CN103265531A - Fluorophenychinoline imidazole blue organic light-emitting material and preparation method thereof - Google Patents
Fluorophenychinoline imidazole blue organic light-emitting material and preparation method thereof Download PDFInfo
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- CN103265531A CN103265531A CN2013102193273A CN201310219327A CN103265531A CN 103265531 A CN103265531 A CN 103265531A CN 2013102193273 A CN2013102193273 A CN 2013102193273A CN 201310219327 A CN201310219327 A CN 201310219327A CN 103265531 A CN103265531 A CN 103265531A
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Abstract
The invention discloses a fluorophenychinoline imidazole blue organic light-emitting material shown as formula I and a preparation method thereof. According to the invention, three fluorophenychinoline structural units are introduced to positions 2, 4 and 5 of an imidazole ring to form a functional three-substituent midazole compound of fluorophenychinoline. The preparation method provided by the invention is simple to operate, and the material is convenient to synthesize and easy to purify. The fluorophenychinoline imidazole compound obtained is stable in structure and easy to store, shows good ultraviolet absorption and fluorescence-emission performances, has potential application value in the fields of fluorescence sensitivity and the like and can be used for light-emitting apparatuses. The research and application field of the fluorophenychinoline imidazole compound is expanded.
Description
Technical field:
The present invention relates to technical field of organic luminescence materials, be specifically related to a kind of fluoro phenylquinoline imidazoles blue organic luminous material and preparation method thereof.
Background technology:
Luminous organic material is widely used in fields such as organic electroluminescence device (OLED), organic solid laser apparatus, organic photovoltaic battery and organic fluorescence sensor.Therefore, design and develop have high fluorescence efficiency, the luminous organic material of wavelength-tunable, industry development is very urgent and necessary for organic optoelectronic, also is a job that has challenge and significance simultaneously.
Quinolines is important fluorescent chemicals, and this compounds has excellent optical physics characteristic and higher fluorescence quantum yield, has been applied among the fields such as electroluminescent device and photovoltaic cell.Glyoxaline compound is the important heterogeneous ring compound of a class, is widely used in aspects such as medicine, white dyes, laser dyes, fluorescent probe, two-photon absorption.
Sun Yifeng etc. have reported a series of tri-substituted imidazoles, find that this compounds has two-Photon Absorption Properties (Yi-Feng Sun preferably, Wei Huang, Chang-Gui Lu, Yi-Ping Cui, The synthesis, two-photon absorptionand blue upconversion fluorescence of novel, nitrogen-containing heterocyclic chromophores, Dyesand Pigments, 2009,81,10-17.), adjustable solid emission characteristic (Yi-Feng Sun, Zhi-Yong Chen, Li Zhu, Shu-Hong Xu, Ren-Tao Wu, Yi-Ping Cui, Tunable solid-state fluorescence emission and redupconversion luminescence of novel anthracene-based fluorophores, Coloration Technology, 2013,129,165-175.), and to strengthen with quenching of fluorescence or fluorescence be sensitive fluorescent performance (the Yi-Feng Sun of feature, Liu Zhong, Xian-Ming Hou, Shi-Ying Ma, Wen-Zeng Duan, Ren-Tao Wu, Synthesis and fluorescenceproperties of novel benzoxazole-and chromone-functionalized bis (arylvinylene) imidazoles, Coloration Technology, 2012,128,331-339.).
Yet, fluoro phenylquinoline structural unit is incorporated on the imidazole ring, especially at 2 of imidazole ring, 4, introduce three fluoro phenylquinoline structural units on the 5-position, contain the glyoxaline compound of phenyl polyfluoride base quinoline functionalization thereby form, and investigate the research of aspects such as its optical physics characteristic, do not appear in the newspapers.
Summary of the invention:
The purpose of this invention is to provide a kind of fluoro phenylquinoline imidazoles blue organic luminous material and preparation method thereof.
