CN101250404A - Blue-light emitting functional material and uses thereof - Google Patents
Blue-light emitting functional material and uses thereof Download PDFInfo
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- CN101250404A CN101250404A CNA2007101920171A CN200710192017A CN101250404A CN 101250404 A CN101250404 A CN 101250404A CN A2007101920171 A CNA2007101920171 A CN A2007101920171A CN 200710192017 A CN200710192017 A CN 200710192017A CN 101250404 A CN101250404 A CN 101250404A
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Abstract
The invention relates to a blue light emitting functional material and the application, which relates to star shooting shape oligomer blue light emitting functional material and the application. The material is monodisperse star shooting shape oligomer on the basis of minami carbazolyl element, the oligomer has the structure of a general formula 1, the material contains minami carbazolyl element, has monodisperse star shooting shape three-dimensional space structure, is easy to form stable amorphous state, and displays excellent filming property and light emitting property. The material has potential application in the fields such as organic electroluminescence, organic laser, organic non-linear optical material and the like. Particularly, organic electroluminescent devices which utilize the functional material to be blue luminescent material have improved luminescent brightness, device efficiency, color purity and spectroscopic stability.
Description
Technical field
The invention belongs to photoelectric material and applied technical field, be specifically related to clear and definite the having of a kind of structure and single disperse oligomer material that star penetrates shape and in the application of field of photovoltaic materials.More specifically, the present invention relates to a kind ofly comprise three and the oligomer functional materials of carbazole primitive, this material has single star that disperses and penetrates the shape three-D space structure, and it is applied to organic electronics fields such as organic electroluminescent, organic laser, organic non-linear optical material.
Technical background
In the evolution of organic electroluminescence device (OLEDs), in order to realize full-color demonstration, blue light material is most important.In order to realize the blue emission of stability and high efficiency, people have developed a large amount of polymkeric substance, oligomer system, but the blue light OLED material that can really have practical value is but very limited.Fluorescent emission performance and good light, thermostability become a kind of very promising blue light material efficiently owing to it for poly-fluorenes and derivative thereof.But a troubling problem is exactly that this class material generally shows relatively poor spectrum-stable performance when making the device use.The effect of heat or electric current can make the spectrum of these materials that tangible red shift phenomenon takes place, and occurs the long wavelength emission of green glow or even gold-tinted in spectrum.The generation of long wavelength emission band can cause the reduction of purity of color of work-ing life, quantum yield and the device of device, has greatly limited the widespread use of poly-fluorenes class material.For spectrographic red shift people generally owing to (as the gathering of material or the generation of excimer) (Adv.Funct.Mater.2007 of physics, 17,538.) or chemical (defective of chemical structure such as the generation of Fluorenone etc.) (Adv.Mater.2002,14,477.) degenerative process of two aspects.In order to stablize blue emission, people have taked many modes to overcome this problem, for example, introduce its form stable performance of the fluorene structured raising of inflexible spiral shell (Advanced Materials, 2000,12 (11): 828-831.), the chain structure of constructing distortion reduces chain interphase interaction (Macromolecules, 2001,34 (17): 5854-5859.), introduce the bigger side group of volume and increase sterically hindered blanketing effect (Journal of the American Chemical Society, 2001,123 (5): 946-953.Journal of the American Chemical Society, 2001,123 (29): 6965-6972.) and poly-fluorene material (Chemistry of Materials, 1999,11 (7): 1800-1805.) or the like of preparation with crosslinking structure.But these methods more or less all exist certain weak point.That how to realize poly-fluorenes class functional materials stability and high efficiency blue coloured electroluminously remains challenging problem.
Different with polymkeric substance, single conjugated structure oligomer that disperses has clear and definite structure and chain length, shows more superior structural homogeneity and chemical purity.For the OLED device, the chemical purity of material and structural homogeneity are the important parameters that influences its device performance, because the impurity of trace or chemical imperfection all will cause the cancellation of exciton in the device working process and the inefficacy of device in the luminescent material.Nearest studies show that, single device performance that disperses the oligomerization fluorenes and spectrum stability be obvious much superior than poly-fluorene material just.But, synthesize the oligomer of enough chain lengths satisfies device application so that they have enough mechanical propertys requirement, its process is very loaded down with trivial details, time-consuming.The long oligomer of short chain need come fabricate devices and is easy to form crystal region and the amorphous thin film that can not form the homogeneous of form stable usually by the method for steaming empty evaporation.Being created in the device working process of crystallizing field is disadvantageous, and it will cause the generation that is separated and can make light generation scattering and loss is unfavorable for the injection and the transmission of electric charge simultaneously.Therefore, design has good morphological stability, is not easy to take place phase morphology and changes, be not easy to the crystalline amorphous material and have great importance for the performance that improves the OLED device.
Summary of the invention
Technical problem: the purpose of this invention is to provide a kind of blue-light emitting functional material and application thereof, this material can be used to make the star-like oligomer blue light material of organic electroluminescence device, the light of its luminous efficiency, material, thermostability and film-forming properties are improved, and have overcome easy crystallization of material and accumulative shortcoming.More particularly, introducing three and carbazole primitive make up has single dispersing material that star is penetrated the shape structure, because its three-dimensional space steric effect, make interaction and accumulation between the stiff molecule chain be restricted, the crystallinity that has suppressed material effectively, improve amorphous performance and film forming properties, reduced the cancellation effect of material when solid-state simultaneously, improved the blue emission performance of material.
