CN111548342B - Dendritic bipolar main body material with triazine as central core, preparation method and application of dendritic bipolar main body material in organic electroluminescent device - Google Patents

Dendritic bipolar main body material with triazine as central core, preparation method and application of dendritic bipolar main body material in organic electroluminescent device Download PDF

Info

Publication number
CN111548342B
CN111548342B CN202010399670.0A CN202010399670A CN111548342B CN 111548342 B CN111548342 B CN 111548342B CN 202010399670 A CN202010399670 A CN 202010399670A CN 111548342 B CN111548342 B CN 111548342B
Authority
CN
China
Prior art keywords
formula
mmol
reaction
compound
solvent
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
CN202010399670.0A
Other languages
Chinese (zh)
Other versions
CN111548342A (en
Inventor
吕剑虹
王淑萌
张明明
王兴东
赵磊
陈亮
王利祥
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.)
Changchun Institute of Applied Chemistry of CAS
Original Assignee
Changchun Institute of Applied Chemistry of CAS
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 Changchun Institute of Applied Chemistry of CAS filed Critical Changchun Institute of Applied Chemistry of CAS
Priority to CN202010399670.0A priority Critical patent/CN111548342B/en
Publication of CN111548342A publication Critical patent/CN111548342A/en
Application granted granted Critical
Publication of CN111548342B publication Critical patent/CN111548342B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
    • C07F7/0816—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring comprising Si as a ring atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
    • C07F7/083—Syntheses without formation of a Si-C bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
    • C07F9/6584—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms having one phosphorus atom as ring hetero atom
    • 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
    • H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
    • 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
    • H10K85/6574—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
    • 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
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/104—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with other 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
    • C09K2211/1044—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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/10—Triplet emission
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/40—Interrelation of parameters between multiple constituent active layers or sublayers, e.g. HOMO values in adjacent layers

Abstract

The invention provides a compound with a structure of a formula (I), a preparation method and application thereof, wherein the compound with the structure of the formula (I) is a dendritic bipolar main body material taking triazine as a central core, which is different from a D-pi-A type structure of a traditional dendritic bipolar main body, and the D-A type dendritic bipolar main body formed by directly connecting the central core triazine as an electron acceptor (A) and peripheral branches as an electron donor (D) maintains a high triplet state energy level (2.8-3.3 eV) by directly connecting the acceptors, thereby being beneficial to the application of the compound on a blue light OLED device; experiments show that the maximum current efficiency of the blue phosphorescence electroluminescent device prepared by taking the compound as the main material can reach 46.7cd/A, and the maximum workThe efficiency can reach 50.11m/W, and the maximum brightness can reach 32000cd/m 2 The turn-on voltage was 2.4V.

