A kind of and fluorene derivative and its organic electroluminescence deviceTechnical field
The present invention relates to organic photoelectrical material technical fields, and in particular to a kind of and fluorene derivative and its organic electroluminescentDevice.
Background technology
With the progress of information industry, traditional display has been unable to meet the requirement of people, such as：Cathode-ray tube(cathode ray tube, CRT) display volume is big, driving voltage is high；Liquid crystal display (liquid crystalDisplay, LCD) brightness is low, narrow viewing angle, operating temperature range are small；Plasma display (plasma display panel,PDP it) involves great expense, resolution ratio is not high, power consumption is big.
Organic electroluminescent LED (organic light-emitting diodes, OLEDs) is as a kind of completely newDisplay technology possesses the unmatched advantage of existing display technology in each performance, such as have it is all solid state, from main light emission, brightnessHeight, high-resolution, visual angle wide (170 degree or more), fast response time, thickness is thin, it is small, light-weight, can be used flexible base board,Low-voltage direct-current drives (3-10V), low in energy consumption, operating temperature range is wide etc. so that its application market is very extensive, such as illuminatesSystem, communication system, car-mounted display, portable electronic device, fine definition show even military field.
Electroluminescent organic material is constantly realized in recent years to be broken through, and the progress to attract people's attention is achieved, to traditionalDisplay material constitutes strong challenge.After flexible OLED commercialization, associated scientific research and business in the world at presentStrength is all in the work for the development this respect done one's utmost.Although electroluminescent organic material research have been achieved with it is huge atFruit, but OLED also has some urgent problems to be solved during commercialized.
Luminescent material is divided into fluorescent material and phosphor material, and the forming method of luminescent layer is that phosphorus is adulterated in fluorescent host materialThe method of method and fluorescent host material doping fluorescent (organic matter for including nitrogen) dopant of luminescent material (organic metal).It is commonMaterial of main part can generally be divided into several, such as hole transport material of main part, electron-transport material of main part, bipolar material of main part, lazyProperty material of main part, fluorescence complex material of main part and phosphorescent complexes material of main part.
In the organic luminescent device prepared using phosphor material, worked as mostly containing trianilino group material using TPD etc.Make the main body luminescent material of luminescent layer.However, the thermal stability of this kind of material is poor, lead to organic hair using phosphor materialThe service life of optical device is shorter, thus reduces the usage degree of such material.The better material of new performance how is designed to carry outIt adjusts, is always those skilled in the art's urgent problem to be solved.
Invention content
The object of the present invention is to provide a kind of and fluorene derivative and its organic electroluminescence device, in the present invention and fluorenes spreads outBiology has larger conjugate planes structure so as to provide high electron mobility；Short of electricity subbase group is introduced, is more conducive to connectBy electronics；Introduce bridged linkage, increase compound molecular weight, so as to get material there is high glass-transition temperature and canPrevent the effect of crystallization.It is used the compound as the material of main part in luminescent layer and manufactured organic electroluminescence device,The advantage that driving voltage is low, luminous efficiency is high is shown, is the luminous organic material of function admirable.
Present invention firstly provides a kind of and fluorene derivatives, have structure shown in following general formula (I)：
A is indicated by general formula (II)：
Wherein R is selected from methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, n-hexyl, phenyl, xenyl or two RConnection cyclization；
X it is identical or different be selected from CR6Or N, wherein R6It is identical or different not take selected from H, halogen, substitution orThe C1-C30 alkyl in generation, the aryl of substituted or unsubstituted C6-C30, substituted or unsubstituted C3~C30 heteroaryl in oneKind；
L is selected from the divalent of singly-bound, the divalent aryl of substituted or unsubstituted C6-C30, substituted or unsubstituted C3~C30One kind in heteroaryl；
B is indicated by general formula (III)：
Wherein R1Selected from hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6-The aryl of C30, substituted or unsubstituted C3~C30 heteroaryl in one kind；
X1、X2It is independent to be selected from CR3R4、NR2, S, O or singly-bound, wherein R2、R3、R4It is independent to be selected from hydrogen, substitution or unsubstitutedC1-C30 alkyl, the aryl of substituted or unsubstituted C6-C30, one in the heteroaryl of substituted or unsubstituted C3~C30Kind；
X3Selected from CR5Or N, wherein R5Selected from hydrogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6-The aryl of C30, substituted or unsubstituted C3~C30 heteroaryl in one kind.