The present invention is achieved by the following technical programs:
Fluoro phenylquinoline imidazoles blue organic luminous material shown in a kind of formula I:
The synthetic route of fluoro phenylquinoline imidazoles blue organic luminous material of the present invention is as follows:
The preparation method of fluoro phenylquinoline imidazoles blue organic luminous material of the present invention comprises the steps:
A, with 1,3-dimethyl diketone (compound IV) and 2-cyclopropyl-4-(4-fluoro phenyl) quinoline-3-formaldehyde (compound III) is dissolved in the organic solvent by the mol ratio of 1:2.0～2.1, after under stirring fast, in this solution, adding the piperidines of catalytic amount then, stirring and refluxing reaction 6～8 hours; After being cooled to room temperature, obtain yellow solid 1 through aftertreatment, 6-two (3-(2-cyclopropyl-4-(4-fluoro phenyl) quinolyl))-1,5-hexadiene-3,4-diketone (compound ii);
B, with step a obtain 1,6-two (3-(2-cyclopropyl-4-(4-fluoro phenyl) quinolyl))-1,5-hexadiene-3,4-diketone (compound ii), 2-cyclopropyl-4-(4-fluoro phenyl) quinoline-3-formaldehyde (compound III) and ammonium acetate, mol ratio by 1:1～1.1:9～15 is dissolved in the glacial acetic acid, and back flow reaction is 7～10 hours under stirring fast; Be cooled to room temperature after reaction finishes, with in the reaction solution impouring frozen water, regulate pH=7 with alkaline solution under stirring, gained solid matter decompress filter washes with water, and thick product obtains target product through recrystallization.
The described organic solvent of step a is preferably anhydrous methanol or dehydrated alcohol;
Alkaline solution described in the step b is preferably the aqueous sodium hydroxide solution of ammoniacal liquor or 10%, or 10% potassium hydroxide aqueous solution.
The present invention also protects the application of fluoro phenylquinoline imidazoles blue organic luminous material, is used for luminescent device, and can also be used for the sensitive fluorescent field as fluorescent material.
The present invention introduces 2,4 of imidazole rings with three fluoro phenylquinoline structural units, and the 5-position has formed the tri-substituted imidazoles of fluoro phenylquinoline functionalization.The present invention introduces cyclopropyl in the 2-position of quinoline ring, has strengthened the electronic action that pushes away in the compound conjugated system on the one hand; The introducing of cyclopropyl can effectively increase the sterically hindered of molecule on the other hand, reduces concentration quenching; Simultaneously, the introducing of cyclopropyl can also increase the solubleness of tri-substituted imidazole compounds.
Of the present inventionly contain fluoro phenylquinoline glyoxaline compound Stability Analysis of Structures, be easy to preserve, show good uv-absorbing and fluorescent emission performance, the fluorescent emission wavelength in tetrahydrofuran solution is 476nm, is positioned at the blue-light-emitting scope.Moreover this compound has sensitivity characteristic to fluorion and alkali in tetrahydrofuran solution, add a certain amount of fluorion after, its emission wavelength red shift is to 499nm; And the interpolation of the alkali of q.s can make its fluorescent emission wavelength reach 606nm, is red fluorescence.Therefore, has potential using value and can be used for luminescent device in fields such as sensitive fluorescents.
The method that the present invention proposes, simple to operate, synthetic convenient, easy purifying.The present invention has expanded research and the Application Areas of fluoro phenylquinoline glyoxaline compound.
Description of drawings:
Fig. 1 is the uv absorption spectra of compound in tetrahydrofuran solution that embodiment 1 obtains;
Fig. 2 is compound the exciting and emmission spectrum figure in tetrahydrofuran solution that embodiment 1 obtains.
Embodiment:
Below be to further specify of the present invention, rather than limitation of the present invention.
Embodiment 1:2-(3-(2-cyclopropyl-4-(4-fluoro phenyl) quinolyl))-4, the preparation of 5-two (2-(3-(2-cyclopropyl-4-(4-fluoro phenyl) quinolyl)) vinyl)-1H-imidazoles (compound I)
Step a, intermediate 1,6-two (3-(2-cyclopropyl-4-(4-fluoro phenyl) quinolyl))-1,5-hexadiene-3, the preparation of 4-diketone (compound I I)
In 100 milliliters of round-bottomed flasks of drying, add 1,3-dimethyl diketone (compound IV) 0.86g(0.01mol), 2-cyclopropyl-4-(4-fluoro phenyl) quinoline-3-formaldehyde (compound III) 5.82g(0.02mol), and 35 milliliters of dehydrated alcohols, under stirring fast, in this solution, add 0.5 milliliter of piperidines then, afterwards, the stirring and refluxing reaction is 6～8 hours.After being cooled to room temperature, separate out yellow solid, decompress filter is used absolute ethanol washing, at room temperature after the drying, and with ethanol-N, dinethylformamide mixed solvent recrystallization, vacuum-drying obtains yellow powder 1.3g, productive rate 21%.Fusing point is 235 ℃ of 233 –.
