CN108191916A - A kind of organometallic complex and luminescent device - Google Patents
A kind of organometallic complex and luminescent device Download PDFInfo
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- CN108191916A CN108191916A CN201711478961.3A CN201711478961A CN108191916A CN 108191916 A CN108191916 A CN 108191916A CN 201711478961 A CN201711478961 A CN 201711478961A CN 108191916 A CN108191916 A CN 108191916A
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- 0 CC(C)*1=CC=C*(*=C)C=C1c(cccc1)c1N Chemical compound CC(C)*1=CC=C*(*=C)C=C1c(cccc1)c1N 0.000 description 4
- RSOXCJOZWRVICC-UHFFFAOYSA-N Cc1cc(CI)cc(-c2cc(cccc3)c3cn2)c1 Chemical compound Cc1cc(CI)cc(-c2cc(cccc3)c3cn2)c1 RSOXCJOZWRVICC-UHFFFAOYSA-N 0.000 description 1
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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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- 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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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Abstract
The present invention relates to technical field of organic luminescence materials, and in particular to a kind of organometallic complex material and luminescent device with 3 phenyl isoquinolin quinoline structures.The organometallic complex of the present invention is selected from such as at least one of general formula I compounds represented.The organometallic complex of the present invention is a kind of red illuminating material, has the technical advantage that main emission peak wavelength range is wide, luminous efficiency is high and excitation purity is high.
Description
Technical field
The present invention relates to technical field of organic luminescence materials, and in particular to a kind of organic with 3- phenyl isoquinolin quinoline structures
Metal complex materials and luminescent device.
Background technology
Organic Light Emitting Diode (Organic Light Emitting Diode), i.e. OLED refer in forward bias voltage drop electricity
Electric energy is converted into light by organic molecule, metal-organic complexes or polymer molecule luminescent material under the action of
A kind of luminescence phenomenon of energy.OLED due to it with fast response time, driving voltage is low, luminous efficiency and high resolution, comparison
Degree is high, visual angle is wide, and is from main light emission, the features such as without backlight, thus by academia and the extensive concern of industrial quarters.
In addition it can also be produced on the even flexible plastics of cheap glass, metal, therefore also has that at low cost, production technology is simple
List can carry out the advantages that large area production, it has also become full-color display of new generation and lighting engineering are consolidated in full-color display and plane
State lighting area has wide and huge application prospect.
Luminescent material is mainly organic molecule fluorescent material used by earlier devices, can only utilize electroexcitation
It is in the molecule of singlet afterwards, spin statistics quantum shows that its theoretical internal quantum is only 25%.There is 75% to be excited
Molecule is in excited triplet state, and phosphorescence can be sent out by returning to ground state by radiation transistion, and general organic molecule chemical combination
Object is difficult to send out phosphorescence at room temperature.Until the electrophosphorescence for being found that metal-organic complexes material at room temperature shows
As, using the strong spin(-)orbit coupling of heavy metal atom can effectively facilitate electronics by singlet to triplet state be leap up more
(ISC), produced all singlets and triplet state exciton (exciton) are electrically excited so as to which OLED device can make full use of,
The theoretical internal quantum of luminescent material is made to can reach 100%.So far the research of luminous organic material is made to enter one entirely
New period.
Red phosphorescent complex of iridium still has the problem of luminous quantum efficiency is low, excitation purity is poor at present.Cause this shape
The main reason for condition be because feux rouges comes from Yue Gan between the relatively narrow energy level of energy gap, and the heavy metal complex of low energy gap into
There are certain difficulty during row ligand design, secondly in red light material system there is the interaction of stronger pi-pi bond, ligand it
Between have very strong charge transfer characteristic, so as to make the presence of more radiationless relaxation channels in narrow band gap, exacerbate phosphor
Quenching, reduce the quantum yield of feux rouges system.Therefore the red phosphorescence material of design synthesis high comprehensive performance, will become
The important topic of electroluminescent organic material research.
To sum up, existing red emitting material there are excitation purity it is insufficient, be difficult to realize the defects of industry chemical conversion production etc..In view of
This, spy proposes the present invention.
Invention content
In consideration of it, the present invention proposes a kind of organometallic complex and the luminescent device using the organometallic complex.
In a first aspect, the present invention proposes a kind of organometallic complex, in such as general formula I compounds represented at least
It is a kind of；
Wherein, R1、R2、R3、R4、R5、R6、R7、R8、R9、R10It is independently selected from as hydrogen, deuterium, halogen, substitution or does not take
The C in generation1~C12Alkyl, substituted or unsubstituted C1~C12Alkoxy, substituted or unsubstituted C3~C36Heteroaryl, substitution or not
Substituted C6~C36Aryl, substituted or unsubstituted silylation, substituted or unsubstituted amido；And R6、R7、R8、R9And R10In extremely
Few one is deuterium, substituted or unsubstituted C1~C12Alkyl；
Substituent group is selected from deuterium, halogen, C1~C12Alkyl, C1~C12At least one of deuteroalkyl；
M is selected from Pt or Ir, L1Represent bidentate ligand, m represents 1~3 integer, and n represents 0,1 or 2.
Second aspect, the present invention also proposes a kind of organometallic complex, selected from as in general formula II compounds represented
It is at least one；
Wherein, R21、R22、R23、R24It is independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted C1~C12Alkyl takes
Generation or unsubstituted C3~C36Heteroaryl, substituted or unsubstituted C6~C36Aryl；And R21、R22、R23And R24In at least one be
Deuterium, substituted or unsubstituted C1~C12Alkyl；
Substituent group is selected from deuterium, halogen, C1~C6Alkyl, C1~C6Deuteroalkyl；
M is Ir or Pt, L2Represent bidentate ligand, m represents 1~3 integer, and n represents 0,1 or 2；
Work as L2It representsWhen, R21、R22、R23、R24In it is at least one be methyl or hydrogen atom；
And the general formula II compounds represented do not include compound shown in formula 1：
The third aspect, the present invention propose the application of the organometallic complex of first aspect, are particularly applicable to Organic Electricity
Sub-component, such as organic electronic assembly for Organic Light Emitting Diode, light emitting diode, compact fluorescent lamp, incandescent lamp, have
Machine photovoltaic cell, organic field effect tube or light-emitting electrochemical cell, especially organic luminescent device.
Technical scheme of the present invention at least has following beneficial effect：
The organometallic complex of the present invention is a kind of red illuminating material, wide, luminous with main emission peak wavelength range
The efficient and high technical advantage of excitation purity.
Description of the drawings
Fig. 1 is the structure diagram of the luminescent device of the embodiment of the present invention；
Fig. 2 is the mass spectrogram of compound S7；
Fig. 3 is the mass spectrogram of compound S10；
Fig. 4 is the mass spectrogram of compound S12；
Fig. 5 is the normalization UV absorption figure of compound S12；
Fig. 6 is the normalized emission spectra figure of compound S12；
Fig. 7 is the chromaticity coordinates figure (position shown in point X) of compound S7 and S12；
Fig. 8 is the schematic diagram that complementary colours forms white light.