Description

Dendritic bipolar main body material with triazine as central core, preparation method and application of dendritic bipolar main body material in organic electroluminescent device
Technical Field
The invention relates to the field of organic semiconductor photoelectric materials, in particular to a dendritic bipolar main body taking triazine as a central core, and a preparation method and application thereof.
Background
Organic Light Emitting Diodes (OLEDs) have characteristics of ultra-thin, flexible, surface light source, etc., and have been gradually applied to the fields of flat panel display, solid state lighting, etc. The solution processing type OLED has received extensive attention in academia and industry due to its low cost, easy large area processing, and the like. In the preparation of solution processed OLED devices, in order to enhance device performance, a luminescent guest is typically doped into the host material to suppress the adverse processes of triplet-triplet quenching (TTA), triplet-polaron quenching (TPA) in the light emitting layer. Thus, the choice of host material has a crucial impact on the performance of the OLED device. Currently, solution processing type host materials can be divided into three types: small molecules, polymers, and dendrimers. Wherein, the dendritic molecule has the advantage of definite small molecular structure, thus realizing higher chemical purity. In addition, dendrimers also have excellent solution processability of polymeric materials. Therefore, the dendritic main body material with the advantages of small molecules and polymers has wide application prospect in liquid processing type OLED.
The dendritic host material can be further divided into a monopolar host and a bipolar host according to the carrier transport capability. The bipolar main body material composed of the electron donor unit (D) and the electron acceptor unit (A) has both hole and electron transmission capability, is favorable for realizing hole/electron transmission balance in the luminescent layer, enlarges the exciton recombination area, and can further inhibit TTA and TPA processes caused by overlarge exciton concentration. At present The reported dendritic bipolar host material mainly adopts a D-pi-A type structure with a conjugated segment (pi) connected with a D and A unit, and the molecular design can increase the conjugation length of the molecule and reduce the triplet energy level (T) 1 ) Making it unusable for assembling high performance blue OLED devices.
Therefore, it is of great importance to provide a dendritic bipolar host material with a high triplet energy level suitable for use in blue-light OLED devices.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a dendritic bipolar body with triazine as a central core, and a preparation method and application thereof.
Compared with the prior art, the compound with the structure of the formula (I) is a dendritic bipolar main body material taking triazine as a central core, and is different from a D-pi-A type structure of a traditional dendritic bipolar main body, and the D-A type dendritic bipolar main body formed by directly connecting the central core triazine as an electron acceptor (A) and peripheral branches as an electron donor (D) maintains a high triplet state energy level (2.8-3.3 eV) by the acceptor, so that the compound is beneficial to the application of the compound on a blue light OLED device; experiments show that the maximum current efficiency of the blue phosphorescence electroluminescent device prepared by taking the compound as a main material can reach 46.7cd/A, the maximum power efficiency can reach 50.1lm/W, and the maximum brightness can reach 32000cd/m 2 The turn-on voltage was 2.4V.
Drawings
FIG. 1 is a film fluorescence spectrum of the host material of formula (1) prepared in example 1 of the present invention;
FIG. 2 is a film phosphorescence spectrum of the host material of formula (1) prepared in example 1 of the present invention;
FIG. 3 is a cyclic voltammogram of the host material of formula (1) prepared in example 1 of the present invention;
FIG. 4 is an electroluminescence spectrum of a blue phosphorescent device prepared based on formula (1) of the host material according to the present invention;
FIG. 5 is a graph showing voltage-current density-luminance curves of a blue phosphorescent device prepared based on formula (1) of the host material according to the present invention;
FIG. 6 is a graph showing luminance versus current efficiency for a blue phosphorescent device prepared based on formula (1) of the host material according to the present invention;
FIG. 7 is a graph showing luminance versus power efficiency for a blue phosphorescent device prepared based on formula (1) of the host material according to the present invention;
FIG. 8 is a film fluorescence spectrum of the host material of formula (3) prepared in example 3 of the present invention;
FIG. 9 is a film phosphorescence spectrum of the host material of formula (3) prepared in example 3 of the present invention;
FIG. 10 is a cyclic voltammogram of the host material of formula (3) prepared in example 3 of the present invention;
FIG. 11 is an electroluminescence spectrum of a blue phosphorescent device prepared based on formula (3) of the host material according to the present invention;
FIG. 12 is a graph showing voltage-current density-luminance curves of a blue phosphorescent device prepared based on formula (3) of the host material according to the present invention;
FIG. 13 is a graph showing luminance versus current efficiency for a blue phosphorescent device prepared based on formula (3) of the host material according to the present invention;
fig. 14 is a luminance-power efficiency curve of a blue phosphorescent device prepared based on formula (3) of the host material according to the present invention.
Detailed Description
The invention provides a dendritic bipolar host material taking triazine as a center, which has a structure shown in a formula (I),
wherein Ar is 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 Independently selected from electron-donating aryl, electron-donating heteroaryl, or hydrogen;
Z 1 、Z 2 、Z 3 independently selected from single bond, oxygen atom, sulfur atom, And->One or more of them are connected together to form a combination; wherein R is 1 、R 2 Independently selected from hydrogen, C1-C12 alkyl, C6-C30 aryl or C5-C25 heteroaryl.
In the invention, ar is as follows 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 Independently selected from C6-C50 electron donating aryl, C5-C50 electron donating heteroaryl or hydrogen; wherein the hetero atom in the heteroaryl is one or more of N, S, O, B and Si; preferably, the Ar 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 Independently selected from the following groups:
wherein the L is 1 、L 2 、L 3 、L 4 Independently selected from the group consisting of C1-C22 straight chain alkyl, C1-C22 branched chain alkyl, C3-C22 cycloalkyl, C1-C22 alkoxy, and C6-C30 aryl, preferably, said L 1 、L 2 、L 3 、L 4 Independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, hexyl, heptyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, t-butoxy, n-pentoxy, isopentoxy, hexoxy, heptoxy, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, naphthyl, anthracyl, phenanthryl, or fluorenyl.
In the invention, the R 1 、R 2 Independently selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, hexyl,Heptyl, phenyl, naphthyl, anthryl, phenanthryl, fluorenyl, furyl, pyridyl, piperidinyl or thienyl.
More specifically, the triazine-centered core dendritic bipolar host material has the following structure:
/>
/>
/>
/>
/>
/>
/>
/>
/>
the invention also provides a preparation method of the compound, which comprises the following steps:
reacting a compound of the structure of formula (VI-1), a compound of the structure of formula (VI-2), a compound of the structure of formula (VI-3) and a compound of the structure of formula (VII) to obtain a compound of the structure of formula (I),
wherein Ar is 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 Independently selected from electron-donating aryl, electron-donating heteroaryl, or hydrogen;
Z 1 、Z 2 、Z 3 Independently selected from single bond,An oxygen atom, a sulfur atom, And->One or more of them are connected together to form a combination; wherein R is 1 、R 2 Independently selected from hydrogen, C1-C12 alkyl, C6-C30 aryl or C5-C25 heteroaryl.
According to the invention, a compound with a structure of formula (VI-1), a compound with a structure of formula (VI-2), a compound with a structure of formula (VI-3) and a compound with a structure of formula (VII) are reacted to obtain a compound with a structure of formula (I); specifically, the invention firstly mixes a compound with a structure of a formula (VI-1), a compound with a structure of a formula (VI-2), a compound with a structure of a formula (VI-3) and n-butyllithium, and then adds a compound with a structure of a formula (VII) to react to obtain a compound with a structure of a formula (I); wherein the compound of the structure shown in (VII): (Compound of formula (VI-1) +Compound of formula (VI-2) +Compound of formula (VI-3): the molar ratio of n-butyllithium is preferably 1: (3-5): (3-6); the solvent for the reaction is preferably N, N-dimethylformamide, tetrahydrofuran or dimethyl sulfoxide; the reaction temperature is preferably-78-100 ℃; more specifically, the invention preferably adds n-butyllithium slowly to a solution containing a compound of formula (VI-1), a compound of formula (VI-2) and a compound of formula (VI-3) for reaction under the protection of inert atmosphere, wherein the reaction is carried out by (the compound of formula (VI-1) +the compound of formula (VI-2) +the compound of formula (VI-3): the molar ratio of N-butyllithium is preferably 1 (1-3), the reaction temperature is preferably-78-0 ℃, the reaction time is preferably 1-8 h, and the reaction solvent is preferably N, N-dimethylformamide, tetrahydrofuran or dimethyl sulfoxide; after the reaction is complete, adding the structural compound shown in the formula (VII) into the reaction system to obtain the compound shown in the formula (I), wherein the structural compound shown in the formula (VII): the molar ratio of (compound of formula (VI-1) +compound of formula (VI-2) +compound of formula (VI-3)) is preferably 1: (3.6-5), the reaction temperature is preferably 0-100 ℃, and the reaction time is preferably 6-24 h.
According to the invention, the compound of formula (VI-1) is preferably prepared according to the following method:
mixing the compound shown in the formula (II-1) or the formula (III-1) with sodium hydride and tert-butyldimethyl chlorosilane (TBS-Cl) for reaction to obtain a compound with a structure shown in the formula (IV-1) or the formula (V-1); wherein the solvent for the reaction is N, N-dimethylformamide, tetrahydrofuran or dimethyl sulfoxide, and the reaction temperature is 0-70 ℃. More specifically, in the invention, naH is preferably slowly added into a solution with a structure shown in (II-1) or (III-2) for reaction under the protection of inert atmosphere, wherein the reaction temperature is preferably 0-10 ℃, the reaction time is preferably 1-3 h, and the molar ratio of the formula (II-1) or (III-1) to NaH is preferably 1: (1-2); then tert-butyldimethylchlorosilane (TBS-Cl) is added for reaction to obtain the compound with the structure shown in (IV-1) or (V-1), wherein the molar ratio of the formula (II-1) or (III-1) to TBS-Cl is preferably 1: (1-2), the reaction temperature is preferably 0-30 ℃, and the reaction time is preferably 8-24 hours.
Mixing a compound having a structure represented by (IV-1) or (V-1) with Ar 1 -H and Ar 2 H is mixed and reacted to obtain the structure shown in (VI-1); preferably, NH is added at room temperature after the mixing reaction is finished 4 FBu 4 Reacting for 2-8 hours to obtain a structure shown in (VI-1); the catalyst of the reaction is palladium acetate, tetrakis (triphenylphosphine) palladium or tris (dibenzylideneacetone) dipalladium; the ligand of the reaction is tri-tert-butylphosphine tetrafluoroborate, triphenylphosphine, tricyclohexylphosphine, tri-tert-butylphosphine or 2-dicyclohexyl phosphorus-2, 4, 6-triisopropylbiphenyl; the alkali of the reaction is potassium hydroxide, sodium carbonate, sodium tert-butoxide, potassium carbonate, cesium carbonate or potassium phosphate; the solvent for the reaction is toluene, xylene, mesitylene or o-dichlorobenzene; the junction shown in (IV-1) or (V-1)A compound of the structure: (Ar) 1 -H+Ar 2 -H): catalyst: ligand: alkali: NH (NH) 4 FBu 4 Preferably 1: (1-5): (0.2-0.5): (0.3-0.6): (3-8): (3-5); the reaction temperature is 60-140 ℃, preferably 70-130 ℃, and the reaction time is 12-30 h.
The compound with the structure of the formula (VI-2) is prepared by the following method:
mixing the compound shown in the formula (II-2) or the formula (III-2) with sodium hydride and tert-butyldimethyl chlorosilane (TBS-Cl) for reaction to obtain a compound with a structure shown in the formula (IV-2) or the formula (V-2); the solvent of the reaction is N, N-dimethylformamide, tetrahydrofuran or dimethyl sulfoxide, and the reaction temperature is 0-70 ℃. More specifically, in the invention, naH is preferably slowly added into a solution with a structure shown in (II-2) or (III-2) for reaction under the protection of inert atmosphere, wherein the reaction temperature is preferably 0-10 ℃, the reaction time is preferably 1-3 h, and the molar ratio of the formula (II-2) or (III-2) to NaH is preferably 1: (1-2); after subsequent reaction with addition of t-butyldimethylchlorosilane (TBS-Cl), the structures of formula (IV-2) or (V-2) are obtained, wherein the molar ratio of formula (II-2) or formula (III-2) to TBS-Cl is preferably 1: (1-2), the reaction temperature is preferably 0-30 ℃, and the reaction time is preferably 8-24 hours.
