CN109575038A - A kind of compound of the fluorenes of xanthene containing spiral shell and its application on organic electroluminescence device - Google Patents

A kind of compound of the fluorenes of xanthene containing spiral shell and its application on organic electroluminescence device Download PDF

Info

Publication number
CN109575038A
CN109575038A CN201710901085.4A CN201710901085A CN109575038A CN 109575038 A CN109575038 A CN 109575038A CN 201710901085 A CN201710901085 A CN 201710901085A CN 109575038 A CN109575038 A CN 109575038A
Authority
CN
China
Prior art keywords
molar ratio
compound
thickness
layer
raw material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201710901085.4A
Other languages
Chinese (zh)
Inventor
王立春
王芳
张兆超
李崇
张小庆
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.)
Jiangsu Sunera Technology Co Ltd
Original Assignee
Jiangsu Sanyue Optoelectronic Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangsu Sanyue Optoelectronic Technology Co Ltd filed Critical Jiangsu Sanyue Optoelectronic Technology Co Ltd
Priority to CN201710901085.4A priority Critical patent/CN109575038A/en
Publication of CN109575038A publication Critical patent/CN109575038A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
    • C07D491/048—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being five-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/10—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
    • C07D491/052—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being six-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C07D491/056—Ortho-condensed systems with two or more oxygen atoms as ring hetero atoms in the oxygen-containing ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D498/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
    • C07D498/14—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
    • C07D513/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/18—Carrier blocking layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen 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
    • H10K2101/40—Interrelation of parameters between multiple constituent active layers or sublayers, e.g. HOMO values in adjacent layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301—Details of OLEDs

Landscapes

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

Abstract

The invention discloses a kind of compound of fluorenes of xanthene containing spiral shell and its applications on organic electroluminescence device, this compound is because fluorene structured containing spiral shell xanthene, with very strong rigidity, and after connecting carbazole derivates long branched chain structure, so that the compound has the characteristics that intermolecular be not easy to crystallize, assemble, good filming；The compounds of this invention is because parent nucleus has bipolarity, and branch is electron donating group, and branched group electron donation is strong and weak different, and therefore, the HOMO energy level of material is different, can be used as the use of different function layer material；In addition, the compounds of this invention triplet with higher, can effectively stop energy loss and be conducive to energy transmission.Therefore, after the compounds of this invention is applied to OLED device as organic electroluminescent functional layer material, the current efficiency of device, power efficiency and external quantum efficiency are greatly improved；Meanwhile device lifetime is promoted clearly.