Wherein：
10- luminescent devices；
11- first electrodes；
12- hole transmission layers；
13- luminescent layers；
14- electron transfer layers；
15- second electrodes.
Specific embodiment
With reference to specific embodiment, the application is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.
At present about the research of red emitting material, match primarily directed to containing phenylquinoline ligands and 1- phenyl isoquinolin quinolines
The metal complex of body, as shown in compound (RD1) and compound (RD2)：
Good display and illuminating effect in order to obtain, particularly obtain ideal white light, and solution may be used red
Turquoise three primary colors recombination luminescence forms white light, and red plus blue complementary colours can also be used to shine to form white light.Red plus blue
Complementary colours forms the solution of white light, less compared to a three primary colors solution luminescent material, the complexity of late stage process
Property reduce, advantageously reduce cost.However, compound (RD1) and compound (RD2) and the derivative based on mother nucleus structure,
Hair is dark red coloured light, the improper white luminous device for being used to prepare red plus blue complementary colours and shining.This is because peony
The complementary colours material of light is blue-green, and the spectrum of blue portion is inadequate, shows or illuminates, cross-color is apparent.And
And due to lacking stable navy blue luminescent material, deep blue light emitting material is with yellow green luminescent material in this complementation
Value in color technical solution is smaller.Therefore, in white luminous device, it is badly in need of the complementary colours material for sky blue luminescent material
Material --- the luminescent material of orange light.
The present invention has found after sharp study, and when phenyl connect to form ligand L Q3 with isoquinolin, spectral color is bright
Bright orange red (in polar solvent), so as to obtain the high red illuminating material of a kind of structure novel, excitation purity.
The embodiment of the present invention proposes a kind of red emitting material of the metal complex of 3- phenyl isoquinolins quinoline ligand, structure
Shown in formula general formula I；
Wherein, R1、R2、R3、R4、R5、R6、R7、R8、R9、R10It is independently selected from as hydrogen, deuterium, halogen, substitution or does not take
The C in generation1~C12Alkyl, substituted or unsubstituted C1~C12Alkoxy, substituted or unsubstituted C3~C36Heteroaryl, substitution or not
Substituted C6~C36Aryl, substituted or unsubstituted silylation, substituted or unsubstituted amido；And R1、R2、R3、R4In at least
One is not hydrogen atom, R6、R7、R8、R9And R10In it is at least one for deuterium, substituted or unsubstituted C1~C12Alkyl；
Substituent group is selected from deuterium, halogen, C1~C12Alkyl, C1~C12At least one of deuteroalkyl；
M is selected from Pt or Ir, L1Represent bidentate ligand, m represents 1~3 integer, and n represents 0,1 or 2.
The red emitting material that the embodiment of the present invention proposes is main emission peak wave-length coverage in 560~780nm.Further
, according to the difference of emission spectrum, aubergine, peony, orange red, yellowish red color etc. can be divided into.So as to fully meet
Prepare the needs of white luminous device.Also, the organometallic complex of the present invention also has, and luminous efficiency is high, excitation purity is high
Technical advantage.
Wherein, when m is selected from 2, n is selected from 1；Or when m is selected from 3, n is selected from 0；Or m be selected from 1 when, n be selected from 1.
Further alternative, m is selected from 2, n and is selected from 1.
In Formulas I, bidentate ligand may be selected from the bidentate ligand containing nitrogen-atoms and carbon atom, also selected from containing oxygen atom
With the bidentate ligand of carbon atom, it is further selected from the bidentate ligand containing oxygen atom, nitrogen-atoms and carbon atom.
Further, in the metal complex of the embodiment of the present invention,
Substituent R in isoquinoline structure6、R7、R8、R9And R10In it is at least one for deuterium, substituted or unsubstituted C1~C12
Alkyl, preferably R6、R7、R8、R9And R10In at least two for deuterium, substituted or unsubstituted C1~C12Alkyl, more preferable R6、R7、R8、
R9And R10In at least two be substituted or unsubstituted C2~C12Alkyl.
Substituent R on phenyl structure1、R2、R3And R4In at least one for hydrogen, preferably R1、R2、R3And R4In at least one
A is deuterium, substituted or unsubstituted C1~C12Alkyl, preferably R1、R2、R3And R4In at least two for deuterium, substituted or unsubstituted C1
~C12Alkyl, more preferable R1、R2、R3And R4In at least two be substituted or unsubstituted C2~C12Alkyl.
Alkyl is introduced on isoquinoline structure, phenyl structure, particularly introduce the alkyl of larger steric hindrance or is introduced more
A multiple alkyl that can cause larger space steric hindrance, can weaken central metal by external influence, it is possible to reduce pi-pi bond phase
Interaction on the basis of original luminescent properties are kept, reduces the quenching of spectrum, further improves luminous efficiency.In isoquinolin
D-atom or deuteroalkyl are introduced in structure, phenyl structure, it is normal can to improve coupling by the heavy atoms effect of deuterium element
Number, and then improve luminescent lifetime.
In above-mentioned substituent group：
Carbon atom number is 1~12 alkyl, and alkyl can be chain-like alkyl or cycloalkyl, on the ring of cycloalkyl
Hydrogen can be replaced by alkyl, such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tertiary butyl, positive penta
Base, isopentyl, sec-amyl, neopentyl, hexyl, heptyl, half base, nonyl, decyl, dodecyl etc..
Carbon atom number is 6~36 aryl, also thick including two or more phenyl including the biphenyl that multiple phenyl are connected
Obtained condensed formed fused ring compound is closed, can specifically be enumerated：Phenyl, naphthalene, xenyl etc..
The heteroaryl that carbon atom number is 3~36 refers to monocyclic and polycyclic aromatics ring system：At least one in its ring members
A is not carbon.It can specifically enumerate：Furyl, imidazole radicals, isothiazolyl, isoxazolyls, morpholinyl, oxazolyls (such as：1,2,
3- oxadiazolyls, 1,2,5- oxadiazolyls, 1,3,4- oxadiazolyls), piperazinyl, piperidyl, pyrazinyl, pyrazolyl, pyridazinyl,
Pyridyl group, pyrimidine radicals, pyrrole radicals, pyrrolidinyl, tetrahydrofuran base, THP trtrahydropyranyl, tetrazine base (such as：1,2,4,5- tetrazines
Base), tetrazole radical (such as：1,2,3,4- tetrazole radicals, 1,2,4,5- tetrazole radicals), thiadiazolyl group (such as：1,2,3- thiadiazolyl groups,
1,2,5- thiadiazolyl groups and 1,3,4- thiadiazolyl groups), thiazolyl, thienyl, triazine radical (such as：Cyanuro 1,3,5,1,2,4-
Triazine radical), triazolyl (such as：1,2,3- triazolyls, 1,3,4- triazolyls) etc..
