CN109837082A - A kind of electroluminescent material and the preparation method and application thereof - Google Patents
A kind of electroluminescent material and the preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses based electroluminescent materials and the preparation method and application thereof.Wherein sulphur dibenzofuran acene unit is seven yuan of condensed cyclic structures, and preferable flatness is conducive to the injection and transmission of carrier, improves the photoelectric properties of material；And ring structure makes sulphur dibenzofuran acene unit have preferable rigidity, is conducive to the heat resistance for improving material, meets material functionization demand.The present invention, which obtains the electroluminescent material based on sulphur dibenzofuran acene unit by Suzuki coupling reaction, Liv Ullmann coupling reaction, still coupling reaction etc., has preferable dissolubility, common organic solvents dissolution can be used, by spin coating, inkjet printing or printing film forming, the luminescent layer of light emitting diode is prepared.
Description
Technical field
The invention belongs to organic photoelectric technical field, in particular to based electroluminescent material and preparation method thereof with answer
With.
Background technique
Organic/material LED, organic field effect tube, the electronics such as organic solar batteries or photoelectronic industry
It grows rapidly, wherein the product based on Organic Light Emitting Diode (OLED) comes out already, but adopts due to preparing OLED device at present
It is vacuum evaporation process, instrument and equipment is expensive.Stock utilization is low (~20%), so that OLED product price occupies height not
Under.Solution processing technology can make up the deficiency of vacuum evaporation, gradually attract the concern of scientific research institution and manufacturer, company.Material has
The advantages that good filming, machining property, is suitble to solution processing, therefore develops the material of new and effective stable solution processable
Material becomes key.
S, S- dioxy-hexichol acene unit are a kind of blue light star's unit haveing excellent performance, fluorescence volume with higher
Sub- yield；Sulfuryl improves the electron affinity and electron mobility of molecule in structure；Sulphur atom has preferable inoxidizability
Deng wherein containing 3,7 substitution-S, S- dioxy-hexichol acene unit polymer shows superior photoelectric properties." materials chemistry
C " (Journal of Materials Chemistry C) is reported to introduce 3,7-S, S- dioxy-dibenzo in polyfluorene main chain
The polymer of benzene unit is that the maximum lumen efficiency of the single layer device of luminescent layer is up to 7.1cd/A, chromaticity coordinates be (0.16,
It 0.18), is the highest blue light frequency-doubling of current efficiency.But the electron-withdrawing ability of S, S- dioxo-dibenzothiophene unit is strong, contains S,
Apparent intramolecular interaction can occur for the electroluminescent organic material of S- dioxo-dibenzothiophene unit, cause spectrum red
It moves, the material of chromaticity coordinates cannot be expected.Therefore, research has both S, S- dioxo-dibenzothiophene advantage but electron-withdrawing ability is slightly
Weak novel blue light unit is very necessary.
Summary of the invention
The primary purpose of the present invention is that providing a kind of electricity for current organic/polymer LED (O/PLED)
Electroluminescent material.The electroluminescent material has preferable dissolubility, and more excellent photoelectric properties are suitable for solution processing and spray
Ink printing, has huge application potential.
Another object of the present invention is to provide the preparation methods of the electroluminescent material.
A further object of the present invention is to provide the applications of the electroluminescent material.
The purpose of the present invention is realized by following proposal:
One based electroluminescent material, the material include following structural formula:
In formula, R is with hole or electron injection or transmission performance group or solubilization radical.
Preferably, R be the straight chain of alkyl with 1~2 carbon atom or alkoxy or 3~20 carbon atoms, branch or
The cricoid alkyl of person or alkoxy, or straight chain, branch or the ring-type of the alkenyl with 2 carbon atoms or 3~20 carbon atoms
Alkenyl, or straight chain, branch or the cricoid alkynyl of the alkynyl with 2 carbon atoms or 3~20 carbon atoms, or have 2
Straight chain, branch or the cricoid alkyl-carbonyl of~20 carbon atoms, or aryl or heteroaryl with 4~20 annular atoms,
Or aralkyl or heteroaryl alkyl with 4~20 annular atoms, or aryloxy group or heteroaryl oxygen with 4~20 annular atoms
Base, or alkoxy aryl or heteroarylalkoxy with 4~20 annular atoms；Or triphenylamine and its derivative, carbazole and its
Derivative, phenoxazine and its derivative, phenthazine and its derivative, acridine and its derivative；Or pyridine and its derivatives, evil two
Azoles and its derivative, benzimidazole and its derivative, triazole and its derivative, triazine and its derivative, quinoxaline and its derivative
Object.
