CN1219018C - Red fluorescent dye possessing star project type structure and its synthesis method and use - Google Patents
Red fluorescent dye possessing star project type structure and its synthesis method and use Download PDFInfo
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Abstract
The present invention belongs to the synthesis field of fluorescent dye, particularly to fluorescent dye which is in a star project type structure and can emit red light, a synthesis method and application thereof. Substituted or non-substituted trianilinoaldehyde and catalysts are added into solution of substituted 4-dicyanomethenyl-2-methyl-4H-pyran, wherein the molar ratio of the substituted or non-substituted trianilinoaldehyde to the substituted 4-dicyanomethenyl-2-methyl-4H-pyran is 2 to 5:1, and the molar ratio of the catalysts to the substituted 4-dicyanomethenyl-2-methyl-4H-pyran is 0.5 to 4:1. Through a heating reflux step and a distillation step, solvent is removed. Solid is eluted with solvent and dried, and the red fluorescent dye is obtained. The dye is used in organic photoconductors and organic non-linear optical material, and is also used as luminescent material, etc. in an EL device. A fluorescence emission spectrum of the fluorescent dye is positioned in a red light area of a visible spectrum. The fluorescent dye has the high fluorescence quantum yield.
Description
Technical field
The invention belongs to the synthetic field of fluorescence dye, particularly have fluorescence dye and the synthetic method and the purposes of the red emission of star project type structure.
Background technology
Along with developing rapidly of information technology, people have had higher requirement to the technique of display of high-density and high definition.C.W.Tang in 1987 and S.A.Van Slyke have utilized the method for vacuum moulding machine plated film first in " Applied Physics wall bulletin " 1987 51 volumes 913-915 page or leaf, make hole transmission layer with diamine derivative, oxine aluminium has realized that as luminescent layer brightness is 1000cd/m under the driving voltage of 10V
2Green emission, and the efficient of device is 1.5lm/W, the life-span is more than 100 hours.Since then, organic electroluminescence device is because its volume is little, in light weight, driving voltage is little, and response is fast, the visual angle is wide and can realize red, green, advantages such as blue broken colour demonstration make it realize that big area full color flat pannel display becomes possibility, and become the focus of research, fabulous commerce and market outlook are arranged.
Dyestuff is the core in the organic electroluminescence device.Because can realize dyestuff luminous in designated wavelength range by molecular designing, therefore in the electroluminescent material field, the exploitation of organic functions dyestuff becomes an important research project.Researched and developed green glow and blue light dyestuff preferably at present, green glow is as 8-hydroxyquinoline aluminum (Alq
3); Blue light is as in " Applied Physics wall bulletin " nineteen ninety-fives 67 3853 pages of volumes the carbazole derivative BCzVB of report and BczVBi etc.And the also rare report of red light-emitting dyestuff of present excellent property.
People such as C.W.Tang have proposed to utilize the object luminescent material to be entrained in the method that realizes red emission in the main body luminescent material in United States Patent (USP) (U.S.Pat.No.4,769,292).In this patent, utilize 4-(dicyan methene)-6-methyl-2-(4-dimethylamino styryl)-4H-pyrans (DCM) and 4-(dicyan methene)-6-methyl-2-(julolidine-9-vinyl)-4H-pyrans (DCJ, structural formula 1, R=H), be entrained in main body luminescent material Alq as the object luminescent material
3Realized the red emission of DCM and DCJ in the matrix.Because the object luminescent material is entrained in the main body luminescent material and not only can realizes red emission, but also can improve the efficient of device, therefore, the object doped luminescent material becomes an important component part in the electroluminescent organic material efficiently.