Can be alkoxy when aforementioned be previously mentioned in alkyl containing oxygen atom.
Silylation passes through-SiR ' R " R " ' expressions, wherein R ', R " and R " ' hydrogen or alkane described herein can independently be
Base, alkoxy, alkenyl, alkynyl, aryl or heteroaryl.
Amido passes through-NH-R ' or-NR ' R " expressions, and wherein R ', R " is alkyl of the present invention, aryl or heteroaryl.
Further alternative, organometallic complex shown in general formula I is further selected from as in general formula IA compounds represented
At least one；
Wherein, R1、R2、R3、R4、R6、R7、R8、R9It is independently selected from as hydrogen, deuterium, halogen, substituted or unsubstituted C1
~C12Alkyl, substituted or unsubstituted C1~C12Alkoxy, substituted or unsubstituted C3~C36It is heteroaryl, substituted or unsubstituted
C6~C36Aryl；And R1、R2、R3、R4In at least one for hydrogen atom, R6、R7、R8And R9In it is at least one for deuterium, substitution or
Unsubstituted C1~C12Alkyl；
Substituent group is selected from deuterium, halogen, C1~C12Alkyl, C1~C12At least one of deuteroalkyl；
M is selected from Pt or Ir, L1Represent bidentate ligand, m represents 1~3 integer, and n represents 0,1 or 2.
In the organometallic complex of the embodiment of the present application, in the phenyl ring part of isoquinolin, larger steric group is introduced
Or heavy atom (such as D-atom), it is on the basis of original luminescent properties are kept, to reduce the quenching of spectrum, further carry
High-luminous-efficiency.
Optionally, the organometallic complex as shown in general formula IA is further selected from as shown in general formula IAa, general formula IAb
At least one of compound；
Wherein, R1、R2、R3、R7、R8It is independently selected from as deuterium, halogen, substituted or unsubstituted C1~C12Alkyl, and
R7、R8In it is at least one for deuterium, substituted or unsubstituted C1~C12Alkyl；
Substituent group is selected from deuterium, halogen, C1~C12Alkyl, C1~C12At least one of deuteroalkyl；
M is selected from Pt or Ir, L1Represent bidentate ligand.
Optionally, the bidentate ligand L in the organometallic complex of the embodiment of the present invention1Selected from shown in following structural formula
Bidentate ligand：
Wherein, R11、R12It is independently selected from as hydrogen, deuterium, halogen, substituted or unsubstituted C1~C12Alkyl, substitution or
Unsubstituted C3~C36Heteroaryl, substituted or unsubstituted C6~C36Aryl；Substituent group is selected from deuterium, halogen, C1~C12Alkyl, C1
~C12At least one of deuteroalkyl；
K1、K2、K3It is independently selected from carbon atom or nitrogen-atoms；A, b is independently selected from 1~4 integer.
Optionally, the organometallic complex of the embodiment of the present invention can be further selected from as shown in general formula IAa1, IAb1
At least one of compound；
Wherein, a is selected from 2~3 integer.
Further alternative, during bidentate ligand part can be introduced on the position of substituent group, preferably at least there are one substituent groups
For D-atom, C1~C12Alkyl, C1~C12Deuteroalkyl, specifically, bidentate ligand L15 may be selected from two shown in following structural formula
Tooth ligand, but it is not limited to this：
Optionally, the organometallic complex of the embodiment of the present invention is selected from what following chemical formula compound represented was formed
In group, however it is not limited to this：
The present invention passes through sharp study, it is also proposed that a kind of metal combination for having 3- phenyl isoquinolin quinoline ligands as shown in general formula II
The red emitting material of object：
Wherein, R21、R22、R23、R24It is independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted C1~C12Alkyl takes
Generation or unsubstituted C3~C36Heteroaryl, substituted or unsubstituted C6~C36Aryl；And R21、R22、R23And R24In at least one be
Deuterium, substituted or unsubstituted C1~C12Alkyl；
Substituent group is selected from deuterium, halogen, C1~C6Alkyl, C1~C6Deuteroalkyl；
M is Ir or Pt, L2Represent bidentate ligand, m represents 1~3 integer, and n represents 0,1 or 2；
Work as L2It representsWhen, R21、R22、R23、R24In it is at least one be methyl or hydrogen atom；
And general formula II compounds represented do not include 1 compound represented of formula：
It is further alternative, R21、R22、R23And R24In at least two for deuterium, substituted or unsubstituted C1~C12Alkyl；It is excellent
Choosing, R21、R22、R23And R24In at least two for deuterium, substituted or unsubstituted C2~C12Alkyl.Alkane is introduced on phenyl structure
Base particularly introduces the alkyl of larger steric hindrance or introduces multiple multiple alkyl that can cause larger space steric hindrance, can be with
Weaken central metal by external influence, it is possible to reduce pi-pi bond interacts, and on the basis of original luminescent properties are kept, subtracts
The quenching of few spectrum, further improves luminous efficiency.D-atom or deuterated alkane are introduced on isoquinoline structure, phenyl structure
Base can improve coupling constant, and then improve luminescent lifetime by the heavy atoms effect of deuterium element.
As a kind of improvement of organometallic complex of the embodiment of the present invention, L2Match selected from two teeth shown in following structural formula
Body：
Wherein, R11、R12It is independently selected from as hydrogen, deuterium, halogen, substituted or unsubstituted C1~C12Alkyl, substitution or
Unsubstituted C3~C36Heteroaryl, substituted or unsubstituted C6~C36Aryl；Substituent group is selected from deuterium, halogen, C1~C6Alkyl, C1
~C6At least one of deuteroalkyl；
K1、K2、K3Carbon atom or nitrogen-atoms are independently selected from, a, b are independently selected from 1~4 integer.
Further alternative, during bidentate ligand part can be introduced on the position of substituent group, preferably at least there are one substituent groups
For D-atom, C1~C12Alkyl, C1~C12Deuteroalkyl, specifically, bidentate ligand L25 selected from two teeth shown in following structural formula
Ligand：
Optionally, the organometallic complex of the embodiment of the present invention is selected from what following chemical formula compound represented was formed
In group, however it is not limited to this：
The preparation method for the metal complex that the embodiment of the present invention is provided is continued with, the intention of specific synthesis example is only public
Present disclosure is opened, and is not intended to limitation range.Although made great efforts to ensure about numerical value (for example, amount, temperature
Deng) accuracy, but be contemplated that some errors and deviation.Unless otherwise stated, otherwise number be parts by weight, temperature be with
DEG C for unit or at ambient temperature, and pressure be under atmospheric pressure or near.