Description

The compound of a kind of fluorenes of xanthene containing spiral shell and its on organic electroluminescence device Using
Technical field
The present invention relates to technical field of semiconductors, more particularly, to a kind of change containing oxa- spiro fluorene and nitrogenous five-ring heterocycles Close object, and its application on organic electroluminescence device.
Background technique
Organic electroluminescent (OLED:Organic Light Emission Diodes) device technology can not only be used to New display product is manufactured, can be also used for production novel illumination product, and be expected to substitute existing liquid crystal display and fluorescent lamp Illumination, be widely used prospect.OLED luminescent device is a kind of sandwich structure, including electrode material film layer, with And it is clipped in the organic functional material between Different electrodes film layer, various different function materials are overlapped mutually together altogether depending on the application With composition OLED luminescent device.As current device, when the two end electrodes application voltage to OLED luminescent device, and pass through electric field The positive and negative charge in organic layer functional material film layer is acted on, positive and negative charge is further compound in luminescent layer, i.e. generation OLED electricity Photoluminescence.
Currently, OLED display technology in smart phone, applied by the fields such as tablet computer, further will also be to electricity Depending on etc. large scales application field extension, still, the luminous efficiency of OLED device, the application requirement of the performances such as service life and product Compared to needing further to be promoted.Research for improving OLED luminescent device performance specifically includes that the driving electricity for reducing device Pressure, improves the luminous efficiency of device, improves the service life etc. of device.In order to realize OLED device performance continuous promotion, Not only OLED device structure and manufacture craft are innovated, also oled light sulfate ferroelectric functional material is constantly studied and created Newly, to create the OLED functional material of higher performance.Oled light sulfate ferroelectric functional material applied to OLED device is from purposes Two major classes, i.e. charge injection transmission material and luminescent material can be substantially divided into, charge injection transmission material can be divided into electricity again Son injection transmission material, electron-blocking materials, hole injection transmission material and hole barrier materials, and luminescent material includes main body Luminescent material and dopant material.High performance OLED luminescent device, it is desirable that various organic functional materials must have good light Electrical characteristics, for example, as charge transport materials, it is desirable that there is good carrier mobility, higher glass transition temperature There is good bipolarity Deng, the material of main part of luminescent layer, HOMO/LUMO appropriate can rank etc..
The oled light sulfate ferroelectric functional material film layer for constituting OLED device includes at least two layers or more structure, applies in industry OLED device structure then includes hole injection layer, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electronics biography A variety of film layers such as defeated layer, electron injecting layer, that is to say, that the photoelectric functional material applied to OLED device is infused including at least hole Enter material, hole mobile material, luminescent material, electron transport material etc., material type and collocation form with rich and more The characteristics of sample.In addition, used photoelectric functional material has stronger for the collocation of the OLED device of different structure Selectivity, performance of the identical material in different structure device, it is also possible to completely totally different.Therefore, for current OLED The industry application requirement of device and the different function film layer of OLED device, the photoelectric characteristic demand of device, it is necessary to which selection is more suitable It closes, OLED functional material or combination of materials with high performance, is just able to achieve the comprehensive of the high efficiency of device, long-life and low-voltage Close characteristic.For current OLED shows the actual demand of Lighting Industry, the development of OLED material at present also lags far behind face The requirement of plate manufacturing enterprise, the organic functional material as material enterprise development higher performance are particularly important.
Summary of the invention
In view of the above-mentioned problems existing in the prior art, the applicant provide a kind of fluorenes of xanthene containing spiral shell compound and its Application on organic electroluminescence device.It is fluorene structured that the compounds of this invention contains spiral shell xanthene, and vitrifying with higher turns Temperature and molecule thermal stability, suitable HOMO and lumo energy can effectively improve device after being applied to OLED device production Luminous efficiency and OLED device service life.
Technical scheme is as follows: a kind of compound of the fluorenes of xanthene containing spiral shell, the structure of the compound such as general formula (1) It is shown:
Wherein, Ar1、Ar2、Ar3、Ar4Independently be expressed as singly-bound, substituted or unsubstituted C6-60Arlydene contains One of one or more substituted or unsubstituted 5~60 yuan of heteroarylidenes of hetero atom；The hetero atom be nitrogen, oxygen or sulphur, Ar1、Ar2、Ar3、Ar4It is identical or different；
M, n, p, q independently be expressed as number 0 or 1, and m+n+p+q >=1；
R1、R2、R3、R4Independently be expressed as structure shown in general formula (2)；R1、R2、R3、R4It is identical or different；
In general formula (2), R5、R6Independently be expressed as hydrogen atom, general formula (3), general formula (4), general formula (5) or general formula (6) Shown structure；R5、R6It is identical or different；
In general formula (3) and general formula (4), X1、X2、X3Independently be expressed as oxygen atom, sulphur atom, C1-10Straight chain or branch One in imido grpup that alkylidene, alkyl-substituted imido grpup or the aryl of alkylidene, aryl substitution that alkyl group replaces replace Kind；
General formula (3), general formula (4), general formula (5) pass through CL1-CL2Key, CL2-CL3Key, CL3-CL4Key, CL’1-CL’2Key, CL'2- CL’3Key or CL’3-CL’4Key is connected with general formula (2) and ring；
In general formula (6), R7、R8Independently be expressed as substituted or unsubstituted C6-60Aryl, containing one or more miscellaneous One of substituted or unsubstituted 5-60 unit's heteroaryl of atom；The hetero atom is nitrogen, oxygen or sulphur.
Based on the above technical solution, the present invention can also be improved as follows.
Further, any one of described general formula (1) structure meeting formula (I)-(II):
Further, any one of described general formula (1) structure meeting formula (III)-(VIII):
Further, any one of described general formula (1) structure meeting formula (I)-(VIII):
Further, any one of described general formula (1) structure meeting formula (1-1)-(1-8):
Further, in above-mentioned general formula, Ar used1、Ar2、Ar3、Ar4Independently indicate are as follows: Or one of singly-bound.
Further, R7、R8Independently be expressed as phenyl, naphthalene, dibiphenylyl, terphenyl, dibenzofurans, two One of benzothiophene, 9,9- dimethyl fluorene or N- phenyl carbazole.
Further, the concrete structure formula of the compound are as follows:
Any one of.
The present invention also provides a kind of preparation methods of compound as described above, comprising:
Work as Ar1、Ar2、Ar3、Ar4When being expressed as singly-bound, the reaction equation that occurs in preparation process are as follows:
The specific reaction process of above-mentioned reaction equation are as follows:
1) by raw material A and H-R1It is dissolved with toluene, wherein the raw material A and H-R1Molar ratio be 1:(1.0~1.5)；
2) Pd is added into the reaction system in 1)2(dba)3, tri-tert-butylphosphine and sodium tert-butoxide, obtain mixed solution；
Wherein, the Pd2(dba)3It is (0.005~0.01) with the molar ratio of raw material A: 1, the tri-tert-butylphosphine and former The molar ratio for expecting A is (0.005~0.02): 1, the molar ratio of the sodium tert-butoxide and raw material A is (1.5~3.0): 1；
3) under the protection of inert gas, above-mentioned mixed solution reacts to 10 under the conditions of 95~110 DEG C of temperature~ For 24 hours, cooled to room temperature is filtered reaction solution, then rotates to filtrate, finally crosses neutral silica gel column, obtains To intermediate M；
4) by intermediate M and H-R2It is dissolved with toluene, wherein the intermediate M and H-R2Molar ratio be 1:(1.0~ 1.5)；
5) Pd is added into reaction system 4)2(dba)3, tri-tert-butylphosphine and sodium tert-butoxide, obtain mixed solution；
Wherein, the Pd2(dba)3Be (0.005~0.01) with the molar ratio of intermediate M: 1, the tri-tert-butylphosphine with The molar ratio of intermediate M is (0.005~0.02): 1, the molar ratio of the sodium tert-butoxide and intermediate M are (1.5~3.0): 1；
6) under the protection of inert gas, above-mentioned mixed solution reacts to 10 under the conditions of 95~110 DEG C of temperature~ For 24 hours, cooled to room temperature, and filtering reacting solution, filtrate rotate to solvent-free, cross neutral silica gel column, obtain intermediate N；
7) by intermediate N and H-R3It is dissolved with toluene, wherein the intermediate N and H-R3Molar ratio be 1:(1.0~ 1.5)；
8) Pd is added into reaction system 7)2(dba)3, tri-tert-butylphosphine and sodium tert-butoxide, obtain mixed solution；
Wherein, the Pd2(dba)3Be (0.005~0.01) with the molar ratio of intermediate N: 1, the tri-tert-butylphosphine with The molar ratio of intermediate N is (0.005~0.02): 1, the molar ratio of the sodium tert-butoxide and intermediate N are (1.5~3.0): 1；
9) under the protection of inert gas, above-mentioned mixed solution reacts to 10 under the conditions of 95~110 DEG C of temperature~ For 24 hours, cooled to room temperature, and filtering reacting solution, filtrate rotate to solvent-free, cross neutral silica gel column, obtain intermediate P；
10) by intermediate P and H-R4It is dissolved with toluene, wherein the intermediate P and H-R4Molar ratio be 1:(1.0~ 1.5)；
11) Pd is added into reaction system 10)2(dba)3, tri-tert-butylphosphine and sodium tert-butoxide, obtain mixed solution；
Wherein, the Pd2(dba)3Be (0.005~0.01) with the molar ratio of intermediate P: 1, the tri-tert-butylphosphine with The molar ratio of intermediate P is (0.005~0.02): 1, the molar ratio of the sodium tert-butoxide and intermediate P are (1.5~3.0): 1；
12) under the protection of inert gas, above-mentioned mixed solution reacts to 10 under the conditions of 95~110 DEG C of temperature~ For 24 hours, cooled to room temperature, and filtering reacting solution, filtrate rotate to solvent-free, cross neutral silica gel column, obtain target chemical combination Object；
Work as Ar1、Ar2、Ar3、Ar4When not being expressed as singly-bound, the reaction equation that occurs in preparation process are as follows:
The specific reaction process of above-mentioned reaction equation are as follows:
1) with raw material A andBoronic acid compounds are raw material, and toluene dissolution, the toluene dosage is every gram of original Expect that A uses 30-50ml toluene, wherein the raw material A and the molar ratio of boronic acid compounds are 1:(1.0~1.5)；
2) Pd (PPh is added into reaction system 1)3)4And sodium carbonate, obtain mixed solution；
Wherein, the Pd (PPh3)4It is (0.005~0.01) with the molar ratio of raw material A: 1, the sodium carbonate and raw material A Molar ratio is (1.5~3.0): 1；
3) it under nitrogen protection, by above-mentioned mixed solution in 95~110 DEG C, reacts 10~24 hours, naturally cools to room Temperature, and filtering reacting solution, filtrate carry out vacuum rotary steam, cross neutral silica gel column, obtain intermediate N；