Structural formula 1
Although adulterating method has certain advantage, adulterating method makes the preparation technology of organic electroluminescence device become complicated.The organic molecule light-emitting film normally utilizes the method for vacuum plating to prepare.The preparation of main body light-emitting film is to utilize to carry out the evaporation of single source under certain vacuum tightness; And dye adulterated normally under identical vacuum degree condition, carry out dual-source evaporation, control vaporator rate by the temperature of controlling different evaporation sources, thus the doping content of control dyestuff.Therefore dye adulterated method Billy is more complicated with the method for main body luminescent material, and the control of condition is also strict more; In addition, because the interaction between main body luminescent material and the object luminescent material usually makes the external luminous of device become complicated, as: if the transmission ofenergy that occurs between the subject and object is incomplete, the luminous of main body can not be completely by the quencher of object luminescent material institute so, the external luminous of device this moment will keep the luminous of main body luminescent material, and can not obtain the luminous of pure object luminescent material.In addition, utilize the dye adulterated method of object also to require the object dyestuff to meet the following conditions: (1) dyestuff has high fluorescence quantum yield; (2) emitted energy of main body luminescent material wants high, and the absorption spectrum of object luminescent material will have enough overlapping with the main body luminescent spectrum; (3) glow peak of object luminescent material preferably drops in red, green, blue three color ranges; (4) glow peak of object luminescent dye is narrow, to guarantee the purity of glow color.Therefore, although dye adulterated have some advantages, people more wish the main body luminescent material that can search out to replace using adulterated method.
Because there is the significant concn quenching effect in DCM, when using DCM as the main body luminescent material, device does not almost observe red emission (C.W.Tang, S.A.VanSlyke and C.H.Chen " applicating physical magazine " rolled up 3610 pages in 1989 65).Simultaneously, because the red shift with the increase of concentration of DCM luminescent spectrum, so the doping content of DCM too hour, and the external glow color of device is yellow partially, and can not get real ruddiness; And the doping content of DCM when big device efficiency (as: doping content of DCM is that the luminous efficiency of 0.5% o'clock device is 2.3% to the maximum, but the CIE value of its external luminescent spectrum is X=0.56Y=0.44, and color is Huang partially because concentration quenching effect reduces; C.W.Tang, S.A.VanSlyke and C.H.Chen " applicating physical magazine " rolled up 3610 pages in 1989 65).Although people such as C.W.Tang are at United States Patent (USP) (U.S.Pat.No.4,769,292) (structural formula 1 R=H) change the yellow partially shortcoming of its glow color, but this compound concentrations quenching effect does not improve still to have proposed to utilize julolidine derivative DCJ in.
The DCM that mentions in above-mentioned patent and the document, compounds such as DCJ belong to " donor-pi-acceptor " model compound, promptly comprise one in the molecule and give body group and an acceptor groups, and these two groups link to each other by a π key.As: acceptor groups is 6-methyl-4-(dicyan methene)-4H-pyrans in the DCM molecule, and giving the body group is the 4-dimethylamino-aniline, and they link to each other by an ethylene linkage (π key).Such " donor-pi-acceptor " system forms a chromophoric group.Because a such chromophoric group is planar basically, therefore such molecule is close mutually easily under high density, causes the luminous intensity of dyestuff under high density to descend, i.e. concentration quenching effect.The intensive concentration quenching effect makes dyestuff can not be used as the main body luminescent material; And because concentration quenching effect make that the doping content of dyestuff in device can not be too big, otherwise can reduce the efficient of device, and doping content is not enough, device but can not get pure red emission.
People such as C.W.Tang have designed Compound D CJT (structural formula 1, R=CH according to the mechanism of this concentration quenching
3).Introducing four methyl groups at the DCJT molecule increases the sterically hindered of molecule, is reduced in the interaction between dye molecule under the high density state.This design can more efficiently reduce the concentration quenching effect of dyestuff, and wherein the doping content of DCJT in device can reach 1.5% (C.H.Chen, C.W.Tang, J.Shi, 327 pages of 2000 363 volumes of and K.P.Klubek " solid film ").But the reacting precursor raw material 1,1,7 that this design is used, the synthetic complexity of 7-tetramethyl-julolidine has increased production cost; DCJT is still a kind of " donor-pi-acceptor " architecture compound simultaneously, its spatial configuration of molecules is still a kind of hither plane structure, therefore this class design still can not effectivelyly prevent concentration quenching effect, and resulting compound still can not be used as the main body luminescent material.
Summary of the invention
One of purpose of the present invention provides a kind of red fluorescence dyestuff with star project type structure, and the fluorescence emission spectrum of this fluorescence dye is positioned at the ruddiness zone of visible spectrum, and has very high fluorescence quantum yield.
A further object of the present invention provides a kind of synthetic method with red fluorescence dyestuff of star project type structure, and this method has advantages such as reactions steps is few, yield is high, the product separation and purification is easy.
