CN106699747A - Coumarin derivative based on thermal activation delayed fluorescence mechanism and preparation method and application thereof in organic electroluminescence devices - Google Patents
Coumarin derivative based on thermal activation delayed fluorescence mechanism and preparation method and application thereof in organic electroluminescence devices Download PDFInfo
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Abstract
The invention discloses a coumarin derivative based on a thermal activation delayed fluorescence mechanism and a preparation method and application thereof in an organic electroluminescence device. The coumarin derivative can be preferably a fluorescent doped dye with thermal activation delayed fluorescence properties, and can be particularly used as a lighting layer of the organic electroluminescence device in a doped manner. The organic electroluminescence device consisting of a fluorescent doping agent has the characteristics of being low in driving voltage, high in efficiency, low in efficiency degradation and the like. Therefore, the coumarin derivative disclosed by the invention can be used as a constitution component of the organic electroluminescence device which is low in driving voltage, high in efficiency, low in efficiency degradation and the like. The invention further discloses a preparation method of the coumarin derivative, and organic electronic devices of the compound.
Description
Technical field
Preferably it is the fluorescence doping with efficient hot activation delayed fluorescence property the present invention relates to coumarin derivative
Dyestuff, can especially use as the doping of the luminescent layer of organic electroluminescence device.The present invention relates to the preparation of coumarin derivative
The organic electronic device of method and these compounds.
Background technology
Organic electroluminescence device is a kind of current mode light emitting semiconductor device based on organic material, its basic structure category
In sandwich type structure, it is to make one layer of luminous organic material on ito glass to make hair light emitting active layer, luminescent layer that classical architecture is
Top adds layer of metal electrode.By further optimization, boost device efficiency can increase electron transfer layer and hole transport
Layer.When there is applied voltage to add device, the hole and electronics that positive pole and negative pole are produced are combined into exciton in luminescent material, swash
The energy transfer of son makes the electronics in light emitting molecule be excited to excitation state to light emitting molecule, by fluorescence or phosphorescence processes to
Emission photon.Because it has all solid state, self-luminous, wide viewing angle, fast response time, low driving voltage, low energy consumption etc. many
Feature, has huge application prospect in FPD and solid light source field.
Luminescent layer is typically made up of material of main part and dopant dye, singlet is compounded to form in luminescent layer and triplet state swashs
The ratio of son is 1：3, conventional fluorescent device can only be luminous using singlet exciton, and maximum internal quantum efficiency is about 25%.And phosphorus
Because Ir and Pt atoms are introduced in luminescent material, the internal quantum efficiency of convergence 100% can be obtained.But, due in phosphor material
Heavy metal high cost and non-renewable, limits its actual application value to a certain extent.In recent years, hot activation delay mechanism is glimmering
Luminescent material is widely used in the luminescent dye of OLED, and this kind of dyestuff can simultaneously using the substance of generating probability 25%
State exciton and 75% triplet exciton are so as to obtain luminous efficiency high.
Although disclosing the example [reference -1] during coumarin derivative is applied to organic electroluminescence device recently,
The Electron rich aromatic amido of the compound the reported and non-immediate carbonyl contraposition with coumarin derivative is connected, and reported
The organic electroluminescence device of coumarin derivative be not hot activation mechanism organic electroluminescence device, with richness of the invention
Electronics aromatic radical nitrogen is directly different with the derivative that the carbonyl contraposition of coumarin derivative is connected.
The content of the invention
It is an object of the present invention to provide when being used as organic electroluminescence device, low voltage drive, imparting can be used
Organic electroluminescence device high efficiency, while the coumarin derivative of the new structure but also with low efficiency roll-off.
Another object of the present invention is to, there is provided beneficial to the preparation scheme of the coumarin derivative of commercial Application.
The further object of the present invention is, there is provided being capable of the Organic Electricity that roll-offs of low voltage drive, high efficiency and poor efficiency
Electroluminescence device.
Inventor solves the above problems and conducts in-depth research, and as a result finds, coumarin derivative of the invention
Amorphous thin film can be formed by conventional methods such as the vacuum evaporations of doping, using them as organic electroluminescence device
Fluorescent dopants can realize the reduction of driving voltage, the raising of quantum efficiency and the reduction of efficiency roll-off.