Another object of the present invention provides a kind of el light emitting device that adopts this blue light emitting material as luminescent material.More specifically, it penetrates shape oligomer blue light material by using this star, has improved luminosity, device efficiency, purity of color and the stability of photoluminescence of organic electroluminescence device.
Technical scheme: that realizes stability and high efficiency blue coloured electroluminously remains challenging problem.
Especially, use it to have the device performance of improvement as the electroluminescent device of blue emitting material, its purity of color and spectrum stability are improved.
One aspect of the present invention provides a kind of blue-light emitting functional material, promptly contains three and the star-like oligomer material of carbazole primitive, and it has the structure as shown in the formula 1:
Wherein, R
1To R
3Respectively do for oneself the independently cycloalkyl of heteroaralkyl, replacement or unsubstituted C5-C30 aryloxy, replacement or unsubstituted C2-C30 heteroaryloxy, replacement or the unsubstituted C3-C30 of heteroaryl, replacement or unsubstituted C6-C30 aralkyl, replacement or the unsubstituted C2-C30 of aryl, replacement or the unsubstituted C2-C30 of alkyl, replacement or the unsubstituted C6-C30 of hydrogen, replacement or unsubstituted C1-C30 and the Heterocyclylalkyl of replacement or unsubstituted C2-C30;
R
4To R
12The independently hydrogen of respectively doing for oneself;
Ar is the heteroaryl of aryl, replacement or the unsubstituted C2-C30 of replacement or unsubstituted C6-C30;
X is a capping group, is selected from the heteroaryl of aryl, replacement or unsubstituted C2-C30 of alkoxyl group, replacement or unsubstituted amino, replacement or the unsubstituted C6-C30 of alkyl, replacement or the unsubstituted C1-C30 of hydrogen, hydroxyl, carboxyl, aldehyde radical, cyano group, halogen atom, replacement or unsubstituted C1-C30;
N represents the number of repeat unit of Ar aryl, is the integer between the 1-5.
Described Ar unit is the combination that is selected from a kind of of the group shown in the following formula 1a to li or some kinds:
Wherein, R
13To R
20Respectively do for oneself the independently cycloalkyl of alkoxyl group, replacement or unsubstituted amino, replacement or the unsubstituted C3-C12 of alkyl, replacement or the unsubstituted C1-C12 of hydrogen, replacement or unsubstituted C1-C12 and the Heterocyclylalkyl of replacement or unsubstituted C2-C12.
Three and the star-like oligomer material of carbazole be the compound of representing by one of following formula 2 or formula 3:
Wherein, R
1To R
3, R
13To R
16The independently alkoxyl group of alkyl, replacement or the unsubstituted C1-C12 of hydrogen, replacement or unsubstituted C1-C12 of respectively doing for oneself.
X is a capping group, is selected from the heteroaryl of aryl, replacement or the unsubstituted C2-C20 of hydrogen, replacement or unsubstituted C6-C20;
N is a number of repeat unit, gets the integer between the 1-4.
More specifically, three and the star-like oligomer material of carbazole be the compound shown in one of following formula 4 or formula 5:
Wherein, n gets 1,2,3, or 4.
Another aspect of the present invention is to provide a kind of organic EL device with this material in the example that is applied as aspect the organic electroluminescent, and it comprises the organic layer that places between the pair of electrodes.This organic layer contains based on three and the star-like oligomer material of carbazole.Can be applicable in Organic Light Emitting Diode, organic laser diode or the nonlinear optical system.
Beneficial effect: introducing three and carbazole primitive make up has single dispersing material that star is penetrated the shape structure, because its three-dimensional space steric effect, make interaction and accumulation between the stiff molecule chain be restricted, the crystallinity that has suppressed material effectively, amorphous performance and film forming properties have been improved, reduce the cancellation effect of material when solid-state simultaneously, improved the blue emission performance of material.By using this star to penetrate shape oligomer blue light material, improved luminosity, device efficiency, purity of color and the stability of photoluminescence of organic electroluminescence device.Thereby such oligomer material has the prospect that is applied to organic electroluminescence device as blue-light emitting functional material efficiently.
Description of drawings:
Fig. 1 is blue coloured electroluminous three and the film absorption spectrum and the fluorescence emission spectrum of carbazole derivative.
Fig. 2 is that device architecture is the electroluminescent spectrum of ITO/PEDOT/ blue coloured electroluminous three and carbazole derivative/Ca/Al based on blue coloured electroluminous three and the single layer device of carbazole derivative.
Embodiment
As can be seen from Figure 1, the maximum absorption wavelength of this material is at 373nm; The peak value of its fluorescence emission spectrum is positioned at 442nm, and an acromion is arranged at the 466nm place simultaneously.As can be seen from Figure 2, the emission peak of the electroluminescent spectrum of this material is positioned at 444nm, and acromion appears at the 466nm place, and the fluorescence emission spectrum under its spectrum peak and peak value and its filminess is identical substantially, illustrates that this material has light emission performance preferably.
By with reference to the accompanying drawings with describe its exemplary embodiment in detail, will be easier to understand These characteristics of the present invention and advantage.
Compound shown in the following formula 1 comprises three and carbazole unit in its main chain backbone.Three and carbazole unit have strong electron donation, have excellent charge transport ability, particularly cavity transmission ability, and an excellent blue emission performance.In addition, because three oligomer arms are connected three and the C-3 of carbazole, C-8 and C-13 position, make and have the bending type structure of distortion more between arm and the nuclear, this will help the order of saboteur in microtexture, can suppress the crystallization of material effectively, improve its amorphous performance and film forming properties; Simultaneously because its three-dimensional space steric effect can suppress interaction and accumulation between the stiff molecule chain effectively, reduced material when solid-state because self aggregation produces the self-quenching phenomenon, help to strengthen its light emission performance.