Narration is used for a variety of methods of the preparation method of compound disclosed by the invention in embodiment.These methods are provided
To illustrate a variety of preparation methods, but it is not intended to be limited to any of method described in the embodiment of the present invention.Therefore, it is of the invention
The affiliated technical staff for issuing domain can easily change described method or utilize different approach to prepare disclosed change
Close the one or more of object.Following aspect is only exemplary, and be not intended to limit scope of the present disclosure.Temperature, catalysis
Agent, concentration, reactant composition and other process conditions can be changed, and for desired complex, belonging to present disclosure
The technical staff in field can readily select suitable reactant and condition.
Under request in person the synthetic method and structural characterization for providing the compounds of this invention.
Synthesis example 1：The synthesis of S1
(1) synthesis of S1-3：
20mmol S1-1,30.0mmol S1-2,0.20mmol palladiums (II) catalyst and 36mmol tri- are hydrated phosphorus
Sour potassium is dissolved in 30mL toluene：Ethyl alcohol：Water (2:1:2) in the mixed solvent heats 12h at 70 DEG C.Cooling, is extracted with dichloromethane
Take (50mL × 3) three times.Organic phase is collected, uses petroleum ether：Dichloromethane mixed solvent (10:1) eluant, eluent silica gel column chromatography obtains
To the S1-3 (yields of 8.5mmol：42.5%).
(2) synthesis of S1-4：
Take 8mmol S1-3,16mmol isobutaneboronic acids, 0.5mmol triphenylphosphines, tri- hypophosphite monohydrate potassium of 40mmol and
0.5mmol palladiums are dissolved in 20mL toluene, back flow reaction 12h.Cooling, extracts (50mL × 3), collection has with dichloromethane
Machine phase, with petroleum ether dichloromethane (8：1) eluant, eluent silica gel column chromatography obtains the S1-4 of 3.8mmol, yield (47.5%).
(3) synthesis of S1-5：
The iridous chloride of the S1-4 and 2.8mmol of 3mmol is taken to be dissolved in the ethoxy ethanol of 10mL：Water (3:1) mixing
In solvent, flow back 20h at 140 DEG C.After cooling, there is red precipitate precipitation, filter, washed with ethanol solution.Product vacuum is dried,
Obtain 1.2mmol S1-5 (yields：50.0%).
(4) synthesis of S1：
Under anhydrous and oxygen-free, the S1-6 of the S1-5 and 3.0mmol of 1.0mmol is taken to be dissolved in the ethoxy ethanol solution of 10mL
In.Then it reacts for 24 hours at 130 DEG C, (50mL × 3) is extracted with dichloromethane after reaction, using petroleum ether and dichloromethane
Using volume ratio as 1:1 carried out column purification, and after being spin-dried for solvent, vacuum drying obtains 1.3mmol product (yields：65.0%).Matter
Compose MS (ESI-TOF):Karyoplasmic ratio m/z measured values are 769.3 [(M-acac)+].
Metal complex S1 emits main peak in 581nm, is a kind of red light material.
Synthesis example 2：The synthesis of S2
The synthesis of S2
Under anhydrous and oxygen-free, the S2-6 of the S1-5 and 3.0mmol of 1.0mmol in synthesis example 1 is taken to be dissolved in the ethyoxyl of 10mL
In ethanol solution.Then react for 24 hours at 130 DEG C, extract (50mL × 3) with dichloromethane after reaction, using petroleum ether and
Dichloromethane is using volume ratio as 1:1 carried out column purification, and after being spin-dried for solvent, vacuum drying obtains 1.2mmol product (yields：
60.0%).MS(ESI-TOF):Karyoplasmic ratio m/z measured values are 980.3 [M+].
Its mass spectrogram is as shown in Figure 3.
Metal complex S2 emits main peak in 582nm, is a kind of red light material.
Synthesis example 3：The synthesis of S3
The synthesis of S3
Under anhydrous and oxygen-free, the S2-6 of the S1-5 and 3.0mmol of 1.0mmol in synthesis example 1 is taken to be dissolved in the ethyoxyl of 10mL
In ethanol solution.Then react for 24 hours at 130 DEG C, extract (50mL × 3) with dichloromethane after reaction, using petroleum ether and
Dichloromethane is using volume ratio as 1:1 carried out column purification, and after being spin-dried for solvent, vacuum drying obtains 1.4mmol product (yields：
70.0%).MS(ESI-TOF):Karyoplasmic ratio m/z measured values are 924.2 [M+].
Metal complex S3 emits main peak in 582nm, is a kind of red light material.
Synthesis example 4：The synthesis of S4
The synthesis of S4：
Using the identical experimental implementation of the compound (S1-3) with embodiment 1, raw material (S1-1) is only replaced with into (S4-
1) (S1-2), is replaced with into (S4-2), obtains 7.3mmol solid S4-3 (yields：36.5%).
The synthesis of S4-4
Take 5.0mmol S4-3,12mmol isobutaneboronic acids, 0.5mmol triphenylphosphines, tri- hypophosphite monohydrate potassium of 40mmol with
And 0.5mmol palladiums are dissolved in 20mL toluene, back flow reaction 12h.Cooling, is extracted (50mL × 3) with dichloromethane, is collected
Organic phase, with petroleum ether dichloromethane (8：1) eluant, eluent silica gel column chromatography obtains S4-4 2.2mmol, yield (44.0%).
The synthesis of S4-5
The iridous chloride of the S4-4 and 1.8mmol of 2.0mmol is taken to be dissolved in the ethoxy ethanol of 10mL：Water (3:1) mixed
In bonding solvent, flow back 20h at 140 DEG C.After cooling, there is red precipitate precipitation, filter, washed with ethanol solution.Product vacuum is done
It is dry, obtain 0.48mmol S4-5 (yields：53.3%).
The synthesis of S4
Under anhydrous and oxygen-free, take the S4-5 and 1.2mmol of 0.4mmol acetylacetone,2,4-pentanedione be dissolved in 10mL ethoxy ethanol it is molten
In liquid.Then it reacts for 24 hours at 140 DEG C, (50mL × 3) is extracted with dichloromethane after reaction, using petroleum ether and dichloromethane
Alkane is using volume ratio as 1:1 carried out column purification, is dried in vacuo after being spin-dried for solvent, obtains 0.54mmol product (yields：67.5%).
Mass spectrum MS (ESI-TOF):Karyoplasmic ratio m/z measured values are 924.2 [M+].
Metal complex S4 emits main peak in 585nm, is a kind of red light material.
Synthesis example 5：
The synthesis of S5
Under anhydrous and oxygen-free, the S3-6 in S4-5 the and 1.2mmol synthesis examples 3 in 0.4mmol synthesis examples 4 is taken to be dissolved in 10mL
Ethoxy ethanol solution in.Then it reacts for 24 hours at 140 DEG C, is extracted (50mL × 3) with dichloromethane after reaction, used
Petroleum ether and dichloromethane are using volume ratio as 1:1 carried out column purification, and after being spin-dried for solvent, vacuum drying obtains 0.49mmol productions
Object (yield：61.3%).MS(ESI-TOF):Karyoplasmic ratio m/z measured values are 980.3 [M+]
Metal complex S5 emits main peak in 586nm, is a kind of red light material.