Preferably, structural unit Ar1To Ar12It is one of hydrogen or following structural unit:
Wherein,
X=O, S, Se, Te, N-R；
Y=C, Si, Ge；
R1、R2、R3、R4It is H, deuterium, F, alkenyl, alkynyl, itrile group, amido, nitro, acyl group, alkoxy, carbonyl, sulfuryl, virtue
Base, triphenylamine, carbazole, the alkyl of carbon atom number 1~30, the naphthenic base of carbon atom number 3~30, carbon atom number are 6~60 fragrance
The aromatic heterocycle that race's alkyl or carbon atom number are 3~60.
The preparation method of electroluminescent material, includes the following steps:
(1) esterification occurs for o-bromobenzoic acid and ethyl alcohol, and dehydration obtains o-bromo-benzoic acid ethyl ester, is then dissolved completely in
It refines in anhydrous tetrahydro furan, in an inert atmosphere, 2- isopropoxy -4,4,5,5- tetramethyls -1,3,2- dioxy is added
Miscellaneous borine, -78 DEG C of reactions, obtains ethyl 2- (4,4,5,5- tetramethyls -1,3,2- dioxaborinate -2- base) ethyl benzoate；
(2) under inert gas environment, 3,7- bis- bromo- S, S- dioxydibenze bithiophene and ethyl 2- (4,4,5,5- tetramethyls-
1,3,2- dioxaborinate -2- base) ethyl benzoate by Suzuki be coupled, obtain 2,2 '-(5,5- dioxies of compound diethyl
Hexichol [b, d] bithiophene -3,7- base) naphthoic acid ethyl ester；
(3) compound diethyl 2,2 '-(5,5- dioxydibenze [b, d] bithiophene -3,7- base) naphthoic acid ethyl ester is complete
It is dissolved in purification anhydrous tetrahydro furan, under normal temperature conditions, alkyl grignard reagent is added, is heated to 80 DEG C, react 16h, obtain
To compound 3,7- bis- (2- (2- dialkyl group alcohol -2- base) dibenzo [b, d] thiophene] 5,5- dioxide；
(4) by compound 3,7- bis- (2- (2- dialkyl group alcohol -2- base) dibenzo [b, d] thiophene] 5,5- dioxide is dissolved in
In anhydrous methylene chloride, glacial acetic acid is added, reacts 1h, obtains 12,12,15,15- tetraalkyl -12,15- of white solid after purification
Dihydro-dibenzo [3 '-d of 3,2-b:2 '] thiophene 6,6- dioxide；
(5) by compound 12,12,15,15- tetraalkyl -12,15- dihydro-dibenzo [3 '-d of 3,2-b:2 '] thiophene 6,6-
Dioxide is dissolved in anhydrous chloroform, under cryogenic, bromine is added and carries out bromination, obtains white solid bromine after purification
Change -12,12,15,15- tetraalkyl -12,15- dihydro-dibenzo [3 '-d of 3,2-b:2 '] thiophene 6,6- dioxide；
(6) C-C coupling reaction or C-N coupling reaction
(i) C-C coupling reaction: under inert gas environment, by bromination -12,12,15,15- tetraalkyl -12,15- dihydros two
Benzo [3,2-b:2 ' 3 '-d] thiophene 6,6- dioxide are dissolved in tetrahydrofuran, and aryl-boric acid ester or aryl boric acid, carbon is added
Sour aqueous solutions of potassium and tetrakis triphenylphosphine palladium carry out Suzuki coupling reaction, obtain after purification described based on sulphur dibenzofuran acene
The electroluminescent material of unit；
(ii) C-N coupling reaction: under inert gas environment, by bromination -12,12,15,15- tetraalkyl -12,15- dihydros two
Benzo [3,2-b:2 ' 3 '-d] thiophene 6,6- dioxide are dissolved in toluene solution, and fragrant amine monomers, tert-butyl sodium alkoxide, vinegar are added
Sour palladium and tri-tert-butylphosphine carry out C-N coupling reaction, obtain the electroluminescent based on sulphur dibenzofuran acene unit after purification
Material.
Preferably, in synthesis step, the inert gas is argon gas；In the step (5), the temperature of the low temperature is-
20~25 DEG C, described 12,12,15,15- tetraalkyl -12,15- dihydro-dibenzos [3,2-b:2 ' 3 '-d] thiophene 6,6- titanium dioxide
The molar ratio of object and bromine is 1:1~12.
Preferably, in the C-C coupling reaction of the step (6), the bromination -12,12,15,15- tetraalkyls -12,15-
Dihydro-dibenzo [3 '-d of 3,2-b:2 '] thiophene 6,6- dioxide, aryl-boric acid ester or aryl boric acid, potassium carbonate and four (three
Phenylphosphine) palladium molar ratio be 1:2~6:5~10:0.02~0.1, C-C coupling reaction be at 50~120 DEG C, reaction 8~48
Hour.
