CN1737080A - Fluorenes oligomer electroluminescent material and its synthesis method - Google Patents
Fluorenes oligomer electroluminescent material and its synthesis method Download PDFInfo
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- CN1737080A CN1737080A CN 200510029515 CN200510029515A CN1737080A CN 1737080 A CN1737080 A CN 1737080A CN 200510029515 CN200510029515 CN 200510029515 CN 200510029515 A CN200510029515 A CN 200510029515A CN 1737080 A CN1737080 A CN 1737080A
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Abstract
The invention, included in electroluminescence material technology sphere, relates an oligomer material of fluorenes and synthetic method. The invention comprises the following steps: making a series of conjugate fragment with different conjugate length by using fluorenes and anthracenes, terminating them with group and finally getting the said electroluminescence material. The said material can be used to prepare organic electroluminescence device of excellent property, photovoltaic cell, information storage, thin film transistor, and other organic photoconducting devices.
Description
Technical field
The invention belongs to organic information functional material technical field, be specifically related to the oligomer electroluminescent material and the synthetic method thereof of fluorenes.
Background content
The organic/polymer electroluminescent device is one of focus forward position of current scientific research, the indicating meter made from it has high image quality, screen size can arbitrarily be adjusted, energy consumption is low, light weight and approaching, adopt the flexible macromolecule substrate collapsible, advantage such as tooling cost is low, thus represented the development trend of following technique of display.In display of organic electroluminescence, realize that the big area full color shows that stable red, green and blue three primary colours must be arranged.But have only red at present and greenly just have necessary luminous efficiency of business development and life-span, the high stable, high-level efficiency of realizing the material blue emission at present or a difficult problem.The common material that is used to prepare organic electroluminescent LED has benzene, fluorenes, carbazole, to phenylacetylene support, thiophene and their derivative etc.Poly-fluorenes is a kind of compound with rigid plane biphenyl modular construction, can go up limited several reflecting points by ring, and particularly the carbon on No. 9 positions obtains a series of derivatives.
Poly-fluorenes is to be obtained by human iron trichloride oxidative coupling fluorenes such as Fukuda the earliest, the polymkeric substance that obtains is because molecular weight is low, branching is more serious, and because residual iron ion strong absorption exciton, finally cause the polymer materials can't be luminous and do not have a practical value.Through constantly improving, on the polymer manufacture of fluorenes, obtained significant progress afterwards.The wherein ground-breaking work of tool is that people such as Suzuki finish.They are by the poly-fluorenes molecular weight height that the Suzuki reaction obtains, and the degree of branching is little, and molecular weight distribution is narrow.Wherein the poly-fluorenes photodiode of green light can be 22lm/W in peak efficient, under the situation of driving voltage less than 6V, and the luminous continuously 10000cd/m that surpasses
2
Fluorenes and derivative thereof can become the research focus of luminescent material, and this mainly is the energy gap owing to the fluorenes broad, higher characteristics such as luminous efficiency.But the electron affinity of fluorenes is little, and the solvability of poly-fluorenes is limited.No. 9 position carbon atoms of fluorenes become carbonyl again than being easier to oxidation, this easily forms " trap " to the exciton that electronics, hole-recombination produced and certain " cancellation " effect is arranged, and can reduce the luminescent lifetime of device.In order to improve the comprehensive electroluminescent properties of fluorenes, mainly at present adopt preparation small molecules fluorenes fluorescent material, introduce on fluorenes that different side group post polymerization prepares fluorenes homopolymer, fluorenes monomer and other monomer copolymerizations and preparation is derived and next methods such as branch-shape polymer by fluorenes.Reaction commonly used has Suzuki reaction, Yamamoto reaction, the reaction of Witti gram and Stille reaction etc. in material synthetic process, wherein again with the Suzuki reaction because nontoxic, condition is easy to control and uses morely.Because it is shorter that the organic electroluminescent phenomenon is found the time, the luminous basic theory of relevant material is not still set up fully, and this makes and can run into many parameters in the research process of electroluminescent organic material.Macromolecular material is because structure has the characteristics of polymolecularity, no matter from the operability of experiment, aspects such as the purifying aspect of final product and sign all have unpredictalbe mutability, and this makes and occurs self-contradictory result sometimes unexpectedly by the repeated bad of result of study.And the electroluminescent material structure of organic molecule is clear and definite, and the performance and the orthogonality relation between the structure of material are direct, and experiment also than being easier to control, can obtain material with very high purity.In addition, such material has the irreplaceable advantage of high-molecular luminous material at aspects such as solvability and workabilitys, and therefore synthetic fluorenes class oligomer electroluminescent material with various structures just becomes a kind of very important research means.