Synthesis example 6：
The synthesis of S6
Under anhydrous and oxygen-free, the S2-6 in S4-5 the and 1.2mmol synthesis examples 2 in 0.4mmol synthesis examples 4 is taken to be dissolved in 10mL
Ethoxy ethanol solution in.Then it reacts for 24 hours at 140 DEG C, is extracted (50mL × 3) with dichloromethane after reaction, used
Petroleum ether and dichloromethane are using volume ratio as 1:1 carried out column purification, and after being spin-dried for solvent, vacuum drying obtains 0.46mmol productions
Object (yield：57.5%).MS(ESI-TOF):Karyoplasmic ratio m/z measured values are 1036.4 [M+].
Metal complex S6 emits main peak in 586nm, is a kind of red light material.
Synthesis example 7：
The synthesis of S7-3：
20mmol S7-1,30.0mmol S7-2,0.20mmol palladiums (II) catalyst and 36mmol tri- are hydrated phosphorus
Sour potassium is dissolved in 30mL toluene：Ethyl alcohol：Water (2:1:2) in the mixed solvent heats 12h at 70 DEG C.Cooling, uses dichloromethane
It extracts (50mL × 3).Organic phase is collected, uses petroleum ether：Dichloromethane mixed solvent (10：1) eluant, eluent silica gel column chromatography obtains
Solid S7-37.1mmol (yields：35.5%).
The synthesis of S7-4
Take 5.0mmol S7-3,1mmol isobutaneboronic acids, 0.5mmol triphenylphosphines, tri- hypophosphite monohydrate potassium of 40mmol and
0.5mmol palladiums are dissolved in 20mL toluene, back flow reaction 12h.Cooling, extracts (50mL × 3), collection has with dichloromethane
Machine phase, with petroleum ether dichloromethane (8：1) eluant, eluent silica gel column chromatography obtains S4-4 2.3mmol, yield (46.0%).
The synthesis of S7-5
The iridous chloride of the S7-4 and 1.8mmol of 2.0mmol is taken to be dissolved in the ethoxy ethanol of 10mL：Water (3：1) mixed
In bonding solvent, flow back 20h at 140 DEG C.After cooling, there is red precipitate precipitation, filter, washed with ethanol solution.Product vacuum is done
It is dry, obtain 0.49mmol S7-5 (yields：54.4%).
The synthesis of S7
Under anhydrous and oxygen-free, take the S7-5 and 1.2mmol of 0.4mmol acetylacetone,2,4-pentanedione be dissolved in 10mL ethoxy ethanol it is molten
In liquid.Then it reacts for 24 hours at 140 DEG C, (50mL × 3) is extracted with dichloromethane after reaction, using petroleum ether and dichloromethane
Alkane is using volume ratio as 1：1 carried out column purification, and after being spin-dried for solvent, vacuum drying obtains 0.51mmol product (yields：
63.8%).MS(ESI-TOF):Karyoplasmic ratio m/z measured values are 868.1 [M+].
Its mass spectrogram is as shown in Figure 2.
Metal complex S7 emits main peak in 585nm, is a kind of red light material.
Synthesis example 8：
The synthesis of S8
Under anhydrous and oxygen-free, the S3-6 in S7-5 the and 1.2mmol synthesis examples 2 in 0.4mmol synthesis examples 7 is taken to be dissolved in 10mL
Ethoxy ethanol solution in.Then it reacts for 24 hours at 140 DEG C, is extracted (50mL × 3) with dichloromethane after reaction, used
Petroleum ether and dichloromethane are using volume ratio as 1：1 carried out column purification, and after being spin-dried for solvent, vacuum drying obtains 0.47mmol productions
Object (yield：58.8%).MS(ESI-TOF):Karyoplasmic ratio m/z measured values are 924.4 [M+].
Metal complex S8 emits main peak in 586nm, is a kind of red light material.
Synthesis example 9：
The synthesis of S9
Under anhydrous and oxygen-free, the S2-6 in S7-5 the and 1.2mmol synthesis examples 2 in 0.4mmol synthesis examples 7 is taken to be dissolved in 10mL
Ethoxy ethanol solution in.Then it reacts for 24 hours at 140 DEG C, is extracted (50mL × 3) with dichloromethane after reaction, used
Petroleum ether and dichloromethane are using volume ratio as 1：1 carried out column purification, and after being spin-dried for solvent, vacuum drying obtains 0.43mmol productions
Object (yield：53.8%).MS(ESI-TOF):Karyoplasmic ratio m/z measured values are 981.3 [(M+1)+].
Metal complex S9 emits main peak in 586nm, is a kind of red light material.
Synthesis example 10：
(1) synthesis of S10-4
Take 8mmol S1-3,16mmol isopropyls ylboronic acid, 0.5mmol triphenylphosphines, tri- hypophosphite monohydrate potassium of 40mmol and
0.5mmol palladiums are dissolved in 20mL toluene, back flow reaction 12h.Cooling, extracts (50mL × 3), collection has with dichloromethane
Machine phase, with petroleum ether, dichloromethane (8：1) eluant, eluent silica gel column chromatography obtains the S10-4 of 3.8mmol, yield (47.5%).
(2) synthesis of S10-5
The iridous chloride of the S10-4 and 2.8mmol of 3mmol is taken to be dissolved in the ethoxy ethanol of 10mL：Water (3:1) mixing
In solvent, flow back 20h at 140 DEG C.After cooling, there is red precipitate precipitation, filter, washed with ethanol solution.Product vacuum is dried,
Obtain 1.2mmol S10-5 (yields：50.0%).
(3) synthesis of S10
Under anhydrous and oxygen-free, the S1-6 of the S10-5 and 3.0mmol of 1.0mmol is taken to be dissolved in the ethoxy ethanol solution of 10mL
In.Then it reacts for 24 hours at 130 DEG C, (50mL × 3) is extracted with dichloromethane after reaction, using petroleum ether and dichloromethane
Using volume ratio as 1:1 carried out column purification, and after being spin-dried for solvent, vacuum drying obtains 1.3mmol product (yields：65.0%).MS
(ESI-TOF):Karyoplasmic ratio m/z measured values are 952.4 [M+].
Its mass spectrogram is as shown in Figure 3.
Metal complex S1 emits main peak in 581nm, is a kind of red light material.
Synthesis example 11
The synthesis of S11
Under anhydrous and oxygen-free, the S11-6 of the S10-5 and 3.0mmol of 1.0mmol is taken to be dissolved in the ethoxy ethanol solution of 10mL
In.Then it reacts for 24 hours at 130 DEG C, (50mL × 3) is extracted with dichloromethane after reaction, using petroleum ether and dichloromethane
Using volume ratio as 1：1 carried out column purification, and after being spin-dried for solvent, vacuum drying obtains 1.3mmol product (yields：65.0%).MS
(ESI-TOF):Karyoplasmic ratio m/z measured values are 938.2 [M+].
