CN100400537C - Red fluorescent dye compound. preparation process and application thereof - Google Patents
Red fluorescent dye compound. preparation process and application thereof Download PDFInfo
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- CN100400537C CN100400537C CNB2005100680557A CN200510068055A CN100400537C CN 100400537 C CN100400537 C CN 100400537C CN B2005100680557 A CNB2005100680557 A CN B2005100680557A CN 200510068055 A CN200510068055 A CN 200510068055A CN 100400537 C CN100400537 C CN 100400537C
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- fluorescent dye
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Abstract
The present invention discloses a red fluorescent dye compound, and a preparation method and application thereof. The structure of the red fluorescent dye compound provided by the present invention discloses in the formula I, wherein R is an alkyl. The preparation method of the compound comprises the following steps: 1) synthesizing 4-diethylamino-2-alkoxy phenyl formaldehyde from 4-diethylamino-salicylal; 2) carrying out Knoevenagel condensation reaction with 4-dicyanoethylene-2-methyl-6-methyl-4H pyrane under the catalytic action of hexahydropyridine. The compound of the present invention has the advantages of convenient and simple synthetic method, excellent electroluminescence performance and wide application prospect.
Description
Technical field
The present invention relates to compound and preparation method thereof and application, particularly relate to a kind of red fluorescent dye compound and preparation method thereof and application.
Background technology
(Organic light-emitting diodes is in the present photoelectric device field OLEDs) to organic electroluminescent, and one progressively tends to new technique ripe and that have huge use prospect.From (C.W.Tang such as C.W.Tang in 1987, S.A.VanSlyke, Appl.Phys.Lett.1987,51,913-915) organic electroluminescent has been done pioneering research since, OLEDs has just attracted the extensive concern of scientific circles and playing an active part in of international renowned company, is generally believed it is the most competitive technology in the technique of display of new generation.Specifically, organic electroluminescent has following characteristics:
1) adopt organism, the material range of choice is wide, can realize the demonstration of any color from the blue light to ruddiness;
2) driving voltage is low, only needs the volts DS of 3-10 volt;
3) luminosity and luminous efficiency height;
4) full solidified active illuminating;
5) visual angle is wide, and response speed is fast;
6) preparation process is simple, and expense is low;
7) ultrathin membrane, in light weight;
8) can be produced on the softish substrate, device is expected bending fold.
Electroluminescent organic material designs, synthesizes red (R) of series, green (G) and blue (B) luminescent material through 20 years of development.High performance green and blue emitting material be practicability, wants much less and can satisfy the red light-emitting material that practicability requires.The shortage of high-performance red light material becomes the bottleneck that full color OLEDs device is realized the practicability development, causes the major cause of this situation to have:
1) transition corresponding to red emission all is the less transition of energy gap, the highest occupied molecular orbital (HOMO) and the energy level difference between the lowest unoccupied molecular orbital (LUMO) that promptly produce the compound of luminescence emissions are less, the non-radiative inactivation of excited state dye molecule is comparatively effective, and therefore the fluorescence quantum yield of most of red illuminating materials is not high;
2) under high density or solid film state, the distance between the dye molecule is less, and molecular interaction is strong, and the non-radiative energy inactivation sharply increases, and causes fluorescent quenching;
3) red light material is difficult with energy matching ratio between the carrier transport, thereby can not make electronics and hole compound in luminescent layer effectively.
Summary of the invention
The purpose of this invention is to provide a kind of red fluorescent dye compound and preparation method thereof.
Red fluorescent dye compound provided by the present invention, its structural formula are formula I,
Wherein, R is an alkyl.
R is preferably the alkyl that carbonatoms is 1-4, as methyl, ethyl, propyl group, butyl etc.
