device, and method for manufacturing organic electroluminescent device
CN110903158A (en) * 2018-09-18 2020-03-24 上海和辉光电有限公司 Organic luminescent material containing anthracene derivative, preparation method thereof and electroluminescent device

Also Published As

Publication number Publication date
CN112479987A (en) 2021-03-12

Similar Documents

Publication Publication Date Title
CN111004201B (en) Organic electroluminescent compound, preparation method thereof and organic electroluminescent device
CN112375071B (en) Organic light-emitting compound and preparation method and application thereof
CN112010908A (en) Iridium complex for red light electroluminescent material, preparation method thereof and photoelectric device
CN112939990B (en) Luminescent compound with organic condensed rings, preparation method thereof and organic electroluminescent device
CN112079806A (en) Organic electroluminescent compound, preparation method thereof and organic electroluminescent device
CN111205289A (en) Phosphorescent material, preparation method thereof and organic electroluminescent device
CN110760305A (en) Phosphorescent compound, preparation method thereof and organic electroluminescent device comprising phosphorescent compound
CN110790796A (en) Novel organic metal iridium complex, preparation method thereof and organic electroluminescent device containing metal iridium complex
CN110845421A (en) Electron transport compound, synthesis method thereof and organic electroluminescent device
CN116332933A (en) Condensed ring organic compound, luminous composition and organic electroluminescent device
CN112830900B (en) Phosphorescent compound, method of preparing the same, and organic electroluminescent device comprising the same
CN111116670B (en) Organic metal iridium complex and preparation method and application thereof
CN112812123B (en) Hole compound, preparation method thereof and organic electroluminescent device
CN112479987B (en) Fluorene phosphorescent compound, preparation method thereof and organic electroluminescent device
CN113896719A (en) Pure organic fluorescent micromolecules with high exciton utilization rate and application thereof
CN111233862A (en) Phosphorescent organic compound, preparation method thereof and organic electroluminescent device
CN112079833A (en) Organic electroluminescent compound and preparation method and application thereof
CN112500396A (en) Dibenzopyran spiro organic luminescent compound and preparation method and application thereof
CN105777809A (en) Organic electroluminescence material and organic electroluminescence device
CN111004290A (en) Organic phosphorus luminescent compound, preparation method thereof and organic electroluminescent device
CN112062765B (en) Organic photoelectric luminescent compound and preparation method thereof
CN111187265B (en) Organic main body material, preparation method thereof and organic electroluminescent device
CN114874169B (en) Organic compound, material containing the same, and organic light-emitting device
CN112079875B (en) Organic electroluminescent material, preparation method thereof and organic electroluminescent device
CN111777609B (en) Anthracene-containing derivative 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
GR01 Patent grant
GR01 Patent grant