That is, in an embodiment of the invention there is provided a kind of coumarin derivative, the coumarin derivative is such as
Shown in following formulas (1).
【Chemical formula 1】
In formula (1), Y is represented and is joined directly together oxygen atom, sulphur atom or contains the coupled subunit of other aryl or alkyl.
In addition, providing the coumarin derivative shown in a kind of following formulas (1) in another embodiment of the invention
Preparation method, it is characterised in that according to circumstances and in the presence of base, in the presence of palladium catalyst, make 6- substituted benzenes fragrant
Legumin derivative (3) carries out coupling reaction with Electron rich aromatic substitution base (2) comprising at least one nitrogen；
【Chemical formula 2】
In formula (2), Y is represented and is joined directly together oxygen atom, sulphur atom or contains the coupled Asia of other aryl or alkyl
Base.
【Chemical formula 3】
In formula (3), X represents leaving group.
A kind of benzo coumarin derivative is provided in an embodiment of the invention.The benzo cumarin derives
Shown in for example following formulas (4) of thing.
【Chemical formula 4】
In formula (4), Y is represented and is joined directly together oxygen atom, sulphur atom or contains the coupled subunit of other aryl or alkyl；
W is represented can represent carbon or hetero atom in the substitution base of aryl optional position substitution, Z, and hetero atom can be any in right side aryl
Unsubstituted position.
【Chemical formula 5】
In formula (5), X represents leaving group；W is represented can represent carbon or miscellaneous in the substitution base of aryl optional position substitution, Z
Atom, hetero atom can be in any unsubstituted position of right side aryl.
In addition, the benzo cumarin provided in another embodiment of the invention shown in a kind of following formulas (4) spreads out
Biological preparation method, it is characterised in that according to circumstances and in the presence of base, in the presence of palladium catalyst, replace 9-
Benzo coumarin derivative (5) carries out coupling reaction with Electron rich aromatic substitution base (2) comprising at least one nitrogen.
Additionally, provide a kind of organic electroluminescence device in another embodiment of the invention, its with formula (1) and
The coumarin derivative of formula (4) is constituent.
The beneficial effects of the invention are as follows by legumin derivative of the invention with fluorescence quantum yield higher, with heat
The property of delayed fluorescence is activated, therefore can be used for the material of organic electroluminescence device, be used especially for fluorescent dopants.As
The features such as there is the organic electroluminescence device that fluorescent dopants are constituted low driving voltage, high efficiency and poor efficiency to roll-off.Cause
This, can be used as to be roll-offed with low voltage drive, efficient and poor efficiency by legumin derivative (1) (4) of the invention has
Organic electroluminescence devices constituent.
Brief description of the drawings
Fig. 1 be show by legumin derivative (1) (4) of the invention as luminescent layer dopant material organic electroluminescent
One schematic diagram of example of the cross-section structure of device；
1. the glass substrate of ito transparent electrode is carried；2. hole injection layer；
3. hole transmission layer；4. electronic barrier layer；
5. luminescent layer；6. electron transfer layer；
7. cathode layer.
Specific embodiment
The present invention described further below.
In formula (1), Y is represented and is joined directly together oxygen atom, sulphur atom or coupled containing other aryl or alkyl
Subunit.
In formula (1), represented as Y be joined directly together oxygen atom, sulphur atom or containing other aryl or alkyl and its
The example of connected subunit, can enumerate phenoxazine -10- bases, 9,9- dimethyl acridinium -10- bases, phenthazine -10- bases, spiral shell [a word used for translation
Pyridine -9,9- fluorenes] -10- bases etc., from from the point of view of functional as material for organic electroluminescent device, phenoxazine -10- bases
It is preferred.
In formula (4), Y is represented and is joined directly together oxygen atom, sulphur atom or coupled containing other aryl or alkyl
Subunit.
In formula (4), represented as Y be joined directly together oxygen atom, sulphur atom or containing other aryl or alkyl and its
The example of connected subunit, can enumerate phenoxazine -10- bases, 9,9- dimethyl acridinium -10- bases, phenthazine -10- bases, spiral shell [a word used for translation
Pyridine -9,9- fluorenes] -10- bases etc., from synthesis easily, it is functional as material for organic electroluminescent device from the point of view of, phenoxazine
Piperazine -10- bases are preferred.