Preferably, any one of the A in structure as follows：
Preferably, any one of the L in singly-bound or structure as follows：
Preferably, the B is indicated by any one of general formula (III-a)-(III-h)：
Wherein R1Selected from hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6-The aryl of C30, substituted or unsubstituted C3~C30 heteroaryl in one kind；
Wherein R2、R3、R4It is independent to be selected from hydrogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C3~C30 heteroaryl in one kind；
Wherein X3Selected from CR5Or N, wherein R5Selected from hydrogen, substituted or unsubstituted C1-C30 alkyl, substitution or unsubstitutedThe aryl of C6-C30, one kind in the heteroaryl of substituted or unsubstituted C3~C30.
Preferably, any one of described and fluorene derivative in structure as follows：
The present invention also provides a kind of organic electroluminescence device, the organic electroluminescence device include anode, cathode withAnd several organic function layers between the anode and the cathode, the organic function layer contain described and fluorenesDerivative any one or at least two combination.
Preferably, the organic function layer includes luminescent layer, the luminescent layer include described and fluorene derivative it is arbitraryIt is a kind of or at least two combination.
Preferably, described and fluorene derivative is used as material of main part in luminescent layer.
Beneficial effects of the present invention：
For the problems such as thermal stability for solving phosphorescent light body material in the prior art is poor, and service life is short, the present invention is firstFirst provide it is a kind of containing and fluorene structured derivative, the compound there is structure shown in formula (I).In the present invention and fluorene derivativeWith larger conjugate planes structure, so as to provide high electron mobility；Introduce electron deficient dibenzofurans, dibenzoThe structures such as thiophene, acridine, phenoxazines, phenothiazines, are more conducive to receive electronics, make it have good transmission performance；Introduce bridgeLink structure, on the one hand can increase compound molecular weight, so as to get material have and high glass-transition temperature and can preventThe effect only crystallized improves its film forming on the other hand so that this analog derivative has certain distortion on stereoeffect.It is used the compound as the material of main part in luminescent layer and manufactured organic electroluminescence device, shows driving voltageAdvantage low, luminous efficiency is high is the luminous organic material of function admirable.
Specific implementation mode
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, stillIt should be appreciated that these descriptions are only the feature and advantage further illustrated the present invention, rather than to the claims in the present inventionLimitation.
It should be noted that unless otherwise prescribed, the meaning of scientific and technical terminology used in the present invention and people in the artThe meaning that member is generally understood is identical.
Alkyl of the present invention refers to alkyl made of minusing a hydrogen atom in alkane molecule, can be straight chain alkaneBase, branched alkyl or naphthenic base, example may include methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tertiary fourthBase, amyl, isopentyl, cyclopenta, cyclohexyl etc., but not limited to this.
Aryl of the present invention refer to aromatic hydrocarbon molecule aromatic core carbon on remove a hydrogen atom after, be left univalent perssad it is totalClaiming, can be monocyclic aryl or fused ring aryl, example may include phenyl, xenyl, naphthalene, anthryl, phenanthryl or pyrenyl etc., butIt is without being limited thereto.
Heteroaryl of the present invention refers to the total of the group that one or more aromatic core carbon are substituted by hetero atom in arylClaim, the hetero atom includes but not limited to oxygen, sulphur, nitrogen or silicon atom, and the heteroaryl can be monocycle or condensed ring, and example can wrapInclude pyridyl group, phenothiazinyl, phenoxazine base, pyrimidine radicals, benzo pyrimidine radicals, carbazyl, triazine radical, benzothiazolyl, benzo miaowOxazolyl, acridinyl etc., but not limited to this.