In the formula, R
1To R
3Respectively do for oneself the independently cycloalkyl of heteroaralkyl, replacement or unsubstituted C5-C30 aryloxy, replacement or unsubstituted C2-C30 heteroaryloxy, replacement or the unsubstituted C3-C30 of heteroaryl, replacement or unsubstituted C6-C30 aralkyl, replacement or the unsubstituted C2-C30 of aryl, replacement or the unsubstituted C2-C30 of alkyl, replacement or the unsubstituted C6-C30 of hydrogen, replacement or unsubstituted C1-C30 and the Heterocyclylalkyl of replacement or unsubstituted C2-C30;
R
4To R
12The independently hydrogen of respectively doing for oneself;
Ar is the heteroaryl of aryl, replacement or the unsubstituted C2-C30 of replacement or unsubstituted C6-C30;
X is a capping group, is selected from the heteroaryl of aryl, replacement or unsubstituted C2-C30 of alkoxyl group, replacement or unsubstituted amino, replacement or the unsubstituted C6-C30 of alkyl, replacement or the unsubstituted C1-C30 of hydrogen, hydroxyl, carboxyl, aldehyde radical, cyano group, halogen atom, replacement or unsubstituted C1-C30;
N represents the number of repeat unit of Ar aryl, is the integer between the 1-5.
The Ar unit of formula 1 is the combination that is selected from a kind of of the group shown in the following formula 1a to li or some kinds:
Wherein, R
13To R
20Respectively do for oneself the independently cycloalkyl of alkoxyl group, replacement or unsubstituted amino, replacement or the unsubstituted C3-C12 of alkyl, replacement or the unsubstituted C1-C12 of hydrogen, replacement or unsubstituted C1-C12 and the Heterocyclylalkyl of replacement or unsubstituted C2-C12.
In the compound shown in the formula 1, when described Ar unit is selected from group shown in top formula 1f or the 1g, can be the compound shown in following formula 2 or the formula 3.To have the substituted fluorene structure be feature to this compound to comprise in the side chain.This oligomer material can have good luminous property and solubility property.Penetrate the shape structure owing to have three arm stars of bending type in the molecular structure of compounds, make the material of gained have good amorphous performance and anti-crystallization energy.Simultaneously, its three-dimensional branched structure makes rigidity conjugated molecule chain by effective isolation, thereby effectively suppress to be excited the formation of excimer, reduced material when solid-state because self aggregation produces the self-quenching phenomenon, make described compound-material have high luminous efficiency and high purity of color.
Wherein, R
1To R
3, R
13To R
16The independently alkoxyl group of alkyl, replacement or the unsubstituted C1-C12 of hydrogen, replacement or unsubstituted C1-C12 of respectively doing for oneself.
X is a capping group, is selected from the heteroaryl of aryl, replacement or the unsubstituted C2-C20 of hydrogen, replacement or unsubstituted C6-C20;
N is a number of repeat unit, gets the integer between the 1-4.
More specifically, formula 2 or formula 3 can be preferably the compound shown in following formula 4 or the formula 5:
Wherein, n gets 1,2,3, or 4.
To be that example illustrates this penetrating property of class star oligomer preparation methods with three shown in formula 2 and carbazole star oligomer preparation methods below.
The preparation of target product comprises three parts, at first is the preparation of multifunction three and carbazole nuclear; Next is the preparation of single functionalization oligomer branch; Be the preparation that star is penetrated the shape target product at last.
Particularly, at first, prepare three functionalization three and carbazole compounds 3 according to reaction scheme Fig. 1.
[reaction scheme Fig. 1]
In the formula, R
1, R
2And R
3The independently alkoxyl group of alkyl, replacement or the unsubstituted C1-C12 of hydrogen, replacement or unsubstituted C1-C12 of respectively doing for oneself.Compound 1 is alkylation three and carbazole derivative, and it sloughs halogen atom under the effect of Pd/C catalyzer, can make compound 2.Obtain tribromide three and carbazole derivative 3 by the selectivity bromination reaction.
Then, according to reaction scheme Fig. 2, adopt the preparation of multiple method progressively to have single functionalization oligomerization fluorenes monomer 5,7,9 and 11 etc. of clear and definite structure and chain length.
[reaction scheme Fig. 2]
In the formula, R
13And R
14The independently alkoxyl group of alkyl, replacement or the unsubstituted C1-C12 of hydrogen, replacement or unsubstituted C1-C12 of respectively doing for oneself;
X is a capping group, is selected from the heteroaryl of aryl, replacement or the unsubstituted C2-C20 of hydrogen, replacement or unsubstituted C6-C20;
Main reaction process mainly comprises following several reaction type:
1) 9,9-dialkyl group-2, the two monomeric preparations of bromo fluorenes of 7-
With 2,7-two bromo fluorenes and excessive bromoalkane are dissolved in the DMSO solution, add potassium hydroxide aqueous solution again, react under nitrogen protection, reaction product is poured in the water, separated organic phase, after the washed several times with water, dry, concentrated repeatedly, recrystallization obtains 9,9-dialkyl group-2, the two bromo fluorenes of 7-;
2) 9, the 9-dialkyl group-monomeric preparation of 2-bromo fluorenes
2-bromo fluorenes and excessive bromoalkane are dissolved in the DMSO solution, add potassium hydroxide aqueous solution again, under nitrogen protection, react, reaction product is poured in the water, separate organic phase, after the washed several times with water, dry, concentrated repeatedly, recrystallization or column chromatography are purified, and obtain 9,9-dialkyl group-2-bromo fluorenes;
3) (reaction process a) for the monomeric acid esterification of single bromination oligomerization fluorenes
N-Butyl Lithium is joined under-78 ℃-0 ℃ in the monomeric tetrahydrofuran solution of single bromination oligomerization fluorenes, and stirring reaction adds excessive 2-isopropoxy-4 down at-78 ℃-0 ℃, 4,5,5-tetramethyl--1,3,2-dioxo borine, the stirring at room reaction is poured reaction mixture in the water into, separate organic phase, after the washed several times with water, dry, concentrated repeatedly, behind silica gel column chromatography, obtain single functionalization oligomerization fluorenes boric acid ester and derivative thereof.