Another object of the present invention provides a kind of purposes with red fluorescence dyestuff of star project type structure.
The present invention is directed to the defective of current single " donor-pi-acceptor " model compound, designed the dye molecule of a class star project type.Its molecule has following structure:
In the formula, R
1, R
2Be alkyl, substituted alkyl, alkoxyl group, substituted alkoxy, aryl or the substituted aryl etc. that contain carbon number 1 to 10 respectively or simultaneously; R
3Be hydrogen, the alkyl that contains carbon number 1 to 10, substituted alkyl alkoxyl group or substituted alkoxy; R
4For hydrogen, contain alkyl, the substituted alkyl of carbon number 1 to 10 or R
4Same R
2Form the replacement or the unsubstituted carbocyclic ring chain of 5,6 or 7 yuan of rings; R
5For hydrogen, contain the alkyl or the substituted alkyl of carbon number 1 to 10; R
6For hydrogen, contain alkyl, the substituted alkyl of carbon number 1 to 10 or R
6Same R
5Form the replacement or the unsubstituted carbocyclic ring chain of 5,6 or 7 yuan of rings; R
7, R
8Respectively or simultaneously for hydrogen, halogen, contain alkyl, substituted alkyl, alkoxyl group or the substituted alkoxy etc. of carbon number 1 to 10.
Have three acceptors and one in the star project type molecule of the present invention design and give body unit, and each is subjected to body unit to pass through a π key with linking to each other to body unit, thereby form " donor-pi-acceptor " luminescence system.Therefore, the present invention designs and has three chromophoric groups in the synthetic molecule.Simultaneously, because the space structure of the formed uniqueness of triphenylamine, make three chromophoric groups in the molecule be in the on-plane surface state, it is close mutually to make that like this dye molecule is difficult under the high density state, reduce intermolecular interaction under the high density, thereby reduce the luminous concentration self quenching phenomenon of dyestuff greatly.
The synthetic method of red fluorescence dyestuff of the present invention have raw material be simple and easy to, advantage such as reactions steps is few, yield is high, the product separation and purification is easy.It is synthetic to be undertaken by following reaction formula:
Wherein raw material A is the 4-dicyan methene-2-methyl-4H-pyrans of replacement, and it has following structure:
In the formula, R
1, R
2Be alkyl, substituted alkyl, alkoxyl group, substituted alkoxy, aryl or the substituted aryl etc. that contain carbon number 1 to 10 respectively or simultaneously; R
3Be hydrogen, the alkyl that contains carbon number 1 to 10, substituted alkyl alkoxyl group or substituted alkoxy; R
4For hydrogen, contain alkyl, the substituted alkyl of carbon number 1 to 10 or R
4Same R
2Form the replacement or the unsubstituted carbocyclic ring chain of 5,6 or 7 yuan of rings; R
5For hydrogen, contain the alkyl or the substituted alkyl of carbon number 1 to 10; R
6For hydrogen, contain alkyl, the substituted alkyl of carbon number 1 to 10 or R
6Same R
5Form the replacement or the unsubstituted carbocyclic ring chain of 5,6 or 7 yuan of rings.
Raw material B is for replacing or unsubstituted triphenylamine aldehyde, and it has following structure:
R in the above-mentioned formula
7, R
8Respectively or simultaneously for hydrogen, halogen, contain alkyl, substituted alkyl, alkoxyl group or the substituted alkoxy etc. of carbon number 1 to 10.
Concrete synthetic method is as follows:
In replacing 4-dicyan methene-2-methyl-4H-pyrans solution, add and replace or unsubstituted triphenylamine aldehyde and catalyzer, wherein, the volumetric molar concentration that replaces 4-dicyan methene-2-methyl-4H-pyrans solution is 0.01-0.5mol/L, replacement or unsubstituted triphenylamine aldehyde are 2-5 with the mol ratio that replaces 4-dicyan methene-2-methyl-4H-pyrans: 1, catalyzer is 0.5-4 with the mol ratio that replaces 4-dicyan methene-2-methyl-4H-pyrans: 1, and reflux 5-35 hour; Distillation removes and desolvates, the solid eluent solvent, and drying obtains red fluorescence dyestuff.
