CN107384377A - Red iridium phosphor material, its preparation method and the application of a kind of Nitrogen-Containing Heterocyclic Ligand - Google Patents
Red iridium phosphor material, its preparation method and the application of a kind of Nitrogen-Containing Heterocyclic Ligand Download PDFInfo
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- CN107384377A CN107384377A CN201710686512.1A CN201710686512A CN107384377A CN 107384377 A CN107384377 A CN 107384377A CN 201710686512 A CN201710686512 A CN 201710686512A CN 107384377 A CN107384377 A CN 107384377A
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- Prior art keywords
- indolizine
- hydrogen
- isoquinolin
- base
- raw material
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
- C07F15/0033—Iridium compounds
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
Abstract
The invention belongs to red iridium phosphor material, its preparation method and the application of field of organic electroluminescence, more particularly to a kind of Nitrogen-Containing Heterocyclic Ligand.Not only luminous efficiency is high for iridium phosphor material produced by the present invention, and the wavelength for launching light can be in a wide range of interior regulation, and its maximum emission wavelength can be 608 716nm.The main part of such complex of iridium has similar skeleton structure, merely because position of the hetero atom on main part is different, so as to realize that wavelength of transmitted light is adjusted on a large scale from red light to peony light.In addition, the preparation method of different colours luminescent material is essentially identical, it is simple to operate.
Description
Technical field
The invention belongs to field of organic electroluminescence, more particularly to a kind of red iridium phosphor material of Nitrogen-Containing Heterocyclic Ligand,
Its preparation method and application.
Background technology
Organic Light Emitting Diode (English name OrganicLight-EmittingDiode, abbreviation OLED) is one kind by having
The solid-state devices of machine material film composition, can light after applying voltage.Compared to traditional light emitting diode (LED) and liquid crystal
Show (LCD), OLED has wide self-luminous, clear beautiful, frivolous, fast response time, visual angle, low-power consumption, Applicable temperature scope
Greatly, the features such as manufacturing process is simple.OLED can do the dreamlike display for being rolled over everywhere as imaging wallpaper, rolling up, paste, hanging, and be expected to take
For liquid crystal display, it is described as " ultimate Display Technique ".In addition, OLED is as planar light source, either in structure or in light
Source quality, selling point etc. all have the advantage that traditional LED illumination can not reach.
Luminescent material is one of core material of OLED.Substantial amounts of research shows that transient metal complex is conduct
Electroluminescent organic material has unique advantage, for example high efficiency, illuminant colour coverage rate are wide etc..Wherein iridium (III) complex
The features such as good with thermostabilization, lifetime of excited state is short, and luminous efficiency is high, and glow color is easily adjusted.
In OLED white-light illuminatings field, in addition to using the colors of RGB tri- synthesis white light, blue light and gold-tinted can also be used mutual
Mend synthesis white light.
The content of the invention
The technical problem to be solved by the invention is to provide a kind of red iridium phosphor material of Nitrogen-Containing Heterocyclic Ligand, its system
Preparation Method and application.
The technical scheme that the present invention solves above-mentioned technical problem is as follows：A kind of red iridium phosphorescence material of Nitrogen-Containing Heterocyclic Ligand
Material, its structural formula are as follows：
Wherein, R1、R2、R3、R4、R5、R6It is each independently hydrogen, alkyl or aromatic group；
R7、R8It is each independently hydrogen, deuterium, alkyl, cycloalkyl, hydroxyl, amino, sulfydryl, alkenyl, alkynyl, aryl, heteroaryl
Base, alkoxy, aryloxy group, amido, silylation, halogen, CN, SCN, NO2Or CF3；
X is N or C；Y is N or C.
Further, R1、R2、R3、R4、R5、R6It is each independently hydrogen, methyl, ethyl, phenyl, isopropyl or 2- methyl-different
Propyl group.