3) the Suzuki linked reaction prepares single functionalization oligomerization fluorenes monomer (reaction process b)
With single functionalization oligomerization fluorenes boric acid ester, 9 of 1.5-10 times of mol ratio, 9-two replaces-2, and the two bromo fluorenes monomers of 7-are dissolved among the THF, and adding mol ratio then is 2-10 2.0M wet chemical doubly.Under nitrogen protection and 50-100 ℃ of temperature, four (triphenyl phosphorus) that add the 0.05%-10% mol ratio are changed palladium, react 24-120 hour.After mixture is chilled to room temperature, use dichloromethane extraction, organic layer washes with water, anhydrous Na
2SO
4Drying after concentrating under reduced pressure is removed solvent, through column chromatography, obtains single bromination oligomerization fluorenes white solid product of higher algebraically.
Repeat above a and b experimentation, can obtain the single functionalization oligomerization fluorenes boric acid ester and the derivative thereof of different chain length.
At last, prepare star according to reaction scheme Fig. 3 by the Suzuki linked reaction and penetrate shape structure three and carbazole target compound.
[reaction scheme Fig. 3]
Wherein, R
1To R
3, R
13To R
16The independently alkoxyl group of alkyl, replacement or the unsubstituted C1-C12 of hydrogen, replacement or unsubstituted C1-C12 of respectively doing for oneself.
X is a capping group, is selected from the heteroaryl of aryl, replacement or the unsubstituted C2-C20 of hydrogen, replacement or unsubstituted C6-C20;
N is a number of repeat unit, gets the integer between the 1-4.
Its preparation method is as follows:
Single functionalization oligomerization fluorenes boric acid ester of tribromide three and carbazole monomers, 3-10 times mol ratio is dissolved among the THF, and adding mol ratio then is 2-10 2.0M wet chemical doubly.Under nitrogen protection and 50-100 ℃ of temperature, four (triphenyl phosphorus) that add the 0.05%-10% mol ratio are changed palladium, react 24-240 hour.After mixture is chilled to room temperature, successively use the HCl aqueous solution, the saturated common salt water washing organic layer of 1M, use anhydrous Na then
2SO
4Dry.Behind the concentrating under reduced pressure, crude product obtains target compound through column chromatography, vacuum drying.
Analogize by above experimental technique and experiment route, single functionalization branch arm that can make other oligomer also and according to similar coupling method obtains three and the carbazole target compound that star is penetrated shape, suc as formula the derivative in 3.At this, different is that the fluorenes monomer that contains the aromatic base replacement prepares as follows.
1) 9,9-diaryl-2, the two monomeric preparations of bromo fluorenes of 7-
At first, with 2, the 7-dibromo fluorenone is dissolved in the ether; add the aryl grignard reagent under nitrogen protection, back flow reaction is prepared 9-hydroxyl-9-aryl-2; 7-two bromo fluorenes, with 9-hydroxyl-9-aryl-2,7-two bromo fluorenes slowly drip in the sulphuric acid soln of aromatic hydrocarbons; back flow reaction is poured reaction product in the water into, separates organic phase; after the washed several times with water, dry, concentrated repeatedly, recrystallization; obtain 9,9-diaryl-2, the two bromo fluorenes of 7-.
2) 9, the 9-diaryl-monomeric preparation of 2-bromo fluorenes
At first, 2-bromine Fluorenone is dissolved in the ether, under nitrogen protection, adds the aryl grignard reagent; back flow reaction is prepared 9-hydroxyl-9-aryl-2-bromo fluorenes, and 9-hydroxyl-9-aryl-2-bromo fluorenes is slowly dripped in the sulphuric acid soln of aromatic hydrocarbons; back flow reaction; reaction product is poured in the water, separated organic phase, repeatedly after the washed several times with water; dry, concentrated; recrystallization obtains 9,9-diaryl-2-bromo fluorenes.
Other experimental technique and experiment route are the same.
Penetrate the shape compound according to the star that embodiment of the present invention obtains, not substituted alkyl wherein can be methyl, ethyl, propyl group, isobutyl-, sec-butyl, the tertiary butyl, amyl group, isopentyl, hexyl and octyl group etc.One or more H atoms on this alkyl can be replaced by following group: halogen atom;-OH;-NO
2-CN; Replacement or unsubstituted amino (as-NH
2-NH (R); or-NH (R ') (R "), wherein R ' and R " be the C1-C10 alkyl independently of one another), heteroaryl or the C6-C20 heteroaralkyl of the aryl of the assorted alkyl of the alkynyl of the thiazolinyl of the haloalkyl of the alkyl of amidino groups, hydrazine, hydrazone, carboxyl, alkylsulfonyl, phosphoryl, C1-C20, C1-C20, C1-C20, C1-C20, C1-C20, C6-C20, C6-C20 aralkyl, C6-C20.