Preferably, in the C-N coupling reaction of the step (6), the bromination -12,12,15,15- tetraalkyls -12,15-
Dihydro-dibenzo [3 '-d of 3,2-b:2 '] thiophene 6,6- dioxide, fragrant amine monomers, tert-butyl sodium alkoxide, palladium acetate molar ratio
For 1:1~12:4.1~10:0.02~0.1, the molar ratio of palladium acetate and tri-tert-butylphosphine is 1:1~4, preferred palladium acetate with
The molar ratio of tri-tert-butylphosphine is 1:2, and the C-N coupling reaction is reacted 8~48 hours at 50~120 DEG C.
The application of electroluminescent material, the electroluminescent material for light emitting diode, light emitting diode luminescent layer,
Organic field effect tube, organic solar batteries or organic laser diode.
Preferably, include the following steps, the electroluminescent material is dissolved with organic solvent, then pass through spin coating, ink-jet
Printing or printing film forming, the organic solvent is at least one of chlorobenzene, dichloro benzene,toluene,xylene, tetrahydrofuran, chloroform.
Preferably, the structure of the LED device successively include stacking substrate, anode layer, hole injection layer,
Hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer, or successively include substrate, the cathode of stacking
Layer, electron injecting layer, electron transfer layer, luminescent layer, hole transmission layer, hole injection layer and anode layer.
Compared with present technology, the invention has the following advantages that
(1) sulphur dibenzofuran acene unit of the present invention, the introducing of low pole phenyl is so that the new unit of sulphur dibenzofuran acene point
D-A effect is weaker in son, weakens Intramolecular electron transfer effect, avoids the red shift of spectrum, guarantees sulphur dibenzofuran acene unit
It is still blue light unit.
(2) present invention is the electroluminescent material based on sulphur dibenzofuran acene, and the condensed cyclic structure of sulphur dibenzofuran acene unit is compared
Single S, S- dioxy-hexichol acene unit, there is coplanar rigid structure, and modifiable site is more, the introducing of solubilization radical
It can be obviously improved the dissolubility of new unit, molecular structure is more stable, and thermal stability is more preferable., it is evident that the sulphur oxygen from structure
Fluorenes acene unit has four alkyl chains, single S, and S- dioxo-dibenzothiophene at most only has two alkyl chains, the former works as dissolubility
It is so good.Sulphur dibenzofuran acene is polynary condensed cyclic structure, and coplanarity, single double bond alternating, is rock-steady structure, rigidity is than single S, S- bis-
Oxygen-dibenzothiophenes is good, and thermostabilization and rigidity are proportional.
(3) electroluminescent material of the invention based on sulphur dibenzofuran acene, due to seven yuan of condensed ring of sulphur dibenzofuran acene unit
Structure, can modification activities site it is more, chemical modification is stronger, and can introduce long alkyl chain improves its dissolubility, and material has preferable
Dissolubility, based on the luminescent layer of the material when preparing electroluminescent device without annealing so that preparation process is simpler
It is single.
(4) novel condensed ring structure-sulphur dibenzofuran acene unit that the present invention synthesizes is saving S, S- dioxo-dibenzothiophene list
While first advantage, planar structure is increased, is conducive to the electronic transmission performance for improving material.
(5) the present invention relates to the electroluminescent material based on sulphur dibenzofuran acene unit because having preferable dissolution
Performance is suitable for solution processing and preferable fluorescence quantum yield, is conducive to the blue light device that luminescent device obtains efficient stable
Part performance can be realized simultaneously the raising of the luminous efficiency and service life of device, can satisfy the requirement of full-color display.So
There are huge development potentiality and prospect in organic electronic display field.
Detailed description of the invention
Fig. 1 compound B-11~B4 differential scanning calorimetric curve.
UV-vis absorption spectrum of Fig. 2 compound B-11 under filminess.
Fluorescence spectrum of Fig. 3 compound B-11 under filminess.
Specific embodiment
The present invention is further illustrated combined with specific embodiments below.