Mixing a compound having a structure represented by (IV-2) or (V-2) with Ar 3 -H and Ar 4 H is mixed and reacted to obtain the structure shown in (VI-2); preferably, NH is added at room temperature after the mixing reaction is finished 4 FBu 4 Reacting for 2-8 hours to obtain a structure shown in (VI-2); the catalyst of the reaction is palladium acetate, tetrakis (triphenylphosphine) palladium or tris (dibenzylideneacetone) dipalladium; the ligand of the reaction is tri-tert-butylphosphine tetrafluoroborate, triphenylphosphine, tricyclohexylphosphine, tri-tert-butylphosphine or 2-dicyclohexyl phosphorus-2, 4, 6-triisopropylbiphenyl; the alkali of the reaction is potassium hydroxide, sodium carbonate, sodium tert-butoxide, potassium carbonate, cesium carbonate or potassium phosphate; the solvent for the reaction is toluene and xyleneMesitylene or o-dichlorobenzene; the compound of the structure shown in (IV-2) or (V-2): (Ar) 3 -H+Ar 4 -H): catalyst: ligand: alkali: NH (NH) 4 FBu 4 Preferably 1: (1-5): (0.2-0.5): (0.3-0.6): (3-8): (3-5); the temperature of the reaction is preferably 60 to 140 ℃, more preferably 70 to 130 ℃, and the time of the reaction is 12 to 30 hours.
The compound with the structure of the formula (VI-3) is prepared by the following method:
mixing the compound shown in the formula (II-3) or the formula (III-3) with sodium hydride and tert-butyldimethyl chlorosilane (TBS-Cl) for reaction to obtain a compound with a structure shown in the formula (IV-3) or the formula (V-3); the solvent for the reaction is N, N-dimethylformamide, tetrahydrofuran or dimethyl sulfoxide, and the reaction temperature is 0-70 ℃. More specifically, in the invention, naH is preferably slowly added into a solution with a structure shown in (II-3) or (III-3) for reaction under the protection of inert atmosphere, wherein the reaction temperature is preferably 0-10 ℃, the reaction time is preferably 1-3 h, and the molar ratio of the formula (II-3) or (III-3) to NaH is preferably 1: (1-2); after subsequent reaction with addition of t-butyldimethylchlorosilane (TBS-Cl), the structures of formula (IV-2) or (V-2) are obtained, wherein the molar ratio of formula (II-3) or (III-3) to TBS-Cl is preferably 1: (1-2), the reaction temperature is preferably 0-30 ℃, and the reaction time is preferably 8-24 hours.
/>
Mixing a compound having a structure represented by (IV-3) or (V-3) with Ar 5 -H and Ar 6 H is mixed and reacted to obtain the structure shown in (VI-3); preferably, NH is added at room temperature after the mixing reaction is finished 4 FBu 4 Reacting for 2-8 hours to obtain a structure shown in (VI-3); the catalyst of the reaction is palladium acetate, tetrakis (triphenylphosphine) palladium or tris (dibenzylideneacetone) dipalladium; the ligand of the reaction is tri-tert-butylphosphine tetrafluoroborate, triphenylphosphine, tricyclohexylphosphine, tri-tert-butylphosphine or 2-dicyclohexyl phosphorus-2, 4, 6-triisopropylbiphenyl; the alkali for the reaction is potassium hydroxide, sodium carbonate, sodium tert-butoxide and carbonPotassium acid, cesium carbonate or potassium phosphate; the solvent for the reaction is toluene, xylene, mesitylene or o-dichlorobenzene; the compound of the structure shown in (IV-3) or (V-3): (Ar) 5 -H+Ar 6 -H): catalyst: ligand: alkali: NH (NH) 4 FBu 4 Preferably 1: (1-5): (0.2-0.5): (0.3-0.6): (3-8): (3-5); the reaction temperature is preferably 60 to 140 ℃, more preferably 70 to 130 ℃, and the reaction time is 12 to 30 hours.
The protective gas used in the reaction is not particularly limited, and may be a conventional protective atmosphere widely known, and may be selected and adjusted by a skilled person according to the practical circumstances of the experiment, and the protective atmosphere is preferably an inert gas, more preferably argon.
The invention also provides an organic electroluminescent device, wherein the main material in the device comprises the triazine-based compound; the device is an illumination element or a display element.
The invention has no special requirement on the structure of the organic electroluminescent device, and preferably comprises the following steps:
a substrate; the invention has no special requirement on the substrate, preferably glass or plastic, and the thickness of the substrate is preferably 0.3-0.7 mm;
an anode disposed on the substrate; the anode is a material which is easy for hole injection, preferably a conductive metal or conductive metal oxide, more preferably indium tin oxide;
an organic layer disposed on the anode; the organic layer can be 1 layer or multiple layers, and at least one layer of the organic layers is an organic electroluminescent layer; the organic electroluminescent layer comprises one or more dendritic bipolar main body materials disclosed by the invention;
a cathode disposed on the organic layer; the cathode is preferably a metal including, but not limited to, calcium, magnesium, barium, aluminum, and silver, preferably aluminum.
In order to improve the performance and efficiency of the device, the organic layer between the anode and the organic electroluminescent layer preferably further comprises a hole injection layer, a hole transport layer and an electron blocking layer; the organic layer between the organic electroluminescent layer and the cathode preferably further includes a hole blocking layer and an electron injection/transport layer. The materials and thicknesses of the hole injection layer, the hole transport layer, the electron blocking layer, the hole blocking layer, and the electron injection/transport layer are not particularly limited in the present invention, and may be selected according to materials and thicknesses well known to those skilled in the art.
The method for preparing the organic electroluminescent device is not particularly limited, and is preferably prepared according to the following method:
forming an anode on a substrate; the formation mode of the anode is not particularly limited in the present invention, and may be according to a method well known to those skilled in the art;
cleaning a substrate with an anode by using distilled water, isopropanol, acetone and the like which are organic solvents, then performing drying treatment, and then performing ultraviolet/ozone (UVO) treatment;
forming a hole injection layer on the anode selectively by a spin coating method, and drying; the hole injection layer material is preferably water-soluble PEDOT: PSS;
forming an organic electroluminescent layer on the hole injection layer; the organic electroluminescent layer is formed by doping iridium complex, platinum complex or copper complex and the like into the dendritic bipolar main body material; the organic electroluminescent layer is preferably prepared by adopting a solution spin coating method, and the organic solvent is preferably toluene or chlorobenzene; carrying out heat treatment after spin coating, wherein the heat treatment temperature is preferably 80-120 ℃;
forming a hole blocking layer and an electron injection/transport layer on the organic electroluminescent layer; the hole blocking layer and the electron injection/transport layer are preferably prepared by a vacuum deposition method;
Finally, forming a cathode on the hole blocking layer and the electron injection/transport layer; the present invention is not particularly limited in the manner of forming the cathode, and is preferably a method well known to those skilled in the art, including but not limited to vacuum deposition; the cathode is preferably a metal including, but not limited to, calcium, magnesium, barium, aluminum, and silver, preferably aluminum.
The following description of embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is shown, however, only some, but not all embodiments of the invention are shown. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The synthetic route of formula (1) is as follows:
(1) Synthesis of intermediate 1: 2, 7-dibromo-9, 10-dihydro-9, 9-dimethylacridine (30.0 g,81.7 mmol) and 200ml THF are mixed and stirred at 0℃under argon. Subsequently, a solution of NaH (2.4 g,98.1 mmol) in THF was slowly dropped, then the reaction was continued for 2 hours at room temperature, and then t-butyldimethylchlorosilane (14.8 g,98.1 mmol) was added to the reaction flask and stirred overnight. After the completion of the reaction, the solvent was evaporated under reduced pressure, and the crude product was purified by column separation with petroleum ether to give 1 (32.5 g, yield 83%) as a white solid. MALDI-TOF (m/z): 479.0; c (C) 21 H 27 Br 2 NSi elemental analysis theoretical (%): c,52.40; h,5.65; n,2.91; measured value (%): c,52.42; h,5.61; n,2.90
(2) Synthesis of intermediate 2: 1 (10.0 g,20.78 mmol), 9, 10-dihydro-9, 9-dimethylacridine (10.4 g,49.86 mmol), pd under an argon atmosphere 2 (dba) 3 (0.96g，1.04mmol)、HP(t-Bu) 3 BF 4 (1.20 g,4.16 mmol), t-Buona (6.0 g,62.32 mmol), and 120ml toluene were mixed and stirred and heated to 110℃for 24h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was directly used for the next reaction without purification.
(3) Synthesis of intermediate 3: dissolving 2 with dichloromethane at room temperature, adding tetrabutylammonium fluorideTHF solution (5.0 eq, 1.0M) and stirred for 1h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was purified with petroleum ether: column separation and purification of methylene chloride (3:1) gave 3 (10.8 g, 83%) as a white solid. MALDI-TOF (m/z): 623.3; c (C) 45 H 41 N 3 Theoretical value of elemental analysis (%): c,86.64; h,6.62; n,6.74; measured value (%): c,86.60; h,6.62; n,6.76
(4) Synthesis of formula (1): 3 (2.0 g,3.12 mmol) was added to 30ml tetrahydrofuran under argon atmosphere, 1.4ml n-butyllithium (2.5M, 3.44 mmol) was added dropwise at-78℃after 1h cyanuric chloride (0.16 g,0.88 mmol) and heated to 60℃for 18h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was purified by petroleum ether: column separation and purification of methylene chloride (3:1) gave a white solid (1) (650 mg, 38%). MALDI-TOF (m/z): 1930; c (C) 138 H 120 N 12 Theoretical value of elemental analysis (%): c,85.15; h,6.21; n,8.63; measured value (%): c,85.12; h,6.25; n,8.70
Example 2: the synthetic route of formula (2) is as follows:
(2)
(1) Synthesis of intermediate 4:1 (6.0 g,12.46 mmol), carbazole (5.0 g,29.92 mmol), pd under an argon atmosphere 2 (dba) 3 (0.57g，0.62mmol)、HP(t-Bu) 3 BF 4 (0.72 g,2.49 mmol), t-Buona (3.6 g,37.40 mmol), and 80ml toluene were mixed and stirred and heated to 110℃for 24h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was directly used for the next reaction without purification.
(2) Synthesis of intermediate 5: the 4 was dissolved with dichloromethane under stirring at room temperature, a solution of tetrabutylammonium fluoride in THF (5.0 eq,1.0 m) was added, and stirred for 2h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was purified with petroleum ether: column separation and purification of methylene chloride (4:1) gave 5 (5.5 g, 82%) as a white solid. MALDI-TOF (m/z): 539.2; c (C) 39 H 29 N 3 Theoretical value of elemental analysis (%): c,86.80; h,5.42; n,7.79; measured value (%): c,86.79; h,5.40; n,7.82
(3) Synthesis of formula (2): 5 (2.0 g,3.71 mmol) was added to 30ml tetrahydrofuran under argon, 1.56ml n-butyllithium (2.5M, 3.89 mmol) was added dropwise at-78℃and after 1h cyanuric chloride (0.19 g,1.04 mmol) was added and heated to 60℃for 18h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was purified by petroleum ether: column separation and purification of methylene chloride (5:1) gave white solid (2) (650 mg, 37%). MALDI-TOF (m/z): 1692.6; c (C) 120 H 84 N 12 Theoretical value of elemental analysis (%): c,85.08; h,5.00; n,9.92; measured value (%): c,85.10; h,5.00; n,9.90
Example 3: the synthetic route of formula (3) is as follows:
/>
(1) Synthesis of intermediate 6:1 (8.5 g,17.66 mmol), 3, 6-di-tert-butylcarbazole (12.0 g,42.38 mmol), pd under an argon atmosphere 2 (dba) 3 (0.81g，0.88mmol)、HP(t-Bu) 3 BF 4 (1.00 g,3.53 mmol), t-Buona (5.1 g,52.98 mmol), and 100ml toluene were mixed and stirred and heated to 110℃for 24h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was directly used for the next reaction without purification.
(2) Synthesis of intermediate 7: the 6 was dissolved with dichloromethane under stirring at room temperature, a solution of tetrabutylammonium fluoride in THF (5.0 eq,1.0 m) was added, and stirred for 2h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was purified with petroleum ether: column separation and purification of methylene chloride (3:1) gave 7 (11.5 g, 85%) as a white solid. MALDI-TOF (m/z): 763.5; c (C) 55 H 61 N 3 Theoretical value of elemental analysis (%): c,86.45; h,8.05The method comprises the steps of carrying out a first treatment on the surface of the N,5.50; measured value (%): c,86.42; h,8.01; n,5.47
(3) Synthesis of formula (3): 7 (2.0 g,2.62 mmol) was added to 30ml tetrahydrofuran under argon atmosphere, 1.15ml n-butyllithium (2.5M, 2.88 mmol) was added dropwise at-78℃after 1h cyanuric chloride (0.13 g,0.73 mmol) and heated to 60℃for 18h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was purified by petroleum ether: column separation and purification were performed with methylene chloride (6:1) to obtain a white solid (3) (600 mg, 34%). MALDI-TOF (m/z): 2366.5; c (C) 168 H 180 N 12 Theoretical value of elemental analysis (%): c,86.24; h,7.66; n,7.10; measured value (%): c,86.22; h,7.63; n,7.08