Described unsubstituted cycloalkyl is meant the unit price monocycle system that contains C5-C30 carbon atom.One or more H atoms on this cycloalkyl can be by being replaced at those the identical substituting groups described in the alkyl.
Described unsubstituted aryl is meant the carbocyclic aromatic series system that contains one or more rings, and the form that this ring can be used as with side group interconnects or condenses mutually.Here, aryl can be an aromatic base, and as phenyl, naphthyl, tetralyl etc., in aryl, at least one H atom can be substituted as above-mentioned unsubstituted alkyl.
Described heteroaryl is meant that wherein the annular atoms number is the ring-type aromatic series of 5-30.In the case, at least a different annular atoms is selected from N, O, P, and S.The ring of this heteroaryl can side group form connect or condense.One or more H on this heteroaryl can resemble and be substituted the above-mentioned unsubstituted alkyl.
Described unsubstituted alkoxyl group can be methoxyl group, oxyethyl group, propoxy-, isobutoxy, sec-butoxy, pentyloxy, isopentyloxy, hexyloxy, octyloxy etc.In unsubstituted alkoxyl group second month in a season, at least one H atom can be as being substituted in unsubstituted alkyl.
Described aralkyl is meant some H atoms by low alkyl group, for example the aryl of replacements such as methyl, ethyl, propyl group.Aralkyl can be phenmethyl, styroyl etc.In aralkyl, at least one H atom can be substituted as above-mentioned unsubstituted alkyl.
Described heteroaralkyl is meant the heteroaryl that some H atoms are replaced by low alkyl group.Be included in the heteroaralkyl heteroaryl as previously mentioned.In heteroaralkyl, at least one H atom can resemble and be substituted the above-mentioned unsubstituted alkyl.
The example of described aryloxy comprises phenoxy group and naphthyloxy.One or more H atoms on this aryloxy can resemble and be substituted base the above-mentioned not substituted alkyl and replace.
Described heteroaryloxy can be benzyloxy and phenoxy group etc.In heteroaryloxy, at least one H atom can resemble and be substituted base the above-mentioned unsubstituted alkyl and replace.
Described cycloalkyl is meant the monovalence single-loop system, and wherein carbonatoms is 5-30.In this cycloalkyl, at least one H atom can such as above-mentioned unsubstituted alkyl, be substituted the base replacement.
Described Heterocyclylalkyl specifically is meant and contains the unit price monocycle system that an above annular atoms is heteroatomic 5-30 the carbon atom of N, O, P and S.In this Heterocyclylalkyl, at least one H atom can be substituted as above-mentioned not substituted alkyl.
Described amino can be-NH
2,-NH (R), or-N (R ') (and R "), in the formula, R ' and R " be the alkyl of 1-10 carbon atom independently of one another.
Organic electroluminescence device according to embodiment of the present invention can prepare by the conventional preparation method method of using the electroluminescent polymer material, without any need for special equipment or method.
In this prepared organic electroluminescence device, both can be used as the luminescent layer material according to the functional materials of embodiment of the present invention, also can be used as hole transport layer material.
Because resulting star is penetrated the shape functional materials and had good light emission performance according to the present invention, in organic laser and nonlinear optical organic system, have potential simultaneously and use.
Below, will describe the present invention in detail in conjunction with embodiment more specifically, but described embodiment only is for more specific description, the scope that is not meant to limit the present invention.
Embodiment 1:2,3,7,8,12,13-hexabromo-5,10,15-three hexyls three are synthesizing of carbazole also
2,3,7,8,12,13-hexabromo-three and carbazole (2.45g, 3mmol) and KOH (1.4g 25mmol) is dissolved in THF (100ml), is heated to backflow, and (2.23g 13.5mmol) dropwise joins in the above-mentioned solution backflow 3h to hexyl bromide 1 bromohexane.Mixture is chilled to room temperature, uses CH
2Cl
210%HCl solution, saturated NaCl solution washing organic layer are used in dilution then successively, use anhydrous Na at last
2SO
4Dry.Remove the crude product that obtains behind the organic solvent and use column chromatography product, obtain white solid (2.96g, 92%).
Embodiment 2:5,10,15-three hexyls three are synthesizing of carbazole also
2,3,7,8,12,13-hexabromo-5,10,15-three hexyls three and carbazole (2.40g, 2.24mmol), triethylamine (2.5ml), formic acid (0.68ml) and 10%Pd/C (712.3mg, THF solution (20ml) reflux 0.67mmol) 3 hours.Mixture filters, and filtrate is diluted with chloroform, and anhydrous Na is used in 10% aqueous hydrochloric acid washing
2SO
4Dry organic layer is removed solvent at last.The crude product that obtains uses column chromatography product, obtains white solid powder (1.25 g, 93%).
Embodiment 3:3,8,13-three bromo-5,10,15-three hexyls three are synthesizing of carbazole also
5,10, (1.0g 1.67mmol) is dissolved among the 30ml THF for 15-three hexyls three and carbazole; Under-78 ℃ of temperature, dropwise add DMF (5ml) solution of NBS (0.94g).Mixture rises to room temperature naturally and stirs half an hour under the room temperature again.In an amount of water gaging of mixture impouring, organic layer chloroform extraction, anhydrous Na
2SO
4Dry.Revolve boil off desolventize after, crude product uses column chromatography, and obtains white solid powder (1.15g, 82.4%).