1H?NMR(300MHz,CDCl
3/TMS)δ:1.09-1.15(m,4H),1.41-1.45(m,4H),2.34-2.39(m,2H),7.13(d,J=16.5Hz,2H),7.20-7.23(m,8H),7.36-7.38(m,4H),7.64-7.70(m,2H),7.89(d,J=16.5Hz,2H),7.99(d,J=8.4Hz,2H)。
Step b, 2-(3-(2-cyclopropyl-4-(4-fluoro phenyl) quinolyl))-4, the preparation of 5-two (2-(3-(2-cyclopropyl-4-(4-fluoro phenyl) quinolyl)) vinyl)-1H-imidazoles (compound I)
In 100 milliliters of round-bottomed flasks of drying, add intermediate 1,6-two (3-(2-cyclopropyl-4-(4-fluoro phenyl) quinolyl)-1,5-hexadiene-3,4-diketone (compound I I) 0.88g(0.0014mol), ammonium acetate 0.97g(0.0126mol 2-cyclopropyl-4-(4-fluoro phenyl) quinoline-3-formaldehyde (compound III) 0.41g(0.0014mol)), and 30 milliliters of glacial acetic acids, stirred down back flow reaction fast 7～10 hours.After being cooled to room temperature, with in the reaction solution impouring frozen water, regulate pH=7 with ammoniacal liquor under stirring fast, gained solid matter decompress filter washes for several times drying at room temperature with water.With ethanol-N, dinethylformamide mixed solvent recrystallization, vacuum-drying obtains yellow powder 0.69g, productive rate 55%.Fusing point is 180 ℃ of 178 –.
1H NMR (300MHz, CDCl
3/ TMS) δ: 0.91-0.95 (m, 2H), 1.02-1.06 (m, 4H), 1.30-1.33 (m, 2H), and 1.40-1.44 (m, 4H), 2.22-2.30 (m, 1H), and 2.37-2.40 (m, 1H), 2.53-2.56 (m, 1H), 6.33 (d, J=16.8Hz, 1H), 6.46 (d, J=15.6Hz, 1H), 6.50 (d, J=16.5Hz, 1H), 7.02 (d, J=6.9Hz, 4H), and 7.09-7.40 (m, 14H), 7.43 (d, J=8.4Hz, 1H), 7.56-7.68 (m, 3H), 7.88 (d, J=8.1Hz, 1H), 7.95 (d, J=8.4Hz, 2H), 8.78 (s, 1H).
13C NMR (75MHz, CDCl
3/ TMS) δ: 10.61,11.36,15.74,16.35,16.53,115.05,115.33,115.68,121.21,122.20,123.17,124.99,125.11,125.49,125.94,126.01,126.33,126.62,128.95,129.12,130.26,131.38,131.49,131.73,131.83,131.97,132.08,144.36,146.65,147.15,148.01,161.65.ESI-MS m/z:904.5 (M)
+(or 903.1 (M-H)
-).
Embodiment 2:2-(3-(2-cyclopropyl-4-(4-fluoro phenyl) quinolyl))-4, the preparation of 5-two (2-(3-(2-cyclopropyl-4-(4-fluoro phenyl) quinolyl)) vinyl)-1H-imidazoles (compound I)
Press the method for embodiment 1, obtain by two-step reaction, different is, among the step a, the mol ratio of 1,3-dimethyl diketone and 2-cyclopropyl-4-(4-fluoro phenyl) quinoline-3-formaldehyde is 1:2.1, and productive rate is 20%; Among the step b, 1,6-two (3-(2-cyclopropyl-4-(4-fluoro phenyl) quinolyl))-1,5-hexadiene-3, the mol ratio of 4-diketone, 2-cyclopropyl-4-(4-fluoro phenyl) quinoline-3-formaldehyde and ammonium acetate is 1:1.1:15, productive rate is 57%.
Embodiment 3:2-(3-(2-cyclopropyl-4-(4-fluoro phenyl) quinolyl))-4, the fluorescence property test of 5-two (2-(3-(2-cyclopropyl-4-(4-fluoro phenyl) quinolyl)) vinyl)-1H-imidazoles (compound I)
It is 1.68 * 10 that the compound I that embodiment 1 is obtained is mixed with concentration
-5The M tetrahydrofuran solution.Absorb and three-dimensional fluorescence scanning spectrometer its uv-absorbing of mensuration and fluorescence property at HORIBA Jobin Yvon Aqualog with 1 centimetre of fluorescence pond, the result as depicted in figs. 1 and 2.As shown in Figure 1, the compound I molecule of embodiment 1 has three tangible absorption bands at 240nm～450nm wave band, and peak position is respectively 244nm, 293nm and 367nm, and is not having obvious absorption greater than the 450nm wave band.As shown in Figure 2, the maximum excitation wavelength of embodiment 1 compound I molecule is 395nm, and its fluorescence emission peak is positioned at 476nm, is blue-light-emitting.
