CN105669577B - Space charge transfer compounds and the Organic Light Emitting Diode and display device for using it - Google Patents
Space charge transfer compounds and the Organic Light Emitting Diode and display device for using it Download PDFInfo
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Abstract
The invention discloses a kind of space charge transfer compounds and using its Organic Light Emitting Diode and display device, the space charge transfer compounds include: paracyclophane core；Electron donor moiety in the group being made of carbazole and diphenylamine；With the electron acceptor moiety in the group being made of pyrimidine, diphenyl triazine and triazole.The electron donor moiety and the electron acceptor moiety respectively through linker or without linker and with the paracyclophane is internuclear connects or bind directly.
Description
Cross reference to related applications
This application claims the Korean Patent application submitted on December 5th, 2,014 10-2014-0173911 and 2015
Korean Patent application 10-2015-0144199 priority and right that on October 15, in submits, herein by quoting
It is all completely incorporated to respectively.
Technical field
Embodiments of the present invention are related to Organic Light Emitting Diode (OLED), more specifically, are related to the hair for having excellent
The space charge transfer compounds of light efficiency and the OLED and display device for using the space charge transfer compounds.
Background technique
Development of the panel display apparatus as image display device is promoted for the demand of large scale display device.Flat
In plate display device, OLED is rapidly developed.
In OLED, (electricity is injected as hole when the electronics from cathode (as electron injection electrode) and from anode
Pole) hole when injecting luminous material layer, electrons and holes are compound and become disappearances, so that luminous from OLED.Flexible base board, such as
Plastic base may be used as the bulk substrate of OLED, and OLED has the spy of excellent driving voltage, energy consumption and excitation purity
Property.
OLED includes to be located on substrate as the first electrode of anode, the second electricity as cathode opposite with first electrode
Pole and therebetween organic luminous layer.
In order to improve luminous efficiency, organic luminous layer may include the hole injection layer stacked gradually on the first electrode
(HIL), hole transmission layer (HTL), luminous material layer (EML), electron transfer layer (HTL) and electron injecting layer (EIL).
Hole is transferred in EML by first electrode through HIL and HTL, and electronics is transferred to EML through EIL and ETL by second electrode
In.
Electrons and holes compound generation exciton in EML, exciton transit to ground state by excitation state to shine.
External quantum efficiency (the η of the luminescent material of EMLext) can indicate are as follows:
ηext=ηint×Γ×Φ×ηout-coupling
In above formula, " ηint" it is internal quantum efficiency, " г " is charge balance coefficient, and " Φ " is radiative quantum efficiency,
“ηout-coupling" it is extraction efficiency.
Balance when charge balance coefficient " г " refers to generating exciton between hole and electronics.Usually it is assumed that hole and electricity
Sub- 1:1 matching, then the value of charge balance coefficient is " 1 ".Radiative quantum efficiency " Φ " is effective luminous efficiency with luminescent material
Related value.In host-dopant system, radiative quantum efficiency depends on the fluorescence quantum efficiency of dopant.
Internal quantum efficiency " ηint" it is the exciton for generating light and the ratio between the exciton by hole and the compound generation of electronics.In fluorescence
In compound, the maximum value of internal quantum efficiency is 0.25.When hole and the compound generation exciton of electronics, singlet excitons with it is triple
The ratio between state exciton is 1:3 according to spin structure.But, in fluorescent chemicals, only singlet excitons rather than triplet exciton
It participates in shining.
Extraction efficiency " ηout-coupling" it is the light that display device issues and the ratio between the light that EML is issued.When in hot evaporation method
When middle deposition isotropism chemical combination object forms film, luminescent material random orientation.In the case, the extraction efficiency of display device
Can be assumed to be 0.2.
Therefore, the maximum luminous efficiency comprising fluorescent chemicals as the OLED of luminescent material is less than about 5%.
The shortcomings that luminous efficiency in order to overcome fluorescent chemicals, singlet excitons and triplet are developed for OLED
Both excitons are involved in luminous phosphorescent compound.
It has proposed and has developed red and green phosphorescent compound with greater efficiency.But, it still shines without meeting
The blue phosphorescent compound that efficiency and reliability requires.
Summary of the invention
Therefore, embodiments of the present invention are related to space charge transfer compounds and use the space charge transfer compounds
OLED and display device, which substantially eliminates the one or more problems as caused by limitations and shortcomings of the prior art.
One purpose of embodiments of the present invention is to provide the space charge transfer compounds with high-luminous-efficiency.
Another purpose of embodiments of the present invention is to provide OLED and display device with improved luminous efficiency.
Other features and advantages of the present invention will illustrate in subsequent explanation, partially will be obvious by the explanation, or
It can be understood by implementing the present invention.The objectives and other advantages of the invention by by the specification write and its claim and
The structure specifically noted in attached drawing is realized and is reached.