Embodiment 4:9,9-dihexyl-2-(4,4,5,5-tetramethyl--1,3,2-dioxo boric acid ester group) fluorenes synthetic
(15.4mL, the hexane solution of 1.6M 24.6mmol) join 9 under-78 ℃ with n-BuLi, 9-dihexyl-2-bromo fluorenes (8.5g, 20.56mmol) THF (30ml) solution in, stirring reaction 1.5h adds 2-isopropoxy-4 then, 4,5,5-tetramethyl--1,3,2-dioxo borine (5.7g, 30.8mmol).Behind the reaction 12h, reaction mixture is poured in the water, used the extracted with diethyl ether separatory, with the saturated common salt washing, behind the anhydrous sodium sulfate drying, concentrating under reduced pressure is removed solvent.Crude product silica gel column chromatography after concentrating obtains colorless oil thickness product 9,9-dihexyl-2-(4,4,5,5-tetramethyl--1,3,2-dioxo boric acid ester group) fluorenes (8.6g, 91%).
Embodiment 5:9,9-dihexyl-2-bromine two difluorenes synthetic
With 9, and 9-dihexyl-2-(4,4,5,5-tetramethyl--1,3,2-dioxo boric acid ester group) fluorenes (1.74g, 4.6mmol), 9,9-dihexyl-2, (6.8g 13.8mmol) is dissolved among the THF the two bromo fluorenes of 7-, adds 2M K then
2CO
3The aqueous solution (12.0ml, 24.0mmol).Under nitrogen protection, add Pd (PPh
3)
4(100mg, 0.0865mmol) back flow reaction is 2 days.After mixture is chilled to room temperature, use dichloromethane extraction, organic layer washes with water, anhydrous Na
2SO
4Drying after concentrating under reduced pressure is removed solvent, through column chromatography, obtains white solid product 9,9-dihexyl-2-bromine two difluorenes (2.88g, 84%).
Embodiment 6:9,9-dihexyl-2-(4,4,5,5-tetramethyl--1,3,2-dioxo boric acid ester group)-two difluorenes synthetic
(3.14mL, the hexane solution of 1.6M 5.03mmol) join 9 under-78 ℃ with n-BuLi, 9-dihexyl-2-bromine two difluorene (2.5g, 3.35mmol) THF (15ml) solution in, stirring reaction 1.5h adds 2-isopropoxy-4 then, 4,5,5-tetramethyl--1,3,2-dioxo borine (2.05ml, 10.05mmol).Behind the reaction 12h, reaction mixture is poured in the water, used the extracted with diethyl ether separatory, with the saturated common salt washing, behind the anhydrous sodium sulfate drying, concentrating under reduced pressure is removed solvent.Crude product silica gel column chromatography after concentrating obtains white solid product 9,9-dihexyl-2-(4,4,5,5-tetramethyl--1,3,2-dioxo boric acid ester group)-two difluorenes (2.31g, 86%).
Embodiment 7:9,9-dihexyl-2-bromine three difluorenes synthetic
With 9, and 9-dihexyl-2-(4,4,5,5-tetramethyl--1,3,2-dioxo boric acid ester group)-two difluorenes (3.65g, 4.6mmol), 9,9-dihexyl-2, (6.8g 13.8mmol) is dissolved among the THF the two bromo fluorenes of 7-, adds 2M K then
2CO
3The aqueous solution (12.0ml, 24.0mmol).Under nitrogen protection, add Pd (PPh
3)
4(100mg, 0.0865mmol) back flow reaction is 2 days.After mixture is chilled to room temperature, use dichloromethane extraction, organic layer washes with water, anhydrous Na
2SO
4Drying after concentrating under reduced pressure is removed solvent, through column chromatography, obtains white solid product 9,9-dihexyl-2-bromine three difluorenes (4.1g, 83%).
Embodiment 8:9,9-dihexyl-2-(4,4,5,5-tetramethyl--1,3,2-dioxo boric acid ester group)-three difluorenes synthetic.
(3.14mL, the hexane solution of 1.6M 5.03mmol) join 9 under-78 ℃ with n-BuLi, 9-dihexyl-2-bromine three difluorene (3.61g, 3.35mmol) THF (15ml) solution in, stirring reaction 1.5h adds 2-isopropoxy-4 then, 4,5,5-tetramethyl--1,3,2-dioxo borine (2.05ml, 10.05mmol).Behind the reaction 12h, reaction mixture is poured in the water, used the extracted with diethyl ether separatory, with the saturated common salt washing, behind the anhydrous sodium sulfate drying, concentrating under reduced pressure is removed solvent.Crude product silica gel column chromatography after concentrating obtains white solid product 9,9-dihexyl-2-(4,4,5,5-tetramethyl--1,3,2-dioxo boric acid ester group)-three difluorenes (3.0g, 81%).
Embodiment 9:3,8,13-three (9,9-dihexyl fluorenes)-5,10,15-three hexyls three are synthesizing of carbazole also
With 3,8,13-three bromo-5,10, (166.9mg, 0.20mmol), 9, (359.2mg 0.78mmol) is dissolved among the THF fluorenes 9-dihexyl-2-(4,4,5,5-tetramethyl--1,3,2-dioxo boric acid ester group), adds 2M K then for 15-three hexyls three and carbazole
2CO
3The aqueous solution (0.75mL, 1.5mmol).Under nitrogen protection, add Pd (PPh
3)
4(70mg, 0.06mmol) back flow reaction is 5 days.After mixture is chilled to room temperature, successively use the HCl aqueous solution, the saturated common salt water washing organic layer of 1M, use anhydrous Na then
2SO
4Dry.Behind the concentrating under reduced pressure, crude product obtains target compound (162.3mg, 51%) through column chromatography, vacuum drying.