Example 4: the synthetic route of formula (4) is as follows:
(1) Synthesis of intermediate 8: 1 (5.0 g,10.39 mmol), 3, 6-dimethoxycarbazole (5.7 g,24.93 mmol), pd under an argon atmosphere 2 (dba) 3 (0.48g，0.52mmol)、HP(t-Bu) 3 BF 4 (0.60 g,2.08 mmol), t-Buona (3.0 g,31.16 mmol), and 80ml toluene were mixed and stirred and heated to 110℃for 24h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was directly used for the next reaction without purification.
(2) Synthesis of intermediate 9: the 8 was dissolved with methylene chloride under stirring at room temperature, and a solution of tetrabutylammonium fluoride in THF (5.0 eq,1.0 m) was added and stirred for 2h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was purified with petroleum ether: column separation and purification of methylene chloride (2:1) gave 9 (4.9 g, 72%) as a white solid. MALDI-TOF (m/z): 660.2; c (C) 43 H 37 N 3 O 4 Theoretical value of elemental analysis (%): c,78.28; h,5.65; n,6.37; measured value (%): c,78.2; h,5.70; n (N)，6.40
(3) Synthesis of formula (4): 9 (2.0 g,3.03 mmol) was added to 30ml tetrahydrofuran under argon, 1.27ml n-butyllithium (2.5M, 3.18 mmol) was added dropwise at-78℃and after 1h cyanuric chloride (0.15 g,0.85 mmol) was added and heated to 60℃for 18h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was purified by petroleum ether: column separation and purification of methylene chloride (4:1) gave white solid (4) (450 mg, 26%). MALDI-TOF (m/z): 2052.8; c (C) 132 H 108 N 12 O 12 Theoretical value of elemental analysis (%): c,77.17; h,5.30; n,8.18; measured value (%): c,77.2; h,5.35; n,8.16
Example 5: the synthetic route of formula (5) is as follows:
(1) Synthesis of intermediate 10: 1 (8.5 g,17.66 mmol), 3, 6-diphenylcarbazole (15.9 g,49.86 mmol), pd under an argon atmosphere 2 (dba) 3 (0.95g，1.04mmol)、HP(t-Bu) 3 BF 4 (1.20 g,4.16 mmol), t-Buona (6.0 g,62.33 mmol), and 150ml toluene were mixed and stirred and heated to 110℃for 24h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was directly used for the next reaction without purification.
(2) Synthesis of intermediate 11: 10 was dissolved with methylene chloride under stirring at room temperature, a solution of tetrabutylammonium fluoride in THF (5.0 eq, 1.0M) was added, and stirred for 2h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was purified with petroleum ether: column separation and purification of methylene chloride (4:1) gave 11 (13.2 g, 75%) as a white solid. MALDI-TOF (m/z): 843.2; c (C) 63 H 45 N 3 Theoretical value of elemental analysis (%): c,89.65; h,5.37; n,4.98; measured value (%): c,89.62; h,5.36; n,5.02
(3) The [ (x) ray ]5) Is synthesized by the following steps: 11 (2.0 g,2.37 mmol) was added to 50ml tetrahydrofuran under argon, 1.0ml n-butyllithium (2.5M, 2.49 mmol) was added dropwise at-78℃and after 1h cyanuric chloride (0.12 g,0.66 mmol) was added and heated to 60℃for 18h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was purified by petroleum ether: column separation and purification of methylene chloride (6:1) gave a white solid (5) (660 mg, 38%). MALDI-TOF (m/z): 2605.1; c (C) 192 H 132 N 12 Theoretical value of elemental analysis (%): c,88.45; h,5.10; n,6.45; measured value (%): c,88.40; h,5.12; n,6.48
Example 6: the synthetic route of formula (6) is as follows:
(1) Synthesis of intermediate 12: 1 (10.0 g,20.77 mmol), 3, 6-dicyclohexylcarbazole (16.5 g,49.86 mmol), pd under an argon atmosphere 2 (dba) 3 (0.95g，1.04mmol)、HP(t-Bu) 3 BF 4 (1.20 g,4.16 mmol), t-Buona (6.0 g,62.33 mmol), and 120ml toluene were mixed and stirred and heated to 110℃for 24h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was directly used for the next reaction without purification.
(2) Synthesis of intermediate 13: 12 was dissolved with methylene chloride under stirring at room temperature, a solution of tetrabutylammonium fluoride in THF (5.0 eq,1.0 m) was added, and stirred for 2h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was purified with petroleum ether: column separation and purification of methylene chloride (4:1) gave 13 (12.2 g, 68%) as a white solid. MALDI-TOF (m/z): 867.8; c (C) 63 H 69 N 3 Theoretical value of elemental analysis (%): c,87.15; h,8.01; n,4.84; measured value (%): c,87.18; h,8.00; n,4.82
(3) Synthesis of formula (6): 13 (2.0 g,2.30 mmol) was treated under argon) To 50ml of tetrahydrofuran was added dropwise 0.96ml of n-butyllithium (2.5M, 2.42 mmol) at-78℃and after 1h cyanuric chloride (0.12 g,0.64 mmol) was added and heated to 60℃for 18h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was purified by petroleum ether: column separation and purification were performed with methylene chloride (8:1) to obtain a white solid (5) (550 mg, 32%). MALDI-TOF (m/z): 2677.8; c (C) 192 H 204 N 12 Theoretical value of elemental analysis (%): c,86.05; h,7.67; n,6.27; measured value (%): c,86.04; h,7.68; n,6.28
Example 7: the synthetic route of formula (7) is as follows:
/>
(1) Synthesis of intermediate 14: 3, 6-Diiodocarbazole (53.1 g,126.73 mmol) was dissolved in 200ml DMF. Subsequently, a solution of NaH (4.56 g,190.10 mmol) in DMF was slowly added dropwise at 0deg.C, and after 1h, t-butyldimethylchlorosilane (28.7 g,190.10 mmol) was added to the reaction flask and stirred overnight. After the reaction was completed, the reaction solution was poured into a large amount of water, and filtered to obtain a white solid. After drying the white solid in vacuo, the solid was dried over petroleum ether: column separation and purification of methylene chloride (8:1) gave product 14 (60.5 g, 90%). MALDI-TOF (m/z): 533.1; c (C) 18 H 21 I 2 NSi elemental analysis theoretical (%): c,40.54; h,3.97; n,2.63; measured value (%): c,40.52; h,3.98; n,2.64
(2) Synthesis of intermediate 15: 14 (20.0 g,37.53 mmol), 2, 6-dimethylbromobenzene (16.6 g,90.06 mmol), pd under an argon atmosphere 2 (dba) 3 (1.72g，1.88mmol)、HP(t-Bu) 3 BF 4 (2.18 g,7.50 mmol), t-Buona (10.8 g,112.58 mmol), and 200ml toluene were mixed and stirred and heated to 110℃for 24h. After the reaction is completed, the solvent is evaporated to dryness under reduced pressure, and the residual solid is directly used without purification In the next step.
(3) Synthesis of intermediate 16: at room temperature, 15 was dissolved with tetrahydrofuran under stirring, a solution of tetrabutylammonium fluoride in THF (5.0 eq,1.0 m) was added, and stirred for 2h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was purified with petroleum ether: column separation and purification of methylene chloride (6:1) gave 16 (11.0 g, 78%) as a white solid. MALDI-TOF (m/z): 375.0; c (C) 28 H 25 Theoretical value of N element analysis (%): c,89.56; h,6.71; n,3.73; measured value (%): c,89.60; h,6.66; n,3.74
(4) Synthesis of intermediate 17: under an argon atmosphere, 1 (5.0 g,10.39 mmol), 16 (9.4 g,24.93 mmol), pd 2 (dba) 3 (0.48g，0.52mmol)、HP(t-Bu) 3 BF 4 (0.60 g,2.08 mmol), t-Buona (3.0 g,31.16 mmol), and 60ml toluene were mixed and stirred and heated to 110℃for 24h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was directly used for the next reaction without purification.
(5) Synthesis of intermediate 18: 17 was dissolved with tetrahydrofuran under stirring at room temperature, a solution of tetrabutylammonium fluoride in THF (5.0 eq, 1.0M) was added, and stirred for 2h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was purified with petroleum ether: column separation and purification of methylene chloride (5:1) gave 18 (7.1 g, 72%) as a white solid. MALDI-TOF (m/z): 955.5; c (C) 71 H 61 N 3 Theoretical value of elemental analysis (%): c,89.18; h,6.43; n,4.39; measured value (%): c,89.16; h,6.45; n,4.39
(6) Synthesis of formula (7): 18 (2.0 g,2.09 mmol) was added to 30ml tetrahydrofuran under argon atmosphere, 0.88ml n-butyllithium (2.5M, 2.20 mmol) was added dropwise at-78℃and after 1h cyanuric chloride (0.11 g,0.59 mmol) was added and heated to 60℃for 18h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was purified by petroleum ether: column separation and purification of methylene chloride (8:1) gave a white solid (7) (65mg, 38%). MALDI-TOF (m/z): 2942.4; c (C) 216 H 180 N 12 Theoretical value of elemental analysis (%): c,88.13; h,6.16; n,5.71; measured value (%): c,88.16; h,6.18; n,5.66
Example 8: the synthetic route of formula (8) is as follows:
(1) Synthesis of intermediate 19: 14 (20.0 g,37.53 mmol), 2,4, 6-trimethylbromobenzene (17.8 g,90.06 mmol), pd under an argon atmosphere 2 (dba) 3 (1.72g，1.88mmol)、HP(t-Bu) 3 BF 4 (2.18 g,7.50 mmol), t-Buona (10.8 g,112.58 mmol), and 200ml toluene were mixed and stirred and heated to 110℃for 24h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was directly used for the next reaction without purification.
(2) Synthesis of intermediate 20: the 19 was dissolved with tetrahydrofuran under stirring at room temperature, and a solution of tetrabutylammonium fluoride in THF (5.0 eq,1.0 m) was added and stirred for 2h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was purified with petroleum ether: column separation and purification of methylene chloride (6:1) gave 21 (11.3 g, 75%) as a white solid. MALDI-TOF (m/z): 403.1; c (C) 30 H 29 Theoretical value of N element analysis (%): c,89.29; h,7.24; n,3.47; measured value (%): c,89.41; h,7.19; n,3.40
(3) Synthesis of intermediate 21: under an argon atmosphere, 1 (5.0 g,10.39 mmol), 20 (10.1 g,24.93 mmol), pd 2 (dba) 3 (0.48g，0.52mmol)、HP(t-Bu) 3 BF 4 (0.60 g,2.08 mmol), t-Buona (3.0 g,31.16 mmol), and 60ml toluene were mixed and stirred and heated to 110℃for 24h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was directly used for the next reaction without purification.
(4) Synthesis of intermediate 22: at room temperature, 21 was dissolved with tetrahydrofuran under stirring, a THF solution (5.0 eq,1.0 m) of tetrabutylammonium fluoride was added, and stirred for 2h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was purified with petroleum ether: column separation and purification of methylene chloride (5:1) gave 22 (7.1 g, 72%) as a white solid. MALDI-TOF (m/z): 1011.5; c (C) 75 H 69 N 3 Theoretical value of elemental analysis (%): c,88.98; h,6.87; n,4.15; actual measurementValue (%): c,89.88; h,6.91; n,4.21
(5) Synthesis of formula (8): 22 (2.0 g,1.98 mmol) was added to 30ml tetrahydrofuran under argon atmosphere, 0.83ml n-butyllithium (2.5M, 2.08 mmol) was added dropwise at-78℃after 1h cyanuric chloride (0.10 g,0.55 mmol) was added and heated to 60℃for 18h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was purified by petroleum ether: column separation and purification were performed with methylene chloride (8:1) to obtain a white solid (8) (620 mg, 36%). MALDI-TOF (m/z): 3110.6; c (C) 228 H 204 N 12 Theoretical value of elemental analysis (%): c,87.99; h,6.61; n,5.40; measured value (%): c,88.00; h,6.60; n,5.40
Example 9: the synthetic route of formula (11) is as follows:
(1) Synthesis of intermediate 24: 2 (6.0 g,12.47 mmol), phenoxazine (5.5 g,29.92 mmol), pd under an argon atmosphere 2 (dba) 3 (0.57g，0.62mmol)、HP(t-Bu) 3 BF 4 (0.72 g,2.49 mmol), t-Buona (3.6 g,37.40 mmol), and 80ml toluene were mixed and stirred and heated to 110℃for 24h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was directly used for the next reaction without purification.
(2) Synthesis of intermediate 25: 24 was dissolved with methylene chloride under stirring at room temperature, a solution of tetrabutylammonium fluoride in THF (5.0 eq,1.0 m) was added, and stirred for 2h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was purified with petroleum ether: column separation and purification of methylene chloride (5:1) gave 25 (6.1 g, 85%) as a white solid. MALDI-TOF (m/z): 571.2; c (C) 39 H 29 N 3 O 2 Theoretical value of elemental analysis (%): c,81.94; h,5.11; n,7.35; measured value (%): c,81.98; h,5.10; n,7.32
(3) Synthesis of formula (11): 25 (2.0 g,3.50 mmol) was added to 30ml tetrahydrofuran under argon atmosphere, 1.48ml n-butyllithium (2.5M, 3.68 mmol) was added dropwise at-78℃after 1h cyanuric chloride (0.18 g,0.98 mmol) was added and heated to 60℃for 18h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was purified by petroleum ether: column separation and purification of methylene chloride (4:1) gave a white solid (11) (596 mg, 26%). MALDI-TOF (m/z): 1790.6; c (C) 120 H 84 N 12 O 6 Theoretical value of elemental analysis (%): c,80.52; h,4.73; n,9.39; measured value (%): c,80.50; h,4.75; n,9.39
Example 10: the synthetic route of formula (12) is as follows:
(1) Synthesis of intermediate 25: under an argon atmosphere, 1 (6.0 g,12.47 mmol), phenothiazine (6.0 g,29.92 mmol), pd 2 (dba) 3 (0.57g，0.62mmol)、HP(t-Bu) 3 BF 4 (0.72 g,2.49 mmol), t-Buona (3.6 g,37.40 mmol), and 80ml toluene were mixed and stirred and heated to 110℃for 24h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was directly used for the next reaction without purification.
(2) Synthesis of intermediate 26: 25 was dissolved with methylene chloride under stirring at room temperature, a solution of tetrabutylammonium fluoride in THF (5.0 eq, 1.0M) was added, and stirred for 2h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was purified with petroleum ether: column separation and purification of methylene chloride (3:1) gave 26 (6.2 g, 83%) as a white solid. MALDI-TOF (m/z): 603.2; c (C) 39 H 29 N 3 S 2 Theoretical value of elemental analysis (%): c,77.58; h,4.84; n,6.96; measured value (%): c,77.60; h,4.86; n,6.92