4) with intermediate N andBoronic acid compounds are raw material, and toluene dissolution, the toluene dosage is every gram Intermediate N uses 30-50ml toluene, wherein the molar ratio of the intermediate N and boronic acid compounds is 1:(1.0~1.5)；
5) Pd (PPh is added into reaction system 4)3)4And sodium carbonate, obtain mixed solution；
Wherein, the Pd (PPh3)4It is (0.005~0.01) with the molar ratio of intermediate N: 1, the sodium carbonate and intermediate The molar ratio of body N is (1.5~3.0): 1；
6) it under nitrogen protection, by above-mentioned mixed solution in 95~110 DEG C, reacts 10~24 hours, naturally cools to room Temperature, and filtering reacting solution, filtrate carry out vacuum rotary steam, cross neutral silica gel column, obtain intermediate M.
7) with intermediate M andBoronic acid compounds are raw material, and toluene dissolution, the toluene dosage is every gram Intermediate M uses 30-50ml toluene, wherein the molar ratio of the intermediate M and boronic acid compounds is 1:(1.0~1.5)；
8) Pd (PPh is added into reaction system 7)3)4And sodium carbonate, obtain mixed solution；
Wherein, the Pd (PPh3)4It is (0.005~0.01) with the molar ratio of intermediate M: 1, the sodium carbonate and intermediate The molar ratio of body M is (1.5~3.0): 1；
9) it under nitrogen protection, by above-mentioned mixed solution in 95~110 DEG C, reacts 10~24 hours, naturally cools to room Temperature, and filtering reacting solution, filtrate carry out vacuum rotary steam, cross neutral silica gel column, obtain intermediate P；
10) with intermediate P andBoronic acid compounds are raw material, and toluene dissolution, the toluene dosage is every gram Intermediate P uses 30-50ml toluene, wherein the molar ratio of the intermediate P and boronic acid compounds is 1:(1.0~1.5)；
11) Pd (PPh is added into reaction system 10)3)4And sodium carbonate, obtain mixed solution；
Wherein, the Pd (PPh3)4It is (0.005~0.01) with the molar ratio of intermediate P: 1, the sodium carbonate and intermediate The molar ratio of body P is (1.5~3.0): 1；
12) it under nitrogen protection, by above-mentioned mixed solution in 95~110 DEG C, reacts 10~24 hours, naturally cools to room Temperature, and filtering reacting solution, filtrate carry out vacuum rotary steam, cross neutral silica gel column, obtain target compound.
The present invention also provides a kind of organic electroluminescence device, the organic electroluminescence device includes at least one layer of function Layer contains the compound of the above-mentioned fluorenes of xanthene containing spiral shell.
Based on the above technical solution, the present invention can also be improved as follows.
Further, the organic electroluminescence device, including hole transmission layer/electronic barrier layer, the hole transport Layer/electronic barrier layer contains the compound of the fluorenes of xanthene containing spiral shell as described above.
Further, the organic electroluminescence device, including luminescent layer, the luminescent layer contain as described above containing spiral shell The compound of xanthene fluorenes.
The present invention also provides a kind of illumination or display elements, including organic electroluminescence device as described above.
The present invention is beneficial to be had the technical effect that
The compounds of this invention connects carbazole derivates long branched chain structure, due to branched group using spiral shell xanthene fluorenes as skeleton Electron donation is strong and weak different, adjust the HOMO energy level of compound entirety structure can freely, the shallow compound of HOMO energy level can As hole transmission layer/electronic barrier layer materials'use；The material of HOMO energy level depth can be used as the luminous layer main body material of inclined cavity type Material uses.
In addition, spiral shell xanthene fluorene group is bipolarity group, branch is backbone, destroys the symmetrical of molecular structure Property, avoid intermolecular aggtegation；It using spiral shell xanthene fluorenes as parent nucleus, avoids group and rotates freely, enhance center mother The rigidity of core group, the branched group of the compounds of this invention also have very strong rigidity, and therefore, molecule is not easy accumulative crystallization, has Good film forming, and glass transition temperature with higher and thermal stability, so, the compounds of this invention is applied to OLED When device, membranous layer stability after can keeping material filming improves OLED device service life.
In addition, the compounds of this invention has high triplet, it can effectively stop energy loss and be conducive to energy to pass It passs.Therefore, after compound of the present invention is applied to OLED device as organic electroluminescent functional layer material, the electric current of device Efficiency, power efficiency and external quantum efficiency are greatly improved；Meanwhile device lifetime is promoted clearly, in OLED There is good application effect in luminescent device, there is good industrialization prospect.
Detailed description of the invention
Fig. 1 is the structural schematic diagram that material cited by the present invention is applied to OLED device；
Wherein, 1 is transparent substrate layer, and 2 be ito anode layer, and 3 be hole injection layer, and 4 be hole transmission layer, and 5 hinder for electronics Barrier, 6 be luminescent layer, and 7 be hole barrier/electron transfer layer, and 8 be electron injecting layer, and 9 be cathode reflection electrode layer；
Fig. 2 is the efficiency curve diagram that device measures at different temperatures.
Specific embodiment
Below in conjunction with drawings and examples, the present invention is specifically described.
Work as Ar1、Ar2、Ar3、Ar4When not being expressed as singly-bound,
Intermediate boronic acid compounds's Synthesis:
(1) under nitrogen atmosphere, R is weighed1- H and Br-Ar1- Cl is dissolved in toluene, then by Pd2(dba)3, tri-tert-butylphosphine It is added, stirs mixture, add sodium tert-butoxide, by the mixed solution of above-mentioned reactant at 95~110 DEG C of reaction temperature, add Heat reflux 10~for 24 hours, it after reaction, is cooled to room temperature, and filtering reacting solution, filtrate rotates to solvent-free, excessively neutral silicon Rubber column gel column obtains intermediate R1-Ar1-Cl；
(2) under nitrogen atmosphere, intermediate R is weighed1-Ar1- Cl is dissolved in tetrahydrofuran (THF), then will be bis- (pinacol root Base) two boron, (1,1 '-bis- (diphenylphosphine) ferrocene) dichloro palladium (II) and potassium acetate addition, mixture is stirred, it will be above-mentioned anti- The mixed solution of object is answered to be heated to reflux at 70-90 DEG C of reaction temperature 5-10 hours；After reaction, add water cooling and will mix Close object filtering and the drying in vacuum drying oven.Residue obtained is crossed into silica gel column separating purification, obtains intermediate
Ar used above1、Ar2、R1、R2The meaning of equal symbols is identical as the definition of specification Summary.
By taking the synthesis of intermediate B 1 as an example:
(1) in the there-necked flask of 250ml, lead under nitrogen protection, 0.02mol raw material B2,0.024mol para chlorobromobenzene be added, 0.04mol sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-tert phosphorus, 150ml toluene are heated to reflux 24 Hour, sample contact plate, fully reacting；Natural cooling, filtering, filtrate revolving, column chromatograph to obtain intermediate A 1, HPLC purity 99.4%, yield 71.3%；
Elemental analysis structure (molecular formula C27H20ClN): theoretical value C, 82.33；H,5.12；Cl,9.00；N,3.56；Test Value: C, 82.32；H,5.11；Cl,9.02；N,3.55.ESI-MS(m/z)(M+): theoretical value 393.13, measured value are 393.58。
(2) in 250mL there-necked flask, it is passed through nitrogen, 0.02mol intermediate A 1 is added and is dissolved in 150ml tetrahydrofuran, Again by 0.024mol bis- (pinacol foundation) two boron, 0.0002mol (1,1 '-bis- (diphenylphosphine) ferrocene) dichloro palladium (II) with And 0.05mol potassium acetate is added, stirring mixture heats back by the mixed solution of above-mentioned reactant at 80 DEG C of reaction temperature Stream 5 hours；After reaction, it cools down and is added 100ml water and mixture is filtered and is dried in vacuum drying oven.It will be obtained The residue obtained crosses silica gel column separating purification, obtains intermediate B 1；HPLC purity 99.5%, yield 92.1%.
Elemental analysis structure (molecular formula C33H32BNO2): theoretical value C, 81.65；H,6.64；B,2.23；N,2.89；O, 6.59；Test value: C, 81.68；H,6.65；B,2.21；N,2.88；O,6.58.ESI-MS(m/z)(M+): theoretical value is 485.25 measured value 485.61.
Intermediate B is prepared with the synthetic method of intermediate B 1, specific structure is as shown in table 1.
Table 1
Embodiment 1: the synthesis of compound 8:
In the there-necked flask of 250ml, lead under nitrogen protection, 0.01mol raw material A 1,0.012mol raw material B1,150ml is added Toluene is stirred, then addition 0.03mol sodium tert-butoxide, and 5 × 10-5molPd2(dba)3, 5 × 10-5Mol tri-tert-butylphosphine, 105 DEG C are heated to, back flow reaction 24 hours, samples contact plate, display is without bromo-derivative residue, fully reacting；Cooled to room temperature, Filtering, filtrate carry out vacuum rotary steam (- 0.09MPa, 85 DEG C), cross neutral silica gel column, obtain target product, HPLC purity 99.3%, yield 84.7%；
Elemental analysis structure (molecular formula C49H30N2O): theoretical value C, 88.80；H,4.56；N,4.23；O,2.41；Test Value: C, 88.75；H,4.65；N,4.05；O,2.56.ESI-MS(m/z)(M+): theoretical value 662.24, measured value are 662.79。
Embodiment 2: the synthesis of compound 15:
In the there-necked flask of 250ml, lead under nitrogen protection, 0.01mol raw material A 1,0.012mol raw material B2,150ml is added Toluene is stirred, then addition 0.03mol sodium tert-butoxide, and 5 × 10-5molPd2(dba)3, 5 × 10-5Mol tri-tert-butylphosphine, 105 DEG C are heated to, back flow reaction 24 hours, samples contact plate, display is without bromo-derivative residue, fully reacting；Cooled to room temperature, Filtering, filtrate carry out vacuum rotary steam (- 0.09MPa, 85 DEG C), cross neutral silica gel column, obtain target product, HPLC purity 99.5%, yield 82.9%；
Elemental analysis structure (molecular formula C46H31NO): theoretical value C, 90.02；H,5.09；N,2.28；O,2.61；Test Value: C, 90.08；H,5.13；N,2.26；O,2.65.ESI-MS(m/z)(M+): theoretical value 613.24, measured value are 613.76。
Embodiment 3: the synthesis of compound 16:
The preparation method is the same as that of Example 1 for compound 16, the difference is that replacing raw material B1 with raw material B3.
Elemental analysis structure (molecular formula C49H30N2O): theoretical value C, 88.80；H,4.56；N,4.23；O,2.41；Test Value: C, 88.77；H,4.49；N,4.09；O,2.37.ESI-MS(m/z)(M+): theoretical value 662.24, measured value are 662.59。
Embodiment 4: the synthesis of compound 23:
The preparation method is the same as that of Example 1 for compound 23, the difference is that replacing raw material B1 with raw material B4.
Elemental analysis structure (molecular formula C46H31NO): theoretical value C, 90.02；H,5.09；N,2.28；O,2.61；Test Value: C, 90.07；H,5.12；N,2.25；O,2.57.ESI-MS(m/z)(M+): theoretical value 613.24, measured value are 613.77。
Embodiment 5: the synthesis of compound 40:
The preparation method is the same as that of Example 1 for compound 40, the difference is that replacing raw material A 1 with raw material A 5, is replaced with raw material B5 Change raw material B1.
Elemental analysis structure (molecular formula C46H31NO2): theoretical value C, 87.73；H,4.96；N,2.22；O,5.08；Test Value: C, 87.69；H,4.95；N,2.19；O,5.03.ESI-MS(m/z)(M+): theoretical value 629.24, measured value are 629.86。
Embodiment 6: the synthesis of compound 46:
The preparation method is the same as that of Example 1 for compound 46, the difference is that replacing raw material B1 with raw material B6.
Elemental analysis structure (molecular formula C52H36N2O): theoretical value C, 88.61；H,5.15；N,3.97；O,2.27；Test Value: C, 88.58；H,5.13；N,3.91；O,2.26.ESI-MS(m/z)(M+): theoretical value 704.28, measured value are 704.87。
Embodiment 7: the synthesis of compound 60:
The preparation method is the same as that of Example 1 for compound 60, the difference is that replacing raw material B1 with raw material B7.
Elemental analysis structure (molecular formula C64H44N2O): theoretical value C, 89.69；H,5.17；N,3.27；O,1.87；Test Value: C, 89.67；H,5.14；N,3.25；O,1.85.ESI-MS(m/z)(M+): theoretical value 856.35, measured value are 856.87。