Metal complex S11 emits main peak in 585nm, is a kind of red light material.
Synthesis example 12
(1) synthesis of S12-3
20mmol S12-1,30.0mmol S12-2,0.20mmol palladiums (II) catalyst and 36mmol tri- are hydrated
Potassium phosphate is dissolved in 30mL toluene：Ethyl alcohol：Water (2：1：2) in the mixed solvent heats 12h at 70 DEG C.Cooling, uses dichloromethane
Alkane extracts (50mL × 3).Organic phase is collected, uses petroleum ether：Dichloromethane mixed solvent (10：1) eluant, eluent silica gel column chromatography obtains
To solid S12-38.9mmol (yields：44.5%)
(2) synthesis of S12-4
The iridous chloride of the S12-3 and 1.8mmol of 2.0mmol is taken to be dissolved in the ethoxy ethanol of 10mL：Water (3：1) mixed
In bonding solvent, flow back 20h at 140 DEG C.After cooling, there is red precipitate precipitation, filter, washed with ethanol solution.Product vacuum is done
It is dry, obtain 0.50mmol S12-4 (yields：55.6%).
(3) synthesis of S12
Under anhydrous and oxygen-free, the S3-6 of the S12-4 and 1.2mmol of 0.4mmol is taken to be dissolved in the ethoxy ethanol solution of 10mL
In.Then it reacts for 24 hours at 140 DEG C, (50mL × 3) is extracted with dichloromethane after reaction, using petroleum ether and dichloromethane
Using volume ratio as 1：1 carried out column purification, and after being spin-dried for solvent, vacuum drying obtains 0.51mmol product (yields：63.8%).
MS(ESI-TOF):Karyoplasmic ratio m/z measured values are 812.4 [M+].
The mass spectrogram of compound S12 is as shown in Figure 4.
Compound S12 normalization ultra-violet absorption spectrum as shown in figure 5, the normalized emission spectra figure of compound S12 such as
Shown in Fig. 6.
It will be appreciated from fig. 6 that emission spectrum of the S12 compounds in polar solvent dichloromethane and nonpolar solvent petroleum ether is several
It being completely superposed, illustrates that solvent influences very little to the emission spectrum of S12 compounds, S12 compounds are not easy to be polarized, this
It is extremely advantageous to device exploitation.
The chromaticity coordinates figure (position shown in point X) of compound S7 and S12 as shown in fig. 7, chromaticity coordinates shown in point X for (0.56,
0.44).As can be seen that the chromaticity coordinates of two compounds is almost what is be overlapped, illustrates the substitution of alkyl chain and introduce to material
Chromaticity coordinates influence is minimum, and it is also extremely advantageous that this, which designs device and develops,.
Complementary colours as shown in Figure 8 forms white light schematic diagram it is found that the position wherein where symbol C is standard white light
CIE chromaticity coordinates (0.33,0.33) is intersected by the straight line of the point with CIE most edges, you can to obtain corresponding complementary color spectrum
The wavelength of emission peak.As shown in Figure 8, chromaticity coordinates is located at the most marginal position of entire CIE curves, color saturation be it is high, with
Corresponding complementary colours formed white light be also advantageous.The chromaticity coordinates figure position of the compound S7 and S12 of the embodiment of the present invention
In entire CIE curves most marginal position shown in Fig. 8, illustrate that the compound S7 and S12 of the embodiment of the present invention are very suitable for shape
Into white light, for the preparation of White OLED.
Synthesis example 13：
The synthesis of S13
Under anhydrous and oxygen-free, the S2-6 in S12-4 the and 1.2mmol synthesis examples 2 in 0.4mmol synthesis examples 10 is taken to be dissolved in
In the ethoxy ethanol solution of 10mL.Then it reacts for 24 hours at 140 DEG C, extracts (50mL × 3) with dichloromethane after reaction,
Petroleum ether and dichloromethane are used using volume ratio as 1：1 carried out column purification, and after being spin-dried for solvent, vacuum drying obtains
0.44mmol product (yields：55.0%).MS(ESI-TOF):Karyoplasmic ratio m/z measured values are 868.1 [M+].
Metal complex S13 emits main peak in 589nm, is a kind of red light material.
Synthesis example 14：
Under anhydrous and oxygen-free, the S11-6 in S12-4 the and 1.2mmol synthesis examples 11 in 0.4mmol synthesis examples 12 is taken to be dissolved in
In the ethoxy ethanol solution of 10mL.Then it reacts for 24 hours at 140 DEG C, extracts (50mL × 3) with dichloromethane after reaction,
Petroleum ether and dichloromethane are used using volume ratio as 1：1 carried out column purification, and after being spin-dried for solvent, vacuum drying obtains
0.44mmol product (yields：55.0%).MS(ESI-TOF):Karyoplasmic ratio m/z measured values are 854.1 [M+].
Metal complex S14 emits main peak in 593nm, is a kind of red light material.
Synthesis example 15
(1) synthesis of S15-3
20mmol S15-1,30.0mmol S15-2,0.20mmol palladiums (II) catalyst and 36mmol tri- are hydrated
Potassium phosphate is dissolved in 30mL toluene：Ethyl alcohol：Water (2:1:2) in the mixed solvent heats 12h at 70 DEG C.Cooling, uses dichloromethane
Alkane extraction (50mL × 3) is three times.Organic phase is collected, uses petroleum ether：Dichloromethane mixed solvent (10:1) eluant, eluent silica gel column layer
Analysis, obtains solid S15-3 8.9mmol (yields：44.7%)
(2) synthesis of S15-4
The iridous chloride of the S15-3 and 1.8mmol of 2.0mmol is taken to be dissolved in the ethoxy ethanol of 10mL：Water (3:1) mixed
In bonding solvent, flow back 20h at 140 DEG C.After cooling, there is red precipitate precipitation, filter, washed with ethanol solution.Product vacuum is done
It is dry, obtain 0.50mmol S15-4 (yields：65.6%).
(3) synthesis of S15
Under anhydrous and oxygen-free, the S2-6 of the S15-4 and 1.2mmol of 0.4mmol is taken to be dissolved in the ethoxy ethanol solution of 10mL
In.Then it reacts for 24 hours at 140 DEG C, (50mL × 3) is extracted with dichloromethane after reaction, using petroleum ether and dichloromethane
Using volume ratio as 1：1 carried out column purification, and after being spin-dried for solvent, vacuum drying obtains 0.51mmol product (yields：63.8%).
MS(ESI-TOF):Karyoplasmic ratio m/z measured values are 840.3 [M+].
Metal complex S15 emits main peak in 586nm, is a kind of red light material.
It is not use toxic tertiary butyl amido as the synthetic method of the present invention, also without containing by unstable
Alkynes raw material or intermediate, but use it is general for coupling technology well known to those skilled in the art in the industry, can industrialness be
Significantly.