Reference:
[1]Tang?C?W，Vanslyke?S?A.Appl.Phys.Lett.，1987，51(12)：913-920
[2]Avilov?I，Marsal?P，Beljonne?D.Adv.Mater.，2004，16(18)：1624-1629
[3]Friend?R?H，Gymer?R?W，Homes?A?B，etal.Nature.，1999，397(6715)：121-123
[4]Berggren?M，Inganas?D，Gustaflson?G.，et?al.Nature.，1994，372(6588)：444-445
[5]Granstron?M，Inganns?O.Appl.Phys.Lett.，1996，68(26)：147-152
[6]Andersson?M?R，Thomas?O，Mammo?W，et?al.J.Mater.Chem.，1999，9(9)：1933-1938
[7]Fukuda?K，Sawaka?K，Yoshino?J.J.Polym.Sci.Part?A：Polym?Chem.，1993，31(12)：2465-2469
Summary of the invention
It is clear and definite to the objective of the invention is to propose a kind of structure, reacts controlled fluorenes oligomer electroluminescent material and synthetic method thereof.
The oligomer electroluminescent material of the fluorenes that the present invention proposes is the conjugation fragment of synthesizing a series of different lengths conjugate units as main construction unit with fluorenes or anthracene, and apparatus obtains after the group end capping of linear or branched structure is arranged.Its general structural formula is expressed as follows:
Wherein, conjugation fragment and capping group S all are made up of some conjugated benzene, fluorenes, pyridine or other aromatic nucleus, also can be that the arbitrary combination of above-mentioned group constitutes.The segmental repeating unit number of conjugation is generally between 1-3.On conjugation fragment and the capping group S, also can contain the long chain alkane that can improve reactive hydrogen on material dissolves and 9 carbon of substituted fluorene, the carbon atom number of this long chain alkyl group is 4.
The synthetic method of oligomer of the present invention is: synthesize the conjugation fragment that contains the active end group bromine earlier.Resynthesis goes out to contain equally the capping group S of end group bromine, by butyllithium the bromine on the aromatic ring among the capping group S is converted into the product of boration then; The boration product of active end group bromine by fluorenes and capping group S carries out the Suzuki linked reaction and promptly obtains target oligomer material at last.
The concrete good electroluminescence characters of the oligomer of synthetic fluorenes of the present invention can be used for the preparation of organic electroluminescence device, also can be used for organic electro-optic device, as the preparation of photovoltaic cell, message memory, thin film transistor etc.
Description of drawings
Fig. 1 is a 9-bromo-anthracene
1H-NMR (CDCl
3, 400MHz, δ ppm) collection of illustrative plates.
Fig. 2 is 2-(4-ethyl ketone benzene)-9,9-dibutyl fluorenes
1H-NMR (CDCl
3, 400MHz, δ ppm) and collection of illustrative plates.
Fig. 3 is a compound 4
1H-NMR (CDCl
3, 400MHz, δ ppm) and collection of illustrative plates.
Fig. 4 be compound 4 flight time mass spectrum (MALDI-TOF) collection of illustrative plates (molecular ion peak: theoretical value: 939.11, experimental value: 939.2).
Below by some embodiment material synthetic embodiment involved in the present invention is described further, but embodiment does not limit covering scope of the present invention.
One: conjugation is segmental synthetic:
Embodiment 1
Choose 2; 7-two bromo-9; 9-two butane-fluorenes and 9; two boration products of 9-two butane-fluorenes; be composite catalyst, be solvent with toluene with triphenyl phosphorus palladium (O) title complex/yellow soda ash; in temperature is to carry out the Suzuki reaction under 90 ℃, just can obtain three difluorene products of the two protections of silane, productive rate about 50%.Three difluorenes of two protections just can obtain the two iodo conjugation fragments of target by go protection with IC1.Concrete experiment condition is:
1: in 50 milliliters two-neck bottle of magneton and nitrogen conduit is housed, add 9 of 1.7 grams, 9-dibutyl-2,7-dibromo fluorenes, anhydrous and oxygen-free is handled, add 25 milliliters of anhydrous and oxygen-free tetrahydrofuran (THF) solubilizing reaction things with the exsiccant syringe, after the stirring two-neck bottle is added dry ice-propanone and bathe.After treating that temperature-stable arrives-78 ℃, in 30 minutes, slowly splash into 2.5 milliliters of the butyllithium liquid of 1.6M ,-78 ℃ of following continuously stirring reactions after 1 hour, with the trimethylchlorosilane of 0.6 milliliter of the dry disposable quick injection of syringe of crossing.Remove acetone the dry ice bath, slowly elevated temperature continuously stirring reaction 1 hour after the room temperature.Add a large amount of water, cancellation reaction back petroleum ether extraction, dry separation obtains organic phase, obtains being flaxen liquid after revolving steaming.With the sherwood oil is that eluent carries out column chromatography, obtains colourless transparent liquid, and general productive rate can reach more than 90%.