In order to achieve these and other advantages and according to the embodiments of the present invention for embodying and broadly illustrating herein
Purpose, embodiments of the present invention are related to a kind of space charge transfer compounds, it includes paracyclophane core, selected from by carbazole
The electron donor moiety in group formed with diphenylamine, and in the group being made of pyrimidine, diphenyl triazine and triazole
Electron acceptor moiety, wherein the electron donor moiety and the electron acceptor moiety are respectively through linker (linker) or not
Through linker with the paracyclophane is internuclear connects or bind directly.
Embodiments of the present invention further relate to a kind of space charge transfer compounds:
Wherein D is selected from
And A is selected fromWherein, L1 and L2 each are selected fromAnd n1 and n2 are respectively 0 (zero) or 1, and wherein, R is selected from the group being made of hydrogen and C1 alkyl~C10 alkyl.
Embodiments of the present invention further relate to a kind of Organic Light Emitting Diode, it includes: first electrode, with first electrode phase
Pair second electrode, and between first electrode and second electrode and include space charge transfer compounds organic light emission
Layer, wherein the space charge transfer compounds include paracyclophane core, in the group being made of carbazole and diphenylamine
Electron donor moiety and the electron acceptor moiety in the group being made of pyrimidine, diphenyl triazine and triazole, wherein described
Electron donor moiety and the electron acceptor moiety respectively through linker or without linker and with the paracyclophane is internuclear connects
Or it binds directly.
Embodiments of the present invention further relate to a kind of Organic Light Emitting Diode, it includes: first electrode, with first electrode phase
Pair second electrode, and between first electrode and second electrode and include space charge transfer compoundsOrganic luminous layer, wherein
D is selected fromAnd
A is selected fromWherein, L1 and L2 each are selected fromAnd n1 and n2 are respectively 0 (zero) or 1, and wherein, R is selected from the group being made of hydrogen and C1 alkyl~C10 alkyl.
Embodiments of the present invention further relate to a kind of display device, it includes: substrate；Organic light emission two on substrate
Pole pipe, the Organic Light Emitting Diode include first electrode, the second electrode opposite with first electrode and positioned at first electrode and the
Between two electrodes and include space charge transfer compounds organic luminous layer；Encapsulating film on Organic Light Emitting Diode；
With the lid window being located on encapsulating film, wherein the space charge transfer compounds include paracyclophane core, selected from by carbazole and two
Electron donor moiety in the group of phenyl amine composition, and the electronics in the group being made of pyrimidine, diphenyl triazine and triazole
Acceptor portion, wherein the electron donor moiety and the electron acceptor moiety respectively through linker or without linker and with
The paracyclophane is internuclear to be connect or binds directly.
Embodiments of the present invention further relate to a kind of display device, it includes: substrate；Organic light emission two on substrate
Pole pipe, the Organic Light Emitting Diode include first electrode, the second electrode opposite with first electrode and positioned at first electrode and the
Between two electrodes and include formula 1 space charge transfer compounds organic luminous layer；Envelope on Organic Light Emitting Diode
Fill film；Be located at encapsulating film on lid window,
[formula 1]
Wherein,
D is selected fromAnd
A is selected fromWherein, L1 and L2 each are selected fromAnd n1 and n2 are respectively 0 (zero) or 1, and wherein, R is selected from the group being made of hydrogen and C1 alkyl~C10 alkyl.
It should be understood that aforementioned general remark and following detailed description are examples and are explanatory, and it is intended to offer pair
The further explanation of claimed invention.
Detailed description of the invention
It include that attached drawing and being incorporated into forms part of this specification in order to provide a further understanding of the present invention,
Drawing illustration embodiments of the present invention, and opened together with specification and play the role of explaining the principle of the invention.
Fig. 1 is the diagram for illustrating the luminescence mechanism of space charge transfer compounds of the invention.
Fig. 2A~2C is the figure for showing the delayed fluorescence property of space charge transfer compounds of the invention.
Fig. 3 is the schematic cross-section of Organic Light Emitting Diode of the invention (OLED).
Specific embodiment
The meaning for the term recorded in this specification should understand as follows.
Singular is interpreted as also including plural form, unless the context clearly determines otherwise.Term " first ", " the
Two " etc. for distinguishing any element with other element, it is not intended to be limited by these terms the scope of the present invention.
Term " including ", " including " etc. be interpreted as being not excluded for more than one other feature, entirety, step, operation, element, ingredient or
The presence or addition of a combination thereof.Term "at least one" is understood to include the institute that can be enlightened by one or more associations project
There is combination.For example, the meaning of " selected from first item, second item and third item at least one " not only includes first item
Each of mesh, second item and third item, and including the two or more by first item, second item and third item
All combinations for these projects that can be enlightened.In addition, when any element be referred to as another element " on " when, can be straight
Connect on the upper surface of another element or be also likely to be present third intermediate elements.
It reference will now be made in detail illustrative embodiments, the example is illustrated in the accompanying drawings.
Space charge transfer compounds of the invention have electron donor moiety and electron acceptor moiety through linker or not
Through linker in conjunction with paracyclophane core or connection structure.The space charge transfer compounds can have following formula 1.
[formula 1]
In formula 1, n1 and n2 are respectively 0 (zero) or 1.It is selected from down it is, the space charge transfer compounds of formula 1 have
The structure of formula 2-1~2-4.