The preparation method of red fluorescent dye compound of the present invention, comprise the steps: 1) synthetic 4-diethylin-2-alkoxy benzene formaldehyde: 4-(diethylin)-salicylic aldehyde and halohydrocarbon are reacted under the effect of phase-transfer catalyst and alkali, obtain structure suc as formula the diethylin of the 4-shown in the II-2-alkoxy benzene formaldehyde; Wherein, R is an alkyl among the formula II; Described phase-transfer catalyst is tetrabutylammonium iodide, Tetrabutyl amonium bromide, tetraethylammonium bromide or tetraethyl ammonium iodide;
2) synthetic 4-(dicyano ethylene)-2-methyl-6-(2-alkoxyl group-4-diethylin vinylbenzene) 4H-pyrans: 4-diethylin-2-alkoxy benzene formaldehyde and 4-(dicyano ethylene)-2-methyl-6-methyl-4H pyrans are carried out the Knoevenagel condensation reaction, obtains described red fluorescence dyestuff under the hexahydropyridine katalysis.
Wherein, reaction alkali commonly used is salt of wormwood, yellow soda ash, potassium hydroxide or sodium hydroxide in the step 1); Temperature of reaction is 30-70 ℃.Step 2) temperature of reaction of Knoevenagel condensation reaction is 60-100 ℃, and reaction solvent is anhydrous acetonitrile or dehydrated alcohol.
Another object of the present invention provides the purposes of The compounds of this invention.
The compounds of this invention is a kind of good electroluminescent material, can be used to make electroluminescent device, and therefore, the electroluminescent device that contains red fluorescence dyestuff of the present invention is also in protection scope of the present invention.
This electroluminescent device generally comprises the Conducting Glass layer, hole injection layer, and hole transmission layer, luminescent layer, electron transfer layer and cathode layer, the guest materials of luminescent material is a red fluorescence dyestuff of the present invention in the luminescent layer; What the guest materials of luminescent material was commonly used in the luminescent layer is 8-hydroxyquinoline aluminum.This device can be prepared according to ordinary method.
Red fluorescent dye compound of the present invention has been strengthened the electronic action that pushes away in Compound D-π-A structure on the one hand by introduce alkoxyl group in the 2-position, helps spectral red shift; Secondly, introduce alkoxyl group, can effectively increase the sterically hindered of molecule, reduce intermolecular pi-pi accumulation effect, thereby reduce concentration quenching under high doping, improve quantum yield.Be that (chromaticity coordinates x=0.63, y=0.37), maximum brightness is all above 8000cd/m at 608-616nm for the electroluminescent device emission wavelength of fluorescent material with this compound
2, top efficiency is 2.04 lumens/watt (2.60 Kan Tela/amperes), it is dye adulterated in material of main part 8-hydroxyquinoline aluminum (Alq to surpass the bibliographical information small molecules
3) in top efficiency.The The compounds of this invention simple synthetic method, electroluminescent properties is good, has broad application prospects.
Description of drawings
Fig. 1 is the structural representation of electroluminescent device of the present invention;
Fig. 2 is the emmission spectrum figure of electroluminescent device of the present invention;
Fig. 3 is the voltage-to-current curve of electroluminescent device of the present invention;
Fig. 4 is the voltage-brightness curve of electroluminescent device of the present invention.
Embodiment
The preparation of embodiment 1,4-(dicyano ethylene)-2-methyl-6-(2-methoxyl group-4-diethylin vinylbenzene) 4H-pyrans (compd A)
1, preparation 4-diethylin-2-methoxybenzaldehyde
19.3g 4-(diethylin) salicylic aldehyde is dissolved in the 250ml acetone, adds 14g exsiccant Anhydrous potassium carbonate (K
2CO
3), add the 15.7g methyl iodide more respectively, add the 0.4g Tetrabutyl amonium bromide, under nitrogen protection, 60 ℃ of back flow reaction 36h.Suction filtration, the solid washed with dichloromethane after filtrate is spin-dried for, with the methylene dichloride dissolving, is used the NaOH solution washing of pH=13 then, washes twice with deionized water again, the organic phase anhydrous Na
2SO
4Drying is filtered, and after being spin-dried for, uses sherwood oil: ether (v: v=1: 1) be eluent, collect yellow band.Product is spin-dried for the back and adds the sherwood oil recrystallization, puts into refrigerator and cooled and freezes, and until there being a large amount of solids to separate out, filtration, drying obtain 4-diethylin-2-methoxybenzaldehyde.