Divalent aryl of the present invention refer to aromatic hydrocarbon molecule two aromatic core carbon on respectively remove a hydrogen atom after, be leftBivalent group general name, can be valentbivalent monocyclic aryl or divalent fused ring aryl, such as can be selected from phenylene, sub- biphenylBase, sub- terphenyl, naphthylene, anthrylene, phenanthrylene, sub- pyrenyl, fluorenylidene or sub- benzo phenanthryl etc., but not limited to this.
Divalent heteroaryl radical of the present invention refers to that one or more of divalent aryl aromatic core carbon is replaced to obtain by hetero atomGroup general name, the hetero atom includes but not limited to oxygen, sulphur or nitrogen-atoms, and the divalent heteroaryl radical can be valentbivalent monocyclicHeteroaryl or divalent fused ring heteroaryl, such as sub-pyridyl group, sub- quinolyl, sub- carbazyl, sub- thienyl, sub- benzo can be selected fromThienyl, furylidene, sub- benzofuranyl, sub- pyrimidine radicals, sub- benzo pyrimidine radicals, sub- imidazole radicals or sub- benzimidazolyl etc.,But not limited to this.
In substituted alkyl of the present invention, substituted aryl, substituted heteroaryl etc., the substituent group can be independentSelected from D-atom, cyano, nitro, halogen atom, the alkyl of C1-C10, the alkoxy of C1-C10, the alkylthio group of C1-C10, C6-The heteroaryl of the aryl of C30, the aryloxy group of C6-C30, the arylthio of C6-C30, C3-C30, the silylation of C1~C30, C2~The alkylamino radical of C10, aryl amine of C6~C30 etc., such as D-atom, cyano, nitro, halogen, methyl, ethyl, propyl, isopropylBase, tertiary butyl, methoxyl group, methyl mercapto, phenyl, xenyl, terphenyl, naphthalene, anthryl, phenanthryl, benzo phenanthryl, base, pyreneBase, fluorenyl, 9,9- dimethyl fluorenyl, benzyl, phenoxy group, thiophenyl, hexichol amido, dimethylamino, carbazyl, 9- phenyl clicksOxazolyl, furyl, thienyl, triphenyl silicon substrate, trimethyl silicon substrate, trifluoromethyl, phenothiazinyl, phenoxazine group, acridinyl, piperazinePiperidinyl, pyridyl group, pyrazinyl, triazine radical, pyrimidine radicals etc., but not limited to this.
Present invention firstly provides a kind of and fluorene derivatives, have the structural formula as shown in formula (I)：
A is indicated by general formula (II)：
Wherein R is selected from methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, n-hexyl, phenyl, xenyl or two RConnection cyclization；
X it is identical or different be selected from CR6Or N, wherein R6It is identical or different not take selected from H, halogen, substitution orThe C1-C30 alkyl in generation, the aryl of substituted or unsubstituted C6-C30, substituted or unsubstituted C3~C30 heteroaryl in oneKind；
L is selected from the divalent of singly-bound, the divalent aryl of substituted or unsubstituted C6-C30, substituted or unsubstituted C3~C30One kind in heteroaryl；
B is indicated by general formula (III)：
Wherein R1Selected from hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6-The aryl of C30, substituted or unsubstituted C3~C30 heteroaryl in one kind；
X1、X2It is independent to be selected from CR3R4、NR2, S, O or singly-bound, wherein R2、R3、R4It is independent to be selected from hydrogen, substitution or unsubstitutedC1-C30 alkyl, the aryl of substituted or unsubstituted C6-C30, one in the heteroaryl of substituted or unsubstituted C3~C30Kind；
X3Selected from CR5Or N, wherein R5Selected from hydrogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6-The aryl of C30, substituted or unsubstituted C3~C30 heteroaryl in one kind.