Embodiment 8: the synthesis of compound 65:
The preparation method is the same as that of Example 1 for compound 65, the difference is that replacing raw material B1 with raw material B8.
Elemental analysis structure (molecular formula C45H27NO): theoretical value C, 90.43；H,4.55；N,2.34；O,2.68；Test Value: C, 90.45；H,4.57；N,2.26；O,2.65.ESI-MS(m/z)(M+): theoretical value 597.21, measured value are 597.72。
Embodiment 9: the synthesis of compound 80:
The preparation method is the same as that of Example 1 for compound 80, the difference is that replacing raw material A 1 with raw material A 2, is replaced with raw material B9 Change raw material B1.
Elemental analysis structure (molecular formula C49H30N2O): theoretical value C, 88.80；H,4.56；N,4.23；O,2.41；Test Value: C, 88.88；H,4.51；N,4.21；O,2.47.ESI-MS(m/z)(M+): theoretical value 662.79, measured value are 662.92。
Embodiment 10: the synthesis of compound 68:
The preparation method is the same as that of Example 1 for compound 68, the difference is that replacing raw material B1 with raw material B10.
Elemental analysis structure (molecular formula C58H40N2O): theoretical value C, 89.20；H,5.16；N,3.59；O,2.05；Test Value: C, 89.22；H,5.17；N,3.62；O,2.07.ESI-MS(m/z)(M+): theoretical value 780.31, measured value are 780.97。
Embodiment 11: the synthesis of compound 104:
The preparation method is the same as that of Example 1 for compound 104, the difference is that raw material A 1 is replaced with raw material A 3, with raw material B11 Replace raw material B1.
Elemental analysis structure (molecular formula C43H25NOS): theoretical value C, 85.55；H,4.17；N,2.32；S,5.31；O, 2.65；Test value: C, 85.57；H,4.15；N,2.33；S,5.32；O,2.63.ESI-MS(m/z)(M+): theoretical value is 603.17 measured value 603.74.
Embodiment 12: the synthesis of compound 108:
The preparation method is the same as that of Example 1 for compound 108, the difference is that raw material A 1 is replaced with raw material A 3, with raw material B12 Replace raw material B1
Elemental analysis structure (molecular formula C43H25NOS): theoretical value C, 85.55；H,4.17；N,2.32；S,5.31；O, 2.65；Test value: C, 85.57；H,4.15；N,2.33；S,5.32；O,2.63.ESI-MS(m/z)(M+): theoretical value is 603.17 measured value 603.69.
Embodiment 13: the synthesis of compound 121:
In the there-necked flask of 250ml, lead under nitrogen protection, addition 0.01mol raw material A 1,0.012mol intermediate B 2, 150ml toluene is stirred, then addition 0.02mol sodium carbonate, and 1 × 10-4molPd(PPh3)4, 105 DEG C are heated to, reflux is anti- It answers 24 hours, samples contact plate, display is without bromo-derivative residue, fully reacting；Cooled to room temperature, filtering, filtrate are depressurized It rotates (- 0.09MPa, 85 DEG C), crosses neutral silica gel column, obtain target product, HPLC purity 99.2%, yield 78.5%；
Elemental analysis structure (molecular formula C55H34N2O): theoretical value C, 89.41；H,4.64；N,3.79；O,2.17；Test Value: C, 89.43；H,4.65；N,3.77；O,2015.ESI-MS(m/z)(M+): theoretical value 738.27, measured value are 738.89。
Embodiment 14: the synthesis of compound 133:
The preparation method is the same as that of Example 13 for compound 133, the difference is that replacing raw material A 1 with raw material A 4, uses intermediate B3 replaces intermediate B 2.
Elemental analysis structure (molecular formula C58H39NO): theoretical value C, 90.95；H,5.13；N,1.83；O,2.09；Test Value: C, 90.96；H,5.19；N,1.85；O,2.11.ESI-MS(m/z)(M+): theoretical value 765.30, measured value are 765.86。
Embodiment 15: the synthesis of compound 138:
The preparation method is the same as that of Example 13 for compound 138, the difference is that replacing raw material A 1 with raw material A 4, uses intermediate B4 replaces intermediate B 2.
Elemental analysis structure (molecular formula C61H38N2O): theoretical value C, 89.90；H,4.70；N,3.44；O,1.96；Test Value: C, 89.93；H,4.65；N,3.47；O,2.05.ESI-MS(m/z)(M+): theoretical value 814.30, measured value are 814.95。
Embodiment 16: the synthesis of compound 147:
The preparation method is the same as that of Example 13 for compound 147, the difference is that replacing raw material A 1 with raw material A 4, uses intermediate B5 replaces intermediate B 2.
Elemental analysis structure (molecular formula C58H39NO): theoretical value C, 90.95；H,5.13；N,1.83；O,2.09；Test Value: C, 90.98；H,5.12；N,1.87；O,2.11.ESI-MS(m/z)(M+): theoretical value 765.96, measured value are 765.99。
Embodiment 17: the synthesis of compound 154:
The preparation method is the same as that of Example 1 for compound 154, the difference is that raw material A 1 is replaced with raw material A 6, with raw material B13 Replace raw material B1.
Elemental analysis structure (molecular formula C52H36N2O): theoretical value C, 88.61；H,5.15；N,3.97,O,2.27；Test Value: C, 88.65；H,5.32；N,3.96；O,2.36.ESI-MS(m/z)(M+): theoretical value 704.28, measured value are 704.87。
Embodiment 18: the synthesis of compound 166:
The preparation method is the same as that of Example 13 for compound 166, the difference is that replacing raw material A 1 with raw material A 5, uses intermediate B6 replaces intermediate B 2.
Elemental analysis structure (molecular formula C58H40N2O): theoretical value C, 89.20；H,5.16；N,3.59；O,2.05；Test Value: C, 80.21；H,5.17；N,3.57；O,2.03.ESI-MS(m/z)(M+): theoretical value 780.31, measured value are 780.97。
Embodiment 19: the synthesis of compound 189:
The preparation method is the same as that of Example 1 for compound 189, the difference is that raw material A 1 is replaced with raw material A 6, with raw material B14 Replace raw material B1.
Elemental analysis structure (molecular formula C43H52NO2): theoretical value C, 87.88；H,4.29；N,2.38,O,5.54；Test Value: C, 87.85；H,5.52；N,2.36；O,5.56.ESI-MS(m/z)(M+): theoretical value 587.19, measured value are 587.68。
Embodiment 20: the synthesis of compound 229:
The preparation method is the same as that of Example 1 for compound 230, the difference is that raw material A 1 is replaced with raw material A 7, with raw material B15 Replace raw material B1.
Elemental analysis structure (molecular formula C81H52N4O): theoretical value C, 88.66；H,4.78；N,5.11；O,1.46；Test Value: C, 88.67；H,4.79；N,5.09；O,1.45.ESI-MS(m/z)(M+): theoretical value 1096.41, measured value are 1096.94。
Embodiment 21: the synthesis of compound 234:
In the there-necked flask of 250ml, lead under nitrogen protection, 0.01mol raw material A 8,0.048mol carbazole, 150ml first is added Benzene is stirred, then addition 0.06mol sodium tert-butoxide, and 1 × 10-4molPd2(dba)3, 1 × 10-4Mol tri-tert-butylphosphine, adds Heat samples contact plate, display is without bromo-derivative residue, fully reacting to 105 DEG C, back flow reaction 24 hours；Cooled to room temperature, mistake Filter, filtrate carry out vacuum rotary steam (- 0.09MPa, 85 DEG C), cross neutral silica gel column, obtain target product, HPLC purity 99.1%, Yield 79.6%；
Elemental analysis structure (molecular formula C73H44N4O): theoretical value C, 88.28；H,4.47；N,5.64；O,1.61；Test Value: C, 88.29；H,4.45；N,5.63；O,1.59.ESI-MS(m/z)(M+): theoretical value 992.35, measured value are 993.18。
This organic compound uses in luminescent device, has high glass transition temperature (Tg) and triplet (T1), suitable HOMO, lumo energy act not only as hole transmission layer/electronic barrier layer materials'use, are alternatively arranged as sending out Photosphere materials'use.Carry out hot property, T1 energy level and the test of HOMO energy level, knot respectively to the compounds of this invention and current material Fruit is as shown in table 2.
Table 2
Note: triplet T1 is tested by the F4600 Fluorescence Spectrometer of Hitachi, and the test condition of material is 2*10-5's Toluene solution；Glass transition temperature Tg is by differential scanning calorimetry (DSC, German Nai Chi company DSC204F1 differential scanning calorimeter) Measurement, 10 DEG C/min of heating rate；Highest occupied molecular orbital HOMO energy level and minimum occupied molecular orbital lumo energy be by Photoelectron emissions spectrometer (AC-2 type PESA) test, is tested as atmospheric environment.
By upper table data it is found that NPB, CBP and TPAC material that comparison is applied at present, organic compound of the invention have High glass transition temperature can be improved the phase stability of membrane material, further increase device service life；Material of the present invention While there is similar HOMO energy level with application material, also there is high triplet (T1), luminescent layer energy can be stopped Amount loss, to promote device light emitting efficiency.Therefore, the organic material that the present invention contains xanthene fluorenes is being applied to OLED device Different function layer after, the luminous efficiency and service life of device can be effectively improved.
Below by way of device embodiments 1~21 and device comparative example 1 OLED material that the present invention will be described in detail synthesizes in device Application effect in part.Device embodiments 2~21 of the present invention, the device compared with device embodiments 1 of device comparative example 1 Manufacture craft it is identical, and use identical baseplate material and electrode material, the film thickness of electrode material is also kept Unanimously, except that the emitting layer material in 1~12 pair of device of device embodiments converts；13~21 pairs of device embodiments The hole transmission layer of device/electronic blocking layer material converts, the performance test results of each embodiment obtained device such as 3 institute of table Show.
Device embodiments 1:
As shown in Figure 1, a kind of electroluminescent device, preparation step include:
A) the ito anode layer 2 on transparent substrate layer 1 is cleaned, cleans each 15 with deionized water, acetone, EtOH Sonicate respectively Minute, then handled 2 minutes in plasma cleaner；
B) on ito anode layer 2, hole injection layer material HAT-CN is deposited by vacuum evaporation mode, with a thickness of 10nm, This layer is as hole injection layer 3；
C) on hole injection layer 3, hole mobile material NPB is deposited by vacuum evaporation mode, with a thickness of 60nm, the layer For hole transmission layer 4；
D) on hole transmission layer 4, electron-blocking materials TPAC is deposited by vacuum evaporation mode, it, should with a thickness of 20nm Layer is electronic barrier layer 5；
E) luminescent layer 6 is deposited on electronic barrier layer 5, material of main part is 8 He of compound of preparation of the embodiment of the present invention Compound GHN, dopant material are Ir (ppy)3, compound 8, GHN and Ir (ppy)3Three's mass ratio is 50:50:10, thickness For 30nm；
F) on luminescent layer 6, electron transport material TPBI is deposited by vacuum evaporation mode, with a thickness of 40nm, this layer Organic material is used as hole barrier/electron transfer layer 7；
G) on hole barrier/electron transfer layer 7, vacuum evaporation electron injecting layer LiF, with a thickness of 1nm, which is electricity Sub- implanted layer 8；
H) on electron injecting layer 8, vacuum evaporation cathode Al (100nm), the layer is cathode reflection electrode layer 9；
After the production for completing electroluminescent device according to above-mentioned steps, the driving voltage of measurement device, current efficiency, knot Fruit is shown in Table 3.The molecular structural formula of associated materials is as follows:
Device embodiments 2:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT- CN)/hole transmission layer 4 (thickness: 60nm, material: NPB)/electronic barrier layer 5 (thickness: 20nm, material: TAPC)/luminescent layer 6 (thickness: 40nm, material: the compound 15 and Ir (ppy) of preparation of the embodiment of the present invention3Constituted by weight 88:12 blending)/empty Cave blocking/electron transfer layer 7 (thickness: 35nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al is (thick Degree: 100nm).
Device embodiments 3:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT- CN)/hole transmission layer 4 (thickness: 60nm, material: NPB)/electronic barrier layer 5 (thickness: 20nm, material: TAPC)/luminescent layer 6 (thickness: 40nm, material: the compound 23 and Ir (ppy) of preparation of the embodiment of the present invention3Constituted by weight 92:8 blending)/empty Cave blocking/electron transfer layer 7 (thickness: 35nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al is (thick Degree: 100nm).