The preparation of 1 2- bromobenzoic acid ethyl ester of embodiment
In 500mL there-necked flask, 2- bromobenzoic acid (20.1g, 0.1mol) is dissolved in 200ml ethyl alcohol, and into reaction solution
It is added dropwise to the concentrated sulfuric acid of 20ml, after being stirred 12 hours under room temperature, stops reaction, reaction is quenched with water, is extracted with methylene chloride
It takes and is dried with anhydrous magnesium sulfate, obtain yellow liquid after solution concentration, purified by silica gel column chromatography, petroleum ether/dichloro
The mixed solvent (7/1, v/v) of methane is eluent, yield 84%.1H NMR、13CNMR, MS and elemental analysis are the result shows that institute
Obtained compound is target product, and preparation process chemical equation is as follows:
The preparation of 2 ethyl 2- of embodiment (4,4,5,5- tetramethyl -1,3,2- dioxaborinate -2- base) ethyl benzoate
Under inert gas protection, 2- bromobenzoic acid ethyl ester (17.5g, 76.4mmol) is dissolved in 250ml anhydrous tetrahydro furan
In, and the hexane solution (38.2ml, 91.7mmol) for the n-BuLi that concentration is 2.4mol/L is slowly added dropwise, it is stirred under room temperature
After 1 hour, addition 2- isopropoxy -4,4 into reaction system, 5,5- tetramethyls -1,3,2- dioxaborinate (25.6g,
0.14mol), stop reaction, reaction is quenched with water, extract and be dried with anhydrous magnesium sulfate, solution with methylene chloride
Khaki liquid is obtained after concentration, is purified by silica gel column chromatography, and petroleum ether/methylene chloride mixed solvent (5/1, v/v) is leaching
Lotion obtains white solid, yield 87%.1H NMR、13CNMR, MS and elemental analysis are the result shows that obtained compound is
Target product, preparation process chemical equation are as follows:
The system of 3 2,2 '-(5,5- dioxydibenze [b, d] phenyl -3,7- base) two (benzene -3- formic acid esters) of diethyl of embodiment
It is standby
Under an argon atmosphere, into 500mL three-necked flask, ethyl 2- (4,4,5,5- tetramethyls -1,3,2- dioxa is added
Borine -2- base) ethyl benzoate (8.4g, 30.4mmol), 2,7- bis- bromo- S, S- dioxydibenze acene (20.0g,
45.6mmol), four butyl bromation amine (0.49g, 1.52mmol), catalyst triphenylphosphine palladium (1.76g, 1.52mmol)
And organic base (20mL) and K is added when temperature is stablized at 110 DEG C in 200mL toluene, agitating and heating2CO3(41.95g,
0.30mol) aqueous solution 42mL reacts 12h.It after reaction solution is concentrated, is purified by silica gel column chromatography, petroleum ether and methylene chloride
Mixed solvent (3/1, v/v) is eluent, obtains faint yellow solid, yield 75%.1H NMR、13CNMR, MS and elemental analysis knot
Fruit shows that obtained compound is target product, and preparation process chemical equation is as follows:
4 3,7- bis- of embodiment (2- (bis- propyl alcohol -2- base of 2-) dibenzo [b, d] thiophene] 5,5- dioxide preparation
Under inert gas protection, by diethyl 2,2 '-(5,5- dioxydibenzes [b, d] phenyl -3,7- yl) two (benzene -3-
Formic acid esters) (7.2g, 14mmol) be dissolved in 80ml purification anhydrous THF in, dropwise be added dropwise 1.0mol L-1Octyl magnesium bromide
(70ml, 70mmol) is warming up to 80 DEG C and is heated to reflux, and reacts 16h.It is cooled to room temperature, reaction mixture is poured into water, use second
Acetoacetic ester extraction, it is dry with anhydrous magnesium sulfate after organic layer is washed completely with saline solution.After solution concentration, directly carry out next
Step reaction.
Embodiment 5 12,12,15,15- tetramethyl -12,15- dihydro-dibenzo [3 '-d of 3,2-b:2 '] thiophene 6,6- dioxy
The preparation of compound
By 3,7- bis- (2- (bis- propyl alcohol -2- base of 2-) dibenzo [b, d] thiophene] 5,5- dioxide (3.2g, 6.6mmol)
It is dissolved in glacial acetic acid 80mL, reacts 1h.It after solution concentration, is purified with silica gel column chromatography method, petroleum ether and methylene chloride mixing
Solvent (8/1, v/v) is eluent.Crude product ethyl alcohol recrystallization obtains white crystal, yield 80%.1H NMR、13CNMR, MS and
The result shows that obtained compound is target product, preparation process chemical equation is as follows for elemental analysis:
Bromo- 12,12,15,15- tetramethyl -12,15- dihydro-dibenzo [3 '-d of the 3,2-b:2 '] thiophene of 6 2,10- of embodiment bis-
The preparation of pheno 6,6- dioxide
By 12,12,15,15- tetramethyl -12,15- dihydro-dibenzo [3 '-d of 3,2-b:2 '] thiophene 6,6- dioxide
(2.5g, 5.6mmol) is dissolved in 10ml carbon tetrachloride, under condition of ice bath, is added bromine (1.0g, 6.2mmol), reaction 24
Saturation sodium hydrogensulfite quenching reaction is used after hour, and is extracted with ethyl acetate, and after anhydrous magnesium sulfate is dry, uses silica gel column chromatography
Purification, petroleum ether and methylene chloride mixed solvent (8/1, v/v) are eluent, obtain white solid.Yield: 86%.1H NMR