Then, illustrate represented by formula (1) (4) bromo coumarin derivative (be sometimes referred to as below " compound (1) " and
" compound (4) ") preparation method.
Compound (1) can be prepared by following methods,
【Chemical formula 6】
X, Y be as previously described in formula (1) (2) (3).
X represents leaving group, such as chlorine atom, bromine atoms, iodine atom etc..From prepare easily and the good viewpoint of yield
See, bromine atoms are preferred.
6- substituted cumarin derivatives shown in above-mentioned formula (3) can be used but not limited to the method for " reference -2 " to make
It is standby.
Compound (being sometimes referred to as below " compound (2) ") shown in above-mentioned formula (2) can generally be directly obtained.
" operation 1 " is according to circumstances and in the presence of a base, compound (2) to be allowed under conditions of palladium catalyst presence
Reacted with compound (3), so that the method for preparing coumarin derivative of the present invention (1).It is anti-by Buchwald-Hartwig
Answering the reaction condition of general coupling reactions such as (Buchwald-Hartwig Reaction) can obtain mesh with good yield
Mark product.
As the catalyst specific example that can be used in " operation 1 ", palladium, palladium bichloride, levulinic can be enumerated
The salt such as ketone palladium.Wherein, done with tri-butyl phosphine the palladium of part from yield it is good from the viewpoint of be preferred.In " operation 1 "
As long as the so-called catalytic amount of the catalyst for being used, has no particular limits.From yield it is good from the viewpoint of, palladium chtalyst
Agent and compound (2) mol ratio are 1:30-1:10 is preferred.
As the specific example of the alkali that can be used in " operation 1 ", cesium carbonate, sodium carbonate, potassium carbonate etc. can be enumerated, from
From the viewpoint of yield is good, cesium carbonate is preferred.Alkali is had no particular limits with the molar ratio of compound (3), from receipts
From the viewpoint of rate is good, 2:1 is preferred.
Compound (2) (3) mol ratio used " operation 1 " has no particular limits, from yield it is good from the viewpoint of,
1.5:1 is preferred.
The reaction of " operation 1 " can be implemented in a solvent.As solvent that can be practical in " operation 1 ", can enumerate
Toluene, dimethylbenzene, Isosorbide-5-Nitrae-dioxane, dimethyl sulfoxide, dimethylformamide etc..These solvents can be used with appropriately combined, from
The use of toluene is preferred from the viewpoint of yield is good.
Compound (1) can be obtained after " operation 1 " terminates by carrying out common treatment.Can lead to as needed
The modes such as recrystallization, column chromatography or distillation are crossed to be purified.
With reference to -1：Zheng C, Zhang X, Lee Z, et al.Novel Efficient Blue Fluorophors
with Small Singlet-Triplet Splitting:Hosts for Highly Efficient Fluorescence
and Phosphorescence Hybrid WOLEDs with Simplified Structure[J]
.Adv.Mater.2013,25,2205–2211.
With reference to -2：Kavala V,Yao C,et al.Synthesis of Isocoumarin Derivatives via the
Copper-Catalyzed Tandem Sequential Cyclization of 2-Halo-N-phenyl Benzamides
and Acyclic 1,3-Diketones[J].J.Org.Chem.2012,77,5022-5029
【Chemical formula 7】
X, Y be as previously described in formula (2) (4) (5).In compound shown in formula (7) (being sometimes referred to as below " compound (7) "), W
Representing can be in the substitution base of aryl optional position substitution, and Z represents carbon or hetero atom, and hetero atom can be any not in right side aryl
The position of substitution.Compound (7) adducible specific example, can enumerate：Phenyl boric acid, 4- cyanophenylboronic acids, 4- tert-butyl benzene boron
Acid, 4- pyridine boronic acids, 3- pyridine boronic acids, 2- pyridine boronic acids, 1- naphthalene boronic acids, 2- naphthalene boronic acids etc..From synthesis easily, as Organic Electricity
Electroluminescence device with material property it is good from the point of view of, phenyl is preferred.
X, X1 represent leaving group, such as chlorine atom, bromine atoms, iodine atom etc..From prepare easily and the good sight of yield
From the point of view of, X is bromine atoms, and X1 is preferred for iodine atom.