Device embodiments 4:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT- CN)/hole transmission layer 4 (thickness: 60nm, material: NPB)/electronic barrier layer 5 (thickness: 20nm, material: TAPC)/luminescent layer 6 (thickness: 40nm, material: compound 80, GHN and the Ir (ppy) of preparation of the embodiment of the present invention3By weight 70:30:10 blending Constitute)/hole barrier/electron transfer layer 7 (thickness: 35nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al (thickness: 100nm).
Device embodiments 5:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT- CN)/hole transmission layer 4 (thickness: 60nm, material: NPB)/electronic barrier layer 5 (thickness: 20nm, material: TAPC)/luminescent layer 6 (thickness: 40nm, material: compound 104, GHN and the Ir (ppy) of preparation of the embodiment of the present invention3By weight 60:40:10 blending Constitute)/hole barrier/electron transfer layer 7 (thickness: 35nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al (thickness: 100nm).
Device embodiments 6:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT- CN)/hole transmission layer 4 (thickness: 60nm, material: NPB)/electronic barrier layer 5 (thickness: 20nm, material: TAPC)/luminescent layer 6 (thickness: 40nm, material: compound 108, GHN and the Ir (ppy) of preparation of the embodiment of the present invention3By weight 40:60:10 blending Constitute)/hole barrier/electron transfer layer 7 (thickness: 35nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al (thickness: 100nm).
Device embodiments 7:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT- CN)/hole transmission layer 4 (thickness: 60nm, material: NPB)/electronic barrier layer 5 (thickness: 20nm, material: TAPC)/luminescent layer 6 (thickness: 40nm, material: compound 121, GHN and the Ir (ppy) of preparation of the embodiment of the present invention3By weight 30:70:10 blending Constitute)/hole barrier/electron transfer layer 7 (thickness: 35nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al (thickness: 100nm).
Device embodiments 8:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT- CN)/hole transmission layer 4 (thickness: 60nm, material: NPB)/electronic barrier layer 5 (thickness: 20nm, material: TAPC)/luminescent layer 6 (thickness: 40nm, material: compound 133, GHN and the Ir (ppy) of preparation of the embodiment of the present invention3By weight 50:50:8 blending Constitute)/hole barrier/electron transfer layer 7 (thickness: 35nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al (thickness: 100nm).
Device embodiments 9:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT- CN)/hole transmission layer 4 (thickness: 60nm, material: NPB)/electronic barrier layer 5 (thickness: 20nm, material: TAPC)/luminescent layer 6 (thickness: 40nm, material: compound 138, GHN and the Ir (ppy) of preparation of the embodiment of the present invention3By weight 50:50:12 blending Constitute)/hole barrier/electron transfer layer 7 (thickness: 35nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al (thickness: 100nm).
Device embodiments 10:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT- CN)/hole transmission layer 4 (thickness: 60nm, material: NPB)/electronic barrier layer 5 (thickness: 20nm, material: TAPC)/luminescent layer 6 (thickness: 40nm, material: compound 147, GHN and the Ir (ppy) of preparation of the embodiment of the present invention3By weight 50:50:10 blending Constitute)/hole barrier/electron transfer layer 7 (thickness: 35nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al (thickness: 100nm).
Device embodiments 11:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT- CN)/hole transmission layer 4 (thickness: 60nm, material: NPB)/electronic barrier layer 5 (thickness: 20nm, material: TAPC)/luminescent layer 6 (thickness: 40nm, material: compound 189, GHN and the Ir (ppy) of preparation of the embodiment of the present invention3By weight 50:50:10 blending Constitute)/hole barrier/electron transfer layer 7 (thickness: 35nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al (thickness: 100nm).
Device embodiments 12:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT- CN)/hole transmission layer 4 (thickness: 60nm, material: NPB)/electronic barrier layer 5 (thickness: 20nm, material: TAPC)/luminescent layer 6 (thickness: 40nm, material: compound 234, GHN and the Ir (ppy) of preparation of the embodiment of the present invention3By weight 50:50:10 blending Constitute)/hole barrier/electron transfer layer 7 (thickness: 35nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al (thickness: 100nm).
Device embodiments 13:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT- CN)/hole transmission layer 4 (thickness: 60nm, material: NPB) (thickness: 20nm, material: embodiment of the present invention system of/electronic barrier layer 5 Standby compound 16) (the thickness: 40nm, material: CBP and Ir (ppy) of/luminescent layer 63Constituted by weight 90:10 blending)/hole Blocking/electron transfer layer 7 (thickness: 35nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al (thickness: 100nm)。
Device embodiments 14:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT- CN)/hole transmission layer 4 (thickness: 60nm, material: NPB) (thickness: 20nm, material: embodiment of the present invention system of/electronic barrier layer 5 Standby compound 40) (the thickness: 40nm, material: CBP and Ir (ppy) of/luminescent layer 63Constituted by weight 90:10 blending)/hole Blocking/electron transfer layer 7 (thickness: 35nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al (thickness: 100nm)。
Device embodiments 15:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT- CN)/hole transmission layer 4 (thickness: 60nm, material: NPB) (thickness: 20nm, material: embodiment of the present invention system of/electronic barrier layer 5 Standby compound 46) (the thickness: 40nm, material: CBP and Ir (ppy) of/luminescent layer 63Constituted by weight 90:10 blending)/hole Blocking/electron transfer layer 7 (thickness: 35nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al (thickness: 100nm)。
Device embodiments 16:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT- CN)/hole transmission layer 4 (thickness: 60nm, material: NPB) (thickness: 20nm, material: embodiment of the present invention system of/electronic barrier layer 5 Standby compound 60) (the thickness: 40nm, material: CBP and Ir (ppy) of/luminescent layer 63Constituted by weight 90:10 blending)/hole Blocking/electron transfer layer 7 (thickness: 35nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al (thickness: 100nm)。
Device embodiments 17:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT- CN)/hole transmission layer 4 (thickness: 60nm, material: NPB) (thickness: 20nm, material: embodiment of the present invention system of/electronic barrier layer 5 Standby compound 65) (the thickness: 40nm, material: CBP and Ir (ppy) of/luminescent layer 63Constituted by weight 90:10 blending)/hole Blocking/electron transfer layer 7 (thickness: 35nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al (thickness: 100nm)。
Device embodiments 18:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT- CN)/hole transmission layer 4 (thickness: 60nm, material: NPB) (thickness: 20nm, material: embodiment of the present invention system of/electronic barrier layer 5 Standby compound 68) (the thickness: 40nm, material: CBP and Ir (ppy) of/luminescent layer 63Constituted by weight 90:10 blending)/hole Blocking/electron transfer layer 7 (thickness: 35nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al (thickness: 100nm)。
Device embodiments 19:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT- CN)/hole transmission layer 4 (thickness: 60nm, material: NPB) (thickness: 20nm, material: embodiment of the present invention system of/electronic barrier layer 5 Standby compound 154) (the thickness: 40nm, material: CBP and Ir (ppy) of/luminescent layer 63Constituted by weight 90:10 blending)/empty Cave blocking/electron transfer layer 7 (thickness: 35nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al is (thick Degree: 100nm).
Device embodiments 20:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT- CN)/hole transmission layer 4 (thickness: 60nm, material: NPB) (thickness: 20nm, material: embodiment of the present invention system of/electronic barrier layer 5 Standby compound 166) (the thickness: 40nm, material: CBP and Ir (ppy) of/luminescent layer 63Constituted by weight 90:10 blending)/empty Cave blocking/electron transfer layer 7 (thickness: 35nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al is (thick Degree: 100nm).
Device embodiments 21:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT- CN)/hole transmission layer 4 (thickness: 60nm, material: NPB) (thickness: 20nm, material: embodiment of the present invention system of/electronic barrier layer 5 Standby compound 229) (the thickness: 40nm, material: CBP and Ir (ppy) of/luminescent layer 63Constituted by weight 90:10 blending)/empty Cave blocking/electron transfer layer 7 (thickness: 35nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al is (thick Degree: 100nm).
Device comparative example 1:ITO anode layer 2 (thickness: 150nm)/hole injection layer 3 (thickness: 10nm, material: HAT- CN)/hole transmission layer 4 (thickness: 60nm, material: NPB)/electronic barrier layer 5 (thickness: 20nm, material: TAPC)/luminescent layer 6 (thickness: 40nm, material: CBP and Ir (ppy)3Constituted by weight 90:10 blending)/hole barrier/electron transfer layer 7 (thickness Degree: 35nm, material: TPBI)/electron injecting layer 8 (thickness: 1nm, material: LiF)/Al (thickness: 100nm).Gained electroluminescent The detection data of device is shown in Table 3.
Table 3
Number Current efficiency (cd/A) Color LT95 service life (Hr)@5000nits
Device embodiments 1 53.1 Green light 23.7
Device embodiments 2 48.7 Green light 20.5
Device embodiments 3 46.9 Green light 18.3
Device embodiments 4 56.1 Green light 25.7
Device embodiments 5 54.7 Green light 25.7
Device embodiments 6 53.5 Green light 24.9
Device embodiments 7 53.3 Green light 28.1
Device embodiments 8 51.2 Green light 26.3
Device embodiments 9 54.7 Green light 23.5
Device embodiments 10 53.9 Green light 26.3
Device embodiments 11 52.3 Green light 25.4
Device embodiments 12 53.5 Green light 26.1
Device embodiments 13 41.2 Green light 21.1
Device embodiments 14 43.1 Green light 19.5
Device embodiments 15 40.3 Green light 19.3
Device embodiments 16 43.5 Green light 18.2
Device embodiments 17 40.3 Green light 18.6
Device embodiments 18 39.7 Green light 20.7
Device embodiments 19 42.5 Green light 18.5
Device embodiments 20 41.3 Green light 21.2
Device embodiments 21 41.6 Green light 18.9
Device comparative example 1 32.5 Green light 14.3
Organic compound of the present invention can be applied to the production of OLED luminescent device it can be seen from the result of table 3, and with than It is compared compared with example, either efficiency or service life obtain larger change, the especially service life of device than known OLED material Obtain biggish promotion.The OLED device of further material preparation of the present invention is able to maintain the long-life at high temperature, by device In 85 DEG C of progress high temperature driven life tests, acquired results are as shown in table 4 for part Examples 1 to 20 and device comparative example 1.
Table 4
From the data of table 4 it is found that device embodiments 1~20 are the device architecture of material of the present invention and known materials collocation, It is compared with device comparative example 1, under high temperature, OLED device provided by the invention has the driving service life well.
Work limitation rate is also more stable at low temperature for the OLED device of further material preparation of the present invention, by device reality Example 2,8,12 and device comparative example 1 are applied in -10~80 DEG C of progress efficiency tests, acquired results are as shown in table 5, Fig. 2.
Table 5
From the data of table 5 it is found that device embodiments 2,8,12 are the device architecture of material of the present invention and known materials collocation, It is compared with device comparative example 1, not only Efficiency at Low Temperature is high, but also in temperature elevation process, efficiency is steadily increased.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.