Second object of the present invention is the preparation method for the red iridium phosphor material for providing above-mentioned Nitrogen-Containing Heterocyclic Ligand,
Step is as follows：
(1) raw material I and raw material II are added in solvent, catalyst and alkaline matter are added under the protection of inert gas,
12-24h is reacted under the conditions of 65-110 DEG C, obtains main part；
Wherein, described solvent is one or more kinds of mixing of toluene, dimethylbenzene, ethanol or water；Described catalysis
Agent is Pd (OAc)2、Pd(PPh3)4、Pd(PPh3)2Cl2Or Pd2(dba)3One or both of it is mixed above；Described alkalescence
Material is that one or both of sodium tert-butoxide, potassium tert-butoxide, anhydrous phosphoric acid potassium, potassium carbonate or cesium carbonate are mixed above；
Described raw material I is
Described raw material II is phenylboric acid, 1- naphthalenylboronic acids, the ylboronic acid of indolizine -5,1 hydrogen-cyclopenta [B] pyrrole
Pyridine, 2 hydrogen-cyclopenta [C] pyridine, the ylboronic acid of indolizine -6, the ylboronic acid of indolizine -7, the ylboronic acid of indolizine -3, indolizine -
1 ylboronic acid, 1 hydrogen-indoles, the ylboronic acid of indolizine -2,2 hydrogen-indoles or 1 hydrogen-pyrroles；
Wherein, the main part be 1- (base of indolizine -5) isoquinolin, 1- (base of indolizine -8) isoquinolin, 1- (indolizine -
6 bases) isoquinolin, 1- (base of indolizine -7) isoquinolin, 1- (1 hydrogen-cyclopenta [B] pyridine -1 base) isoquinolin, 1- (2 hydrogen-ring
Pentadiene simultaneously [C] pyridine -2 base) isoquinolin, 1- (base of indolizine -3) isoquinolin, 1- (base of indolizine -1) isoquinolin, 1- (1 hydrogen -
The base of indoles -1) isoquinolin, 1- (the 2 hydrogen-base of iso-indoles -2) isoquinolin or 1- (the 1 hydrogen-base of pyrroles -1) isoquinolin；
(2) the main part that step (1) obtains is dissolved in ethylene glycol monoethyl ether, adds Ir (acac)3, under the conditions of 100 DEG C
8h is reacted, obtains iridium phosphor material.
Further, described inert gas is that one or both of nitrogen, argon gas or helium are mixed above.
Further, in step (1), the mol ratio of raw material I and raw material II is 1：1.05；The mol ratio of raw material I and catalyst
For 1：0.01；The mol ratio of raw material I and alkaline matter is 1：1.2；
In step (2), main part and Ir (acac)3Mol ratio be 3:1.
Compound C1-C91 listed by following formula, be the representative structure for meeting of the invention spirit and principle, it will be appreciated that list with
Lower compound structure, it is intended merely to preferably explain the present invention, is not limitation of the present invention.
The red iridium phosphor material that third object of the present invention is to provide a kind of above-mentioned Nitrogen-Containing Heterocyclic Ligand is as hair
Photosphere material, making the application in organic electroluminescence device field.
Using when, prepared organic electroluminescence device generally comprise the glass substrate being superimposed upwards successively, anode layer,
Hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer.By iridium phosphorus produced by the present invention
Luminescent material is applied in OLED luminescent layer.All functional layers are made of vacuum evaporation process.It is used in such device
Organic compound molecular structural formula it is as follows.
The beneficial effects of the invention are as follows：Not only luminous efficiency is high for iridium phosphor material produced by the present invention, and launches light
Wavelength can be in a wide range of interior regulation, and its maximum emission wavelength can be 608-716nm.The main part of such complex of iridium has close
Skeleton structure, merely because position of the hetero atom on main part is different, so as to realize wavelength of transmitted light from red light to depth
Red light is adjusted on a large scale.In addition, the preparation method of different colours luminescent material is essentially identical, it is simple to operate.
Brief description of the drawings
Fig. 1 is the structural representation of organic electroluminescence device of the present invention；
Fig. 2 is application examples 1-4 emission spectroanalysis figure；
In figure, 1, glass substrate；2nd, anode layer；3rd, hole injection layer；4th, hole transmission layer；5th, luminescent layer；6th, electronics passes
Defeated layer；7th, electron injecting layer；8th, cathode layer.
Embodiment
The principles and features of the present invention are described below, and the given examples are served only to explain the present invention, is not intended to limit
Determine the scope of the present invention.
Embodiment 1
Compound C8 synthesis, reaction equation are as follows：
(1) main part is prepared
(2) object synthesizes
Embodiment 2
Compound C36 synthesis, reaction equation are as follows：
(2) object synthesizes
Embodiment 3
Compound C43 synthesis, reaction equation are as follows：
(1) main part is prepared
(2) object synthesizes
Embodiment 4
Compound C50 synthesis, reaction equation are as follows：
(1) main part is prepared
(2) object synthesizes
The present invention chooses compound C8, compound C36, compound C43, compound C50 as luminescent layer, makes Organic Electricity
Electroluminescence device, each composition of layer compositions of OLED that table 1 is application examples 1-4.