2: with 9 of the above-mentioned 1.6 gram trimethyl silicane list protections that obtain; 9-dibutyl fluorenes is dissolved in 25 milliliters the tetrahydrofuran (THF) of anhydrous and oxygen-free; all the other operations are the same, and behind the triisopropyl boric acid ester of 1.3 milliliters of addings, continuously stirring reaction at room temperature obtained white emulsion liquid after 24 hours.After the hydrochloric acid quencher reaction with excessive 2.0M, with an amount of extracted with diethyl ether, separate, drying is revolved steaming except that after desolvating and is obtained sticky solid.With volume ratio is that 4: 1 sherwood oil ethyl acetate mixed solution is that eluent carries out column chromatography, promptly obtains a certain amount of pure white solid.
3: with 1.9 grams 2; 7-two bromo-9; 9 of 9-dibutyl-fluorenes and the single protection of 3.83 grams boration, 9-dibutyl fluorenes joins and is equipped with in 250 milliliters the three-necked bottle that stirs magneton, spherical condensation tube and nitrogen conduit, and sealing is carried out the anhydrous and oxygen-free operation and is done lucifuge and handle.Add an amount of triphenyl phosphorus palladium (O) catalyzer in glove box, add the aqueous sodium carbonate of the 2M of 150 milliliters toluene and 25 milliliters with syringe, in 90 ℃ oil bath, the continuously stirring reaction is 48 hours under the nitrogen protection.Reaction back dichloromethane extraction separates, and drying is the eluent column chromatography with the sherwood oil, obtains the white three difluorene solids of two protections.
4: three difluorenes of the above-mentioned two protections of 2.16 grams that obtain are dissolved in 50 milliliters the tetracol phenixin; under cryosel bath condition, splash into 3 milliliters of the iodine chloride hexane solutions of 1.0M; stirring reaction is after half hour, reactant stirred to be poured into a large amount of mass concentrations down be colourless to reactant in 5% the sodium thiosulfate solution.Dichloromethane extraction, the organic phase water washing, anhydrous sodium sulfate drying obtains two iodo three difluorenes (compound 1) with methanol wash.Preserve two iodo three difluorene lucifuges sealings standby.The structural formula of two iodo three difluorenes is as follows:
Compound 1
Embodiment 2
Add 0.83 gram anthracene in 50 milliliters of two-neck bottles of magneton and nitrogen conduit are housed, anhydrous and oxygen-free is handled the back nitrogen protection, injects 12 milliliters in tetracol phenixin with syringe.After lucifuge is handled two-neck bottle is transferred in the cryosel bath.The dimethyl formamide solution that will be dissolved with 0.83 gram NBS with constant pressure funnel slowly is added drop-wise in the reaction solution for 10 milliliters.Slowly be warmed up to room temperature, continuously stirring reaction was washed chloroform extraction with sodium sulfite solution after 7 hours, use the anhydrous sodium sulfate drying organic phase, carried out behind the column chromatography purification to such an extent that 1.08 restrain yellow needle-like crystal with sherwood oil, i.e. 9-bromo-anthracene (compound 2),
Its structural formula and reactions steps are:
Embodiment 3
With 4.4 gram 2-bromine 7-trimethyl silanes-9,9-dibutyl fluorenes and 1.68 gram 2,4 difluorobenzene boric acid are mixed in magneton are housed, 50 milliliters of two-neck bottles of spherical condensation tube and nitrogen conduit, and sealing is carried out under the anhydrous and oxygen-free operation back nitrogen protection lucifuge and is handled.Add an amount of triphenyl phosphorus palladium catalyst in glove box, add the aqueous sodium carbonate of the 2M of toluene that 27 milliliters anaerobic handles and 16 milliliters with syringe, in 90 ℃ oil bath, the continuously stirring reaction is 48 hours under the nitrogen protection.Reacted the back dichloromethane extraction, separated, drying is the eluent column chromatography with the sherwood oil, obtain (9,9-dibutyl-2-(2,4 difluorobenzene)-7-trimethyl silicane-fluorenes white fluorenes solid.With obtain (9,9-dibutyl-2-(2,4 difluorobenzene)-7-trimethyl silicane-fluorenes white fluorenes solid is dissolved in the methylene dichloride of 20 milliliters of exsiccant nitrogen protection.In dry ice acetone bath, slowly boron tribromide liquid is added drop-wise in the mixture for 5 milliliters, in-78 ℃ of following continuously stirring reactions 1 hour, elevated temperature, continuously stirring reaction 7 hours with constant pressure funnel.Mixture is slowly joined mass concentration under the high degree of agitation situation be in 10% the potassium hydroxide solution, extracted with diethyl ether, dry, be that eluent carries out column chromatography with sherwood oil and ethyl acetate successively again, obtain the boration product (compound 3) of white, be 2-boric acid-7 (2,4 difluorobenzene)-9,9-dibutyl-fluorenes.