[formula 2-1]
[formula 2-2]
[formula 2-3]
[formula 2-4]
It is, the space charge transfer compounds can have electron donor moiety " D " and electronics as formula 2-1
Acceptor portion " A " directly in conjunction with paracyclophane core or the first structure of connection (n1=n2=0), or as formula 2-2 it is electric
Sub- donor set " D " and electron acceptor moiety " A " are through linker " L1 " and " L2 " in conjunction with paracyclophane core or connection (n1=n2
=1) the second structure.As an alternative, which can have the electron donor moiety as formula 2-3
" D " is integrated to paracyclophane core and electron acceptor moiety " A " (n1=0, n2 directly in conjunction with paracyclophane core through linker " L2 "
=1) third structure.The space charge transfer compounds can have the electron donor moiety " D " as formula 2-4 directly with
Paracyclophane core combines and electron acceptor moiety " A " through linker " L1 " is integrated to the of paracyclophane core (n1=1, n2=0)
Four structures.
In formula 1, electron donor moiety " D " is selected from the group being made of carbazole and diphenylamine.For example, electron donor moiety
" D " can be selected from following formula 3.
[formula 3]
In formula 1, electron acceptor moiety " A " is selected from the group being made of pyrimidine, diphenyl triazine and triazole.For example, electronics
Acceptor portion " A " can be selected from following formula 4.
[formula 4]
In formula 1, linker " L1 " and " L2 " are each independently selected from substituent group or without the benzene of substituent group.Example
Such as, linker " L1 " and " L2 " respectively can be independently selected from following formulas 5.
[formula 5]
In formula 5, R is selected from the group being made of hydrogen and C1 alkyl~C10 alkyl.
In space charge transfer compounds, electron donor moiety and electron acceptor moiety are combined or connect in the molecule,
So that the overlapping between highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) is reduced.As a result, generating
Charge-transfer complex improves the luminous efficiency of space charge transfer compounds.That is, in space charge transfer compounds
In object, triplet exciton is for shining, so that luminous efficiency is improved.
In other words, since space charge transfer compounds of the invention include electron donor moiety and electron acceptor moiety two
Person, therefore charge is easy to shift in the molecule, and improves luminous efficiency.
In space charge transfer compounds of the invention, due to electron donor moiety and electron acceptor moiety and to cyclophane
Alkane core combines or connection, therefore gap between electron donor moiety and electron acceptor moiety or apart from reducing or minimize.
Therefore, electric charge transfer is directly generated by the space between electron donor moiety and electron acceptor moiety, so that space charge turns
The conjugate length moved in compound becomes shorter than other compounds that electric charge transfer is generated by bonding orbital.As a result, can be to prevent
Only luminous red shift problem, and space charge transfer compounds of the invention can provide navy blue and shine.
In addition, space charge transfer compounds of the invention include can make electron donor moiety and electron acceptor moiety it
Between steric hindrance minimize benzene linker so that the stability of compound improves.
Referring to Fig. 1 (diagram for illustrating the luminescence mechanism of space charge transfer compounds of the invention), in sky of the invention
Between in charge transfer compound, triplet exciton and singlet excitons participate in shining, so that luminous efficiency improves.
That is, triplet exciton is converted to intermediate state " I by field activation, triplet exciton and singlet excitons1" simultaneously
Ground state " So " is transitted to shine.In other words, singlet state " S1" and triplet " T1" transit to intermediate state " I1”(S1->I1<-
T1), and it is in intermediate state " I1" singlet excitons and triplet exciton participate in shine so that luminous efficiency improve.With upper
The compound for stating luminescence mechanism is properly termed as field activation delayed fluorescence (FADF) compound.
In prior art fluorescent chemicals, since HOMO and LUMO disperses throughout entire molecule, HOMO and LUMO
Interconversion can not (selection rule).
But, in FADF compound, since the overlapping between the HOMO and LUMO in molecule is relatively small, HOMO
Interaction between LUMO is smaller.Therefore, the variation of the spin state of an electronics has no effect on other electronics, generates not
Follow the new charge-transfer band of selection rule.
Moreover, because mutual space separates in the molecule for electron donor moiety and electron acceptor moiety, therefore in polarization shape
Dipole moment is generated in state.In polarized state dipole moment, the interaction between HOMO and LUMO is further decreased, so that shining
Mechanism does not follow selection rule.Therefore, it in FADF compound, can produce from triplet " T1" and singlet state " S1" in
Between state " I1" transition, allow triplet exciton to participate in shining.
When driving OLED, 25% singlet state " S will be generated1" exciton and 75% triplet " T1" exciton is to intermediate state " I1”
Intersystem transition (intersystem crossing), intermediate state " I1" singlet state and triplet exciton transit to ground state to shine.As a result,
FADF compound has 100% theoretical quantum efficiency.
For example, the space charge transfer compounds of formula 1 can be one of 6 compound of formula.
[formula 6]
Space charge transfer compounds of the invention have wider band gap, so that using the OLED of the compound
Luminous efficiency improves.