Table 1
It should be appreciated that device implementation process and result, are intended merely to preferably explain the present invention, not to the limit of the present invention
System.
Application examples 1
The tin indium oxide (ITO) that a layer thickness is 100nm is deposited on glass end liner 1 and is used as transparent anode layer 2；Transparent
On anode layer 2 vacuum evaporation thickness be 10nm NPB (N, N '-two (1- naphthyls)-N, N '-diphenyl -1,1 '-biphenyl -4-4 ' -
Diamines) hole mobile material as hole injection layer 3, wherein doping mass ratio 3% F4-TCNQ (2,3,5,6- tetra- fluoro- 7,
The cyanogen dimethyl-parabenzoquinone of 7', 8,8'- tetra-)；Be on hole injection layer 3 a layer thickness be 100nm spiro-TAD (2,2', 7,
(the diphenyl amino) -9,9'- of 7'- tetra- spiro-bisfluorenes) it is used as hole transmission layer 4；Vacuum evaporation a layer thickness on hole transmission layer 4
Luminescent layer 5 is used as 40nm TRZ (2,4,6- tri- (9- carbazyls) -1,3,5-triazines), wherein doped with 6wt% complex of iridium
C8；The TPQ (2,3,5,8- tetraphenyls quinoxaline) that vacuum evaporation a layer thickness is 30nm successively on luminescent layer 5 again is as electricity
Sub- transport layer 6, the Liq that thickness is 1nm are finally deposited as electron injecting layer 7 on electron injecting layer 7 using vacuum evaporation coating
Technology deposit thickness is cathode layer 8 of the 100nm metallic aluminium (Al) as device.
Know through performance test, the maximum emission wavelength of the electroluminescent spectrum of the device is located at 677nm, and color is dark red
Color, maximum external quantum efficiency are 8%.
Application examples 2
It is identical with application examples 1, it is with the difference of application examples 1：Luminescent layer 5 is thickness 40nm TRZ (2,4,6- tri-
(9- carbazyls) -1,3,5-triazines), wherein doped with 6wt% complex of iridium C36.
Know through performance test, the maximum emission wavelength of the electroluminescent spectrum of the device is located at 716nm, and color is orange red
Color, maximum external quantum efficiency are 5%.
Application examples 3
It is identical with application examples 1, it is with the difference of application examples 1：Luminescent layer 5 is thickness 40nm TRZ (2,4,6- tri-
(9- carbazyls) -1,3,5-triazines), wherein doped with 6wt% complex of iridium C43.
Know through performance test, the maximum emission wavelength of the electroluminescent spectrum of the device is located at 634nm, and color is red
Color, maximum external quantum efficiency are 12%.
Application examples 4
It is identical with application examples 1, it is with the difference of application examples 1：Luminescent layer 5 is thickness 40nm TRZ (2,4,6- tri-
(9- carbazyls) -1,3,5-triazines), wherein doped with 6wt% complex of iridium C50.
Know through performance test, the maximum emission wavelength of the electroluminescent spectrum of the device is located at 624nm, and color is red
Color, maximum external quantum efficiency are 15%.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent substitution and improvements made etc., it should be included in the scope of the protection.
Claims (6)
1. the red iridium phosphor material of a kind of Nitrogen-Containing Heterocyclic Ligand, it is characterised in that its structural formula is as follows：
Wherein, R1、R2、R3、R4、R5、R6It is each independently hydrogen, alkyl or aromatic group；
R7、R8It is each independently hydrogen, deuterium, alkyl, cycloalkyl, hydroxyl, amino, sulfydryl, alkenyl, alkynyl, aryl, heteroaryl, alkane
Epoxide, aryloxy group, amido, silylation, halogen, CN, SCN, NO2Or CF3；
X is N or C；Y is N or C.
2. red iridium phosphor material according to claim 1, it is characterised in that R1、R2、R3、R4、R5、R6Independently of one another
For hydrogen, methyl, ethyl, phenyl, isopropyl, isobutyl group or 2- methyl-isopropyl.