" operation 2 " is according to circumstances and in the presence of a base, to allow 2- iodine, 4- bromobenzoic acids (6) and phenyl boric acid to derive
Thing (7) reaction is so as to the method for prepare compound (8).
As the specific example of the alkali that can be used in " operation 2 ", potassium carbonate, lithium hydroxide etc. can be enumerated, from yield
From the viewpoint of good, lithium hydroxide is preferred.Alkali is had no particular limits with the molar ratio of compound (3), from yield
From the viewpoint of good, 1.1:1 is preferred.
The reaction of operation 2 " can be implemented in a solvent.As the solvent that can be used in " operation 1 ", N- can be enumerated
Methyl pyrrolidone, water, methyl alcohol, tetrahydrofuran, Isosorbide-5-Nitrae-dioxane, dimethylformamide etc..These solvents can appropriate group
Conjunction is used, from yield it is good from the viewpoint of, use 1-METHYLPYRROLIDONE and water 1:1 is preferred.
As the example that the catalyst for using can be reacted in " operation 2 ", the palladium chloroform of praseodynium two can be enumerated
The salt such as adduct, palladium acetylacetonate, palladium bichloride, palladium, trifluoracetic acid palladium.Wherein, the palladium chloroform adducts of praseodynium two
From yield it is good from the viewpoint of be preferred." operation 2 " as long as used in the so-called catalytic amount of catalyst, do not have
Special limitation.From yield it is good from the viewpoint of, palladium catalyst and compound (2) mol ratio are 1:30-1:10 is preferred.
Compound (8) can be obtained after " operation 1 " terminates by carrying out common treatment.Can lead to as needed
Peracid filtering, column chromatography are purified.
Benzo coumarin derivative shown in above-mentioned " operation 3 " can be used but not limited to the method for " reference example -2 " to make
It is standby.
Above-mentioned " operation 4 " is according to circumstances and in the presence of a base to allow compound (2) and compound (5) to react, from
And prepare compound (4).The reaction of compound (2) and compound (5) obtains target product using with " operation 1 " identical method
Thing.
Compound (2) (5) molar ratio used " operation 4 " has no particular limits, from yield it is good from the viewpoint of,
1.5:1 is preferred.
The reaction of " operation 4 " can be implemented in a solvent.As the solvent that can be used in " operation 1 ", can enumerate
Toluene, tetrahydrofuran, Isosorbide-5-Nitrae-dioxane, dimethyl sulfoxide, dimethylformamide etc..These solvents can be used with appropriately combined,
From yield it is good from the viewpoint of, the use of toluene is preferred.
As can in " operation 4 " catalyst that the reaction of compound (2) and compound (5) is used specific example,
The salt such as palladium, palladium bichloride, trifluoracetic acid palladium, palladium nitrate can be enumerated.Wherein, done with tri-butyl phosphine the palladium of part from
It is preferred from the viewpoint of yield is good." operation 4 " as long as used in the so-called catalytic amount of catalyst, without spy
Other limitation.From yield it is good from the viewpoint of, palladium catalyst and compound (2) mol ratio are 1:30-1:10 is preferred.
As can in " operation 4 " alkali that the reaction of compound (2) and compound (5) is used specific example, can lift
Go out potassium carbonate, sodium carbonate, cesium carbonate etc., from yield it is good from the viewpoint of, cesium carbonate is preferred.To alkali and compound (3)
Molar ratio has no particular limits, from yield it is good from the viewpoint of, 2:1 is preferred.
Compound (4) can be obtained after " operation 4 " terminates by carrying out common treatment.Can lead to as needed
The modes such as recrystallization, column chromatography or distillation are crossed to be purified.