、13CNMR, MS and elemental analysis are the result shows that obtained compound is target product, and preparation process chemical equation is such as
Shown in lower:
The synthesis of 7 compound B-11 of embodiment
Under argon atmosphere, in 100mL there-necked flask, 2,10- bis- bromo- 12,12,15, phytanetriol 2,15- is added
Dihydro-dibenzo [3,2-b:2 ' 3 '-d] thiophene 6,6- dioxide (1.44g, 2.4mol), diphenylamines (0.85g, 5.0mmol),
Tert-butyl sodium alkoxide (1.84g, 19.2mmol), palladium acetate (27mg, 0.12mmol) and 50ml toluene.Heating stirring adds to 85 DEG C
Enter the toluene solution (concentration 2.0mol/L) of 0.12ml tri-tert-butylphosphine, reacts 12h.After stopping reaction, concentrated solvent is thick to produce
For object by column Chromatographic purification, petroleum ether and methylene chloride mixed solvent (4/1, v/v) are eluent, obtain emerald green solid eventually.1H
NMR、13CNMR, MS and elemental analysis are the result shows that obtained compound is target product, preparation process chemical equation
It is as follows:
Differential scanning calorimetry (DSC) curve of compound B-11 is as shown in Figure 1.It can be seen that compound B-11 is entirely adding
In thermal process, there is not melting peak and peak crystallization, glass transition peak only occur, this illustrates compound B-11 under solid conditions
It is that can form unformed shape, is not easy to crystallize in the luminescent layer for preparing Organic Light Emitting Diode, is conducive to the normal use of device.
It is found that the glass transition temperature of compound B-11 is followed successively by 90 DEG C from DSC curve.
Ultraviolet-visible absorption spectroscopy of the compound B-11 under filminess is as shown in Fig. 2, as shown in Figure 2, B1 is in film-form
Maximum absorption band under state is located at 382nm, belongs to the absorption of compound B-11 conjugated main chain.Compound B-11 is in filminess maximum
ABSORPTION EDGE (λmax) it is 430nm, rule of thumb formula has, the optical band gap E of compoundg=1240/ λmax=1240/430eV
=2.88eV has wider band gap.
Compound B-11 is in the fluorescence emission spectrum under filminess as shown in figure 3, from the figure 3, it may be seen that B1 is under filminess
Maximum emission peak be located at 470nm, realize blue emission, half-peak breadth is relatively narrow, be 59nm, colour purity is able to achieve in preparing device
Spend preferable blue emission.
The synthesis of 8 compound B2 of embodiment
Under argon atmosphere, in 100mL there-necked flask, 2,10- bis- bromo- 12,12,15, phytanetriol 2,15- is added
Dihydro-dibenzo [3,2-b:2 ' 3 '-d] thiophene 6,6- dioxide (1.44g, 2.4mol), carbazole (0.84g, 5.0mmol), uncle
Butyl sodium alkoxide (1.84g, 19.2mmol), palladium acetate (27mg, 0.12mmol) and 50ml toluene.Heating stirring is added to 85 DEG C
The toluene solution (concentration 2.0mol/L) of 0.12ml tri-tert-butylphosphine reacts 12h.After stopping reaction, concentrated solvent, crude product
By column Chromatographic purification, petroleum ether and methylene chloride mixed solvent (4/1, v/v) are eluent, obtain beige solid eventually.1H
NMR、13C NMR, MS and elemental analysis are the result shows that obtained compound is target product, preparation process chemical reaction equation
Formula is as follows:
Differential scanning calorimetry (DSC) curve of compound B2 is as shown in Figure 1.It can be seen that compound B2 is entirely adding
In thermal process, there is not melting peak and peak crystallization, glass transition peak only occur, this illustrates compound B2 under solid conditions
It is that can form unformed shape,.It is found that compound B-11~B4 glass transition temperature is followed successively by 92 DEG C from DSC curve.
The synthesis of 9 compound B3 of embodiment
Under argon atmosphere, in 100mL there-necked flask, 2,10- bis- bromo- 12,12,15, phytanetriol 2,15- is added
Dihydro-dibenzo [3,2-b:2 ' 3 '-d] thiophene 6,6- dioxide (1.44g, 2.4mol), benzimidazole boric acid (1.57g,
5.0mmol), aqueous solution (2mol/L, 2.65g/9.6ml deionized water, 19.2mmol), the tetra-triphenylphosphine palladium of potassium carbonate
(139mg, 0.12mmol) and 50ml tetrahydrofuran.Heating stirring reacts 12h to 85 DEG C.After stopping reaction, concentrated solvent, slightly
For product by column Chromatographic purification, petroleum ether and methylene chloride mixed solvent (3/1, v/v) are eluent, obtain beige solid eventually.1H NMR、13CNMR, MS and elemental analysis are the result shows that obtained compound is target product, preparation process chemical reaction side
Formula is as follows:
Differential scanning calorimetry (DSC) curve of compound B3 is as shown in Figure 1.It can be seen that compound B3 is entirely adding
In thermal process, there is not melting peak and peak crystallization, glass transition peak only occur, this illustrates compound B3 under solid conditions
It is that can form unformed shape.It is found that the glass transition temperature of compound B3 is 96 DEG C from DSC curve.