Preferably, any one of the A in structure as follows：
Preferably, any one of the L in singly-bound or structure as follows：
Preferably, the B is indicated by any one of general formula (III-a)-(III-h)：
Wherein R1Selected from hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6-The aryl of C30, substituted or unsubstituted C3~C30 heteroaryl in one kind；
Wherein R2、R3、R4It is independent to be selected from hydrogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C3~C30 heteroaryl in one kind；
Wherein X3Selected from CR5Or N, wherein R5Selected from hydrogen, substituted or unsubstituted C1-C30 alkyl, substitution or unsubstitutedThe aryl of C6-C30, one kind in the heteroaryl of substituted or unsubstituted C3~C30.
Preferably, any one of described and fluorene derivative in structure as follows：
It is enumerated above some specific structure types of the present invention and fluorene derivative, but the invention is not limited inThese listed chemical constitutions, every based on structure shown in formula (I), R, R1、R2、R3、R4All for group as defined aboveIt should be included.
Of the present invention and fluorene derivative, preparation method are as follows：
Dibromide containing A and the coupling of the boric acid ester compound containing L, by gained compound and containing the acid esterification of BObject is closed to be coupled to obtain described and fluorene derivative.
The present invention limitation not special to above-mentioned reaction be using popular response well-known to those skilled in the artCan, the preparation method is easy to operate, is readily produced.
The present invention also provides a kind of organic electroluminescence device, the organic electroluminescence device is those skilled in the artKnown organic electroluminescence device, organic electroluminescence device of the present invention include anode, cathode and are located atSeveral organic function layers between the anode and cathode, the organic function layer includes described and fluorene derivative is arbitraryIt is a kind of or at least two combination.The organic function layer may include hole injection layer, hole transmission layer, electronic barrier layer,At least one layer in luminescent layer, hole blocking layer, electron transfer layer and electron injecting layer, the preferably described organic function layer include hairPhotosphere, the luminescent layer include it is described and fluorene derivative any one or at least two combination.More preferably described and fluorenesDerivative is used as material of main part in luminescent layer.
The present invention is not particularly limited the source of the raw material employed in following embodiment, can be commercial product orIt is prepared using preparation method well-known to those skilled in the art.
Embodiment 1：
The preparation of compound 2
The preparation of intermediate A
2-1 (31.81g, 100.00mmol) is added in the 50.0mL concentrated sulfuric acids, 2h is stirred at room temperature, finds reaction solution colorTurn yellow, be slowly added in 300.0mL water, then has solid precipitation with sodium hydroxide neutralization reaction liquid, filtered after cooling down to neutralSolid 1-2 (21.18g, 75.56mmol).2-2 is dissolved in 150ml ethylene glycol, the hydrazine hydrate reflux that 40ml 30% is added is anti-It answers, during reaction solution cooling is fallen back, filtering precipitation obtains white solid 2-3 (14.29g, 56.12mmol).1-3 is dissolved inIn 150mL toluene, 30g 2-4,1.5g four butyl bromation amines, reflux is added, cold filtration column chromatography obtains white powder(14.76g, 47.55mmol).Finally by its bromo, white powder is dissolved in 100.0mL chloroforms, it is anhydrous that 1.0g is added20.0mL bromines are added dropwise in iron chloride, zero degree, and reaction finishes, washs multiple reaction solution with sodium sulfite saturated solution, be spin-dried for, obtain whiteColor solid (18.83g, 40.22mmol).
The preparation of compound 2-6
By tri-tert-butylphosphine (toluene solution of the 1.0M of 4.4mL, 1.48g, 0.05mmol), palladium (0.4g,1.83mmol) and sodium tert-butoxide (52.7g, 549mmol) is added to 2-6-a (20.423g, 73.42mmol) and 2-6-cThe solution of (11.53g, 73.42mmol) in degassed toluene (500mL), and the mixture is heated 2 hours under reflux.The reaction mixture is cooled to room temperature, is filtered with dilution with toluene and via diatomite.The filtrate water is diluted, first is used in combinationBenzene extracts, and merges organic phase, it is evaporated under vacuum.By the residue via silica gel (heptane/dichloromethane)It is filtered, and is crystallized from isopropanol.Obtain 2-6-b 19.51g, yield 75%；By gained bromide 2-6-b(7.89g, 20mmol), connection boric acid pinacol ester (6.22g, 24mmol), 1,1 '-bis- (diphenylphosphine)-ferrocene-palladium chlorides(II) dichloromethane complex (0.49g, 0.6mmol), potassium acetate (5.90g, 60mmol) and 79ml toluene react under refluxIt is 16 hours, cooling, 26ml water is added, stirs 30 minutes, isolates organic phase, filtered by short bed of diatomaceous earth, it then will be organicSolvent evaporates, and gained crude product recrystallizes in heptane/toluene, obtains compound 2-6 6.58g, yield 82%.