To coumarin derivative (compound (1)) of the present invention of the invention and benzo coumarin derivative (compound (4))
The preparation method of the organic electroluminescence device film for being formed does not have special limitation, it is possible to use vacuum vapour deposition into
Film.Can be carried out in general vacuum deposition apparatus using the film forming of vacuum vapour deposition.In view of organic electroluminescence device
Manufacture pitch time (tact time), manufacturing cost, during with vacuum vapour deposition film forming, the vacuum of vacuum tank preferentially passes through
Diffusion pump, turbomolecular pump (Turbo Molecular Pump), cryogenic pump for generally using etc. can reach 1 × 10-2To 1 ×
10-5Pa or so.Evaporation rate depends on being formed the thickness of film, but 0.05-1nm/s is preferred.In addition, coumarin derivative
(compound (1)) and benzo coumarin derivative (compound (4)) are due in chloroform, dichloromethane, chlorobenzene, toluene, acetic acid second
The middle solubility such as ester or tetrahydrofuran is high, therefore can also pass through method of spin coating, ink-jet method, casting method using common device
(cast method) or infusion process etc. carry out film forming.Spread out by coumarin derivative of the invention (compound (1)) and benzo cumarin
The doping film that biological (compound (4)) are formed has surface smoothness high, heat resistance, oxidation-reduction resistance, water resistance, resistance to
Oxygen, high-luminous-efficiency, hot activation delayed fluorescence performance etc., therefore organic electroluminescence device material is can serve as, especially may be used
As luminescent layer dopant dye etc..Therefore, the film for participating in being formed by compound (1) and compound (4) can be in low-voltage
Lower driving, and can serve as the constituent of efficient organic electroluminescence device.
Embodiment：Hereinafter enumerate embodiment and reference example carrys out the more detailed description present invention, but the present invention does not receive these examples
The limitation of son.
Reference example -1
【Chemical formula 8】
Under argon gas, 6- bromo- 3- methyl benzopyrone 238mg, phenoxazine 270mg, acetic acid are added to two mouthfuls of reactors of 100mL
Palladium 22mg, the toluene solution 0.3mL of 10% tri-butyl phosphine, addition toluene 10mL.Resulting solution is heated to backflow, stirring
24 hours.After being cooled to room temperature, organic solvent is distilled off.Add a large amount of water and dichloromethane extraction organic phase and use anhydrous sulphur
Sour sodium is dried, and after organic liquid phase is distilled off, product petroleum ether and dichloromethane are by column chromatography eluting.Obtained after drying
The green powder (yield 280mg, yield 82.3%) of 6- phenoxazine base -3- methyl benzopyrones.
Reference example -2
【Chemical formula 9】
Under argon gas, lithium hydroxide 0.79g is added to two mouthfuls of reactors of 250mL, adds 1-METHYLPYRROLIDONE and each 50mL of water,
The iodo- 4- bromobenzoic acids of 4.89g 2- and 2g phenyl boric acids are added, stirring is lower to add the palladium chloroform adducts of people's praseodynium two.Then exist
Continue to stir 18 hours at 65 DEG C.After the completion of reaction, hydrochloric acid acidifying is added, extracted with methyl tertiary butyl ether(MTBE), point liquid, organic phase is used
Anhydrous sodium sulfate drying, after organic liquid phase is distilled off, product petroleum ether is by column chromatography eluting.4- is obtained after drying
Bromo- 2- Phenylbenzoic acids white powder (yield 2.9g, yield 70.5%).
And in the white powder whole addition 50ml acetonitriles and 50ml water that will be obtained in two mouthfuls of reactors of backward 250mL, and
7.14g is added to cross sodium thiosulfate.Flowed back 18 hours at 50 DEG C.Room temperature is cooled to, saturated sodium bicarbonate aqueous solution is added
100mL, and extracted with 100mL ethyl acetate.9- bromobenzenes and cumarin white powder (yield 1.4g, yield are obtained after being spin-dried for
50.8%).
Under argon gas, 9- bromine dibenzopyrans ketone 1.1g, phenoxazine 880mg, palladium are added to two mouthfuls of reactors of 100mL
44.8mg, the toluene solution 1.2mL of 10% tri-butyl phosphine, addition toluene 40mL.Resulting solution is heated to backflow, stirring
24 hours.After being cooled to room temperature, organic solvent is distilled off.Add a large amount of water and dichloromethane extraction organic phase and use anhydrous sulphur
Sour sodium is dried, and after organic liquid phase is distilled off, product petroleum ether and dichloromethane are by column chromatography eluting.Obtained after drying
The green powder (yield 1g, yield 70.7%) of 9- phenoxazines base-benzo cumarin.