Claims (13)

1. a kind of compound of the fluorenes of xanthene containing spiral shell, which is characterized in that shown in the structure of the compound such as general formula (1):
Wherein, Ar1、Ar2、Ar3、Ar4Independently be expressed as singly-bound, substituted or unsubstituted C6-60Arlydene contains one Or one of multiple substituted or unsubstituted 5~60 yuan of heteroarylidenes of hetero atom；The hetero atom is nitrogen, oxygen or sulphur；Ar1、 Ar2、Ar3、Ar4It is identical or different；
M, n, p, q independently be expressed as number 0 or 1, and m+n+p+q >=1；
R1、R2、R3、R4Independently be expressed as structure shown in general formula (2)；R1、R2、R3、R4It is identical or different；
In general formula (2), R5、R6Independently be expressed as hydrogen atom, general formula (3), general formula (4), shown in general formula (5) or general formula (6) Structure；R5、R6It is identical or different；
In general formula (3) and general formula (4), X1、X2、X3Independently be expressed as oxygen atom, sulphur atom, C1-10Linear or branched alkyl group One of the imido grpup that alkylidene, alkyl-substituted imido grpup or the aryl of substituted alkylidene, aryl substitution replace；
General formula (3), general formula (4), general formula (5) pass through CL1-CL2Key, CL2-CL3Key, CL3-CL4Key, CL’1-CL’2Key, CL'2-CL’3Key Or CL’3-CL’4Key is connected with general formula (2) and ring；
In general formula (6), R7、R8Independently be expressed as substituted or unsubstituted C6-60Aryl contains one or more hetero atoms One of substituted or unsubstituted 5-60 unit's heteroaryl；The hetero atom is nitrogen, oxygen or sulphur.
2. compound according to claim 1, which is characterized in that in general formula (1) structure meeting formula (I)-(II) It is any:
3. compound according to claim 1, which is characterized in that in general formula (1) structure meeting formula (III)-(VIII) It is any:
4. compound according to claim 1, which is characterized in that in general formula (1) structure meeting formula (I)-(VIII) It is any:
5. compound according to claim 1, which is characterized in that in general formula (1) structure meeting formula (1-1)-(1-8) It is any:
6. -5 any compound according to claim 1, which is characterized in that Ar used1、Ar2、Ar3、Ar4Independently table It is shown as:Or one of singly-bound；
R7、R8Independently be expressed as phenyl, naphthalene, dibiphenylyl, terphenyl, dibenzofurans, dibenzothiophenes, 9, One of 9- dimethyl fluorene or N- phenyl carbazole.
7. compound according to claim 1, which is characterized in that the R in general formula (1)1、R2、R3、R4Table independently It is shown as:
One of.
8. compound according to claim 1, which is characterized in that the concrete structure formula of the compound are as follows:
Any one of.
9. a kind of preparation method of compound as described in any one of claims 1 to 8 characterized by comprising
Work as Ar1、Ar2、Ar3、Ar4When being expressed as singly-bound, the reaction equation that occurs in preparation process are as follows:
The specific reaction process of above-mentioned reaction equation are as follows:
1) by raw material A and H-R1It is dissolved with toluene, wherein the raw material A and H-R1Molar ratio be 1:(1.0~1.5)；
2) Pd is added into the reaction system in 1)2(dba)3, tri-tert-butylphosphine and sodium tert-butoxide, obtain mixed solution；
Wherein, the Pd2(dba)3It is (0.005~0.01) with the molar ratio of raw material A: 1, the tri-tert-butylphosphine and raw material A Molar ratio is (0.005~0.02): 1, the molar ratio of the sodium tert-butoxide and raw material A is (1.5~3.0): 1；
3) under the protection of inert gas, above-mentioned mixed solution reacts to 10 under the conditions of 95~110 DEG C of temperature~for 24 hours, from It is so cooled to room temperature, reaction solution is filtered, then filtrate is rotated, finally cross neutral silica gel column, obtain centre Body M；
4) by intermediate M and H-R2It is dissolved with toluene, wherein the intermediate M and H-R2Molar ratio be 1:(1.0~1.5)；
5) Pd is added into reaction system 4)2(dba)3, tri-tert-butylphosphine and sodium tert-butoxide, obtain mixed solution；
Wherein, the Pd2(dba)3It is (0.005~0.01) with the molar ratio of intermediate M: 1, the tri-tert-butylphosphine and intermediate The molar ratio of body M is (0.005~0.02): 1, the molar ratio of the sodium tert-butoxide and intermediate M are (1.5~3.0): 1；
6) under the protection of inert gas, above-mentioned mixed solution reacts to 10 under the conditions of 95~110 DEG C of temperature~for 24 hours, from It is so cooled to room temperature, and filtering reacting solution, filtrate rotates to solvent-free, crosses neutral silica gel column, obtains intermediate N；
7) by intermediate N and H-R3It is dissolved with toluene, wherein the intermediate N and H-R3Molar ratio be 1:(1.0~1.5)；
8) Pd is added into reaction system 7)2(dba)3, tri-tert-butylphosphine and sodium tert-butoxide, obtain mixed solution；
Wherein, the Pd2(dba)3It is (0.005~0.01) with the molar ratio of intermediate N: 1, the tri-tert-butylphosphine and intermediate The molar ratio of body N is (0.005~0.02): 1, the molar ratio of the sodium tert-butoxide and intermediate N are (1.5~3.0): 1；
9) under the protection of inert gas, above-mentioned mixed solution reacts to 10 under the conditions of 95~110 DEG C of temperature~for 24 hours, from It is so cooled to room temperature, and filtering reacting solution, filtrate rotates to solvent-free, crosses neutral silica gel column, obtains intermediate P；
10) by intermediate P and H-R4It is dissolved with toluene, wherein the intermediate P and H-R4Molar ratio be 1:(1.0~1.5)；
11) Pd is added into reaction system 10)2(dba)3, tri-tert-butylphosphine and sodium tert-butoxide, obtain mixed solution；
Wherein, the Pd2(dba)3It is (0.005~0.01) with the molar ratio of intermediate P: 1, the tri-tert-butylphosphine and intermediate The molar ratio of body P is (0.005~0.02): 1, the molar ratio of the sodium tert-butoxide and intermediate P are (1.5~3.0): 1；
12) under the protection of inert gas, above-mentioned mixed solution reacts to 10 under the conditions of 95~110 DEG C of temperature~for 24 hours, from It is so cooled to room temperature, and filtering reacting solution, filtrate rotates to solvent-free, crosses neutral silica gel column, obtains target compound；
Work as Ar1、Ar2、Ar3、Ar4When not being expressed as singly-bound, the reaction equation that occurs in preparation process are as follows:
The specific reaction process of above-mentioned reaction equation are as follows:
1) with raw material A andBoronic acid compounds are raw material, and toluene dissolution, the toluene dosage is that every gram of raw material A makes With 30-50ml toluene, wherein the raw material A and the molar ratio of boronic acid compounds are 1:(1.0~1.5)；
2) Pd (PPh is added into reaction system 1)3)4And sodium carbonate, obtain mixed solution；
Wherein, the Pd (PPh3)4Molar ratio with raw material A is (0.005~0.01): 1, mole of the sodium carbonate and raw material A Than for (1.5~3.0): 1；
3) it under nitrogen protection, by above-mentioned mixed solution in 95~110 DEG C, reacts 10~24 hours, cooled to room temperature, and Filtering reacting solution, filtrate carry out vacuum rotary steam, cross neutral silica gel column, obtain intermediate N；
4) with intermediate N andBoronic acid compounds are raw material, and toluene dissolution, the toluene dosage is every gram of intermediate N uses 30-50ml toluene, wherein the molar ratio of the intermediate N and boronic acid compounds is 1:(1.0~1.5)；
5) Pd (PPh is added into reaction system 4)3)4And sodium carbonate, obtain mixed solution；
Wherein, the Pd (PPh3)4Molar ratio with intermediate N is (0.005~0.01): 1, the sodium carbonate is with intermediate N's Molar ratio is (1.5~3.0): 1；
6) it under nitrogen protection, by above-mentioned mixed solution in 95~110 DEG C, reacts 10~24 hours, cooled to room temperature, and Filtering reacting solution, filtrate carry out vacuum rotary steam, cross neutral silica gel column, obtain intermediate M；
7) with intermediate M andBoronic acid compounds are raw material, and toluene dissolution, the toluene dosage is every gram of intermediate M uses 30-50ml toluene, wherein the molar ratio of the intermediate M and boronic acid compounds is 1:(1.0~1.5)；
8) Pd (PPh is added into reaction system 7)3)4And sodium carbonate, obtain mixed solution；
Wherein, the Pd (PPh3)4Molar ratio with intermediate M is (0.005~0.01): 1, the sodium carbonate is with intermediate M's Molar ratio is (1.5~3.0): 1；
9) it under nitrogen protection, by above-mentioned mixed solution in 95~110 DEG C, reacts 10~24 hours, cooled to room temperature, and Filtering reacting solution, filtrate carry out vacuum rotary steam, cross neutral silica gel column, obtain intermediate P；
10) with intermediate P andBoronic acid compounds are raw material, and toluene dissolution, the toluene dosage is every gram of centre Body P uses 30-50ml toluene, wherein the molar ratio of the intermediate P and boronic acid compounds is 1:(1.0~1.5)；
11) Pd (PPh is added into reaction system 10)3)4And sodium carbonate, obtain mixed solution；
Wherein, the Pd (PPh3)4Molar ratio with intermediate P is (0.005~0.01): 1, the sodium carbonate is with intermediate P's Molar ratio is (1.5~3.0): 1；
12) it under nitrogen protection, by above-mentioned mixed solution in 95~110 DEG C, reacts 10~24 hours, cooled to room temperature, And filtering reacting solution, filtrate carry out vacuum rotary steam, cross neutral silica gel column, obtain target compound.
10. a kind of organic electroluminescence device, which is characterized in that the organic electroluminescence device includes at least one layer of functional layer Compound containing the fluorenes of xanthene containing spiral shell according to any one of claims 1 to 8.
11. organic electroluminescence device according to claim 10, including hole transmission layer/electronic barrier layer, feature It is, the hole transmission layer/electronic barrier layer contains the chemical combination of the fluorenes of xanthene containing spiral shell according to any one of claims 1 to 8 Object.
12. organic electroluminescence device according to claim 10, including luminescent layer, which is characterized in that the luminescent layer Compound containing the fluorenes of xanthene containing spiral shell according to any one of claims 1 to 8.
13. a kind of illumination or display element, which is characterized in that including the organic electroluminescence hair as described in claim 10~12 is any Optical device.
CN201710901085.4A 2017-09-28 2017-09-28 A kind of compound of the fluorenes of xanthene containing spiral shell and its application on organic electroluminescence device Pending CN109575038A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710901085.4A CN109575038A (en) 2017-09-28 2017-09-28 A kind of compound of the fluorenes of xanthene containing spiral shell and its application on organic electroluminescence device