Synthesis
1. the synthesis of compound 1
(1) compound " a "
[reaction equation 1-1]
In N2In gas purge system, by 4,16- dibromo [2,2] paracyclophane, diphenylamine (1.1 equivalent), Pd (OAc)2
(0.019 equivalent), P (t-Bu)3It is molten that (50 weight %, 0.046 equivalent) and NaOt-Bu (sodium tert-butoxide, 1.9 equivalents) put into toluene
In agent, and stir mixture.Solution 120 DEG C progress return stirring 12 hours.After completion of the reaction, solution is cooled to room
Temperature, and extracted using water and ethyl acetate.Use magnesium sulfate (MgSO4) moisture is removed from the organic layer of extraction, and remove
Remove solvent.Gains carry out wet technique refinement by using the column chromatography of hexane and ethyl acetate, (produce to obtain compound " a "
Rate: 65%).
(2) compound " b "
[reaction equation 1-2]
In N2In gas purge system, compound " a " (17.9mmol) is dissolved in tetrahydrofuran (THF) and is stirred.-
78 DEG C are slowly added to n-BuLi (26.9mmol) into solution, and mixed solution is stirred 1 hour.Keeping cryogenic conditions
In the case of, it adds triethyl borate (21.6mmol), and mixed solution is stirred at room temperature.Mixed solution is stirred at room temperature 12
Hour, complete reaction.It is slowly added to distilled water, and the mixture solution (8:2) of distilled water/hydrochloric acid (HCl) is added to pH2.It is molten
Liquid is extracted using distilled water and ethyl acetate.Moisture is removed from the organic layer of extraction using magnesium sulfate, and removes solvent.
Gains by using the column chromatography of hexane and ethyl acetate carry out wet technique refinement, thus obtain compound " b " (yield:
80%).
(3) compound 1
[reaction equation 1-3]
In N2In gas purge system, by chloro- 4, the 6- diphenyl -1,3,5-triazines of 2-, compound " b " (1 equivalent), carbonic acid
Sodium (Na2CO3, 0.6 equivalent) and it puts into toluene/dioxane/distilled water (1:1:0.7) solvent, and stir.Additionally incorporate Pd
(PPh3)4It (tetrakis triphenylphosphine palladium (0), 0.3 equivalent) and stirs 16 hours.After the reaction was completed, solution is cooled to room temperature.Have
Machine layer carries out washing filtering using distilled water in silica gel.Solvent and distilled water, gains Gossypol recrystallized from chloroform and drying are removed,
To obtain (the yield: 75%) of compound 1.
2. the synthesis of compound 2
(1) compound " c "
[reaction equation 2-1]
In N2In gas purge system, carbazole is dissolved in Isosorbide-5-Nitrae-dioxane solvent, and CuI and K is added3PO4.Separately
Outer addition 4,16- dibromo [2,2] paracyclophane (1.1 equivalent) and anti-form-1,2- diaminocyclohexane.Solution is carried out at 110 DEG C
Return stirring 24 hours.After completion of the reaction, solution is cooled to room temperature, and is extracted using ethyl acetate and distilled water.
Moisture is removed from the organic layer of extraction using magnesium sulfate, and removes remaining solvent.Gains by using ethyl acetate and
The column chromatography of hexane carries out wet technique refinement, to obtain compound " c " (yield: 63%).
(2) compound 2
[reaction equation 2-2]
In N2In gas purge system, by chloro- 4, the 6- diphenyl -1,3,5-triazines of 2-, compound " c " (1 equivalent), carbonic acid
Sodium (Na2CO3, 0.6 equivalent) and it puts into toluene/dioxane/distilled water (1:1:0.7) solvent, and stir.Additionally incorporate Pd
(PPh3)4It (tetrakis triphenylphosphine palladium (0), 0.3 equivalent) and stirs 16 hours.After the reaction was completed, solution is cooled to room temperature.Have
Machine layer carries out washing filtering using distilled water in silica gel.Solvent and distilled water, gains Gossypol recrystallized from chloroform and drying are removed,
To obtain (the yield: 70%) of compound 2.
3. the synthesis of compound 3
[reaction equation 3]
In N2In gas purge system, by reactant compound " a ", 5- pyridiminyl boronic acid (1.5 equivalent), Pd (dppf) Cl2
(4 moles of %) and K3PO4In (2 equivalent) investment toluene solvant and stir.Solution carries out return stirring 24 hours.After the reaction was completed,
Solution is cooled to room temperature, and by the way that dilution with toluene is added.Solution is hydrolyzed with 10%NaOH, and is extracted with ethyl acetate
It takes.Moisture is removed from the organic layer of extraction using magnesium sulfate, and removes remaining solvent.Gains are by using ethyl acetate
Wet technique refinement is carried out with the column chromatography of hexane, to obtain the (yield: 80%) of compound 3.