Employed solvent is an intensive polar solvent in above-mentioned synthetic method, as N, and the mixed solvent of N-diformamide (DMF), chloroform, acetonitrile, acetate, diacetyl oxide, ethanol, methyl alcohol or the arbitrary proportion between them etc.
In above-mentioned synthetic method, employed catalyzer is the mixture of morphine quinoline, hexahydropyridine, triethylamine, diethylamine, formic acid, acetate, phosphoric acid, hydrochloric acid, sulfuric acid or their arbitrary proportions etc.
Dyestuff of the present invention is used for organic photoconductor, organic non linear optical material, fluorescent material, the photoelectric functional device and in electroluminescent device as luminescent material.
The invention provides a kind of brand-new red fluorescence dyestuff, the fluorescence emission spectrum of this fluorescence dye is positioned at the ruddiness zone of visible spectrum; And this fluorescence dye has very high fluorescence quantum yield.
Table 1 has provided several compound of the present invention at solution and the fluorescence data under the solid film state.
Table 1
| Compound | Maximum absorption wavelength (nm) | Maximum fluorescence wavelength (nm) | Fluorescence quantum yield * | ||
| Solid film | Chloroformic solution | Solid film | Chloroformic solution | ||
| Embodiment 1 embodiment 2 embodiment 5 embodiment 6 | 489 512 517 535 | 475 501 507 512 | 632 635 621 656 | 611 615 608 621 | 0.54 0.77 0.87 0.75 |
*: with respect to DCM
Red fluorescence dyestuff of the present invention has the star project type structure system, has formed three chromophoric group in the red fluorescence dyestuff molecule of the present invention.And three chromophoric groups in the molecule are in the on-plane surface state, and such dye molecule is difficult to close mutually under the high density state, reduce intermolecular interaction under the high density, thereby reduce the luminous concentration self quenching phenomenon of dyestuff greatly.
Red fluorescence dyestuff of the present invention has good electroluminescent properties and good red color characteristic, and therefore red fluorescence dyestuff of the present invention can be used as the red light-emitting dyestuff in electroluminescent device.Fig. 2 has provided embodiment 1 as the electroluminescent spectrum figure in the electroluminescent device in Fig. 1 structure.
The present invention relates to the fluorescence dye that synthetic has red emission, have long lifetime of excited state and very high fluorescence quantum yield, and good light, heat, chemical stability and good photoconductive property.The fluorescence dye that the designed synthetic of the present invention has red emission can be used as organic photoconductor, and non-linear organic functional material etc. can be used for making the photoelectric functional device, as: solar cell, organic electroluminescent etc.
Description of drawings
Fig. 1 is for utilizing the electroluminescent device structure of the embodiment of the invention 1 (Red 1) as the main body luminescent material.N wherein, N '-two-(3-aminomethyl phenyl)-N, N '-phenylbenzene-1,1 '-biphenyl-4,4 '-diamines (TPD) is as hole transmission layer, embodiment 1 (Red 1) compound N, N, N-three-4-[2-[(4-dicyan methene)-and 8-methyl-5,6,7,8-tetrahydrochysene-4H-1-chromene] vinyl] aniline is as the main body luminescent layer, LiF is as buffer layer, and plates layer of metal Al on the LiF layer, as the negative electrode of device.
Fig. 2 is the electroluminescent spectrum figure with electroluminescent device of Fig. 1 structure.
Embodiment
Further describe the synthetic method and the advantage thereof of red fluorescence dyestuff of the present invention in conjunction with the following examples and accompanying drawing.
Embodiment 1:N, N, N-three-4-[2-[(4-dicyan methene)-8-methyl-5,6,7,8-tetrahydrochysene-4H-1-chromene] vinyl] aniline
In round-bottomed flask, add 0.90g (4mmol) 4-dicyan methene-2,8-dimethyl-5,6,7,8-tetrahydrochysene-4H-1-chromene, 0.33g (1mmol) N, N, N-three-(4-formyl radical) aniline, 15ml acetonitrile, 0.40ml hexahydropyridine, reflux 24 hours.Steaming is slipped to remove and is desolvated, cooling, and solid is used acetonitrile drip washing repeatedly, and drying gets product 0.67g, yield 70%.