(3) Synthesis of formula (12): 26 (2.0 g,3.31 mmol) was added to 30ml tetrahydrofuran under argon atmosphere, 1.40ml n-butyllithium (2.5M, 3.48 mmol) was added dropwise at-78℃after 1h cyanuric chloride (0.17 g,0.93 mmol) and heated to 60℃for 18h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was purified by petroleum ether: column separation and purification of methylene chloride (5:1) gave white solid (12) (450 mg, 26%). MALDI-TOF (m/z): 1886.2; c (C) 120 H 84 N 12 S 6 Theoretical value of elemental analysis (%): c,76.4; h,4.49; n,8.91; measured value (%): c,76.3; h,4.54; n,8.96
Example 11: the synthetic route of formula (13) is as follows:
(1) Synthesis of intermediate 27: phenoxazine (50.0 g,272.91 mmol) was dissolved in 250ml DMF and cooled with an ice water bath. Subsequently, NBS (97.2 g,545.85 mmol) was dissolved in 120ml DMF and slowly added dropwise to continue the reaction for 12h. After the reaction was completed, the reaction solution was poured into a large amount of water, and filtered to obtain a white solid. After drying in vacuo, petroleum ether: column separation and purification of methylene chloride (10:1) gave 27 as a white solid (74.4 g, 80%). MALDI-TOF (m/z): 338.9; c (C) 12 H 7 Br 2 Theoretical value of NO elemental analysis (%): c,42.27; h,2.07; n,4.11; measured value (%): c,42.24; h,2.03; n,4.12
(2) Synthesis of intermediate 28: 27 (20.0 g,59.01 mmol) and 150ml THF were mixed and stirred at 0deg.C under argon. A solution of NaH (2.1 g,88.52 mmol) in THF was then slowly dropped and allowed to return to room temperature for a further 2h, t-butyldimethylchlorosilane (13.3 g,88.52 mmol) was added to the reaction flask and stirred overnight. After the completion of the reaction, the solvent was evaporated under reduced pressure, and the crude product was purified by column separation with petroleum ether to give 28 (22.4 g, 84%) as a white solid. MALDI-TOF (m/z): 453.0; c (C) 18 H 21 Br 2 Theoretical value of NOSi elemental analysis (%): c,47.49; h,4.65; n,3.08; measured value (%): c,47.43; h,4.60; n,3.09
(3) Synthesis of intermediate 29: 28 (5.0 g,11.04 mmol), phenoxazine (4.9 g,26.49 mmol), pd under an argon atmosphere 2 (dba) 3 (0.51g，0.55mmol)、HP(t-Bu) 3 BF 4 (0.64 g,2.21 mmol), t-Buona (3.2 g,33.11 mmol), and 70ml toluene were mixed and stirred and heated to 110℃for 24h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was directly used for the next reaction without purification.
(4) Synthesis of intermediate 30: 29 was dissolved with methylene chloride under stirring at room temperature, and a solution of tetrabutylammonium fluoride in THF (5.0 eq,1.0 m) was added and stirred for 2h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was purified with petroleum ether: column separation and purification of methylene chloride (3:1) gave 30 (5.0 g, 83%) as a white solid. MALDI-TOF (m/z): 545.2; c (C) 36 H 23 N 3 O 3 Theoretical value of elemental analysis (%): c,79.25; h,4.25; n,7.70; measured value (%): c,79.24; h,4.26; n,7.70
(5) Synthesis of formula (13): 30 (2.0 g,3.66 mmol) was added to 30ml tetrahydrofuran under argon, 1.54ml n-butyllithium (2.5M, 3.85 mmol) was added dropwise at-78℃and after 1h cyanuric chloride (0.19 g,1.03 mmol) was added and heated to 60℃for 18h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was purified by petroleum ether: column separation and purification of methylene chloride (6:1) gave a white solid (13) (650 mg, 37%). MALDI-TOF (m/z): 1710.4; c (C) 111 H 66 N 12 O 9 Theoretical value of elemental analysis (%): c,77.88; h,3.89; n,9.82; measured value (%): c,77.89; h,3.90; n,9.80
Example 12: the synthetic route of formula (16) is as follows:
(1) Synthesis of intermediate 31: phenoxazine (20.0 g,100.36 mmol) was dissolved in 150ml DMF and cooled with an ice-water bath. Subsequently, NBS (37.5 g,210.76 mmol) was dissolved in 50ml DMF and slowly added dropwise to continue the reaction for 12h. After the reaction, the reaction solution was stirredPouring into a large amount of water, and filtering to obtain white solid. After drying in vacuo, petroleum ether: column separation and purification of methylene chloride (10:1) gave 31 (18.6 g, 52%) as a white solid. MALDI-TOF (m/z): 354.9; c (C) 12 H 7 Br 2 NS elemental analysis theoretical (%): c,40.37; h,1.98; n,3.92; measured value (%): c,40.35; h,2.01; n,3.91
(2) Synthesis of intermediate 32: 31 (10.0 g,28.01 mmol) and 70ml THF are mixed and stirred at 0deg.C under argon. A solution of NaH (1.0 g,42.01 mmol) in THF was then slowly dropped and allowed to return to room temperature for a further 2h, t-butyldimethylchlorosilane (6.4 g,42.01 mmol) was added to the reaction flask and stirred overnight. After the completion of the reaction, the solvent was evaporated under reduced pressure, and the crude product was purified by column separation with petroleum ether to give 32 (7.1 g, 54%) as a white solid. MALDI-TOF (m/z): 469.0; c (C) 18 H 21 Br 2 NSSi elemental analysis theory (%): c,45.87; h,4.49; n,2.97; measured value (%): c,45.86; h,4.50; n,2.98
(3) Synthesis of intermediate 33: 32 (5.0 g,10.61 mmol), phenothiazine (5.1 g,25.46 mmol), pd under an argon atmosphere 2 (dba) 3 (0.49g，0.53mmol)、HP(t-Bu) 3 BF 4 (0.62 g,2.12 mmol), t-Buona (3.1 g,31.82 mmol), and 70ml toluene were mixed and stirred and heated to 110℃for 24h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was directly used for the next reaction without purification.
(4) Synthesis of intermediate 34: at room temperature, 33 was dissolved with dichloromethane under stirring, a solution of tetrabutylammonium fluoride in THF (5.0 eq,1.0 m) was added, and stirred for 2h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was purified with petroleum ether: column separation and purification of methylene chloride (5:1) gave 34 (2.7 g, 43%) as a white solid. MALDI-TOF (m/z): 593.1; c (C) 36 H 23 N 3 S 3 Theoretical value of elemental analysis (%): c,72.82; h,3.90; n,7.08; measured value (%): c,72.80; h,3.89; n,7.11
(5) Synthesis of formula (16): 34 (2.0 g,3.37 mmol) was added to 30ml tetrahydrofuran under argon atmosphere at-78 ℃1.41ml of n-butyllithium (2.5M, 3.54 mmol) was added dropwise, after 1h cyanuric chloride (0.17 g,0.94 mmol) was added and the mixture was heated to 60℃and reacted for 18h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was purified by petroleum ether: column separation and purification were performed with methylene chloride (10:1) to obtain a white solid (16) (315 mg, 18%). MALDI-TOF (m/z): 1854.2; c (C) 111 H 66 N 12 S 9 Theoretical value of elemental analysis (%): c,71.82; h,3.58; n,9.05; measured value (%): c,71.89; h,3.51; n,9.05
Example 13: the synthetic route of formula (55) is as follows:
(1) Synthesis of intermediate 35: 3, 6-dibromo-9-hydrogen carbazole (26.6 g,81.7 mmol) and 200ml THF were mixed and stirred at 0℃under argon atmosphere. Subsequently, a solution of NaH (2.4 g,98.1 mmol) in THF was slowly dropped, then the reaction was continued for 2 hours at room temperature, and then t-butyldimethylchlorosilane (14.8 g,98.1 mmol) was added to the reaction flask and stirred overnight. After the completion of the reaction, the solvent was evaporated under reduced pressure, and the crude product was purified by column separation with petroleum ether to give 35 (29.4 g, yield 82%) as a white solid. MALDI-TOF (m/z): 439.0; c (C) 18 H 21 Br 2 NSi elemental analysis theoretical (%): c,49.22; h,4.82; n,3.19; measured value (%): c,49.22; h,4.81; n,3.20
(2) Synthesis of intermediate 36: 35 (9.1 g,20.78 mmol), 9, 10-dihydro-9, 9-dimethylacridine (10.4 g,49.86 mmol), pd under an argon atmosphere 2 (dba) 3 (0.96g，1.04mmol)、HP(t-Bu) 3 BF 4 (1.20 g,4.16 mmol), t-Buona (6.0 g,62.32 mmol), and 120ml toluene were mixed and stirred and heated to 110℃for 24h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was directly used for the next reaction without purification.
(3) Synthesis of intermediate 37: 36 was dissolved with methylene chloride under stirring at room temperature, and a solution of tetrabutylammonium fluoride in THF (5.0 eq,1.0 m) was added and stirred for 1h. After the reaction was completed, the mixture was distilled under reduced pressureDry solvent, petroleum ether for remaining solids: column separation and purification of methylene chloride (3:1) gave 37 (10.3 g, 85%) as a white solid. MALDI-TOF (m/z): 581.3; c (C) 42 H 35 N 3 Theoretical value of elemental analysis (%): c,86.71; h,6.06; n,7.22; measured value (%): c,86.71; h,6.06; n,7.22
(4) Synthesis of formula (55): 37 (1.8 g,3.12 mmol) was added to 30ml tetrahydrofuran under argon atmosphere, 1.4ml n-butyllithium (2.5M, 3.44 mmol) was added dropwise at-78℃after 1h cyanuric chloride (0.16 g,0.88 mmol) and heated to 60℃for 18h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was purified by petroleum ether: column separation and purification were performed with methylene chloride (3:1) to obtain a white solid (55) (560 mg, 35%). MALDI-TOF (m/z): 1819.8; c (C) 129 H 102 N 12 Theoretical value of elemental analysis (%): c,85.12; h,5.65; n,9.23; measured value (%): c,85.12; h,5.64; n,9.24
Example 14: the synthetic route of formula (57) is as follows:
(1) Synthesis of intermediate 38: 35 (7.8 g,17.77 mmol), 3, 6-di-tert-butylcarbazole (12.0 g,42.38 mmol), pd under an argon atmosphere 2 (dba) 3 (0.81g，0.88mmol)、HP(t-Bu) 3 BF 4 (1.00 g,3.53 mmol), t-Buona (5.1 g,52.98 mmol), and 100ml toluene were mixed and stirred and heated to 110℃for 24h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was directly used for the next reaction without purification.
(2) Synthesis of intermediate 39: 38 was dissolved with methylene chloride under stirring at room temperature, a solution of tetrabutylammonium fluoride in THF (5.0 eq,1.0 m) was added, and stirred for 2h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was purified with petroleum ether: column separation and purification of methylene chloride (3:1) gave 39 (11.5 g, 85%) as a white solid. MALDI-TOF (m/z): 721.4; c (C) 52 H 55 N 3 Theoretical value of elemental analysis (%): c,86.50; h,7.68; n,5.82The method comprises the steps of carrying out a first treatment on the surface of the Measured value (%): c,86.50; h,7.68; n,5.82
(3) Synthesis of formula (57): 39 (2.0 g,2.77 mmol) was added to 30ml tetrahydrofuran under argon, 1.15ml n-butyllithium (2.5M, 2.88 mmol) was added dropwise at-78℃and after 1h cyanuric chloride (0.15 g,0.80 mmol) was added and heated to 60℃for 18h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was purified by petroleum ether: column separation and purification were performed with methylene chloride (6:1) to obtain a white solid (57) (600 mg, 34%). MALDI-TOF (m/z): 2240.3; c (C) 159 H 162 N 12 Theoretical value of elemental analysis (%): c,85.21; h,7.29; n,7.50; measured value (%): c,85.21; h,7.30; n,7.49
Example 15: the synthetic route of formula (91) is as follows:
(1) Synthesis of intermediate 40: 2-bromo-9, 10-dihydro-9, 9-dimethylacridine (23.6 g,82.0 mmol) and 200ml THF are mixed and stirred at 0deg.C under argon. Subsequently, a solution of NaH (2.4 g,98.1 mmol) in THF was slowly dropped, then the reaction was continued for 2 hours at room temperature, and then t-butyldimethylchlorosilane (14.8 g,98.1 mmol) was added to the reaction flask and stirred overnight. After the completion of the reaction, the solvent was evaporated under reduced pressure, and the crude product was purified by column separation with petroleum ether to give 40 (28.6 g, yield 87%) as a white solid. MALDI-TOF (m/z): 401.1; c (C) 21 H 28 BrNSi elemental analysis theory (%): c,62.67; h,7.01; n,3.48; measured value (%): c,62.67; h,7.01; n,3.48
(2) Synthesis of intermediate 41: 40 (10.0 g,24.93 mmol), 9, 10-dihydro-9, 9-dimethylacridine (5.7 g,25.35 mmol), pd under an argon atmosphere 2 (dba) 3 (0.48g，0.52mmol)、HP(t-Bu) 3 BF 4 (0.60 g,2.08 mmol), t-Buona (3.0 g,31.16 mmol), and 120ml toluene were mixed and stirred and heated to 110℃for 24h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was directly used for the next reaction without purification.
(3) Synthesis of intermediate 42: at room temperature, 41 was dissolved with dichloromethane under stirring, a solution of tetrabutylammonium fluoride in THF (5.0 eq,1.0 m) was added, and stirred for 1h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was purified with petroleum ether: column separation and purification of methylene chloride (3:1) gave 42 (10.8 g, 83%) as a white solid. MALDI-TOF (m/z): 416.2; c (C) 30 H 28 N 3 Theoretical value of elemental analysis (%): c,86.50; h,6.78; n,6.72; measured value (%): c,86.49; h,6.79; n,6.72
(4) Synthesis of formula (91): 42 (1.3 g,3.12 mmol) was added to 30ml tetrahydrofuran under argon atmosphere, 1.4ml n-butyllithium (2.5M, 3.44 mmol) was added dropwise at-78℃after 1h cyanuric chloride (0.16 g,0.88 mmol) and heated to 60℃for 18h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was purified by petroleum ether: column separation and purification of methylene chloride (3:1) gave a white solid (91) (466 mg, 40%). MALDI-TOF (m/z): 1324.7; c (C) 93 H 81 N 9 Theoretical value of elemental analysis (%): c,84.32; h,6.16; n,9.52; measured value (%): c,84.31; h,6.17; n,9.52
Example 16: the synthetic route of formula (93) is as follows:
(1) Synthesis of intermediate 43: 40 (7.1 g,17.66 mmol), 3, 6-di-tert-butylcarbazole (6.0 g,21.19 mmol), pd under an argon atmosphere 2 (dba) 3 (0.41g，0.44mmol)、HP(t-Bu) 3 BF 4 (0.50 g,1.77 mmol), t-Buona (2.55 g,26.49 mmol), and 100ml toluene were mixed and stirred and heated to 110℃for 24h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was directly used for the next reaction without purification.