1H?NMR(400Hz，CDCl
3，ppm)：δ8.59(s，3H)，7.92-7.69(m，18H)，7.38-7.33(m，9H)，5.07-5.04(t，6H)，2.08-2.06(m，18H)，1.38-1.10(m，54H)，0.86-0.68(m，39H).
13C?NMR(100Hz，CDCl
3，ppm)：δ151.7，151.2，141.9，141.2，141.0，140.3，139.9，136.9，134.3，127.0，126.4，123.1，122.8，122.0，120.8，120.2，119.9，110.9，110.8，109.3，109.1，55.4，53.7，47.7，47.4，40.7，31.8，31.7，30.1，26.7，24.1，22.8，14.3.MALDI-TOF?MS(m/z)：Calcdfor?C
117H
147N
3，Exact?Mass：1594.16，Mol.Wt.：1595.44；Found：1595.4(M
+)，1511.3([M-C
6H
13]
+)，1427.1([M-2C
6H
13]
+).Anal.Calcd?for?C
117H
147N
3：C，88.08；H，9.29；N，2.63.Found：C，88.06；H，9.18；N，2.59.
Film ultraviolet maximum absorption is 351nm, and solid fluorescence emission maximum peak value is 434nm.
The preparation condition of single layer device (device architecture is ITO/PEDOT/sample/Ca/Al) is: the ITO substrate cleans with acetone, deionized water and Virahol in ultrasonic cleaner, before the beginning spin coating, adopt oxygen plasma treatment 4min, the sheet resistance of ITO is 10-20 Ω/; The thick PEDOT-PSS of about 40nm in the spin coating on ITO, 80 ℃ of dry 3h in vacuum drying oven then; The toluene solution of luminescent material is spin-coated on the PEDOT-PSS, and thickness is about 110-130nm; Then on the evaporation-and aluminium electrode that thin layer 150nm is thick, the pressure of evaporation is 2 * 10
-4Pa, the area of luminous zone are 0.15cm
2Spin coating process and device performance test are all finished in the glove box under a nitrogen atmosphere protection; Device is by the encapsulation of photo-curing epoxy resin and thin packaged glass, and brightness is by the optical diode test of calibration, external quantum efficiency by the integrating sphere test (IS080, Labsphere).(Commision Internationale del ' Eclairage is CIE) by reading after the 1931 observed parameter computed in software for chromaticity coordinates.Individual layer electroluminescent device performance is as follows: trigger voltage 6.1V, high-high brightness 625cd/m
2, maximum external quantum efficiency is 0.24%, chromaticity coordinates (0.17,0.14).
Embodiment 10:3,8,13-three (9,9-dihexyl-two difluorene)-5,10,15-three hexyls three are synthesizing of carbazole also
With 3,8,13-three bromo-5,10, (166.9mg, 0.20mmol), 9, (618.6mg 0.78mmol) is dissolved among the THF-two difluorenes 9-dihexyl-2-(4,4,5,5-tetramethyl--1,3,2-dioxo boric acid ester group), adds 2M K then for 15-three hexyls three and carbazole
2CO
3The aqueous solution (0.75mL, 1.5mmol).Under nitrogen protection, add Pd (PPh
3)
4(70mg, 0.06mmol) back flow reaction is 6 days.After mixture is chilled to room temperature, successively use the HCl aqueous solution, the saturated common salt water washing organic layer of 1M, use anhydrous Na then
2SO
4Dry.Behind the concentrating under reduced pressure, crude product obtains target compound (258 mg, 50%) through column chromatography, vacuum drying.
1H?NMR(400?MHz，CDCl
3，ppm)：δ8.62(s，3H)，7.95-7.65(m，36H)，7.37-7.31(m，9H)，5.07-5.02(t，6H)，2.13-2.05(m，30H)，1.28-1.09(m，99H)，0.88-0.72(m，60H).
13C?NMR(100?MHz，CDCl
3，ppm)：δ151.8，151.5，151.0，141.7，140.8，140.7，140.5，140.3，139.4，127.0，126.8，126.3，126.1，126.0，122.9，122.1，121.5，120.0，119.9，119.7，110.8，110.7，110.6，55.3，55.2，40.5，40.4，31.6，31.5，30.1，29.8，29.7，26.6，24.0，23.8，22.6，22.5，14.0，13.9.MALDI-TOF?MS(m/z)：Calcd?for?C
192H
243N
3，Exact?Mass：2590.91，Mol.Wt.：2593.00；Found：2593.6(M
+)，2509.3([M-C
6H
13]
+).Anal.Calcd?for?C
192H
243N
3：C，88.93；H，9.45；N，1.62.Found：C，88.89；H，9.43；N，1.61.
Film ultraviolet maximum absorption is 368nm, and solid fluorescence emission maximum peak value is 444nm.
The preparation condition of single layer device is with embodiment 9.Individual layer electroluminescent device performance is as follows: trigger voltage 3.5V, high-high brightness 4270cd/m
2, maximum external quantum efficiency is 1.35%, chromaticity coordinates (0.16,0.14).