1HNMR：δppm(400MHz)10.12(s，1H)，7.71-7.69(d，1H)，6.30-6.28(m，1H)，6.05(s，1H)，3.89(s，3H)，3.46-3.41(m，4H)，1.25-1.21(t，6H).
m/z(207，48％)，192(100％，-CH
3).
2, preparation 4-(dicyano ethylene)-2-methyl-6-(2-methoxyl group-4-diethylin vinylbenzene) 4H-pyrans (A)
Equimolar 4-(dicyano ethylene)-2-methyl-6-methyl-4H pyrans and 4-diethylin-2-methoxybenzaldehyde are under nitrogen protection; in the exsiccant anhydrous acetonitrile, under hexahydropyridine catalysis, carry out Knoevenagel condensation reaction (S.A.Swanson; G.M.Wallraff; J.P.Chen; W.Zhang, L.D.Bozano, K.R.Carter; J.R.Salem; R.Villa, J.C.Scott, Chem.Mater.2003; 15; 2305.), refluxing behind (80 ℃) reaction 24h, reaction product is after filtration; after the drying; on silicagel column, be that eluent separates, obtain compd A with the methylene dichloride.
1HNMRδppm(400MHz)：7.65-7.61(d，1H)，7.36(d，1H)，6.68-6.64(d，1H)，6.59-6.49(d，1H)，6.33(s，1H)，6.15(s，1H)，3.94(s，3H)，3.46-3.44(m，4H)，2.40(s，3H)，1.57(s，1H)，1.27-1.24(m，8H).
m/z(361，60％)，346(100％，-CH
3).
Ultimate analysis: Calcd.For C
22H
23N
3O
2(M=361.44), C:73.11, H:6.41, N:11.63; Found:73.12,6.64,11.14.
Show that the gained compound structure is correct.
The preparation of embodiment 2,4-(dicyano ethylene)-2-methyl-6-(2-oxyethyl group-4-diethylin vinylbenzene) 4H-pyrans (compd B)
1, preparation 4-diethylin-2-ethoxy-benzaldehyde
Method according to embodiment 1 is prepared, and used halohydrocarbon is a monobromethane, and alkali is anhydrous sodium carbonate, and used phase-transfer catalyst is a tetrabutylammonium iodide, and the temperature of back flow reaction is 80 ℃, obtains 4-diethylin-2-ethoxy-benzaldehyde.
1HNMR：δppm(400MHz)10.19(s，1H)，7.74-7.71(d，1H)，6.31-6.29(d，1H)，6.08(s，1H)，4.41-4.09(q，2H)，3.45-3.39(q，4H)，1.48-1.45(t，3H)，1.24-1.20(t，6H).
m/z(221，42％)，206(100％，-CH
3).
2, preparation compd B
Method according to embodiment 1 is prepared, and used reaction solvent is a dehydrated alcohol, and the back flow reaction temperature is 60 ℃, obtains compd B.
1HNMRδppm(400MHz)：7.65-7.61(d，1H)，7.35(d，1H)，6.67-6.63(d，1H)，6.54-6.48(d，2H)，6.30(s，1H)，6.12(s，1H)，4.14-4.13(d，1H)，3.42-3.41(d，1H)，2.38(s，3H)，1.55(s，1H)，1.53-1.49(t，3H)，1.24-1.21(t，6H).
m/z(375，68％)，360(100％，-CH
3).
Ultimate analysis: Calcd.for C
23H
25N
3O
2(M=375.46), C:73.57, H:6.71, N:11.19; Found:C:72.12, H:6.51, N:11.03.
Show that the gained compound structure is correct.