(2) Synthesis of intermediate 44: 43 was dissolved with methylene chloride under stirring at room temperature, a solution of tetrabutylammonium fluoride in THF (5.0 eq, 1.0M) was added, and stirred for 2h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was purified with petroleum ether: column separation with dichloromethane (3:1)Purification by isolation gave 44 (11.5 g, 85%) as a white solid. MALDI-TOF (m/z): 486.3; c (C) 35 H 38 N 2 Theoretical value of elemental analysis (%): c,86.37; h,7.87; n,5.76; measured value (%): c,86.37; h,7.87; n,5.76
(3) Synthesis of formula (93): 44 (2.0 g,2.62 mmol) was added to 30ml tetrahydrofuran under argon atmosphere, 1.15ml n-butyllithium (2.5M, 2.88 mmol) was added dropwise at-78℃after 1h cyanuric chloride (0.13 g,0.73 mmol) and heated to 60℃for 18h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was purified by petroleum ether: column separation and purification of methylene chloride (6:1) gave a white solid (93) (426 mg, 38%). MALDI-TOF (m/z): 1534.9; c (C) 108 H 111 N 9 Theoretical value of elemental analysis (%): c,84.50; h,7.29; n,8.21; measured value (%): c,84.50; h,7.30; n,8.20
Example 17: the synthetic route of formula (122) is as follows:
(1) Synthesis of intermediate 45: 40 (7.6 g,18.95 mmol), 4- (3, 6-di-tert-butyl-9H-carbazol-9-yl) phenylboronic acid (8.6 g,21.54 mmol), pd (PPh) were reacted under an argon atmosphere 3 ) 4 (0.65g，0.56mmol)、K 2 CO 3 (3.81 g,27.55 mmol) in water, and 120ml toluene were mixed and stirred and heated to 95℃for reaction for 12h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was directly used for the next reaction without purification.
(2) Synthesis of intermediate 46: 45 was dissolved with methylene chloride under stirring at room temperature, a solution of tetrabutylammonium fluoride in THF (5.0 eq,1.0 m) was added, and stirred for 2h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was purified with petroleum ether: column separation and purification of methylene chloride (3:1) gave 46 (7.5 g, 70%) as a white solid. MALDI-TOF(m/z)：562.3；C 41 H 42 N 2 Theoretical value of elemental analysis (%): c,87.50; h,7.52; n,4.98; measured value (%): c,87.51; h,7.53; n,4.98
(3) Synthesis of formula (122): 44 (1.5 g,2.67 mmol) was added to 30ml tetrahydrofuran under argon, 1.15ml n-butyllithium (2.5M, 2.88 mmol) was added dropwise at-78℃and after 1h cyanuric chloride (0.15 g,0.81 mmol) was added and heated to 60℃for 18h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was purified by petroleum ether: column separation and purification of methylene chloride (6:1) gave a white solid (93) (457 mg, 32%). MALDI-TOF (m/z): 1763.0; c (C) 126 H 123 N 9 Theoretical value of elemental analysis (%): c,85.82; h,7.03; n,7.15; measured value (%): c,85.81; h,7.04; n,7.15
Example 18: the synthetic route of formula (133) is as follows:
(1) Synthesis of intermediate 47: 40 (7.7 g,19.20 mmol), 9-phenyl-9H-carbazole-3-boronic acid (6.1 g,21.25 mmol), pd (PPh) were reacted under argon atmosphere 3 ) 4 (0.65g，0.56mmol)、K 2 CO 3 (3.81 g,27.55 mmol) in water, and 120ml toluene were mixed and stirred and heated to 95℃for reaction for 12h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was directly used for the next reaction without purification.
(2) Synthesis of intermediate 48: the 47 was dissolved with dichloromethane under stirring at room temperature, a solution of tetrabutylammonium fluoride in THF (5.0 eq,1.0 m) was added, and stirred for 2h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was purified with petroleum ether: column separation and purification of methylene chloride (3:1) gave 48 (7.5 g, 70%) as a white solid. MALDI-TOF (m/z): 450.2; c (C) 33 H 26 N 2 Theoretical value of elemental analysis (%): c,87.97; h,5.82; n,6.22; measured value (%): c,87.98; h,5.82; n,6.21
(3) Synthesis of formula (133): 48 (1.5 g,267 mmol) was added to 30ml of tetrahydrofuran, 1.15ml of n-butyllithium (2.5M, 2.88 mmol) was added dropwise at-78℃and after 1h cyanuric chloride (0.17 g,0.92 mmol) was added and heated to 60℃for 18h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was purified by petroleum ether: column separation and purification of methylene chloride (6:1) gave a white solid (93) (499 mg, 38%). MALDI-TOF (m/z): 1426.6; c (C) 102 H 75 N 9 Theoretical value of elemental analysis (%): c,85.87; h,5.30; n,8.84; measured value (%): c,85.88; h,5.30; n,8.83
Example 19: the synthetic route of formula (145) is as follows:
(1) Synthesis of intermediate 49: 3-bromo-9-hydrocarbazole (20.1 g,81.7 mmol) and 200ml THF were mixed and stirred at 0deg.C under argon atmosphere. Subsequently, a solution of NaH (2.4 g,98.1 mmol) in THF was slowly dropped, then the reaction was continued for 2 hours at room temperature, and then t-butyldimethylchlorosilane (14.8 g,98.1 mmol) was added to the reaction flask and stirred overnight. After the completion of the reaction, the solvent was evaporated under reduced pressure, and the crude product was purified by column separation with petroleum ether to give 49 (32.7 g, yield 83%) as a white solid. MALDI-TOF (m/z): 359.1; c (C) 18 H 22 BrNSi elemental analysis theory (%): c,59.99; h,6.15; n,3.89; measured value (%): c,59.99; h,6.14; n,3.90
(2) Synthesis of intermediate 50: 49 (7.5 g,20.78 mmol), 9, 10-dihydro-9, 9-dimethylacridine (5.2 g,24.93 mmol), pd under an argon atmosphere 2 (dba) 3 (0.48g，0.52mmol)、HP(t-Bu) 3 BF 4 (0.60 g,2.08 mmol), t-Buona (3.0 g,31.16 mmol), and 120ml toluene were mixed and stirred and heated to 110℃for 24h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was directly used for the next reaction without purification.
(3) Synthesis of intermediate 51: 50 was dissolved with methylene chloride under stirring at room temperature, and a solution of tetrabutylammonium fluoride in THF (5.0 eq, 1.0M) was added and stirred for 1h. After the completion of the reaction, the reaction mixture,the solvent was evaporated to dryness under reduced pressure and the remaining solid was purified with petroleum ether: column separation and purification of methylene chloride (3:1) gave 51 (6.1 g, 79%) as a white solid. MALDI-TOF (m/z): 374.2; c (C) 27 H 22 N 2 Theoretical value of elemental analysis (%): c,86.60; h,5.92; n,7.48; measured value (%): c,86.60; h,5.93; n,7.47
(4) Synthesis of formula (145): 51 (1.2 g,3.23 mmol) was added to 30ml tetrahydrofuran under argon, 1.4ml n-butyllithium (2.5M, 3.44 mmol) was added dropwise at-78℃after 1h cyanuric chloride (0.16 g,0.88 mmol) and heated to 60℃for 18h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was purified by petroleum ether: column separation and purification of methylene chloride (3:1) gave a white solid (145) (369 mg, 35%). MALDI-TOF (m/z): 1197.5; c (C) 84 H 63 N 9 Theoretical value of elemental analysis (%): c,84.18; h,5.30; n,10.52; measured value (%): c,54.18; h,5.30; n,10.52
Example 20: the synthetic route of formula (147) is as follows:
(1) Synthesis of intermediate 52: 49 (6.5 g,18.10 mmol), 3, 6-di-tert-butylcarbazole (6.0 g,21.19 mmol), pd under an argon atmosphere 2 (dba) 3 (0.41g，0.44mmol)、HP(t-Bu) 3 BF 4 (0.50 g,1.77 mmol), t-Buona (2.55 g,26.49 mmol), and 100ml toluene were mixed and stirred and heated to 110℃for 24h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was directly used for the next reaction without purification.
(2) Synthesis of intermediate 53: 52 was dissolved with dichloromethane under stirring at room temperature, tetrabutylammonium fluoride in THF (5.0 eq,1.0 m) was added, and stirred for 2h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was purified with petroleum ether: dichloro-sMethane (3:1) was purified by column separation to give 7 (11.5 g, 85%) as a white solid. MALDI-TOF (m/z): 444.3; c (C) 32 H 32 N 2 Theoretical value of elemental analysis (%): c,86.44; h,7.25; n,6.30; measured value (%): c,86.44; h,7.24; n,6.31
(3) Synthesis of formula (147): 53 (2.0 g,2.62 mmol) was added to 30ml tetrahydrofuran under argon atmosphere, 1.15ml n-butyllithium (2.5M, 2.88 mmol) was added dropwise at-78℃after 1h cyanuric chloride (0.14 g,0.80 mmol) and heated to 60℃for 18h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was purified by petroleum ether: column separation and purification of methylene chloride (6:1) gave a white solid (147) (367 mg, 29%). MALDI-TOF (m/z): 1408.8; c (C) 99 H 93 N 9 Theoretical value of elemental analysis (%): c,84.40; h,6.65; n,8.95; measured value (%): c,84.39; h,6.66; n,8.95
Example 21: the synthetic route of formula (158) is as follows:
/>
(1) Synthesis of intermediate 54: 49 (7.5 g,20.89 mmol), 4- (3, 6-di-tert-butyl-9H-carbazol-9-yl) phenylboronic acid (8.6 g,21.54 mmol), pd (PPh) were reacted under an argon atmosphere 3 ) 4 (0.65g，0.56mmol)、K 2 CO 3 (3.81 g,27.55 mmol) in water, and 120ml toluene were mixed and stirred and heated to 95℃for reaction for 12h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was directly used for the next reaction without purification.
(2) Synthesis of intermediate 55: 54 was dissolved with dichloromethane under stirring at room temperature, a solution of tetrabutylammonium fluoride in THF (5.0 eq,1.0 m) was added, and stirred for 2h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was purified with petroleum ether: column separation and purification are carried out on methylene dichloride (3:1) to obtain white solid 55(8.2g，75％)。MALDI-TOF(m/z)：520.3；C 38 H 36 N 2 Theoretical value of elemental analysis (%): c,87.65; h,6.97; n,5.38; measured value (%): c,87.66; h,6.96; n,5.38
(3) Synthesis of formula (158): 55 (1.3 g,2.50 mmol) was added to 30ml tetrahydrofuran under argon, 1.15ml n-butyllithium (2.5M, 2.88 mmol) was added dropwise at-78℃and after 1h cyanuric chloride (0.15 g,0.81 mmol) was added and heated to 60℃for 18h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was purified by petroleum ether: column separation and purification of methylene chloride (6:1) gave a white solid (93) (385 mg, 29%). MALDI-TOF (m/z): 1636.9; c (C) 117 H 105 N 9 Theoretical value of elemental analysis (%): c,85.84; h,6.46; n,7.70; measured value (%): c,85.84; h,6.48; n,7.68
Example 22: the synthetic route of formula (173) is as follows:
/>
(1) Synthesis of intermediate 56: 49 (7.5 g,20.89 mmol), 9-phenyl-9H-carbazole-3-boronic acid (6.1 g,21.25 mmol), pd (PPh) were reacted under argon atmosphere 3 ) 4 (0.65g，0.56mmol)、K 2 CO 3 (3.81 g,27.55 mmol) in water, and 120ml toluene were mixed and stirred and heated to 95℃for reaction for 12h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was directly used for the next reaction without purification.
(2) Synthesis of intermediate 57: the 56 was dissolved with dichloromethane under stirring at room temperature, a solution of tetrabutylammonium fluoride in THF (5.0 eq,1.0 m) was added, and stirred for 2h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was purified with petroleum ether: column separation and purification of methylene chloride (3:1) gave 57 (7.5 g, 70%) as a white solid. MALDI-TOF (m/z): 408.2; c (C) 30 H 20 N 2 Theoretical value of elemental analysis (%): c,88.21; h,4.94; n,6.86; measured value (%): c,88.21; h,4.92; n,6.88
(3) Synthesis of formula (173): 57 (1.1 g,2.69 mmol) are added to 30ml tetrahydrofuran under argon, 1.15ml n-butyllithium (2.5M, 2.88 mmol) are added dropwise at-78℃and after 1h cyanuric chloride (0.15 g,0.81 mmol) is added and heated to 60℃for 18h. After the reaction was completed, the solvent was evaporated to dryness under reduced pressure, and the remaining solid was purified by petroleum ether: column separation and purification of methylene chloride (6:1) gave a white solid (173) (426 mg, 40%). MALDI-TOF (m/z): 1300.5; c (C) 93 H 57 N 9 Theoretical value of elemental analysis (%): c,85.89; h,4.42; n,9.69; measured value (%): c,85.88; h,4.43; n,9.69
Referring to table 1, table 1 shows photophysical properties of the host material formula (1), formula (3) prepared in the examples of the present invention.
TABLE 1
As can be seen from table 1, example formulas (1) and (3) have high triplet energy levels of 3.05eV and 2.97eV, respectively.
Example materials device preparation:
and cleaning the glass substrate plated with the ITO by distilled water, isopropanol and acetone in sequence, and then placing the glass substrate in an oven for drying, and then carrying out UVR treatment. PEDOT: PSS was spin-coated on the treated glass substrate and placed in an oven at 120℃for baking treatment. After drying, the substrate was transferred into a nitrogen atmosphere glove box, after which the host material shown in the examples was combined with a blue phosphorescent dye Ir (mpim) 3 The chlorobenzene solution of the mixed formulation was spin-coated onto PEDOT: PSS, followed by annealing for 30min on a hot stage at 100 ℃. After the above operation is completed, transferring into a vacuum evaporation bin at a temperature of 4×10 -4 And sequentially depositing an exciton blocking layer TPCz, an electron transport layer TmPyPB and a LiF/Al cathode under the vacuum degree of Pa to obtain the organic electroluminescent device, wherein the specific device structure is ITO/PEDOT: PSS (40 nm)/EML (30 nm)/TPCz (8 nm)/TmPyPB (42 nm)/LiF (1 nm)/Al (100 nm).
FIGS. 4-7 are respectively an electroluminescence spectrum, a voltage-current density-luminance curve, a current efficiency-luminance curve, and a power efficiency-luminance curve of a blue-light phosphorescent device based on formula (1);
FIGS. 11-14 are respectively an electroluminescence spectrum, a voltage-current density-luminance curve, a current efficiency-luminance curve, and a power efficiency-luminance curve of a blue-light phosphorescent device based on formula (3);
table 2 shows the properties of the electroluminescent devices of the formula (1) and the formula (3) as host materials prepared in the examples of the present invention.
TABLE 2
The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.