Embodiment 11:3,8,13-three (9,9-dihexyl-three difluorene)-5,10,15-three hexyls three are synthesizing of carbazole also
With 3,8,13-three bromo-5,10, (83.5mg, 0.10mmol), 9, (439.0mg 0.39mmol) is dissolved among the THF-three difluorenes 9-dihexyl-2-(4,4,5,5-tetramethyl--1,3,2-dioxo boric acid ester group), adds 2M K then for 15-three hexyls three and carbazole
2CO
3The aqueous solution (0.375mL, 0.75mmol).Under nitrogen protection, add Pd (PPh
3)
4(35mg, 0.03mmol) back flow reaction is 6 days.After mixture is chilled to room temperature, successively use the HCl aqueous solution, the saturated common salt water washing organic layer of 1M, use anhydrous Na then
2SO
4Dry.Behind the concentrating under reduced pressure, crude product obtains target compound (172mg, 48%) through column chromatography, vacuum drying.
1H?NMR(400?MHz，CDCl
3，ppm)：δ8.63(s，3H)，7.90-7.63(m，54H)，7.38-7.32(m，9H)，5.08-5.02(t，6H)，2.14-2.06(m，42H)，1.29-1.09(m，120H)，0.86-0.72(m，105H).
13C?NMR(100?MHz，CDCl
3，ppm)：δ152.1，152.0，151.2，141.0，140.7，140.5，140.2，127.2，127.0，126.4，126.2，123.1，121.7，121.6，120.2，120.1，119.9，55.5，55.4，40.8，40.6，31.8，31.7，30.1，30.0，29.9，26.8，24.2，24.1，24.0，22.9，22.8，22.7，14.3，14.2.MALDI-TOF?MS(m/z)：Calcd?for?C
267H
339N
3，Exact?Mass：3587.7，Mol.Wt.：3590.6；Found：3592.5(M
+).Anal.Calcd?for?C
267H
339N
3：C，89.31；H，9.52；N，1.17.Found：C，89.25；H，9.46；N，1.11.
This compound spin coating became on the quartz plate again film absorption spectrum and fluorescence spectrum are seen accompanying drawing 1.Film ultraviolet maximum absorption is 373nm as can be observed from Figure, and solid fluorescence emission maximum peak value is 442nm.
The preparation condition of single layer device is with embodiment 9.Individual layer electroluminescent device performance is as follows: trigger voltage 3.3V, high-high brightness 7714cd/m
2, maximum external quantum efficiency is 2.16%, its electroluminescent spectrum is seen accompanying drawing 2, its chromaticity coordinates (0.16,0.15).
Claims (4)
1. blue-light emitting functional material, it is characterized in that this material for based on three and the monodispersed star of carbazole primitive penetrate the shape oligomer, this oligomer has the structure of general formula 1:
Wherein, R
1To R
3A kind of in the Heterocyclylalkyl of the cycloalkyl of independently heteroaralkyl, replacement or unsubstituted C5-C30 aryloxy, replacement or unsubstituted C2-C30 heteroaryloxy, replacement or the unsubstituted C3-C30 of heteroaryl, replacement or unsubstituted C6-C30 aralkyl, replacement or the unsubstituted C2-C30 of aryl, replacement or the unsubstituted C2-C30 of alkyl, replacement or the unsubstituted C6-C30 of hydrogen, replacement or unsubstituted C1-C30 of respectively doing for oneself and replacement or unsubstituted C2-C30;
R
4To R
12The independently hydrogen of respectively doing for oneself;
Ar is the heteroaryl of aryl, replacement or the unsubstituted C2-C30 of replacement or unsubstituted C6-C30;
X is a capping group, is selected from a kind of in the heteroaryl of aryl, replacement or unsubstituted C2-C30 of alkoxyl group, replacement or unsubstituted amino, replacement or unsubstituted C6-C30 of alkyl, replacement or the unsubstituted C1-C30 of hydrogen, hydroxyl, carboxyl, aldehyde radical, cyano group, halogen atom, replacement or unsubstituted C1-C30;
N represents the number of repeat unit of Ar aryl, is the integer between the 1-5.
2. blue-light emitting functional material as claimed in claim 1, it is characterized in that described three and the monodispersed star of carbazole primitive penetrate in the formula 1 of shape oligomer, the Ar unit is the group shown in the following formula 1a to li:
Wherein, R
13To R
20A kind of in the Heterocyclylalkyl of the cycloalkyl of independently alkoxyl group, replacement or unsubstituted amino, replacement or the unsubstituted C3-C12 of alkyl, replacement or the unsubstituted C1-C12 of hydrogen, replacement or unsubstituted C1-C12 of respectively doing for oneself and replacement or unsubstituted C2-C12.
3. blue-light emitting functional material as claimed in claim 1, it is characterized in that described three and the monodispersed star of carbazole primitive penetrate that the Ar unit has the group shown in one of formula 1f to li in the shape oligomer:
Wherein, R
13To R
20A kind of in the Heterocyclylalkyl of the cycloalkyl of independently alkoxyl group, replacement or unsubstituted amino, replacement or the unsubstituted C3-C12 of alkyl, replacement or the unsubstituted C1-C12 of hydrogen, replacement or unsubstituted C1-C12 of respectively doing for oneself and replacement or unsubstituted C2-C12.
4. as claim 1 or 2 or 3 described blue-light emitting functional materials, it is characterized in that described three and the monodispersed star of carbazole primitive penetrate in the shape oligomer, this oligomer be suc as formula 2 or formula 3 shown in compound:
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| CN107445968B (en) * | 2017-06-14 | 2019-05-17 | 南京邮电大学 | Two indoles of one kind and three and carbazyl multi-arm structure conjugated molecular material and the preparation method and application thereof |
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