Its reactions steps is as follows:
Compound 3
Two: capping group S's is synthetic:
Embodiment 4
Schedule of operation according to the Suzuki of embodiment 3 reaction, choose 2-boric acid-9,9-dibutyl fluorenes and parabromoacetophenone, with triphenyl phosphorus palladium (O) title complex/yellow soda ash is composite catalyst, under 90 ℃, carry out the Suzuki reaction with toluene solvant, can synthesize 1-(4-(9,9-dibutyl fluorenes) methyl phenyl ketone smoothly.With the 0.5 gram 4-(9 that obtains; 9-dibutyl fluorenes) methyl phenyl ketone; 0.23 gram p-bromobenzaldehyde; 10 milliliters of tetrahydrofuran (THF)s and a certain amount of mass concentration are that 2% aqueous sodium hydroxide solution is under nitrogen protection; continuously stirring reaction at room temperature earlier 1 hour; temperature is elevated to 60 ℃, continued stirring reaction 10 hours, obtain being suspended in the yellow solid of solution system.Filter, a large amount of washings, natural air drying obtains yellow solid.With the continuously grinding reaction 2 hours in mortar of the parabromoacetophenone of the yellow solid that obtains and equimolar amount and proper amount of sodium hydroxide solid.With the yellow solid that obtains and excessive ammonium acetate continuously stirring back flow reaction 12 hours in ethanolic soln, filter, use washing with alcohol, obtain yellow solid.Carry out column chromatography with sherwood oil/methylene dichloride mixed solvent (2: 1), obtain light yellow solid (compound 4).
Structural formula and reactions steps are as follows:
According to above-described bromination, boration and Suzuki reactions steps, can synthesize following end-caps:
Compound 5
Three: the oligomer material of fluorenes synthetic:
Embodiment 5-11
Choose above conjugation fragment and capping group S, obtain active fragments by follow-up boration reaction, schedule of operation according to embodiment 3 described Suzuki reactions, these conjugation fragments and capping group S are carried out the various combination coupling, promptly obtain the included part oligomer electroluminescent material of the present invention.Concrete experiment condition can be with reference to embodiment 1,2, and 3 and 4 described methods are carried out.
Compound 1 and compound 5 are carried out the Suzuki coupling, obtain following material:
Compound 9
Compound 1 and compound 6 are carried out the Suzuki coupling, obtain following material:
Change
Compound 10
Compound 1 and compound 7 are carried out the Suzuki coupling, obtain following material:
Compound 11
Compound 1 and compound 8 are carried out the Suzuki coupling, obtain following material:
Compound 12
Compound 1 is proceeded to obtain 9 after the bromination, 10-2 bromo-anthracene, then with 9,10-2 bromo-anthracene and compound 8 carry out the Suzuki coupling, obtain following material:
With 9,10-2 bromo-anthracene carries out obtaining 9 behind the boration, 10-2 boric acid-anthracene, and with 9,10-2 boric acid-anthracene and compound 4 carry out the Suzuki coupling, obtain following material:
Compound 14
Compound 1 is carried out boration, obtain three difluorenes of two borations.Two borations three difluorenes and the compound 4 that obtain are carried out the Suzuki coupling, obtain following material:
Compound 15
With 9,10-2 boric acid-anthracene and 2-3 methyl silicon-7-bromo-9,9-dibutyl-fluorenes and compound 4 carry out substep Suzuki coupling, obtain following material:
Compound 16
The oligomer material of above-mentioned fluorenes all has good electroluminescence characters, can be used for preparing organic electroluminescence device, perhaps is used to prepare other organic electro-optic devices etc.