A kind of 3. preparation method of the red iridium phosphor material of Nitrogen-Containing Heterocyclic Ligand described in claim 1, it is characterised in that step
It is as follows：
(1) raw material I and raw material II are added in solvent, catalyst and alkaline matter is added under the protection of inert gas, in 65-
12-24h is reacted under the conditions of 110 DEG C, obtains main part；
Wherein, described solvent is one or more kinds of mixing of toluene, dimethylbenzene, ethanol or water；Described catalyst is
Pd(OAc)2、Pd(PPh3)4、Pd(PPh3)2Cl2Or Pd2(dba)3One or both of it is mixed above；Described alkaline matter
It is mixed above for one or both of sodium tert-butoxide, potassium tert-butoxide, anhydrous phosphoric acid potassium, potassium carbonate or cesium carbonate；
Described raw material I is
Described raw material II is phenylboric acid, 1- naphthalenylboronic acids, the ylboronic acid of indolizine -5,1 hydrogen-cyclopenta [B] pyridine, 2
Hydrogen-cyclopenta [C] pyridine, the ylboronic acid of indolizine -6, the ylboronic acid of indolizine -7, the ylboronic acid of indolizine -3, the base of indolizine -1
Boric acid, 1 hydrogen-indoles, the ylboronic acid of indolizine -2,2 hydrogen-indoles or 1 hydrogen-pyrroles；
Wherein, the main part is 1- (base of indolizine -5) isoquinolin, 1- (base of indolizine -8) isoquinolin, 1- (base of indolizine -6)
Isoquinolin, 1- (base of indolizine -7) isoquinolin, 1- (1 hydrogen-cyclopenta [B] pyridine -1 base) isoquinolin, 1- (2 hydrogen-rings penta 2
Alkene simultaneously [C] pyridine -2 base) isoquinolin, 1- (base of indolizine -3) isoquinolin, 1- (base of indolizine -1) isoquinolin, 1- (1 hydrogen-indoles -
1 base) isoquinolin, 1- (the 2 hydrogen-base of iso-indoles -2) isoquinolin or 1- (the 1 hydrogen-base of pyrroles -1) isoquinolin；
(2) the main part that step (1) obtains is dissolved in ethylene glycol monoethyl ether, adds Ir (acac)3, reacted under the conditions of 100 DEG C
8h, obtain iridium phosphor material.
4. preparation method according to claim 3, it is characterised in that described inert gas is nitrogen, argon gas or helium
One or both of it is mixed above.
5. preparation method according to claim 3, it is characterised in that in step (1), the mol ratio of raw material I and raw material II
For 1：1.05；The mol ratio of raw material I and catalyst is 1：0.01；The mol ratio of raw material I and alkaline matter is 1：1.2；
In step (2), main part and Ir (acac)3Mol ratio be 3:1.
6. a kind of red iridium phosphor material of Nitrogen-Containing Heterocyclic Ligand described in claim 1 is as emitting layer material, organic making
The application in electroluminescent device field.
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| CN201710686512.1A CN107384377A (en) | 2017-08-11 | 2017-08-11 | Red iridium phosphor material, its preparation method and the application of a kind of Nitrogen-Containing Heterocyclic Ligand |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1013740A2 (en) * | 1998-12-25 | 2000-06-28 | Konica Corporation | Electroluminescent material, electroluminescent element and color conversion filter |
| CN104628779A (en) * | 2013-11-15 | 2015-05-20 | 海洋王照明科技股份有限公司 | Organic iridium metal complex as well as preparation method and application thereof |
| US20150214494A1 (en) * | 2014-01-30 | 2015-07-30 | Universal Display Corporation | Organic electroluminescent materials and devices |
| US20170084849A1 (en) * | 2015-09-21 | 2017-03-23 | Universal Display Corporation | Organic electroluminescent materials and devices |
| CN106661070A (en) * | 2014-06-30 | 2017-05-10 | 默克专利有限公司 | Metal complexes |
-
2017
- 2017-08-11 CN CN201710686512.1A patent/CN107384377A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1013740A2 (en) * | 1998-12-25 | 2000-06-28 | Konica Corporation | Electroluminescent material, electroluminescent element and color conversion filter |
| CN104628779A (en) * | 2013-11-15 | 2015-05-20 | 海洋王照明科技股份有限公司 | Organic iridium metal complex as well as preparation method and application thereof |
| US20150214494A1 (en) * | 2014-01-30 | 2015-07-30 | Universal Display Corporation | Organic electroluminescent materials and devices |
| CN106661070A (en) * | 2014-06-30 | 2017-05-10 | 默克专利有限公司 | Metal complexes |
| US20170084849A1 (en) * | 2015-09-21 | 2017-03-23 | Universal Display Corporation | Organic electroluminescent materials and devices |
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