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710901085.4A CN109575038A (en) 2017-09-28 2017-09-28 A kind of compound of the fluorenes of xanthene containing spiral shell and its application on organic electroluminescence device

Publications (1)

Publication Number Publication Date
CN109575038A true CN109575038A (en) 2019-04-05

Family

ID=65913977

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710901085.4A Pending CN109575038A (en) 2017-09-28 2017-09-28 A kind of compound of the fluorenes of xanthene containing spiral shell and its application on organic electroluminescence device

Country Status (1)

Country Link
CN (1) CN109575038A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109574925A (en) * 2017-09-28 2019-04-05 江苏三月光电科技有限公司 It is a kind of using spiral shell dimethylanthracene fluorenes as the compound of core and its application on organic electroluminescence device
CN109574996A (en) * 2017-09-28 2019-04-05 江苏三月光电科技有限公司 It is a kind of using spiral shell xanthene fluorenes as the compound of core and its application on organic electroluminescence device
CN111675686A (en) * 2020-07-09 2020-09-18 吉林奥来德光电材料股份有限公司 Organic electroluminescent compound and preparation method and application thereof
WO2020218680A1 (en) * 2019-04-25 2020-10-29 두산솔루스 주식회사 Organic compound and organic electroluminescent diode using same
CN112876465A (en) * 2019-11-29 2021-06-01 上海和辉光电有限公司 Oxadiazole-substituted organic light-emitting material and OLED device
CN113816895A (en) * 2020-06-19 2021-12-21 广州华睿光电材料有限公司 Aromatic amine compound, mixture, composition and organic electronic device

Citations (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104781247A (en) * 2012-11-12 2015-07-15 默克专利有限公司 Materials for electronic devices
CN106467548A (en) * 2016-08-03 2017-03-01 江苏三月光电科技有限公司 A kind of compound containing benzimidazole and its application
CN106467523A (en) * 2016-07-29 2017-03-01 江苏三月光电科技有限公司 A kind of organic aromatic compound and its application
CN106800526A (en) * 2016-12-15 2017-06-06 中节能万润股份有限公司 A kind of electroluminescent organic material and its application with cyclic diketones as core
CN106866672A (en) * 2017-02-27 2017-06-20 中节能万润股份有限公司 A kind of preparation method and applications of new OLED material
CN106977521A (en) * 2017-03-23 2017-07-25 中节能万润股份有限公司 A kind of preparation method and applications of new OLED material
CN106977446A (en) * 2017-03-29 2017-07-25 江苏三月光电科技有限公司 It is a kind of using three benzo cycloheptene ketone as the compound of core and its application in OLED
CN107011184A (en) * 2017-04-21 2017-08-04 瑞声光电科技(常州)有限公司 A kind of spiro-compound and its luminescent device
CN107383101A (en) * 2017-08-04 2017-11-24 中节能万润股份有限公司 A kind of organic photoelectrical material, its preparation method and the application of the structure of epoxide containing phosphine
CN107502343A (en) * 2017-09-05 2017-12-22 中节能万润股份有限公司 A kind of electroluminescent organic material and application
CN107955040A (en) * 2017-11-14 2018-04-24 中节能万润股份有限公司 A kind of organic photoelectrical material and its preparation method and application
CN108191867A (en) * 2017-12-06 2018-06-22 中节能万润股份有限公司 A kind of thermal activation delayed fluorescence material and its application
CN108219779A (en) * 2018-03-23 2018-06-29 中节能万润股份有限公司 A kind of thermal activation delayed fluorescence material and application
CN108300459A (en) * 2018-05-09 2018-07-20 中节能万润股份有限公司 A kind of hot activation delayed fluorescence electroluminescent organic material and organic electroluminescence device
CN108358922A (en) * 2017-12-15 2018-08-03 中节能万润股份有限公司 A kind of OLED material of the structure of phenanthridines containing naphtho- and its application
CN108373455A (en) * 2018-01-31 2018-08-07 中节能万润股份有限公司 A kind of organic photoelectrical material and its application
CN108440554A (en) * 2018-03-22 2018-08-24 中节能万润股份有限公司 A kind of electroluminescent organic material, application and its device
CN108707103A (en) * 2018-05-23 2018-10-26 中节能万润股份有限公司 A kind of hot activation delayed fluorescence material and its light-emitting device
CN108794503A (en) * 2018-07-27 2018-11-13 中节能万润股份有限公司 A kind of OLED material, preparation method and application containing benzothiophene and pyrrolo- phenanthridines structure
CN109053729A (en) * 2018-07-23 2018-12-21 中节能万润股份有限公司 A kind of organic photoelectrical material and its preparation method and application
CN109575037A (en) * 2017-09-28 2019-04-05 江苏三月光电科技有限公司 A kind of compound of the fluorenes of dimethylanthracene containing spiral shell and its application