Claims (8)
1, the oligomer electroluminescent material of fluorenes is characterized in that apparatus has the group end capping of linear or branched structure to obtain with fluorenes or the anthracene conjugation fragment with different lengths conjugate unit as main construction unit, and its general structural formula is expressed as follows:
Wherein, conjugation fragment and capping group S form by some conjugation aromatic nucleus.
2, electroluminescent material according to claim 1 is characterized in that described conjugation fragment mainly is made up of fluorenes or anthracene.
3, electroluminescent material according to claim 1 is characterized in that described capping group S is the derivative of fluorenes, or pyridine, 2,4 difluorobenzene, or the various combination of above-mentioned two class aromatic nucleus.
4, electroluminescent material according to claim 1 is characterized in that the segmental repeating unit number of described conjugation is between 1-3.
5, electroluminescent material according to claim 1 on conjugation fragment described in it is characterized in that and the capping group S, contains the long chain alkane that can improve reactive hydrogen on material dissolves and 9 carbon of substituted fluorene, and the carbon atom number of this long chain alkyl group is 4.
6, a kind of synthetic method of oligomer electroluminescent material as claimed in claim 1, it is characterized in that concrete steps are as follows: synthesize the conjugation fragment that contains the active end group bromine earlier, resynthesis goes out to contain equally the capping group S of active end group bromine, by butyllithium the bromine of capping group S is converted into boric acid then, carry out the Suzuki linked reaction by the activity end bromine of fluorenes and the boration product of capping group S at last, promptly obtain the target oligomer.
7, the application of a kind of electroluminescent organic material as claimed in claim 1 in the preparation organic electroluminescence device.
8, the application of a kind of electroluminescent organic material as claimed in claim 1 in organic electro-optic devices such as preparation photovoltaic cell, message memory, thin film transistor.
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| CN102807554A (en) * | 2011-05-31 | 2012-12-05 | 海洋王照明科技股份有限公司 | Organic semiconductor material containing naphthalene, anthracene and dibenzothiophene sulfone unit, preparation method and application thereof |
| CN102838585A (en) * | 2011-06-22 | 2012-12-26 | 海洋王照明科技股份有限公司 | Organic semiconductor material containing dibenzothiophene sulfone, and preparation method and application thereof |
| CN102850320A (en) * | 2011-06-28 | 2013-01-02 | 海洋王照明科技股份有限公司 | Compound containing dibenzothiophene sulfone and preparation method and application thereof |
| CN103232473A (en) * | 2013-04-22 | 2013-08-07 | 南京邮电大学 | Fluorenyl organic framework material, preparation and application method thereof |
| JP2015203027A (en) * | 2014-04-16 | 2015-11-16 | Jnc株式会社 | Anthracene derivative and organic el element |
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| US9512137B2 (en) | 2010-08-05 | 2016-12-06 | Idemitsu Kosan Co., Ltd. | Organic electroluminescence device |
| WO2012133207A1 (en) * | 2011-03-30 | 2012-10-04 | 住友化学株式会社 | Fluorinated compound, and composition and thin film each containing same |
| CN102807554A (en) * | 2011-05-31 | 2012-12-05 | 海洋王照明科技股份有限公司 | Organic semiconductor material containing naphthalene, anthracene and dibenzothiophene sulfone unit, preparation method and application thereof |
| CN102807554B (en) * | 2011-05-31 | 2014-07-09 | 海洋王照明科技股份有限公司 | Organic semiconductor material containing naphthalene, anthracene and dibenzothiophene sulfone unit, preparation method and application thereof |
| CN102838585A (en) * | 2011-06-22 | 2012-12-26 | 海洋王照明科技股份有限公司 | Organic semiconductor material containing dibenzothiophene sulfone, and preparation method and application thereof |
| CN102838585B (en) * | 2011-06-22 | 2014-11-26 | 海洋王照明科技股份有限公司 | Organic semiconductor material containing dibenzothiophene sulfone, and preparation method and application thereof |
| CN102850320A (en) * | 2011-06-28 | 2013-01-02 | 海洋王照明科技股份有限公司 | Compound containing dibenzothiophene sulfone and preparation method and application thereof |
| CN102850320B (en) * | 2011-06-28 | 2015-01-21 | 海洋王照明科技股份有限公司 | Compound containing dibenzothiophene sulfone and preparation method and application thereof |
| CN103232473A (en) * | 2013-04-22 | 2013-08-07 | 南京邮电大学 | Fluorenyl organic framework material, preparation and application method thereof |
| JP2015203027A (en) * | 2014-04-16 | 2015-11-16 | Jnc株式会社 | Anthracene derivative and organic el element |
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