The synthesis of 10 compound B4 of embodiment
Under argon atmosphere, in 100mL there-necked flask, 2,10- bis- bromo- 12,12,15, phytanetriol 2,15- is added
Dihydro-dibenzo [3,2-b:2 ' 3 '-d] thiophene 6,6- dioxide (1.44g, 2.4mol), -2 fluorenyl boric acid of 9,9- dimethyl
Aqueous solution (2mol/L, 2.65g/9.6ml deionized water, 19.2mmol), four triphenyls of (1.19g, 5.0mmol), potassium carbonate
Phosphine palladium (139mg, 0.12mmol) and 50ml tetrahydrofuran.Heating stirring reacts 12h to 85 DEG C.After stopping reaction, it is concentrated molten
Agent, for crude product by column Chromatographic purification, petroleum ether and methylene chloride mixed solvent (4/1, v/v) are eluent, are obtained eventually emerald green
Solid.1H NMR、13The result shows that obtained compound is target product, preparation process chemistry is anti-for CNMR, MS and elemental analysis
Answer equation as follows:
Differential scanning calorimetry (DSC) curve of compound B4 is as shown in Figure 1.It can be seen that compound B4 is entirely adding
In thermal process, there is not melting peak and peak crystallization, glass transition peak only occur, this illustrates compound B4 under solid conditions
It is that can form unformed shape, is not easy to crystallize in the luminescent layer for preparing Organic Light Emitting Diode, is conducive to the normal use of device.
It is found that the glass transition temperature of compound B4 is 94 DEG C from DSC curve.
The synthesis of 11 compound B5 of embodiment
Under argon atmosphere, in 100mL there-necked flask, the addition bromo- S of 3,7- bis-, S- dioxydibenze bithiophene (0.90g,
2.4mol), aqueous solution (2mol/L, the 2.65g/9.6ml of -2 fluorenyl boric acid (1.19g, 5.0mmol) of 9,9- dimethyl, potassium carbonate
Deionized water, 19.2mmol), tetra-triphenylphosphine palladium (139mg, 0.12mmol) and 40ml tetrahydrofuran.Heating stirring to 75 DEG C,
React 12h.After stopping reaction, concentrated solvent, crude product passes through column Chromatographic purification, petroleum ether and methylene chloride mixed solvent (4/
1, v/v) it is eluent, obtains emerald green solid eventually.1H NMR、13CNMR, MS and elemental analysis are the result shows that obtained compound
For target product, preparation process chemical equation is as follows:
Embodiment 12
The preparation of organic electroluminescence device
1) cleaning of ITO electro-conductive glass.Ito glass substrate is placed on film hanger, is cleaned by ultrasonic using ultrasonic device, is washed
It is acetone, isopropanol, dish washing liquid, deionized water and isopropanol that liquid, which is washed, using sequence, and the purpose is to sufficiently remove ito glass substrate
Possible remaining spot such as photoresist in surface etc., and improve interfacial contact.Then it is dried in vacuum drying oven；
2) ITO is placed in oxygen plasma etch instrument, uses oxygen plasma (O2Plasma it) carries out 20 minutes
Bombardment thoroughly removes the possible remaining organic matter of ito glass substrate surface；
3) on ITO spin coating 40nm thickness hole injection layer PEDOT:PSS (Baytron P4083), then at 80 DEG C
It is 12 hours dry in vacuum drying oven；
4) in the glove box of nitrogen atmosphere, the luminous organic matter film of one layer of 80nm thickness of spin coating on PEDOT:PSS layer
Afterwards, heating anneal 20 minutes at a temperature of 80 DEG C on warm table, to remove residual solvent and improve the pattern for the tunic that shines；
5) it is being lower than 3 × 10 in vacuum evaporation storehouse-4One layer of 1.5nm is first deposited under the vacuum degree of Pa on organic thin film
Thick cesium fluoride (CsF), facilitates electron injection.Then the aluminium cathode (Al) of one layer of 110nm thickness is deposited on CsF, wherein fluorine
Change caesium and aluminium layer is vacuum-deposited by mask plate progress.
The effective area of device is 0.16cm2.With the thickness of quartz crystal monitoring thickness gauge measurement organic layer.Device preparation
Polarity solidification and encapsulation in ultraviolet light with epoxy resin and thin layer of glass afterwards.Single layer device structure is (ITO/PEDOT:PSS/
EMITTER(80nm)/CsF(1.5nm)/Al(110nm))。
Photoelectric properties test is carried out respectively to obtained electroluminescent device, test result is as shown in table 1.