The preparation of compound 2
Under argon atmospher, by 2-6 (20.07g, 50mmol), intermediate A (23.30g, 50mmol), tetrakis triphenylphosphine palladium(0.35g, 0.3mmol), toluene (43ml), aqueous sodium carbonate (2M, 21ml) are added in flask, and back flow reaction 8 hours is coolingIt to room temperature, is extracted with toluene, organic phase saturated common salt water washing, after organic phase drying, is purified with column chromatography, obtain chemical combination2 32.14g of object, yield 75%.Mass spectrum m/z：857.15 (calculated values：857.16).Theoretical elemental content (%) C60H44N2S2：C,84.08；H, 5.17；N, 3.27；S, 7.48 actual measurement constituent contents (%)：C, 84.07；H, 5.16；N, 3.26；S, 7.47.It is above-mentionedConfirm that it is target product 2 to obtain product.
Embodiment 2:
The preparation of compound 22
The preparation of compound 22
2-4 in embodiment 1 is replaced with into 22-4 as shown above, 2-6 replaces with 22-6 as shown above and obtains compound 22.Mass spectrum m/z：1041.31 (calculated value：1041.32).Theoretical elemental content (%) C80H52N2：C, 92.28；H, 5.03；N, 2.69Survey constituent content (%)：C, 92.27；H, 5.02；N, it is target product 22 that 2.68 above-mentioned confirmations, which obtain product,.
Embodiment 3:
The preparation of compound 39
The preparation of compound 39-6
With in embodiment 1 compound 2-6 prepare it is identical.
The preparation of compound 39
2-4 in embodiment 1 is replaced with into 39-4 as shown above, 2-6 replaces with 39-6 as shown above, obtains compound39.Mass spectrum m/z：915.11 (calculated values：915.12).Theoretical elemental content (%) C68H42N4：C, 89.25；H, 4.63；N, 6.12Survey constituent content (%)：C, 89.26；H, 4.64；N, 6.13.It is target product 39 that above-mentioned confirmation, which obtains product,.
Embodiment 4:
The preparation of compound 48
The preparation of compound 48-6
With in embodiment 1 compound 2-6 prepare it is identical.
The preparation of compound 48
2-6 in embodiment 1 is replaced with into 48-6 as shown above, obtains compound 48.Mass spectrum m/z：1255.54 (calculatingValue：1255.53).Theoretical elemental content (%) C90H62N8：C, 86.10；H, 4.98；N, 8.92 actual measurement constituent contents (%)：C,86.11；H, 4.97；N, 8.93.It is target product 48 that above-mentioned confirmation, which obtains product,.
Embodiment 5:
The preparation of compound 85
The preparation of 85-6
Under argon atmospher, by 85-6-a (4.89g, 15mmol), 85-6-b (4.76g, 14.3mmol), tetrakis triphenylphosphine palladium(0.35g, 0.3mmol), toluene (43ml), aqueous sodium carbonate (2M, 21ml) are added in flask, and back flow reaction 8 hours is coolingIt to room temperature, is extracted with toluene, organic phase saturated common salt water washing, after organic phase drying, is purified with column chromatography, obtain brominationObject 85-6-c；By 85-6-c (8.11g, 20mmol), connection boric acid pinacol ester (6.22g, 24mmol), 1,1 '-bis- (diphenylPhosphine)-ferrocene-palladium chloride (II) dichloromethane complex (0.49g, 0.6mmol), potassium acetate (5.90g, 60mmol) and79ml toluene reacts 16 hours under reflux, cooling, and 26ml water is added, and stirs 30 minutes, isolates organic phase, pass through short diatomNative bed filtering, then evaporates organic solvent, gained crude product recrystallizes in heptane/toluene, obtains solid 85-6.