Test example -1
With 6- phenoxazine base -3- methyl benzopyrones as the making of the organic electroluminescence device of fluorescence dopant dye with
Performance evaluation.
As substrate, the glass substrate of tin indium oxide (ITO) transparency electrode 2mm wide is used.Vacuum evaporation makes organic
Before luminescent device, first ito substrate is pre-processed, first washed glass substrate with isopropanol, water and acetone, then
Drying in 100 DEG C of air dry oven is put into, then is surface-treated by UV ozone cleaning machine.Base after pre-processing
The vacuum evaporation of each layer is carried out on plate with vacuum vapour deposition, profile light-emitting area 4mm as shown in Figure 1 is made2Organic Electricity
Electroluminescence device.
First, the glass substrate after aforementioned processing is put into vacuum evaporation groove, is decompressed to 1 × 10-4Pa.Then in Fig. 1
In on glass substrate shown in 1, plated film is into hole injection layer 2, hole transmission layer 3, electronic barrier layer 4, luminescent layer 5 and electricity successively
Sub- transport layer 6, and cathode layer 7.Using 1nm thick thickness vacuum evaporation molybdenum trioxide as hole injection layer 2, with 35nm thickness
4, the 4'- cyclohexyl two [N, N- bis- (4- aminomethyl phenyls) aniline] (TAPC) of thickness vacuum evaporation as hole transmission layer 3, with
- three (carbazole -9- bases) triphenylamines (TCTA) of the 4,4' of 10nm thick thickness vacuum evaporation, 4 " are electronic barrier layer 4, thick with 20nm
Thickness vacuum evaporation ratio be 92：- 9H- the carbazoles (mCP) of 9,9'- (1,3- phenyl) two of 8 (quality %) are implemented with the present invention
The 6- phenoxazine base -3- methyl benzopyrones synthesized in example 1 as luminescent layer 5, with 40nm thick thickness vacuum evaporation
3,3'- [5'- [3- (3- pyridine radicals) phenyl] [1,1':3', 1 "-terphenyl] -3,3 "-diyl] two pyridines (TmPyPb) conduct electricity
Sub- transport layer 6.Wherein each organic material passes through resistance heating manner film forming.Heating compound is with the film forming speed of 0.3-0.5nm
Rate vacuum evaporation.It is last that metal mask, evaporation cathode layer 7 are configured in the mode orthogonal with ITO stripeds.Cathode layer 7 be respectively with
The thickness vacuum evaporation lithium fluoride and aluminium of 1nm and 100nm and the double-layer structure that is formed.Each thickness contact pin type determining film thickness device
(DEKTAK) determine.And then, by device sealing in the blanket of nitrogen glove box of water and below oxygen concentration 1ppm.Sealing uses glass
The closure of glass matter and the epoxy ultraviolet curable resin of foregoing substrate for film deposition (Nagase ChemteX Corporation systems
Make).
DC current is applied to prepared organic electroluminescence device, is come using Spectrascan PR655 luminance meters
Luminescent properties are evaluated, the digital sourcemeters of Keithley 2400 controlled using computer measure I-E characteristic.As luminous spy
Property, determine CIE chromaticity coordinates value, high-high brightness (cd/m in the case where changing with impressed DC voltage2), external quantum efficiency (%), work(
Rate efficiency (lm/W).
The measured value of made device is (0.26,0.50), 22000cd/m2, 17.8% and 48.01lm/W.
Test example -2
Commented with performance with 9- phenoxazines base-benzo cumarin as the making of the organic electroluminescence device of fluorescence dopant dye
Valency.
Instead of test example -1 luminescent layer 5 with the thick thickness vacuum evaporation ratios of 20nm be 92：The mCP of 8 (quality %) with
The 9- phenoxazines base-benzo cumarin synthesized in embodiment of the present invention is used as luminescent layer 5.The making same with experimental example -1 has
Organic electroluminescence devices.
The measured value of made device is (0.32,0.50), 35560cd/m2, 19.6% and 60.09lm/W.