Claims (4)

1. A triazine-centered core dendritic bipolar host material having the structure of formula (1) or formula (3):
2. a method of preparing the triazine-centered, core dendritic bipolar host material of claim 1, comprising:
reacting a compound with a structure of formula (VI-1), a compound with a structure of formula (VI-2), a compound with a structure of formula (VI-3) and a compound with a structure of formula (VII) to obtain a dendritic bipolar host material with a structure of formula (I) and a triazine as a central core,
Wherein Ar is 1 、Ar 2 、Ar 3 、Ar 4 、Ar 5 、Ar 6 Independently selected from electron-donating aryl groups or electron-donating heteroaryl groups;
Z 1 、Z 2 、Z 3 independently selected from oxygen atoms a sulfur atom, One or more of them are connected together to form a combination; wherein R is 1 、R 2 Independently selected from hydrogen, C1-C12 alkyl, C6-C30 aryl or C5-C25 heteroaryl.
3. The preparation method according to claim 2, wherein the compound of the structure of formula (VI-1) is prepared according to the following method:
mixing the compound shown in the formula (II-1) or the formula (III-1) with sodium hydride and tert-butyldimethyl chlorosilane (TBS-Cl) for reaction to obtain a compound with a structure shown in the formula (IV-1) or the formula (V-1);
mixing a compound having a structure represented by (IV-1) or (V-1) with Ar 1 -H and Ar 2 H is mixed and reacted to obtain the structure shown in (VI-1);
the compound with the structure of the formula (VI-2) is prepared by the following method:
mixing the compound shown in the formula (II-2) or the formula (III-2) with sodium hydride and tert-butyldimethyl chlorosilane (TBS-Cl) for reaction to obtain a compound with a structure shown in the formula (IV-2) or the formula (V-2);
mixing a compound having a structure represented by (IV-2) or (V-2) with Ar 3 -H and Ar 4 H is mixed and reacted to obtain the structure shown in (VI-2);
the compound with the structure of the formula (VI-3) is prepared by the following method:
mixing the compound shown in the formula (II-3) or the formula (III-3) with sodium hydride and tert-butyldimethyl chlorosilane (TBS-Cl) for reaction to obtain a compound with a structure shown in the formula (IV-3) or the formula (V-3);
Mixing a compound having a structure represented by (IV-3) or (V-3) with Ar 5 -H and Ar 6 H is mixed and reacted to obtain the structure shown in (VI-3).
4. An organic electroluminescent device, characterized in that the host material in the device comprises the triazine-centered, core, dendritic bipolar host material of claim 1.
CN202010399670.0A 2020-05-12 2020-05-12 Dendritic bipolar main body material with triazine as central core, preparation method and application of dendritic bipolar main body material in organic electroluminescent device Active CN111548342B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010399670.0A CN111548342B (en) 2020-05-12 2020-05-12 Dendritic bipolar main body material with triazine as central core, preparation method and application of dendritic bipolar main body material in organic electroluminescent device