The electroluminescent properties data of 1 compound of table
It is ITO/PEDOT:PSS/EMITTER/CsF/Al single layer device by luminescent layer preparation structure of compound B-11~B5,
Its maximum lumen efficiency is respectively 4.09cd/A, 3.50cd/A, 2.78cd/A, 3.96cd/A, 0.65cd/A.Wherein it is based on chemical combination
The maximum brightness of the device of object B1 can be up to 24889cd/m2.Compound B-11~B4 shows preferable photoelectric properties, and equal energy
Realize the preferable blue emission of excitation purity.
Control compounds B4 and B5, in structure, the two difference is core difference: compound B4 is sulphur dibenzofuran acene unit
Bonded fluorenes unit；Compound B5 is single S, the bonded fluorenes unit of S- dioxy-hexichol acene unit.Under identical device architecture,
The two electroluminescent properties have notable difference.The data from table 1 it is found that the maximum lumen efficiency of the device based on compound B5 only
For 1.25cd/A, maximum brightness 3957cd/m2；The maximum lumen efficiency of device based on compound B4 is 3.96cd/A, than
The former performance improves more than two times；Maximum brightness is 10252cd/m2, it is the former 2.6 times, photoelectric properties have clear improvement.
Since the conjugated degree ratio B5 of compound B4 is big, spectrum red shift, chromaticity coordinates increased to by (0.16,0.10) (0.14,
0.16), but still in deep blue region.(deep blue region (x+y≤0.3)).By comparison it is found that being based on sulphur dibenzofuran acene unit
Electroluminescent material be a kind of material for having application potential haveing excellent performance.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention should all
For equivalent substitute mode, it is included within the scope of the present invention.
Claims (10)
1. a based electroluminescent material, which is characterized in that the material includes following structural formula:
In formula, R is with hole or electron injection or transmission performance group or solubilization radical.
2. electroluminescent material according to claim 1, which is characterized in that R be alkyl with 1~2 carbon atom or
The straight chain of alkoxy or 3~20 carbon atoms, branch or cricoid alkyl or alkoxy, or the alkene with 2 carbon atoms
The straight chain of base or 3~20 carbon atoms, branch or cricoid alkenyl, or alkynyl or 3~20 carbon with 2 carbon atoms
The straight chain of atom, branch perhaps cricoid alkynyl or straight chain, branch or cricoid alkyl oxycarbonyl with 2~20 carbon atoms
Base, or aryl or heteroaryl with 4~20 annular atoms, or aralkyl or heteroaryl alkyl with 4~20 annular atoms,
Or aryloxy group or heteroaryloxy with 4~20 annular atoms, or alkoxy aryl or heteroaryl with 4~20 annular atoms
Alkoxy；Or triphenylamine and its derivative, carbazole and its derivative, phenoxazine and its derivative, phenthazine and its derivative；Or
Pyridine and its derivatives, oxadiazoles and its derivative, benzimidazole and its derivative.
3. electroluminescent material according to claim 1, which is characterized in that structural unit Ar1To Ar12It is hydrogen or following knot
One of structure unit:
Wherein,
X=O, S, Se, Te, N-R；
Y=C, Si, Ge；
R1、R2、R3、R4It is H, deuterium, F, alkenyl, alkynyl, itrile group, amido, nitro, acyl group, alkoxy, carbonyl, sulfuryl, aryl, three
Aniline, carbazole, the alkyl of carbon atom number 1~30, the naphthenic base of carbon atom number 3~30, carbon atom number are 6~60 aromatic hydrocarbyls
Or the aromatic heterocycle that carbon atom number is 3~60.