Patent Citations (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104781247A (en) * 2012-11-12 2015-07-15 默克专利有限公司 Materials for electronic devices
CN106467523A (en) * 2016-07-29 2017-03-01 江苏三月光电科技有限公司 A kind of organic aromatic compound and its application
CN106467548A (en) * 2016-08-03 2017-03-01 江苏三月光电科技有限公司 A kind of compound containing benzimidazole and its application
CN106800526A (en) * 2016-12-15 2017-06-06 中节能万润股份有限公司 A kind of electroluminescent organic material and its application with cyclic diketones as core
CN106866672A (en) * 2017-02-27 2017-06-20 中节能万润股份有限公司 A kind of preparation method and applications of new OLED material
CN106977521A (en) * 2017-03-23 2017-07-25 中节能万润股份有限公司 A kind of preparation method and applications of new OLED material
CN106977446A (en) * 2017-03-29 2017-07-25 江苏三月光电科技有限公司 It is a kind of using three benzo cycloheptene ketone as the compound of core and its application in OLED
CN107011184A (en) * 2017-04-21 2017-08-04 瑞声光电科技(常州)有限公司 A kind of spiro-compound and its luminescent device
CN107383101A (en) * 2017-08-04 2017-11-24 中节能万润股份有限公司 A kind of organic photoelectrical material, its preparation method and the application of the structure of epoxide containing phosphine
CN107502343A (en) * 2017-09-05 2017-12-22 中节能万润股份有限公司 A kind of electroluminescent organic material and application
CN109575037A (en) * 2017-09-28 2019-04-05 江苏三月光电科技有限公司 A kind of compound of the fluorenes of dimethylanthracene containing spiral shell and its application
CN107955040A (en) * 2017-11-14 2018-04-24 中节能万润股份有限公司 A kind of organic photoelectrical material and its preparation method and application
CN108191867A (en) * 2017-12-06 2018-06-22 中节能万润股份有限公司 A kind of thermal activation delayed fluorescence material and its application
CN108358922A (en) * 2017-12-15 2018-08-03 中节能万润股份有限公司 A kind of OLED material of the structure of phenanthridines containing naphtho- and its application
CN108373455A (en) * 2018-01-31 2018-08-07 中节能万润股份有限公司 A kind of organic photoelectrical material and its application
CN108440554A (en) * 2018-03-22 2018-08-24 中节能万润股份有限公司 A kind of electroluminescent organic material, application and its device
CN108219779A (en) * 2018-03-23 2018-06-29 中节能万润股份有限公司 A kind of thermal activation delayed fluorescence material and application
CN108300459A (en) * 2018-05-09 2018-07-20 中节能万润股份有限公司 A kind of hot activation delayed fluorescence electroluminescent organic material and organic electroluminescence device
CN108707103A (en) * 2018-05-23 2018-10-26 中节能万润股份有限公司 A kind of hot activation delayed fluorescence material and its light-emitting device
CN109053729A (en) * 2018-07-23 2018-12-21 中节能万润股份有限公司 A kind of organic photoelectrical material and its preparation method and application
CN108794503A (en) * 2018-07-27 2018-11-13 中节能万润股份有限公司 A kind of OLED material, preparation method and application containing benzothiophene and pyrrolo- phenanthridines structure

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109574925A (en) * 2017-09-28 2019-04-05 江苏三月光电科技有限公司 It is a kind of using spiral shell dimethylanthracene fluorenes as the compound of core and its application on organic electroluminescence device
CN109574996A (en) * 2017-09-28 2019-04-05 江苏三月光电科技有限公司 It is a kind of using spiral shell xanthene fluorenes as the compound of core and its application on organic electroluminescence device
WO2020218680A1 (en) * 2019-04-25 2020-10-29 두산솔루스 주식회사 Organic compound and organic electroluminescent diode using same
CN112876465A (en) * 2019-11-29 2021-06-01 上海和辉光电有限公司 Oxadiazole-substituted organic light-emitting material and OLED device
CN112876465B (en) * 2019-11-29 2023-07-04 上海和辉光电股份有限公司 Oxadiazole-substituted organic luminescent material and OLED device
CN113816895A (en) * 2020-06-19 2021-12-21 广州华睿光电材料有限公司 Aromatic amine compound, mixture, composition and organic electronic device
CN113816895B (en) * 2020-06-19 2023-12-26 广州华睿光电材料有限公司 Aromatic amine compounds, mixtures, compositions and organic electronic devices
CN111675686A (en) * 2020-07-09 2020-09-18 吉林奥来德光电材料股份有限公司 Organic electroluminescent compound and preparation method and application thereof

Similar Documents

Publication Publication Date Title
CN107021926B (en) Compound containing azaspirofluorene and nitrogen-containing six-membered heterocycle and application of compound in OLED
Huang et al. Similar or totally different: the control of conjugation degree through minor structural modifications, and deep‐blue aggregation‐induced emission luminogens for non‐doped OLEDs
CN107089990B (en) It is a kind of using fluorenes as the organic compound of core and its application on organic electroluminescence device
CN109748909B (en) Compound containing spiroxanthene fluorene and nitrogen-containing six-membered heterocycle, preparation method thereof and application thereof in organic electroluminescent device
CN109575038A (en) A kind of compound of the fluorenes of xanthene containing spiral shell and its application on organic electroluminescence device
CN107586261B (en) Organic compound containing spiro dibenzosuberene fluorene and application thereof
CN107056783A (en) A kind of compound containing azepine spiro fluorene and nitrogenous hexa-member heterocycle and its application on organic electroluminescence device
CN109912578A (en) A kind of compound of the structure containing spiro fluorene and its application on organic electroluminescence device
CN109575037A (en) A kind of compound of the fluorenes of dimethylanthracene containing spiral shell and its application
CN109574925A (en) It is a kind of using spiral shell dimethylanthracene fluorenes as the compound of core and its application on organic electroluminescence device
CN109748906A (en) It is a kind of to contain anthrone and nitrogenous heterocyclic compound and its application on OLED
CN110294663A (en) It is a kind of using anthracene as the compound of core and its application on organic electroluminescence device
CN109956962A (en) It is a kind of fluorene structured for the compound of parent nucleus and its application on organic electroluminescence device with azaspiro
CN109574996A (en) It is a kind of using spiral shell xanthene fluorenes as the compound of core and its application on organic electroluminescence device
CN110272380A (en) It is a kind of using spiro fluorene as the compound of core, preparation method and its application in organic electroluminescence device
CN109824684A (en) A kind of Spirofluorene derivative species organic compound and its application on organic electroluminescence device
CN110835351A (en) Organic compound with pyrromethene boron complex as core and preparation and application thereof
CN110343048A (en) A kind of organic compound and its application fluorene structured containing spiral shell dibenzocycloheptene
CN106749320B (en) A kind of benzimidazole simultaneously ketone compounds and its application in OLED device
CN110526825A (en) It is a kind of using it is different bend and tertiary aromatic amine structure as the compound of core and its application
CN109575039A (en) A kind of azines organic compound and its application
CN109748916A (en) It is a kind of using azepine spiro fluorene and aryl ketones as the compound of core, preparation method and its application on OLED
CN108203429A (en) Using the nitrogenous hexa-member heterocycle of dibenzo as the compound and organic electroluminescence device of core
CN110294735B (en) Compound with anthracene and phenanthrene as core and application of compound in organic electroluminescent device
CN109574908B (en) Compound containing spirodimethyl anthracene fluorene and application thereof in organic electroluminescent device

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right
TA01 Transfer of patent application right

Effective date of registration: 20200131

Address after: 264006 No. 11 Wuzhishan Road, Yantai economic and Technological Development Zone, Shandong

Applicant after: VALIANT Co.,Ltd.

Address before: 214112 No. 210, Xinzhou Road, Wuxi, Jiangsu

Applicant before: JIANGSU SUNERA TECHNOLOGY Co.,Ltd.

TA01 Transfer of patent application right
TA01 Transfer of patent application right

Effective date of registration: 20211201

Address after: 214112 No.210 Xinzhou Road, Wuxi City, Jiangsu Province

Applicant after: Jiangsu March Technology Co.,Ltd.

Address before: 264006 No. 11 Wuzhishan Road, Yantai economic and Technological Development Zone, Shandong

Applicant before: VALIANT Co.,Ltd.

RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20190405