The preparation of compound 85
2-6 in embodiment 1 is replaced with into 85-6 as shown above, obtains compound 85.Mass spectrum m/z：959.23 (calculateValue：959.24).Theoretical elemental content (%) C68H46O2S2：C, 85.15；H, 4.83；O, 3.34；S, 6.68 actual measurement constituent contents(%)：C, 85.14；H, 4.84；O, 3.33；S, 6.69.It is target product 85 that above-mentioned confirmation, which obtains product,.
Embodiment 6:
The preparation of compound 90
The preparation of compound 90
85-6 in embodiment 5 is replaced with into 90-6 as shown above, obtains compound 90.Mass spectrum m/z：1045.34 (calculatingValue：1045.35).Theoretical elemental content (%) C90H62N4：C, 91.92；H, 5.40；N, 2.68 actual measurement constituent contents (%)：C,91.93；H, 5.41；N, 2.69.It is target product 90 that above-mentioned confirmation, which obtains product,.
Embodiment 7:
The preparation of compound 99
The preparation of compound 99
85-6 in embodiment 5 is replaced with into 99-6 as shown above, obtains compound 99.Mass spectrum m/z：1225.50 (calculatingValue：1225.1).Theoretical elemental content (%) C92H60N2O2：C, 90.17；H, 4.94；N, 2.29；O, 2.62 actual measurement constituent contents(%)：C, 90.18；H, 4.93；N, 2.28；O, 2.61.It is target product 99 that above-mentioned confirmation, which obtains product,.
Embodiment 8:
The preparation of compound 102
The preparation of compound 102
85-6 in embodiment 5 is replaced with into 102-6 as shown above, obtains compound 102.Mass spectrum m/z：1199.51 (meterCalculation value：1199.52).Theoretical elemental content (%) C90H62N4：C, 90.12；H, 5.21；N, 4.67 actual measurement constituent contents (%)：C,90.13；H, 5.22；N, 4.68.It is target product 102 that above-mentioned confirmation, which obtains product,.
[comparison Application Example]
Transparent anode electrode ito substrate is cleaned each 15 minutes with deionized water, acetone, EtOH Sonicate respectively, is then existedIt is cleaned 2 minutes in plasma cleaning device, dry and is evacuated to 5 × 10-5Pa.Then by treated, ito substrate steamsPlating.One layer of HAT-CN is deposited first as hole transmission layer, evaporation rate 0.1nm/s, evaporation thickness 10nm.Followed by it sends outThe light emitting layer material CBP/Ir (ppy) is deposited in the vapor deposition of photosphere, mixing3, as green light phosphorescence dopant material, doping is denseDegree is 5%, evaporation rate 0.005nm/s, evaporation thickness 30nm, the TPBI of 50nm is then deposited as electron transfer layer,Evaporation rate is 0.01nm/s, is used as cathode, thickness 30nm for vacuum evaporation Al layers on the electron transport layer.
[Application Example 1-8]
By the CBP compared in Application Example change into shown compound 2 in embodiment 1-8,22,39,48,85,90,99、102。
Table 1 is compound prepared by the embodiment of the present invention and compares the characteristics of luminescence test of the luminescent device of substance preparationAs a result.
The characteristics of luminescence of [table 1] luminescent device is tested
The above result shows that the compound of the present invention is applied to as green light material of main part in organic electroluminescence device,Luminous efficiency is high, is luminous organic material of good performance.
Although the present invention has carried out special description with exemplary embodiment, but it is understood that without departing from claimDefined by the case of spirit and scope of the invention, those of ordinary skill in the art can carry out various forms and details to itOn change.