The organometallic complex of the embodiment of the present invention is suitable for various organic electronic assemblies, such as optics and phototube
Part includes, but are not limited to Organic Light Emitting Diode (OLED), light emitting diode (LED), compact fluorescent lamp (CFL), incandescent lamp
(Incandescent Lamp), organic photovoltaic battery (OPV), organic field effect tube (OFET) or light-emitting electrochemical cell
(LEEC)。
In addition to this, the organometallic complex of the embodiment of the present invention is alternatively arranged as in biomarker or imaging technique.
The organometallic complex of the embodiment of the present invention can be used in illuminating device, for example, in organic luminescent device,
Efficiency more better than traditional material and/or service life are provided.
The organometallic complex of the embodiment of the present invention as luminescent material, available for Organic Light Emitting Diode (OLED),
In luminescent device and display and other luminescent devices.
Specifically, the present embodiments relate to a kind of luminescent device, which is Organic Light Emitting Diode (OLED).
Including first electrode, relative to the second electrode of first electrode, hole transmission layer, the electron transfer layer relative to hole transmission layer
And at least one organic layer, hole transmission layer and electron transfer layer are set between first electrode and second electrode；It is organic
Layer is set between hole transmission layer and electron transfer layer.The structure diagram of the luminescent device of the present invention is as shown in Figure 1.It shines
Device 10 includes being sequentially depositing the first electrode 11 to be formed, hole transmission layer 12, luminescent layer 13,14 and second electricity of electron transfer layer
Pole 15.Its hole-transporting layer 12, luminescent layer 13, electron transfer layer 14 are organic layer, first electrode 11 and second electrode 15
With being electrically connected；At least include the organometallic complex of the embodiment of the present invention in luminescent layer 13.The embodiment of the present invention it is organic
Metal complex can be as the dopant material in luminescent layer.
Further, the Organic Light Emitting Diode of the embodiment of the present invention is feux rouges OLED or white light OLED.
The luminescent properties of embodiment compound are further illustrated the present invention below by luminescent device.
Ito substrate is the bottom emitting glass of 30mm × 30mm sizes, and there are four light-emitting zone, light-emitting area AA areas are 2mm
× 2mm, the light transmittance of ito thin film are 90%@550nm, surface roughness Ra<1nm, ito film thickness be 1300A, resistance per square 10
Ohms per square.
The cleaning way of ito substrate is first placed in the container for filling acetone soln, which is positioned over super
Sound wave cleaning machine is cleaned by ultrasonic, and scavenging period is 30 minutes, mainly dissolves the organic matter for being attached to ITO surfaces
With dispel；Then ito substrate taking-up cleaning finished, which is placed on hot plate, carries out high temperature of 120 DEG C baking half an hour, mainly
It is the organic solvent and steam for removing ito substrate surface；Then the ito substrate that baking finishes is quickly transferred to UV-ZONE to set
Standby middle carry out O3ITO surfaces are difficult to the organic matter eliminated or foreign matter further use plasma treatment by Plasma processing, processing
Time is 15 minutes, and the ITO being disposed will be quickly transferred in OLED evaporated devices film forming room.
Prepare before OLED vapor depositions：Clean processing is carried out to OLED evaporated devices first, wiping film forming room is carried out using IPA
Cavity inner wall ensures that entire film forming cavity does not have foreign matter or dust.Then, by the crucible equipped with OLED organic materials and equipped with gold
The crucible for belonging to aluminum shot is placed sequentially on organic evaporating source and inorganic evaporation source position.Cavity is closed, just vacuumize and take out
High vacuum step so that vapor deposition degree reaches 10E inside OLED evaporated devices-7Torr。
OLED evaporation film-formings：OLED organic evaporatings source is opened, 100 DEG C of preheatings, preheating time are carried out to OLED organic materials
It is 15 minutes, ensures further to remove the steam in OLED organic materials.Then the organic material that needs are deposited is carried out quick
Heating heat treatment, and the baffle above evaporation source is opened, until the evaporation source of the material has organic material to run out of, while crystal oscillator
It when piece detector detects evaporation rate, is then slowly heated up, increasing extent of temperature is 1~5 DEG C, until evaporation rate stabilization exists
At 1A/ seconds, the baffle immediately below mask plate plate is opened, OLED film forming is carried out, the organic film on ito substrate is observed when computer end
When reaching default film thickness, baffle right over mask plate baffle and evaporation source is closed, closes the evaporation source heater of the organic material.
The evaporation process of other organic materials and cathodic metal material is as described above.
OLED encapsulates flow：The cleaning treatment mode of the cap of 20mm × 20mm such as ito substrate pretreatment mode.Clear
The clean cap extension surrounding finished carries out the coating of UV glue materials or dispensing, and then, the cap for having put UV glue materials is transferred to very
It is vacuum abutted with the ito substrate progress for the OLED organic films that form a film in empty abutted equipment, then, it is transferred in UV curing cavitys, makes
Photocuring is carried out with the ultraviolet light of 365nm wave bands.The ITO devices of photocuring, it is also necessary to the rear heat treatment of 80 DEG C of half an hour is carried out,
So that UV glue materials are fully cured.
In order to assess the electroluminescent properties of the compounds of this invention, tested as follows：
1st, device number A-C：
Organometallic complex S7, S10, S12 of the embodiment of the present invention design OLED device knot as luminescent material respectively
Structure is as follows：
ITO/NPB (30nm)/TCTA (30nm)/5wt% organometallic complexs:CBP(30nm)/TPBi(30nm)/LiF
(0.8nm)/Al(150nm)。
Encapsulation carries out photocuring encapsulation using UV epoxy resin.Sample after encapsulation carries out IVL performance tests, IVL equipment
It is tested using Mc Science M6100, test data is as shown in table 1.
2nd, device number F：
It is as follows that performance comparison (number 1,2) design OLED device structure is carried out using existing red light material：
ITO/NPB (30nm)/TCTA (the 30nm)/existing red light materials of 10wt%:90wt%CBP (30nm)/TPBi
(30nm)/LiF(0.8nm)/Al(150nm)。
Encapsulation carries out photocuring encapsulation using UV epoxy resin.Sample after encapsulation carries out IVL performance tests, IVL equipment
It is tested using Mc Science M6100, test data is also as shown in table 1.
Table 1：
It can be seen that there is higher shine using luminescent device prepared by the organometallic complex of the embodiment of the present invention
Efficiency.
It is not for limiting claim, any this field skill although the application is disclosed as above with preferred embodiment
Art personnel can make several possible variations and modification under the premise of the application design is not departed from, therefore the application
Protection domain should be subject to the range that the application claim is defined.