Nuclear-magnetism
1H NMR (CDCl
3) δ (ppm): 1.38 (d, 9H, J=6.7Hz), 1.55-2.10 (m, 12H), 2.80-3.10 (m, 9H), 6.60 (d, 3H), 6.75 (s, 3H), 7.15 (d, 6H), 7.30 (d, 3H), 7.46 (d, 6H);
Ultimate analysis calculated value (C
63H
51N
7O
3): C, 79.31; H, 5.39; N, 10.28;
Measured value: C, 79.18; H, 5.52; N, 10.11
Mass spectrum (MS
+): 953 (M
+)
Embodiment 2:N, N, N-three-4-[2-[(4-dicyan methene)-6-sec.-propyl-4H-pyrans] vinyl] aniline
In round-bottomed flask, add 0.70g (3.5mmol) 4-dicyan methene-2-methyl-6-sec.-propyl-4H-pyrans; 0.33g (1mmol) N; N; N-three-(4-formyl radical) aniline; the 15ml acetonitrile; 0.40ml catalyzer (its preparation method is: the 5ml hexahydropyridine is dissolved in the 15ml acetate), reflux 12 hours.Steaming is slipped to remove and is desolvated, cooling, and solid is used acetonitrile drip washing repeatedly, and drying gets product 0.59g, yield 65%.
Nuclear-magnetism
1H NMR (CDCl
3) δ (ppm): 1.42 (d, 18H), 2.8 (m, 3H), 6.59 (d, 3H), 6.72 (s, 3H), 6.81 (s, 3H), 7.15 (d, 6H), 7.32 (d, 3H), 7.51 (d, 6H)
Ultimate analysis calculated value (C
57H
45N
7O
2): C, 78.15; H, 5.18; N, 11.19
Measured value: C, 78.32; H, 5.05; N, 11.41
Mass spectrum (MS
+): 875 (M
+)
Embodiment 3:N, N, N-three-4-[2-[(4-dicyan methene)-6-sec.-propyl-4H-pyrans] vinyl] aniline
In round-bottomed flask, add 0.70g (3.5mmol) 4-dicyan methene-2-methyl-6-sec.-propyl-4H-pyrans, 0.33g (1mmol) N, N, N-three-(4-formyl radical) aniline, 15ml acetonitrile, 0.40ml hexahydropyridine, reflux 12 hours.Steaming is slipped to remove and is desolvated, cooling, and solid is used acetonitrile drip washing repeatedly, and drying gets product 0.66g, yield 75%.
Nuclear-magnetism
1H NMR (CDCl
3) δ (ppm): 1.40 (d, 18H), 2.8 (m, 3H), 6.60 (d, 3H), 6.72 (s, 3H), 6.81 (s, 3H), 7.15 (d, 6H), 7.32 (d, 3H), 7.51 (d, 6H)
Ultimate analysis calculated value (C
57H
45N
7O
2): C, 78.15; H, 5.18; N, 11.19
Measured value: C, 78.21; H, 5.15; N, 11.38
Mass spectrum (MS
+): 875 (M
+)
Embodiment 4:N, N, N-three-4-[2-[(4-dicyan methene)-the 6-tertiary butyl-4H-pyrans] vinyl] aniline
In round-bottomed flask, add 0.64g (3mmol) 4-dicyan methene-2-methyl-6-tert butyl-4H-pyrans; 0.33g (1mmol) N; N; N-three-(4-formyl radical) aniline; the 15ml acetonitrile; 0.40ml catalyzer (its preparation method is: the 5ml hexahydropyridine is dissolved in the 15ml acetate), reflux 8 hours.Steaming is slipped to remove and is desolvated, cooling, and solid is used acetonitrile drip washing repeatedly, and drying gets product 0.65g, yield 71%.