4. the synthesis of compound 4
[reaction equation 4]
In N2In gas purge system, by reactant compound " c ", 5- pyridiminyl boronic acid (1.5 equivalent), Pd (dppf) Cl2
(4 moles of %) and K3PO4In (2 equivalent) investment toluene solvant and stir.Solution carries out return stirring 24 hours.After the reaction was completed,
Solution is cooled to room temperature, and by the way that dilution with toluene is added.Solution is hydrolyzed with 10%NaOH, and is extracted with ethyl acetate
It takes.Moisture is removed from the organic layer of extraction using magnesium sulfate, and removes remaining solvent.Gains are by using ethyl acetate
Wet technique refinement is carried out with the column chromatography of hexane, to obtain the (yield: 70%) of compound 4.
5. the synthesis of compound 5
[reaction equation 5]
In N2In gas purge system, by 1,2,4- triazole (1.5 equivalent), compound " c ", K2CO3(2 equivalent) and 3- first
In base Cupric salicylate (I) (0.01 equivalent) investment dimethyl sulfoxide (DMSO) solvent and stir.Solution stirs 3 hours at 110 DEG C simultaneously
It is cooled to room temperature.Solution is filtered and washed with a small amount of dimethyl sulfoxide (DMSO).Solution cold distilled water and ethyl acetate into
Row extraction.Moisture is removed from the organic layer of extraction using magnesium sulfate, and removes remaining solvent.Gains are by using acetic acid
The column chromatography of ethyl ester and hexane carries out wet technique refinement, and is recrystallized, to obtain the (yield: 50%) of compound 5.
5. the synthesis of compound 6
(1) compound " d "
[reaction equation 6-1]
In N2In gas purge system, by carbazole (29.9mmol), Isosorbide-5-Nitrae-dibromobenzene (44.9mmol), acid chloride (II) (2
Mole %), in the tricresyl phosphate tert-butyl ester (5 moles of %) and sodium tert-butoxide (2.03 equivalent) investment toluene solvant and stir.Solution into
Row return stirring is to react 12 hours.After the reaction was completed, solution distilled water and ethyl acetate extraction.Use magnesium sulfate
(MgSO4) moisture is removed from the organic layer of extraction, and remove solvent.Gains by using ethyl acetate and hexane column color
Spectrum carries out wet technique refinement, to obtain compound " d " (yield: 80%).
(2) compound " e "
[reaction equation 6-2]
In N2In gas purge system, compound " d " (17.9mmol) is dissolved in THF solvent and is stirred.At -78 DEG C
It is slowly added into solution n-BuLi (26.9mmol), and mixed solution is stirred 1 hour.The case where keeping cryogenic conditions
Under, it adds triethyl borate (21.6mmol), and mixed solution is stirred at room temperature.Mixed solution in room temperature and is stirred 12 small
When, complete reaction.It is slowly added to distilled water, and the mixture solution (8:2) of distilled water/hydrochloric acid (HCl) is added to pH2.Solution
It is extracted using distilled water and ethyl acetate.Moisture is removed from the organic layer of extraction using magnesium sulfate, and removes solvent.Institute
It obtains object and wet technique refinement is carried out by using the column chromatography of hexane and ethyl acetate, to obtain compound " e " (yield: 87%).
(3) compound " f "
[reaction equation 6-3]
In N2In gas purge system, by 1,2,4- triazole (1 equivalent), Isosorbide-5-Nitrae-dibromobenzene, K2CO3(2 equivalent) and 3- methyl
In Cupric salicylate (I) (0.01 equivalent) investment dimethyl sulfoxide (DMSO) solvent and stir.Solution stirs 3 hours and cold at 110 DEG C
But to room temperature.Solution is filtered and washed with a small amount of DMSO.Solution is extracted with cold distilled water and ethyl acetate.Use sulphur
Sour magnesium removes moisture from the organic layer of extraction, and removes remaining solvent.Gains are by using ethyl acetate and hexane
Column chromatography carries out wet technique refinement, and is recrystallized, to obtain compound " f " (yield: 56%).
(4) compound " g "
[reaction equation 6-4]
In N2In gas purge system, compound " f " is dissolved in THF solvent and is stirred.Delay at -78 DEG C into solution
It is slow that n-BuLi (1.5 equivalent) is added, and mixed solution is stirred 1 hour.In the case where keeping cryogenic conditions, boric acid is added
Triethyl (1.2 equivalent), and mixed solution is stirred at room temperature.Mixed solution in room temperature and is stirred 12 hours, reaction is completed.
It is slowly added to distilled water, and the mixture solution (8:2) of distilled water/hydrochloric acid (HCl) is added to pH2.Solution using distilled water and
Ethyl acetate is extracted.Moisture is removed from the organic layer of extraction using magnesium sulfate, and removes solvent.Gains by using
The column chromatography of hexane and ethyl acetate carries out wet technique refinement, to obtain compound " g " (yield: 79%).
(5) compound " h "
[reaction equation 6-5]
In N2In gas purge system, by reactant 4,16- dibromo [2,2] paracyclophane, compound " e " (1.1 equivalent),
Pd(dppf)Cl2(4 moles of %) and K3PO4In (2 equivalent) investment toluene solvant and stir.Solution carries out return stirring 24 hours.