Claims (16)
1. a kind of organometallic complex, which is characterized in that the organometallic complex is selected from such as general formula I compounds represented
At least one of；
Wherein, R1、R2、R3、R4、R5、R6、R7、R8、R9、R10It is independently selected from as hydrogen, deuterium, halogen, substituted or unsubstituted
C1~C12Alkyl, substituted or unsubstituted C1~C12Alkoxy, substituted or unsubstituted C3~C36Heteroaryl, substitution or unsubstituted
C6~C36Aryl, substituted or unsubstituted silylation, substituted or unsubstituted amido；And R1、R2、R3、R4In at least one
It is not hydrogen atom, R6、R7、R8、R9And R10In it is at least one for deuterium, substituted or unsubstituted C1~C12Alkyl；
Substituent group is selected from deuterium, halogen, C1~C12Alkyl, C1~C12At least one of deuteroalkyl；
M is selected from Pt or Ir, L1Represent bidentate ligand, m represents 1~3 integer, and n represents 0,1 or 2.
2. organometallic complex according to claim 1, which is characterized in that R6、R7、R8、R9And R10In at least two be
Deuterium, substituted or unsubstituted C1~C12Alkyl；Preferably, R6、R7、R8、R9And R10In at least two for deuterium, substitution or unsubstituted
C2~C12Alkyl.
3. organometallic complex according to claim 1, which is characterized in that R1、R2、R3、R4In at least one for deuterium,
Substituted or unsubstituted C1~C12Alkyl；Preferably, R1、R2、R3、R4In at least there are two for deuterium, substituted or unsubstituted C1~
C12Alkyl；It is furthermore preferred that R1、R2、R3、R4In at least there are two for deuterium, substituted or unsubstituted C2~C12Alkyl.
4. organometallic complex according to claim 1, which is characterized in that the organometallic complex is selected from as logical
At least one of Formulas I A compounds represented；
Wherein, R1、R2、R3、R4、R6、R7、R8、R9It is independently selected from as hydrogen, deuterium, halogen, substituted or unsubstituted C1~C12
Alkyl, substituted or unsubstituted C1~C12Alkoxy, substituted or unsubstituted C3~C36Heteroaryl, substituted or unsubstituted C6~
C36Aryl；And R1、R2、R3、R4In at least one for hydrogen atom, R6、R7、R8And R9In it is at least one for deuterium, substitution or not
Substituted C1~C12Alkyl；
Substituent group is selected from deuterium, halogen, C1~C12Alkyl, C1~C12At least one of deuteroalkyl；
M is selected from Pt or Ir, L1Represent bidentate ligand, m represents 1~3 integer, and n represents 0,1 or 2.
5. organometallic complex according to claim 4, which is characterized in that the organometallic complex is selected from as logical
At least one of Formulas I Aa, general formula IAb compounds represented；
Wherein, R1、R2、R3、R7、R8It is independently selected from as deuterium, halogen, substituted or unsubstituted C1~C12Alkyl, and R7、R8
In it is at least one for deuterium, substituted or unsubstituted C1~C12Alkyl；
Substituent group is selected from deuterium, halogen, C1~C12Alkyl, C1~C12At least one of deuteroalkyl；
M is selected from Pt or Ir, L1Represent bidentate ligand.
6. according to Claims 1 to 5 any one of them organometallic complex, which is characterized in that L1Selected from following structural formula institute
The bidentate ligand shown：
Wherein, R11、R12It is independently selected from as hydrogen, deuterium, halogen, substituted or unsubstituted C1~C12Alkyl, substitution do not take
The C in generation3~C36Heteroaryl, substituted or unsubstituted C6~C36Aryl；Substituent group is selected from deuterium, halogen, C1~C12Alkyl, C1~C12
At least one of deuteroalkyl；
K1、K2、K3It is independently selected from carbon atom or nitrogen-atoms；A, b is independently selected from 1~4 integer.
7. organometallic complex according to claim 6, which is characterized in that the bidentate ligand L5 is selected from such as lower structure
Bidentate ligand shown in formula：
8. organometallic complex according to claim 1, which is characterized in that the organometallic complex is selected from following
Organometallic complex shown in chemical formula：
9. a kind of organometallic complex, which is characterized in that the organometallic complex is selected from the chemical combination as shown in general formula II
At least one of object；
Wherein, R21、R22、R23、R24It is independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted C1~C12Alkyl, substitution or
Unsubstituted C3~C36Heteroaryl, substituted or unsubstituted C6~C36Aryl；And R21、R22、R23And R24In it is at least one for deuterium,
Substituted or unsubstituted C1~C12Alkyl；
Substituent group is selected from deuterium, halogen, C1~C12Alkyl, C1~C12Deuteroalkyl；
M is Ir or Pt, L2Represent bidentate ligand, m represents 1~3 integer, and n represents 0,1 or 2；
Work as L2It representsWhen, R21、R22、R23、R24In it is at least one be methyl or hydrogen atom；
And the general formula II compounds represented do not include 1 compound represented of formula：
10. organometallic complex according to claim 9, which is characterized in that R21、R22、R23And R24In at least two be
Deuterium, substituted or unsubstituted C1~C12Alkyl；Preferably, R21、R22、R23And R24In at least two be deuterium, substituted or unsubstituted
C2~C12Alkyl.
11. organometallic complex according to claim 9, which is characterized in that L2Selected from two teeth shown in following structural formula
Ligand：
Wherein, R11、R12It is independently selected from as hydrogen, deuterium, halogen, substituted or unsubstituted C1~C12Alkyl, substitution do not take
The C in generation3~C36Heteroaryl, substituted or unsubstituted C6~C36Aryl；Substituent group is selected from deuterium, halogen, C1~C12Alkyl, C1~C12
At least one of deuteroalkyl；
K1、K2、K3Carbon atom or nitrogen-atoms are independently selected from, a, b are independently selected from 1~4 integer.
12. organometallic complex according to claim 11, which is characterized in that the bidentate ligand L25 selected from following knot
Bidentate ligand shown in structure formula：
13. organometallic complex as claimed in claim 9, which is characterized in that the organometallic complex is selected from following
Organometallic complex shown in chemical formula：
14. a kind of organic electronic assembly, it includes at least one as claim 1 to 13 any one of them organic metal coordinates
Object.
15. a kind of luminescent device, which is characterized in that the luminescent device includes first electrode, second electrode and is set to described
At least one organic layer between first electrode and the second electrode, the organic layer include any one of claim 1 to 13
The organometallic complex.
16. luminescent device according to claim 15, which is characterized in that the luminescent device is white light emitting device.
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| CN112390828A (en) * | 2019-08-16 | 2021-02-23 | 环球展览公司 | Organic electroluminescent material and device |
| US20210098717A1 (en) * | 2019-09-26 | 2021-04-01 | Universal Display Corporation | Organic electroluminescent materials and devices |
| US20220402954A1 (en) * | 2019-09-26 | 2022-12-22 | Universal Display Corporation | Organic electroluminescent materials and devices |
| CN113105507A (en) * | 2020-01-10 | 2021-07-13 | 北京夏禾科技有限公司 | Organic light-emitting material |
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