Nuclear-magnetism
1H NMR (CDCl
3) δ (ppm): 1.39 (d, 27H), 6.54 (d, 3H), 6.70 (s, 3H), 6.78 (s, 3H), 7.12 (d, 6H), 7.33 (d, 3H), 7.55 (d, 6H)
Ultimate analysis calculated value (C
60H
51N
7O
3): C, 78.49; H, 5.60; N, 10.68
Measured value: C, 78.13; H, 5.85; N, 10.84
Mass spectrum (MS
+): 917 (M
+)
Embodiment 5:N, N, N-three-4-[[(4-dicyan methene)-2-sec.-propyl-5,6,7,8-tetrahydrochysene-4H-1-chromene-8-yl] methene] aniline
In round-bottomed flask, add 0.96g (4mmol) 4-dicyan methene-2-sec.-propyl-5; 6; 7; 8-tetrahydrochysene-4H-1-chromene, 0.33g (1mmol) N, N; N-three-(4-formyl radical) aniline; the 15ml acetonitrile, 0.5ml catalyzer (its preparation method is: the 5ml hexahydropyridine is dissolved in the 15ml acetate), reflux 30 hours.Steaming is slipped to remove and is desolvated, cooling, and solid is used acetonitrile drip washing repeatedly, and drying gets product 0.67g, yield 67%.
Nuclear-magnetism
1H NMR (CDCl
3) δ (ppm): 1.42 (d, 18H), 1.5-2.2 (m, 12H), 2.8-3.1 (m, 9H), 6.59 (s, 3H), 6.72 (s, 3H), 7.15 (d, 6H), 7.51 (d, 6H)
Ultimate analysis calculated value (C
66H
57N
7O
3): C, 79.57; H, 5.77; N, 9.84
Measured value: C, 79.13; H, 5.85; N, 9.85
Mass spectrum (MS
+): 995 (M
+)
Embodiment 6:N, N, N-three-[4-[2-[(4-dicyan methene)-6-sec.-propyl-4H-pyrans] vinyl]-the 3-methoxyl group] aniline
In round-bottomed flask, add 0.76g (3.8mmol) 4-dicyan methene-2-methyl-6-sec.-propyl pyrans; 0.42g (1mmol) N; N; N-three-(3-methoxyl group-4-formyl radical) aniline; the 15ml acetonitrile; 0.60ml catalyzer (its preparation method is: the 5ml hexahydropyridine is dissolved in the 15ml acetate), reflux 24 hours.Steaming is slipped to remove and is desolvated, cooling, and solid is used acetonitrile drip washing repeatedly, and drying gets product 0.59g, yield 61%.
Nuclear-magnetism
1H NMR (CDCl
3) δ (ppm): 1.40 (d, 18H), 2.8 (m, 3H), 4.41 (s, 9H), 6.60 (d, 3H), 6.72 (s, 3H), 6.81 (s, 3H), 7.0-7.5 (m, 12H)
Ultimate analysis calculated value (C
60H
51N
7O
6): C, 74.59; H, 5.32; N, 10.15
Measured value: C, 74.31; H, 5.50; N, 10.42
Mass spectrum (MS
+): 965 (M
+)
Embodiment 7:N, N, N-three-[4-[2-(4-dicyan methene)-7-methyl-6,7-dihydro-4 (5H)-cyclopentano pyrans] vinyl] phenylaniline
In round-bottomed flask, add 0.85g (4mmol) 4-dicyan methene-2; 7-dimethyl-6; 7-dihydro-4 (5H)-cyclopentano pyrans; 0.33g (1mmol) N; N, N-three-(4-formyl radical) aniline, 15ml chloroform; 0.40ml catalyzer (its preparation method is: the 5ml hexahydropyridine is dissolved in the 15ml acetate), reflux 35 hours.Steaming is slipped to remove and is desolvated, cooling, and solid is used acetonitrile drip washing repeatedly, and drying gets product 0.47g, yield 68%.
Nuclear-magnetism
1H NMR (CDCl
3) δ (ppm): 1.37 (d, 9H), 1.5-2.1 (m, 6H), 2.89 (m, 9H), 6.60 (d, 3H), 6.75 (s, 3H), 7.15 (d, 6H), 7.32 (d, 3H), 7.51 (d, 6H)
Ultimate analysis calculated value (C
60H
45N
7O
3): C, 79.01; H, 4.97; N, 10.75
Measured value: C, 79.13; H, 5.10; N, 10.54
Mass spectrum (MS
+): 911 (M
+)
Embodiment 8:N, N, N-three-[4-[2-(4-dicyan methene)-7-methyl-6,7-dihydro-4 (5H)-cyclopentano pyrans] vinyl] phenylaniline
In round-bottomed flask, add 0.85g (4mmol) 4-dicyan methene-2; 7-dimethyl-6; 7-dihydro-4 (5H)-cyclopentano pyrans; 0.33g (1mmol) N; N, N-three-(4-formyl radical) aniline, 15ml acetonitrile and 2ml chloroform; 0.50ml catalyzer (its preparation method is: the 5ml hexahydropyridine is dissolved in the 15ml acetate), reflux 24 hours.Steaming is slipped to remove and is desolvated, cooling, and solid is used acetonitrile drip washing repeatedly, and drying gets product 0.61g, yield 89%.