The preparation of embodiment 3,4-(dicyano ethylene)-2-methyl-6-(2-propoxy--4-diethylin vinylbenzene) 4H-pyrans (Compound C)
1, preparation 4-diethylin-2-propoxy-phenyl aldehyde
Method according to embodiment 1 is prepared, and used halohydrocarbon is a N-PROPYLE BROMIDE, and alkali is anhydrous Na OH, and used phase-transfer catalyst is a tetraethyl ammonium iodide, and the temperature of back flow reaction is 30 ℃, obtains 4-diethylin-2-propoxy-phenyl aldehyde.
1HNMR：δppm(400MHz)10.20(s，1H)，7.73-7.71(d，2H)，6.29-6.27(d，2H)，6.03(s，1H)，4.01-3.98(t，2H)，3.45-3.39(q，4H)，1.89-1.84(m，2H)，1.24-1.20(t，6H)，1.09-1.05(t，3H).
m/z(235，36％)，220(100％，-CH
3).
2, preparation Compound C
Method according to embodiment 1 is prepared, and used reaction solvent is an anhydrous acetonitrile, and the back flow reaction temperature is 100 ℃, obtains Compound C.
1HNMRδppm(400MHz)：7.69-7.65(d，1H)，7.35-7.33(d，1H)，6.65-6.61(d，1H)，6.51-6.47(d，2H)，6.30-6.28(d，1H)，6.11(s，1H)，4.02-3.99(t，3H)，3.44-3.39(m，4H)，2.36(s，3H)，1.94-1.87(m，2H)，1.56(s，1H)，1.25(s，1H)，1.24-1.20(t，6H)，1.13-1.09(t，3H).
m/z：389(94％)，374(100％，-CH
3).
Ultimate analysis: Calcd.For C
24H
27N
3O
2(M=389.49), C:74.01, H:6.99, N:10.79; Found:C:72.36, H:6.92, N:10.29.
Show that the gained compound structure is correct.
The preparation of embodiment 4,4-(dicyano ethylene)-2-methyl-6-(2-butoxy-4-diethylin vinylbenzene) 4H-pyrans (Compound D)
1, preparation 4-diethylin-2-butyl phenyl ether formaldehyde
Method according to embodiment 1 is prepared, and used halohydrocarbon is a bromination of n-butane, and alkali is anhydrous K OH, and used phase-transfer catalyst is a tetraethylammonium bromide, and the temperature of back flow reaction is 80 ℃, obtains 4-diethylin-2-butyl phenyl ether formaldehyde.
1HNMR：δppm(400MHz)：10.20(s，1H)，7.74-7.72(d，1H)，6.32-6.30(d，1H)，6.05(s，1H)，4.06-4.03(t，2H)，3.45-3.40(q，4H)，1.86-1.79(m，2H)，1.58-1.48(m，2H)，1.26-1.20(m，6H)，1.00-0.97(t，3H).
m/z(249，35％)，234(100％，-CH
3).
2, preparation Compound D
Be prepared according to the method for embodiment 1 and obtain Compound D.
1HNMRδppm(400MHz)：7.69-7.65(d，1H)，7.51(d，1H)，6.65(d，1H)，6.50d，2H)，4.09-4.08(s，2H)，3.44-3.43(s，4H)，2.38(s，3H)，1.89-1.85(m，2H)，1.60-1.52(m，2H)，1.25(s，8H)，1.04-1.04(t，3H).
m/z：403(100％)，388(65％，-CH
3).
Show that the gained compound structure is correct.
The preparation of embodiment 5, electroluminescent device and performance
One, the preparation of electroluminescent device
General electroluminescent device comprises conductive glass (ITO) substrate layer, hole injection layer CuPc, hole transmission layer NPB, luminescent layer red dye (guest materials) and material of main part (Alq
3), electron transfer layer AlQ and cathode layer.Can make by methods known in the art, as being undertaken by reference (C.W.Tang and S.A.VanSlyke, Appl.Phys.Lett.1987,51,913.) disclosed method.Concrete grammar is: in high vacuum (less than 2 * 10
-7Holder) under the condition, on through conductive glass (ITO) substrate that cleans, deposits hole injection layer, hole mobile material, luminescent material, hole barrier materials, electron transport material and cathode material successively.