After the reaction was completed, solution is cooled to room temperature, and by the way that dilution with toluene is added.Solution is hydrolyzed with 10%NaOH, and uses second
Acetoacetic ester is extracted.Moisture is removed from the organic layer of extraction using magnesium sulfate, and removes remaining solvent.Gains pass through
Wet technique refinement is carried out using the column chromatography of ethyl acetate and hexane, to obtain compound " h " (yield: 80%).
(5) compound 6
[reaction equation 6-6]
In N2In gas purge system, by reactant compound " h ", compound " e " (1.3 equivalent), Pd (dppf) Cl2(4
Mole %) and K3PO4In (2 equivalent) investment toluene solvant and stir.Solution carries out return stirring 24 hours.After the reaction was completed, will
Solution is cooled to room temperature, and by the way that dilution with toluene is added.Solution is hydrolyzed with 10%NaOH, and is extracted with ethyl acetate
It takes.Moisture is removed from the organic layer of extraction using magnesium sulfate, and removes remaining solvent.Gains are by using ethyl acetate
Wet technique refinement is carried out with the column chromatography of hexane, to obtain the (yield: 58%) of compound 6.
The mass spectrometric data of above compound 1~6 is listed in table 1.
Table 1
| Calculated value | Measured value (M (H+) | ||
| Com1 | C43H34N4 | 606.28 | 606.28 |
| Com2 | C43H32N4 | 604.26 | 604.26 |
| Com3 | C32H27N3 | 453.22 | 453.22 |
| Com4 | C32H25N3 | 451.2 | 451.2 |
| Com5 | C30H24N4 | 440.2 | 440.2 |
| Com6 | C42H32N4 | 592.26 | 592.26 |
The luminosity for measuring above compound 1,3 and 5 (Com1, Com3 and Com5), is as a result listed in table 2 and is shown in Fig. 2A
~2C (the Quantarus tau equipment of Hamamatsu Co., Ltd., no O2Condition).
Table 2
As shown in table 2 and Fig. 2A and 2C, compared with fluorescent emission (instant), space charge transfer compounds of the invention
(Com1, Com3 and Com5) shows the delayed fluorescence transmitting (delay) of thousands of to tens of thousands of nanoseconds (ns).
As described above, space charge transfer compounds of the invention are by field activation, so that singlet state " S1" and triplet " T1”
Exciton transition to intermediate state " I1".As a result, singlet state " S1" exciton and triplet " T1" both excitons be involved in it is luminous.
FADF compound is the unimolecule compound in individual molecule with electron donor moiety and electron acceptor moiety,
So that being easy to produce electric charge transfer by the space in molecule.In the FADF compound of specified conditions, charge can be from electronics
Donor set is through being spatially separating electron acceptor moiety between electron donor moiety and electron acceptor moiety.
FADF compound is activated by external factor.This can be tested by comparing the absorption peak and emission peak of compound solution
Card.
(Lippert-Mataga equation)
In above-mentioned equation, " Δ υ " is Stock drift value, and " υ abs " and " υ fl " is maximum absorption band and maximum hair respectively
Penetrate the wave number at peak." h " is Planck's constant, and " c " is the light velocity, and " a " is Lars Onsager chamber radius, and " Δ μ " is the dipole moment of excitation state
And difference (Δ μ=μ of the dipole moment of ground statee–μg)。
" Δ f " is the value for indicating the orientation polarizability of solvent, can be the refractive index of dielectric constant (ε) and solvent of solvent
(n) function.
Since the intensity of the dipole moment of excitation state is determined by peripheral polarity (for example, polarity of solvent), so FADF can be with
Confirm by comparing the absorption peak and emission peak of compound solution.
(orientation polarizability and its molar fraction of each pure solvent can be used to count in Δ f) to the orientation polarizability of mixed solvent
It calculates.When " Δ f " and " Δ υ " is linearly drawn using above-mentioned " Lippert-Mataga equation ", compound can provide FADF hair
It penetrates.
It is, emission peak is with stabilized degree when FADF compound is stabilized with the orientation polarizability of solvent
It drifts about in long wavelength.Therefore, when compound provides FADF transmitting, " Δ f " and " Δ υ " is plotted as straight line.As " Δ f " and
When " Δ υ " is drawn with straight line, compound provides FADF transmitting.
In space charge transfer compounds of the invention, 25% singlet excitons and 75% triplet exciton pass through
External force (field generated when driving OLED) transits to intermediate state (intersystem crossing).The exciton transition of intermediate state makes to ground state
Obtaining luminous efficiency improves.That is, in fluorescent chemicals, since singlet excitons and triplet exciton participate in shining, because
This luminous efficiency improves.
OLED
ITO layer is deposited on substrate and is washed to form anode (3mm*3mm).Vacuum chamber is loaded a substrate into, about 10-6
~10-7Sequentially formed on anode under the pressure of foundation of Torr hole injection layer (NPB (N, N'- bis- (naphthalene -1- base)-N,
N'- diphenylbenzidine)), hole transmission layer (MCP (bis- carbazyl -3,5- benzene of N, N'-)), luminous material layer (
Main body (two { 2- [two (phenyl) phosphines] phenyl } ether oxygen compounds) and dopant (6%)), electron transfer layer (1,3,5- tri-
(phenyl -2- benzimidazole) benzene), electron injecting layer (LiF) and cathode (Al).