Nuclear-magnetism
1H NMR (CDCl
3) δ (ppm): 1.37 (d, 9H), 1.5-2.1 (m, 6H), 2.89 (m, 9H), 6.60 (d, 3H), 6.75 (s, 3H), 7.15 (d, 6H), 7.32 (d, 3H), 7.51 (d, 6H)
Ultimate analysis calculated value (C
60H
45N
7O
3): C, 79.01; H, 4.97; N, 10.75
Measured value: C, 79.13; H, 5.10; N, 10.54
Mass spectrum (MS
+): 911 (M
+)
Embodiment 9: the preparation of electroluminescent device and performance
The electroluminescent device structure of the sign dyestuff among the present invention is a three-decker, is respectively hole transmission layer, luminescent layer, buffer layer.Luminescent layer wherein is the main body luminescent material for utilizing the embodiment of the invention 1.This device architecture is specific as follows:
1.ITO conductive glass, this conductive glass fully cleans with ultrasonic wave successively, and washed with de-ionized water is removed grease in benzene vapour, and in ozone atmosphere with behind the ultra violet lamp several minutes as the substrate and the anode of electroluminescent device.
2. evaporation plates one deck hole transmission layer on ITO, and material is N, N '-two-(3-aminomethyl phenyl)-N, N '-phenylbenzene-1,1 '-biphenyl-4,4 '-diamines (TPD).
4. utilize embodiment 1 as the vacuum plating of main body luminescent material on hole transmission layer.
5. on luminescent layer, plate one deck buffer layer LiF.
6. on the LiF layer, plate layer of metal Al, as the negative electrode of device.
The luminescent spectrum figure of this device when voltage is 15.2V as shown in Figure 2, its maximum emission wavelength is 650nm, brightness is 622cd/m
2, this color is demarcated by CIE chromaticity coordinates in 1931 and is X=0.63, and Y=0.36 is the red light-emitting device of a standard.
Claims (9)
1. red fluorescence dyestuff with star project type structure, it is characterized in that: this dyestuff has following structure:
In the formula, R
1, R
2Be alkyl, substituted alkyl, alkoxyl group, substituted alkoxy, aryl or the substituted aryl that contains carbon number 1 to 10 respectively or simultaneously; R
3Be hydrogen, the alkyl that contains carbon number 1 to 10, substituted alkyl alkoxyl group or substituted alkoxy; R
4For hydrogen, contain alkyl, the substituted alkyl of carbon number 1 to 10 or R
4Same R
2Form the replacement or the unsubstituted carbocyclic ring chain of 5,6 or 7 yuan of rings; R
5For hydrogen, contain the alkyl or the substituted alkyl of carbon number 1 to 10; R
6For hydrogen, contain alkyl, the substituted alkyl of carbon number 1 to 10 or R
6Same R
5Form the replacement or the unsubstituted carbocyclic ring chain of 5,6 or 7 yuan of rings; R
7, R
8Respectively or simultaneously for hydrogen, halogen, contain alkyl, substituted alkyl, alkoxyl group or the substituted alkoxy of carbon number 1 to 10.
2. synthetic method with red fluorescence dyestuff of star project type structure as claimed in claim 1, it is characterized in that: synthetic method is: add replacement or unsubstituted triphenylamine aldehyde and catalyzer in replacing 4-dicyan methene-2-methyl-4H-pyrans solution, wherein replacement or unsubstituted triphenylamine aldehyde are 2-5 with the mol ratio that replaces 4-dicyan methene-2-methyl-4H-pyrans: 1, catalyzer is 0.5-4 with the mol ratio that replaces 4-dicyan methene-2-methyl-4H-pyrans: 1, and reflux; Distillation removes and desolvates, the solid eluent solvent, and drying obtains red fluorescence dyestuff.