Ito glass sheet (3 * 3mm
2) cleaned about 5 minutes with deionized water and organic solvent ultrasonic cleaning and ultraviolet, place in the vacuum plating unit, be lower than 2 * 10
-7Under the high vacuum condition of holder, monitor the thickness of each layer, hole-injecting material, hole mobile material, red fluorescent dye compound are entrained in Alq with quartz resonator
3In, electron transport material and metallic cathode magnesium silver alloys (Mg
0.9Ag
0.1) deposit on the conductive glass successively.The thickness of doping content and each organic layer can change, so that device obtains better brightness and efficient.The structure of prepared multilayer device as shown in Figure 1.
Guest materials so that four compounds of embodiment 1-4 gained are luminescent layer can make following several device:
Device one: CuPc (5nm)/NPB (15nm)/compd A: Alq
3(30nm, 1%)/Alq
3(30nm)
Device two: CuPc (5nm)/NPB (15nm)/compd B: Alq
3(30nm, 1%)/Alq
3(30nm)
Device three: CuPc (5nm)/NPB (15nm)/Compound C: Alq
3(30nm, 1%)/Alq
3(30nm)
Device four: CuPc (5nm)/NPB (15nm)/Compound D: Alq
3(30nm, 0.8%)/Alq
3(30nm)
Two, the performance of electroluminescent device
When measuring element performance and electroluminescent spectrum, the ITO electrode always links to each other with positive pole.The mensuration of electroluminescent spectrum and brightness is on PhotoScan PR650 spectrograph, when applying a constant voltage (usually between the 3-25 volt) to device, writes down its emmission spectrum, and the result as shown in Figure 2.
The voltage-to-current of four devices (I-V) curve and voltage-brightness (L-V) curve are measured by Keithley 2400Sourcemeter Unit, respectively as shown in Figure 3 and Figure 4.
The performance of four devices that the present invention is prepared is as shown in table 1.
The performance data table of four devices of table 1.
| Compound (doping content) | Trigger voltage/volt | Maximum brightness Kan Tela/square metre | The highest luminous efficiency lumens/watt | Maximum efficiency Kan Tela/ampere | Maximum emission wavelength nm | Chromaticity coordinates (CIE) | Peak width at half height (FWHM)/nm |
| A(1％) | 4 | 10440(14) | 2.04(4) | 2.60(4) | 610 | 0.62，0.38 | 81 |
| B(1％) | 5 | 12540(16) | 0.51(7) | 1.14(8) | 615 | 0.63，0.37 | 86 |
| C(1％) | 4 | 8785(15) | 1.91(4) | 2.43(4) | 608 | 0.61，0.39 | 89 |
| D(0.8％) | 4 | 9783(15) | 1.38(4) | 1.76(4) | 616 | 0.61，0.39 | 89 |
By above result as seen, four devices of the present invention and document (X.T.Tao, S.Miyata, H.Sasabe, G.J.Zhang, T.Wada, M.H.Jiang, Appl.Phys.Lett.2001,78,279.) report red dye (3-dicyanomethylene)-5,5-dimethyl-1-(4-dimethylamino-styryl) cyclohexane (be DCDDC, its high-high brightness is every square metre of 5600 Kan Tela, and maximum efficiency is every watt of 1.6 lumen) compares, it is low to have trigger voltage, high brightness, high-efficiency characteristics.The high-high brightness of four kinds of devices surpasses about a times of bibliographical information, and device one, three luminous efficiencies are all above literature value.
Therefore, compare with other small molecules red dye electroluminescent material and device, The compounds of this invention has higher brightness and better electroluminescent efficiency.The high-high brightness of the electroluminescent device of gained of the present invention and efficient are that present red fluorescence dyestuff directly is doped in Alq
3In the highest in the electroluminescent device as luminescent layer.
Claims (7)
1. the red fluorescent dye compound shown in the formula I,
Wherein, R is that carbonatoms is the alkyl of 1-4.