Fluorion (tetrabutyl ammonium fluoride) and alkali (TBAH) have further been studied to the influence of embodiment 1 compound fluorescence property.The tetrahydrofuran solution adding fluorion of embodiment 1 compound I and the fluorescent emission wavelength behind the alkali have been measured, and the fluorescence radiation colour-change of under the 365nm ultraviolet lamp, observing solution, the result is as follows: the emission wavelength of the tetrahydrofuran solution of embodiment 1 compound I is 476nm, is blue-fluorescence; After adding a certain amount of fluorion, the emission wavelength red shift of solution is to 499nm, and it is luminous to present blue-greenish colour; Add alkali again, can make its fluorescent emission wavelength reach 606nm, fluorescence takes on a red color.Illustrate that compound has sensitivity characteristic to fluorion and alkali, and the adding of alkali can not make its quenching of fluorescence, therefore, embodiment 1 compound I has potential using value in fields such as sensitive fluorescents.
Claims (5)
1. the fluoro phenylquinoline imidazoles blue organic luminous material shown in the formula I:
2. the preparation method of the described fluoro phenylquinoline of claim 1 an imidazoles blue organic luminous material is characterized in that, comprises the steps:
A, with 1,3-dimethyl diketone and 2-cyclopropyl-4-(4-fluoro phenyl) quinoline-3-formaldehyde is dissolved in the organic solvent by the mol ratio of 1:2.0～2.1, the piperidines that under stirring fast, adds catalytic amount then, stirring and refluxing reaction 6～8 hours, after being cooled to room temperature, obtain 1,6-two (3-(2-cyclopropyl-4-(4-fluoro phenyl) quinolyl))-1 through aftertreatment, 5-hexadiene-3, the 4-diketone;
B, with step a obtain 1,6-two (3-(2-cyclopropyl-4-(4-fluoro phenyl) quinolyl))-1,5-hexadiene-3,4-diketone, 2-cyclopropyl-4-(4-fluoro phenyl) quinoline-3-formaldehyde and ammonium acetate, mol ratio by 1:1～1.1:9～15 is dissolved in the glacial acetic acid, and back flow reaction is 7～10 hours under stirring fast; Be cooled to room temperature after reaction finishes, with in the reaction solution impouring frozen water, regulate pH=7 with alkaline solution under stirring, gained solid matter decompress filter washes with water, and thick product obtains target product through recrystallization.
3. the preparation method of fluoro phenylquinoline imidazoles blue organic luminous material according to claim 1 is characterized in that the described organic solvent of step a is anhydrous methanol or dehydrated alcohol; Alkaline solution described in the step b is the aqueous sodium hydroxide solution of ammoniacal liquor or 10% or 10% potassium hydroxide aqueous solution.
4. the application of the described fluoro phenylquinoline of claim 1 imidazoles blue organic luminous material.
5. the application of fluoro phenylquinoline imidazoles blue organic luminous material according to claim 4 is characterized in that being used for the sensitive fluorescent field for luminescent device or as fluorescent material.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103555319A (en) * | 2013-10-25 | 2014-02-05 | 泰山学院 | Fluorine-containing cyproquinoline Schiff base blue luminescent material and preparation method thereof |
| CN105061320A (en) * | 2015-08-12 | 2015-11-18 | 中国广州分析测试中心 | Imidazole tri-acylhydrazone compound, application of compound as organic light-emitting material as well as preparation method of compound |
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| CN1333752A (en) * | 1999-01-14 | 2002-01-30 | 日产化学工业株式会社 | Process for producing quinolinecarbaldehyde |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103555319A (en) * | 2013-10-25 | 2014-02-05 | 泰山学院 | Fluorine-containing cyproquinoline Schiff base blue luminescent material and preparation method thereof |
| CN105061320A (en) * | 2015-08-12 | 2015-11-18 | 中国广州分析测试中心 | Imidazole tri-acylhydrazone compound, application of compound as organic light-emitting material as well as preparation method of compound |
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