Industrial applicability, confirms with current material than being applicable the organic electroluminescence of compound of the invention
Part can be roll-offed with low consumption electrification, high-luminous-efficiency and poor efficiency.In addition, compound of the invention is except in the present embodiment
Outside luminescent dopant material, donor of exciplex etc. is applied also for.Meanwhile, apply also for fluorescence luminescent material, phosphorescence
The various organic electroluminescence devices of luminescent material.Further, in addition to the purposes such as flat-panel monitor, apply also for taking into account low
Consumption electric power and efficient lighting use etc..
It is above enlightenment according to desirable embodiment of the invention, by above-mentioned description, related personnel completely can be with
Without departing from the scope of the technological thought of the present invention', various changes and amendments are carried out.The technical scope of this invention
It is not limited to the content on specification, it is necessary to determine the technical scope according to the scope of the claims.
Claims (9)
1. a kind of coumarin derivative based on hot activation delayed fluorescence mechanism, it is characterised in that the coumarin derivative is such as
Shown in following formulas (1) or formula (4)：
In formula (1) and formula (4), Y represents the hetero atom that is joined directly together or contains the coupled Asia of aryl or alkyl
Base；In formula (4), W is represented can be in the substitution base of aryl optional position substitution；Z represents carbon or hetero atom, and hetero atom can be
Any unsubstituted position of right side aryl.
2. coumarin derivative according to claim 1, it is characterised in that：Aligned up in the carbonyl of coumarin derivative
Rare one nitrogenous Electron rich aromatic base and nitrogen are directly connected in the contraposition of the carbonyl of coumarin derivative.
3. coumarin derivative according to claim 1, it is characterised in that：The hexatomic ring being joined directly together with oxygen can be benzene
Ring or heterocycle, can be substituted aromatic hydrocarbyl on ring.
4. coumarin derivative according to claim 1, it is characterised in that：The hetero atom Y is oxygen atom or sulphur atom.
5. a kind of preparation method of coumarin derivative as claimed in claim 1, it is characterised in that：Primary benzene cumarin is set to spread out
Biological to carry out coupling reaction with Electron rich aromatic substitution base (2) comprising at least one nitrogen, formula (2) is as follows：
6. preparation method according to claim 5, it is characterised in that：The primary benzene coumarin derivative is 6- substituted benzenes
Coumarin derivative (3) or 9- replace benzo coumarin derivative (5)；Formula (3) and formula (5) are as follows：
Wherein, the X in formula (3) and formula (5) represents leaving group.
7. preparation method according to claim 5, it is characterised in that：Under alkaline environment, while being entered using palladium catalyst
Row coupling reaction.
8. application of a kind of coumarin derivative as claimed in claim 1 on organic electroluminescence device, it is characterised in that
The luminous of the organic electroluminescence device is made by constituent of the coumarin derivative of formula (1) or/and formula (4)
Layer.
9. application of the coumarin derivative according to claim 8 on organic electroluminescence device, it is characterised in that：Institute
State fluorescent dopants of the coumarin derivative as the luminescent layer of organic electroluminescence device.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111499607A (en) * | 2019-01-30 | 2020-08-07 | 哈尔滨工业大学（深圳） | Preparation method of hexabasic aryl lactone or hexabasic aryl lactam compound |
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| CN102102015A (en) * | 2009-12-21 | 2011-06-22 | 中国科学院理化技术研究所 | Coumarin derivative type organic electroluminescent material and preparation method and applications thereof |
| CN102101852A (en) * | 2009-12-21 | 2011-06-22 | 中国科学院理化技术研究所 | Coumarin derivates, preparation method thereof and application thereof in white-light organic electroluminescent device |
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| CN102102015A (en) * | 2009-12-21 | 2011-06-22 | 中国科学院理化技术研究所 | Coumarin derivative type organic electroluminescent material and preparation method and applications thereof |
| CN102101852A (en) * | 2009-12-21 | 2011-06-22 | 中国科学院理化技术研究所 | Coumarin derivates, preparation method thereof and application thereof in white-light organic electroluminescent device |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111499607A (en) * | 2019-01-30 | 2020-08-07 | 哈尔滨工业大学（深圳） | Preparation method of hexabasic aryl lactone or hexabasic aryl lactam compound |
| CN111499607B (en) * | 2019-01-30 | 2022-04-19 | 哈尔滨工业大学（深圳） | Preparation method of hexabasic aryl lactone or hexabasic aryl lactam compound |
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