4. the preparation method of the described in any item electroluminescent materials of claims 1 to 3, which comprises the steps of:
(1) esterification occurs for o-bromobenzoic acid and ethyl alcohol, and dehydration obtains o-bromo-benzoic acid ethyl ester, is then dissolved completely in purification
In anhydrous tetrahydro furan, in an inert atmosphere, 2- isopropoxy -4,4,5,5- tetramethyls -1,3,2- dioxa boron is added
Alkane, -78 DEG C of reactions, obtains ethyl 2- (4,4,5,5- tetramethyls -1,3,2- dioxaborinate -2- base) ethyl benzoate；
(2) under inert gas environment, 3,7- bis- bromo- S, S- dioxydibenze bithiophene and ethyl 2- (4,4,5,5- tetramethyls -1,3,
2- dioxaborinate -2- base) ethyl benzoate by Suzuki be coupled, obtain 2,2 '-(5,5- dioxydibenzes of compound diethyl
[b, d] bithiophene -3,7- base) naphthoic acid ethyl ester；
(3) compound diethyl 2,2 '-(5,5- dioxydibenze [b, d] bithiophene -3,7- base) naphthoic acid ethyl ester is completely dissolved
In purification anhydrous tetrahydro furan, under normal temperature conditions, alkyl grignard reagent is added, is heated to 80 DEG C, react 16h, changed
Conjunction object 3,7- bis- (2- (2- dialkyl group alcohol -2- base) dibenzo [b, d] thiophene] 5,5- dioxide；
(4) by compound 3,7- bis- (2- (2- dialkyl group alcohol -2- base) dibenzo [b, d] thiophene] 5,5- dioxide be dissolved in it is anhydrous
In methylene chloride, glacial acetic acid is added, reacts 1h, obtains 12,12,15,15- tetraalkyl -12,15- dihydro of white solid after purification
Dibenzo [3 '-d of 3,2-b:2 '] thiophene 6,6- dioxide；
(5) by compound 12,12,15,15- tetraalkyl -12,15- dihydro-dibenzo [3 '-d of 3,2-b:2 '] thiophene 6,6- dioxy
Compound is dissolved in anhydrous chloroform, under cryogenic, bromine is added and carries out bromination, obtains white solid bromination-after purification
12,12,15,15- tetraalkyl -12,15- dihydro-dibenzo [3 '-d of 3,2-b:2 '] thiophene 6,6- dioxide；
(6) C-C coupling reaction or C-N coupling reaction
(i) C-C coupling reaction: under inert gas environment, by bromination -12,12,15,15- tetraalkyl -12,15- dihydro-dibenzos
[3,2-b:2 ' 3 '-d] thiophene 6,6- dioxide are dissolved in tetrahydrofuran, and aryl-boric acid ester or aryl boric acid, potassium carbonate is added
Aqueous solution and tetrakis triphenylphosphine palladium carry out Suzuki coupling reaction, obtain after purification described based on sulphur dibenzofuran acene unit
Electroluminescent material；
(ii) C-N coupling reaction: under inert gas environment, by bromination -12,12,15,15- tetraalkyl -12,15- dihydro-dibenzos
[3,2-b:2 ' 3 '-d] thiophene 6,6- dioxide are dissolved in toluene solution, and fragrant amine monomers, tert-butyl sodium alkoxide, palladium acetate are added
And tri-tert-butylphosphine, C-N coupling reaction is carried out, obtains the electroluminescence material based on sulphur dibenzofuran acene unit after purification
Material.
5. method according to claim 4, which is characterized in that in synthesis step, the inert gas is argon gas；The step
(5) in, the temperature of the low temperature is -20~25 DEG C, described 12,12,15,15- tetraalkyl -12,15- dihydro-dibenzos [3,2-
3 '-d of b:2 '] molar ratio of thiophene 6,6- dioxide and bromine is 1:1~12.
6. method according to claim 4, which is characterized in that in the C-C coupling reaction of the step (6), the bromination -12,
12,15,15- tetraalkyl -12,15- dihydro-dibenzo [3 '-d of 3,2-b:2 '] thiophene 6,6- dioxide, aryl-boric acid ester or virtue
The molar ratio of ylboronic acid, potassium carbonate and tetrakis triphenylphosphine palladium is 1:2~6:5~10:0.02~0.1, and C-C coupling reaction is
At 50~120 DEG C, react 8~48 hours.
7. method according to claim 4, which is characterized in that in the C-N coupling reaction of the step (6), the bromination -12,
12,15,15- tetraalkyl -12,15- dihydro-dibenzo [3 '-d of 3,2-b:2 '] thiophene 6,6- dioxide, fragrant amine monomers, uncle
The molar ratio of butyl sodium alkoxide and palladium acetate is 1:1~12:4.1~10:0.02~0.1；Palladium acetate and tri-tert-butylphosphine rub
You are than being 1:1~4, and the molar ratio of palladium acetate and tri-tert-butylphosphine is 1:2, and the C-N coupling reaction is at 50~120 DEG C, instead
It answers 8~48 hours.
8. the application of the electroluminescent material of claim 1, it is characterised in that: the electroluminescent material is used for light-emitting diodes
Pipe, the luminescent layer of light emitting diode, organic field effect tube, organic solar batteries or organic laser diode.
9. application according to claim 8, which is characterized in that include the following steps, by the electroluminescent material with having
Solvent dissolution, then by spin coating, inkjet printing or printing film forming, the organic solvent is chlorobenzene, dichloro-benzenes, toluene, diformazan
At least one of benzene, tetrahydrofuran, chloroform.
10. application according to claim 8, which is characterized in that the structure of the LED device successively includes layer
Folded substrate, anode layer, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer, or
Person successively includes substrate, cathode layer, electron injecting layer, electron transfer layer, luminescent layer, the hole transmission layer, hole injection of stacking
Layer and anode layer.
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