(7) comparative example (Ref)
Reference compound shown in formula 7 is used as dopant to form OLED.
(2) embodiment 1 (Ex1)
Compound 1 is used as dopant to form OLED.
(3) embodiment 2 (Ex2)
Compound 3 is used as dopant to form OLED.
(4) embodiment 3 (Ex3)
Compound 5 is used as dopant to form OLED.
[formula 7]
Table 3
As shown in table 3, using the OLED of the compound of the present invention (Ex1~Ex3) in the side such as driving voltage and luminous efficiency
Mask is advantageous.
Fig. 3 is the schematic cross-section of OLED of the invention.
As shown in figure 3, OLED " E " is formed on substrate (not shown).OLED " E " includes the first electrode as anode
110, the organic luminous layer 120 as the second electrode of cathode 130 and therebetween.
Although it is not shown, can be further formed comprising at least one inorganic layer and at least one organic layer and cover OLED
The encapsulating film of " E " and the lid window on encapsulating film, to form the display device including OLED " E ".Substrate, encapsulating film and lid
Window can have flexibility, so as to provide flexible display apparatus.
First electrode 110 is formed by the material with higher work-functions, and second electrode 130 is by having the material compared with low work function
Material is formed.For example, first electrode 110 can be formed by tin indium oxide (ITO), second electrode 130 can be closed by aluminium (Al) or Al
Golden (AlNd) is formed.Organic luminous layer 120 may include red, green and blue light-emitting mode.
Organic luminous layer 120 can have single layer structure.As an alternative, in order to improve luminous efficiency, organic luminous layer 120
Including hole injection layer (HIL) 121, the hole transmission layer (HTL) 122, luminous material layer being sequentially laminated in first electrode 110
(EML) 123, electron transfer layer (ETL) 124 and electron injecting layer (EIL) 125.
It include shown in formula 1 selected from least one of HIL 121, HTL 122, EML 123, ETL 124 and EIL 125
Space charge transfer compounds.
For example, EML 123 may include space charge transfer compounds shown in formula 1.Space charge transfer compounds are used
Make dopant, EML 123 can further include main body to emit blue light.In the case, dopant has relative to main body
About 1 weight of weight %~30 %.
HOMO " the HOMO of main bodyMain body" with the HOMO " HOMO of dopantDopant" difference or main body LUMO " LUMOMain body" with mix
Miscellaneous dose of LUMO " LUMODopant" difference be less than 0.5eV (| HOMOMain body-HOMODopant|≤0.5eV or | LUMOMain body-LUMODopant|≤
0.5eV).In the case, the charge transfer effciency from main body to dopant can improve.
The triplet energies of dopant are less than the triplet energies of main body, and the singlet energy of dopant and dopant
The difference of triplet energies is less than 0.3eV (Δ EST≤0.3eV).With poor " Δ EST" become smaller, luminous efficiency is got higher.In the present invention
Space charge transfer compounds in, even if difference " the Δ E of the triplet energies of the singlet energy and dopant of dopantST" be
About 0.3eV (larger), singlet state " S1" exciton and triplet " T1" exciton can also transit to intermediate state " I1”。
For example, the main body for meeting above-mentioned condition (can be successively two [2- (diphenylphosphine) phenyl] ethers selected from the material of formula 8
Oxide (DPEPO), 2,8- bis- (diphenylphosphoryl) dibenzothiophenes (PPT), 2,8- bis- (9H- carbazole -9- base) dibenzo
Thiophene (DCzDBT), two (carbazole -9- base) biphenyl (m-CBP), diphenyl -4- triphenyl-silyl phenyl-phosphine oxide
(TPSO1), 9- (9- phenyl -9H- carbazole -6- base) -9H- carbazole (CCP)).
[formula 8]
On the other hand, space charge transfer compounds of the invention may be used as the main body in EML 123, and EML 123 can
Also to include dopant to emit blue light.In the case, dopant has about 1 weight of weight %~30 % relative to main body.
Since the exploitation of the blue main body with excellent properties is still insufficient, space charge transfer compounds of the invention be may be used as
Main body improves the flexibility ratio of main body.In the case, the triplet energies of dopant can be lower than space charge of the invention
The triplet energies of transfer compounds main body.
EML 123 may include the first dopant, main body and the second doping of space charge transfer compounds of the invention
Agent.The sum of first dopant and the weight % of the second dopant can be about 1~30 weight % to emit blue light.In this situation
Under, it can further improve luminous efficiency and excitation purity.