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010399670.0A CN111548342B (en) 2020-05-12 2020-05-12 Dendritic bipolar main body material with triazine as central core, preparation method and application of dendritic bipolar main body material in organic electroluminescent device

Publications (2)

Publication Number Publication Date
CN111548342A CN111548342A (en) 2020-08-18
CN111548342B true CN111548342B (en) 2024-01-19

Family

ID=72006184

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010399670.0A Active CN111548342B (en) 2020-05-12 2020-05-12 Dendritic bipolar main body material with triazine as central core, preparation method and application of dendritic bipolar main body material in organic electroluminescent device

Country Status (1)

Country Link
CN (1) CN111548342B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112300057B (en) * 2020-10-19 2022-04-19 华南师范大学 D-A-D type hole transport material and synthetic method and application thereof
CN114685458B (en) * 2020-12-29 2024-03-08 广州华睿光电材料有限公司 Organic compound and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101065462A (en) * 2004-11-30 2007-10-31 株式会社半导体能源研究所 Light emitting element and light emitting device having the same
CN103262283A (en) * 2010-12-09 2013-08-21 新日铁住金化学株式会社 Organic electroluminescent element
KR20140004005A (en) * 2012-06-22 2014-01-10 에스에프씨 주식회사 Aromatic compound and organoelectro luminescent device comprising the compound
CN103740359A (en) * 2013-12-27 2014-04-23 深圳市华星光电技术有限公司 Thermal activation delayed fluorescence material, synthesis method thereof and OLED (Organic Light Emitting Diode) device using thermal activation delayed fluorescence material
KR20150022615A (en) * 2013-08-22 2015-03-04 (주)피엔에이치테크 Novel compound for organic electroluminescent device and organic electroluminescent device comprising the same
CN106103428A (en) * 2014-03-12 2016-11-09 出光兴产株式会社 Composition, compound, material for organic electroluminescent element, ink composition, organic electroluminescent element, and electronic device

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5551428B2 (en) * 2009-01-06 2014-07-16 ユー・ディー・シー アイルランド リミテッド Charge transport material and organic electroluminescent device
WO2012077902A2 (en) * 2010-12-08 2012-06-14 제일모직 주식회사 Compound for an organic optoelectronic device, organic light-emitting diode including the compound, and display device including the organic light-emitting diode
DE102015106941A1 (en) * 2015-05-05 2016-11-10 Osram Oled Gmbh Organic emitter layer, organic light-emitting diode and use of heavy atoms in an organic emitter layer of an organic light-emitting diode

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101065462A (en) * 2004-11-30 2007-10-31 株式会社半导体能源研究所 Light emitting element and light emitting device having the same
CN103262283A (en) * 2010-12-09 2013-08-21 新日铁住金化学株式会社 Organic electroluminescent element
KR20140004005A (en) * 2012-06-22 2014-01-10 에스에프씨 주식회사 Aromatic compound and organoelectro luminescent device comprising the compound
KR20150022615A (en) * 2013-08-22 2015-03-04 (주)피엔에이치테크 Novel compound for organic electroluminescent device and organic electroluminescent device comprising the same
CN103740359A (en) * 2013-12-27 2014-04-23 深圳市华星光电技术有限公司 Thermal activation delayed fluorescence material, synthesis method thereof and OLED (Organic Light Emitting Diode) device using thermal activation delayed fluorescence material
CN106103428A (en) * 2014-03-12 2016-11-09 出光兴产株式会社 Composition, compound, material for organic electroluminescent element, ink composition, organic electroluminescent element, and electronic device

Also Published As

Publication number Publication date
CN111548342A (en) 2020-08-18

Similar Documents

Publication Publication Date Title
KR100940938B1 (en) Novel organic electroluminescent compounds and organic electroluminescent device using the same
TWI428424B (en) Compounds for organic electronic devices
KR101788793B1 (en) Pyridine derivative compound and organic electroluminescent devices comprising the same
KR102250389B1 (en) Organic light emitting device
KR101809899B1 (en) Pyridine derivative compound and organic electroluminescent device comprising the same
CN113004290B (en) Organic compound, organic electroluminescent material and application thereof
CN105051014A (en) Materials for electronic devices
JP2007327057A (en) Polymer compound and organic electroluminescence device produced by using the same
KR20110006915A (en) New compounds and organic electronic device using the same
WO2019056932A1 (en) Imidazole derivative, and material and organic light-emitting device comprising same
KR102430998B1 (en) Compound and organic light emitting device comprising the same
JP2023500009A (en) Heterocyclic compound, organic light-emitting device containing the same, composition for organic layer of organic light-emitting device, and method for manufacturing organic light-emitting device
CN111548342B (en) Dendritic bipolar main body material with triazine as central core, preparation method and application of dendritic bipolar main body material in organic electroluminescent device
KR20140058292A (en) Antracenederivatives and organic light-emitting diode including the same
WO2020133833A1 (en) Dibenzo heterocyclic compound, preparation method therefor and use thereof
CN111718280A (en) P-type doped hole injection compound and application thereof
CN111747932B (en) Compound, application thereof and organic electroluminescent device
Wang et al. Improving lifetime of phosphorescent organic light-emitting diodes by using a non-conjugated hybrid host
CN114409659A (en) Organic electroluminescent compound, preparation method thereof and organic electroluminescent device
CN109360905A (en) A kind of organic electroluminescence device
TWI804701B (en) Compounds, organic optoelectronic diode, and display device
JP2023506151A (en) Heterocyclic compound and organic light-emitting device containing the same
Li et al. Novel thieno-[3, 4-b]-pyrazine derivatives for non-doped red organic light-emitting diodes
KR102225901B1 (en) Multicyclic compound and organic light emitting device comprising the same
CN112979535A (en) Compound 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