3. method as claimed in claim 2 is characterized in that: the 4-dicyan methene of described replacement-2-methyl-4H-pyrans, and it has following structure:
In the formula, R
1, R
2Be alkyl, substituted alkyl, alkoxyl group, substituted alkoxy, aryl or the substituted aryl that contains carbon number 1 to 10 respectively or simultaneously; R
3Be hydrogen, the alkyl that contains carbon number 1 to 10, substituted alkyl alkoxyl group or substituted alkoxy; R
4For hydrogen, contain alkyl, the substituted alkyl of carbon number 1 to 10 or R
4Same R
2Form the replacement or the unsubstituted carbocyclic ring chain of 5,6 or 7 yuan of rings; R
5For hydrogen, contain the alkyl or the substituted alkyl of carbon number 1 to 10; R
6For hydrogen, contain alkyl, the substituted alkyl of carbon number 1 to 10 or R
6Same R
5Form the replacement or the unsubstituted carbocyclic ring chain of 5,6 or 7 yuan of rings.
4. method as claimed in claim 2 is characterized in that: described replacement or unsubstituted triphenylamine aldehyde, and it has following structure:
R in the above-mentioned formula
7, R
8Respectively or simultaneously for hydrogen, halogen, contain alkyl, substituted alkyl, alkoxyl group or the substituted alkoxy of carbon number 1 to 10.
5. method as claimed in claim 2 is characterized in that: described solvent is N, N-diformamide, chloroform, acetonitrile, acetate, diacetyl oxide, ethanol, methyl alcohol or their mixed solvent.
6. method as claimed in claim 2 is characterized in that: described catalyzer is morphine quinoline, hexahydropyridine, triethylamine, diethylamine, formic acid, acetate, phosphoric acid, hydrochloric acid, sulfuric acid or their mixture.
7. method as claimed in claim 2 is characterized in that: the volumetric molar concentration of described replacement 4-dicyan methene-2-methyl-4H-pyrans solution is 0.01-0.5mol/L.
8. method as claimed in claim 2 is characterized in that: the described reflux time is 5-35 hour.
9. purposes with red fluorescence dyestuff of star project type structure as claimed in claim 1, it is characterized in that: this dyestuff is used for organic photoconductor, organic non linear optical material, fluorescent material, the photoelectric functional device and in electroluminescent device as luminescent material.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 02146048 CN1219018C (en) | 2002-10-28 | 2002-10-28 | Red fluorescent dye possessing star project type structure and its synthesis method and use |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02146048 CN1219018C (en) | 2002-10-28 | 2002-10-28 | Red fluorescent dye possessing star project type structure and its synthesis method and use |
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| CN1493645A CN1493645A (en) | 2004-05-05 |
| CN1219018C true CN1219018C (en) | 2005-09-14 |
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| CN 02146048 Expired - Fee Related CN1219018C (en) | 2002-10-28 | 2002-10-28 | Red fluorescent dye possessing star project type structure and its synthesis method and use |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1317334C (en) * | 2004-05-20 | 2007-05-23 | 中国科学院化学研究所 | Intermolecular charge transfer type fluorescent dyes and use thereof |
| CN1293164C (en) * | 2004-06-11 | 2007-01-03 | 中国科学院化学研究所 | Host red luminous material with charge transferring structure and its prepn and application |
| CN100389168C (en) * | 2006-04-04 | 2008-05-21 | 吉林大学 | Method for making same dye molecule emit light with different colors by substrate induction |
| WO2014085858A1 (en) * | 2012-12-04 | 2014-06-12 | The University Of Queensland | Method for the detection of analytes via luminescence quenching |
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2002
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Assignee: Zhejiang Osi Chemistry Co., Ltd. Assignor: Technical Institute of Physics and Chemistry, CAS Contract fulfillment period: 2007.6.18 to 2012.6.18 contract change Contract record no.: 2008330000706 Denomination of invention: Red fluorescent dye possessing star project type structure and its synthesis method and use Granted publication date: 20050914 License type: Exclusive license Record date: 2008.9.27 |
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