In the case, the triplet energies of the first dopant (space charge transfer compounds i.e. of the invention) can be small
Triplet energies in main body and the triplet energies greater than the second dopant.In addition, the singlet energy of the first dopant with
The difference of the triplet energies of first dopant is less than 0.3eV (Δ EST≤0.3eV).With poor " Δ EST" become smaller, luminous efficiency becomes
It is high.In space charge transfer compounds of the invention, even if the triplet energies of the singlet energy of dopant and dopant
Difference " Δ EST" it is about 0.3eV (larger), singlet state " S1" exciton and triplet " T1" exciton can also transit to centre
State " I1”。
As described above, in space charge transfer compounds of the invention, due to electron donor moiety and electron acceptor portion
The overlapping for combining or being connected in a molecule and between HOMO and LUMO is divided to reduce, therefore space charge transfer of the invention
Compound is used as charge-transfer complex, so that the luminous efficiency of compound improves.It is, turning in space charge of the invention
It moves in compound, the exciton of triplet participates in shining, so that the luminous efficiency of compound improves.
In addition, since electron donor moiety and electron acceptor moiety in conjunction with paracyclophane core or connect, so electronics supplies
Space between body portion and electron acceptor moiety is reduced or minimized.Therefore, pass through electron donor moiety and electron acceptor portion
/ space directly generate electric charge transfer so that conjugate length reduce.As a result, avoiding luminous red shift problem.Also
It is to say, the OLED using space charge transfer compounds of the invention can emit dark blue light.Therefore, using space of the invention
The OLED of charge transfer compound has advantage in terms of luminous efficiency and image quality.
It will be apparent to one skilled in the art that without departing from the spirit or scope of the present invention, in reality of the invention
Apply in mode that various modifications and changes may be made.Therefore, embodiments of the present invention should cover modifications and variations of the invention,
As long as they come within the scope of the appended claims and their.
Claims (8)
1. a kind of space charge transfer compounds, as shown in formula 1:
[formula 1]
Wherein, D is selected from formula 2, and A is selected from formula 3, wherein and L1 and L2 each is selected from formula 4, and n1 and n2 are respectively 0 or 1,
[formula 2]
[formula 3]
[formula 4]
And
Wherein, R is selected from the group being made of hydrogen and C1 alkyl~C10 alkyl, and
Wherein, the triplet energy of the singlet energy of the space charge transfer compounds and the space charge transfer compounds
The difference of amount is less than 0.3eV.
2. a kind of Organic Light Emitting Diode, it includes:
First electrode；
The second electrode opposite with the first electrode；With
Organic luminous layer between the first electrode and the second electrode, the organic luminous layer include shown in formula 1
Space charge transfer compounds:
[formula 1]
Wherein, D is selected from formula 2, and A is selected from formula 3, wherein and L1 and L2 each is selected from formula 4, and n1 and n2 are respectively 0 or 1,
[formula 2]
[formula 3]
[formula 4]
And
Wherein, R is selected from the group being made of hydrogen and C1 alkyl~C10 alkyl, and
Wherein, the triplet energy of the singlet energy of the space charge transfer compounds and the space charge transfer compounds
The difference of amount is less than 0.3eV.
3. Organic Light Emitting Diode as claimed in claim 2, wherein the organic luminous layer include hole injection layer (HIL),
Hole transmission layer (HTL), luminous material layer (EML), electron transfer layer (ETL) and electron injecting layer (EIL), and
Wherein, at least one of the HIL, the HTL, the EML, the ETL and described EIL include the space charge
Transfer compounds.
4. Organic Light Emitting Diode as claimed in claim 2, wherein the organic luminous layer also includes main body, the space
Charge transfer compound is used as dopant.
5. Organic Light Emitting Diode as claimed in claim 4, wherein the highest occupied molecular orbital (HOMO) of the main body with
The LUMO of the lowest unoccupied molecular orbital (LUMO) of the difference of the HOMO of the dopant or the main body and the dopant it
Difference is less than 0.5eV.
6. Organic Light Emitting Diode as claimed in claim 2, wherein the organic luminous layer also includes dopant, the sky
Between charge transfer compound be used as main body.
7. Organic Light Emitting Diode as claimed in claim 2, wherein the organic luminous layer also includes main body and the first doping
Agent, the space charge transfer compounds are used as the second dopant, and
Wherein, the triplet energies of second dopant are less than the triplet energies of the main body and are greater than described first and mix
Miscellaneous dose of triplet energies.
8. a kind of display device, it includes:
Substrate；
Organic Light Emitting Diode on the substrate, it includes first electrodes, second electricity opposite with the first electrode
Pole and between the first electrode and the second electrode and include the organic of space charge transfer compounds shown in formula 1
Luminescent layer；
Encapsulating film on the Organic Light Emitting Diode；With
Lid window on the encapsulating film,
[formula 1]
Wherein, D is selected from formula 2, and A is selected from formula 3, wherein and L1 and L2 each is selected from formula 4, and n1 and n2 are respectively 0 or 1,
[formula 2]
[formula 3]
[formula 4]
And
Wherein, R is selected from the group being made of hydrogen and C1 alkyl~C10 alkyl, and
Wherein, the triplet energy of the singlet energy of the space charge transfer compounds and the space charge transfer compounds
The difference of amount is less than 0.3eV.
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| Theoretical study of the effects of solvent environment on photophysical properties and electronic structure of paracyclophane chromophores;Artem Masunov.et al.;《The Journal of Chemical Physics》;20050614;第122卷(第22期);第224505-1-10页 |
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