2. the preparation method of the described red fluorescent dye compound of claim 1, comprise the steps: 1) synthetic 4-diethylin-2-alkoxy benzene formaldehyde: 4-(diethylin)-salicylic aldehyde and halohydrocarbon are reacted under the effect of phase-transfer catalyst and alkali, obtain structure suc as formula the diethylin of the 4-shown in the II-2-alkoxy benzene formaldehyde; Wherein, R is that carbonatoms is the alkyl of 1-4 among the formula II; Described phase-transfer catalyst is tetrabutylammonium iodide, Tetrabutyl amonium bromide, tetraethylammonium bromide or tetraethyl ammonium iodide;
2) synthetic 4-(dicyano ethylene)-2-methyl-6-(2-alkoxyl group-4-diethylin vinylbenzene) 4H-pyrans: 4-diethylin-2-alkoxy benzene formaldehyde and 4-(dicyano ethylene)-2-methyl-6-methyl-4H pyrans are carried out the Knoevenagel condensation reaction, obtains described red fluorescence dyestuff under the hexahydropyridine katalysis.
3. preparation method according to claim 2 is characterized in that: the described alkali of step 1) is salt of wormwood, yellow soda ash, potassium hydroxide or sodium hydroxide; Temperature of reaction is 30-80 ℃.
4. according to claim 2 or 3 described preparation methods, it is characterized in that: step 2) temperature of reaction of described Knoevenagel condensation reaction is 60-100 ℃, reaction solvent is anhydrous acetonitrile or dehydrated alcohol.
5. the electroluminescent device that contains the described red fluorescent dye compound of claim 1.
6. electroluminescent device according to claim 5, it is characterized in that: described electroluminescent device comprises the Conducting Glass layer, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and cathode layer, the guest materials of luminescent material is described red fluorescent dye compound in the described luminescent layer.
7. electroluminescent device according to claim 6 is characterized in that: the material of main part of luminescent material is a 8-hydroxyquinoline aluminum in the described luminescent layer.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5945905B2 (en) * | 2009-08-24 | 2016-07-05 | 国立研究開発法人情報通信研究機構 | Second-order nonlinear optical compound and nonlinear optical element including the same |
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| US5908581A (en) * | 1997-04-07 | 1999-06-01 | Eastman Kodak Company | Red organic electroluminescent materials |
| US5935720A (en) * | 1997-04-07 | 1999-08-10 | Eastman Kodak Company | Red organic electroluminescent devices |
| CN1429878A (en) * | 2001-12-30 | 2003-07-16 | 中国科学院理化技术研究所 | Red fluorescent dye and its systhesis method and use |
-
2005
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5908581A (en) * | 1997-04-07 | 1999-06-01 | Eastman Kodak Company | Red organic electroluminescent materials |
| US5935720A (en) * | 1997-04-07 | 1999-08-10 | Eastman Kodak Company | Red organic electroluminescent devices |
| CN1429878A (en) * | 2001-12-30 | 2003-07-16 | 中国科学院理化技术研究所 | Red fluorescent dye and its systhesis method and use |
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| Title |
|---|
| 有机电致发光红色发光材料研究进展. 马昌期，王雪松，张宝文，曹怡.化学进展，第16卷第3期. 2004 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5945905B2 (en) * | 2009-08-24 | 2016-07-05 | 国立研究開発法人情報通信研究機構 | Second-order nonlinear optical compound and nonlinear optical element including the same |
| US9488755B2 (en) | 2009-08-24 | 2016-11-08 | National Institute Of Information And Communications Technology | Second-order nonlinear optical compound and nonlinear optical element comprising the same |
| US9977150B2 (en) | 2009-08-24 | 2018-05-22 | National Institute Of Information And Communications Technology | Second-order nonlinear optical compound and nonlinear optical element comprising the same |
| US10754064B2 (en) | 2009-08-24 | 2020-08-25 | National Institute Of Information And Communications Technology | Second-order nonlinear optical compound and nonlinear optical element comprising the same |
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