CN103242823B - O,O two-tooth type organic boron difluoride fluorescent dye and preparation method thereof - Google Patents
O,O two-tooth type organic boron difluoride fluorescent dye and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an O,O two-tooth type organic boron difluoride fluorescent dye. The dye is the compound shown in the structural general formula I in the specification and is prepared by complexing a beta-dicarbonyl compound and boron trifluoride diethyl ether. The dye has the advantages of simplicity in reaction operation, easiness in obtaining reaction reagents and high product yield. The prepared red fluorescent dye in the general formula I has the characteristic of fluorescence emission in both solution and solid states and can be used for preparing fluorescent probes, OLED (organic light emitting diode) display materials and dye-sensitized solar cells. In particular, the dye also has the characteristic of fluorescence emission in the solid state, and the characteristic greatly widens the application range of the organic boron fluorescent dye.
Description
Technical field
The present invention relates to organic boron difluoride fluorescence dye and preparation method thereof, be specifically related to a kind of organic boron difluoride fluorescence dye taking 2-acyl group indone derivative as part.
Background technology
Boron atom has sky p track and easily attracts π-electron, and makes system that the charge migration of p-π type occur.Organic boron difluoride compound is very important one in fluorescence dye, because it contains boron atom and large pi-conjugated system possesses compared with the feature of charge migration in macromole and rigid structure.According to ligating atom difference, can be divided into N, N bis-flute profiles, N, O bis-flute profiles, O, O bis-flute profile three kinds of (Org.Lett., 2010,12,4010; Org.Lett., 2012,14,1528; Angew.Chem.Int.Ed.2011,50,12214; Org.Lett., 2011,13,6544; Org.Lett., 2010,12,1272; J.Am.Chem.Soc., 2008,130,4089.J.Am.Chem.Soc., 2010,132,13992; Org.Lett., 2010,12,2900).At present, N, N bis-flute profile organic boron difluoride fluorescence dye most species.Wherein again with pyrroles's methine compounds the most representative (Chme.Rev., 2007,107,4891).
O, the research of O bis-flute profile organic boron difluoride fluorescence dyes is relatively less, thus the part of this type is normally used for improving with transiting state metal coordination stability and the reactive behavior (J.Mater.Chem., 2010,20,2063) of its chromic systems.
Although prior art has been carried out systematic research to organic boron difluoride fluorescence dye, some also disclosed had the organic boron difluoride fluorescence dye of special construction.But there is the organic boron difluoride fluorescence dye of solid fluorescence transmitting or fewer from the situation of report, for example in document, report a kind of N with solid fluorescence, O bis-flute profile organic boron difluoride fluorescence dye (Org.Lett., 2011,13,6544).Showing at present about the research of organic boron difluoride fluorescence dye with solid fluorescence, also in the desk study stage, has pending further research, to the solid state fluorescence compound more widely with different fluorescence colors is provided.
Summary of the invention
The object of the invention is to provide a kind of O with solution and solid fluorescence, O bis-flute profile organic boron difluoride fluorescence dyes.Another object of the present invention has been to provide above-mentioned O, the preparation method of O bis-flute profile organic boron difluoride fluorescence dyes, and this preparation method's raw material is easy to get, simple to operate, product yield is high, can greatly save man power and material.
A kind of O, O bis-flute profile organic boron difluoride fluorescence dyes, the general structure of this fluorescent dye compound I is:
In formula: R representative does not have the aryl replacing or has the aryl of replacement.
As preferably, described do not have the aryl replacing to be: phenyl, thienyl and naphthyl.
As preferably, described in have the aryl of replacement to be: 4-bromophenyl, 4-aminomethyl phenyl and 4-p-methoxy-phenyl.
A kind of above-mentioned O, the preparation method of O bis-flute profile organic boron difluoride fluorescence dyes, this preparation method comprises the steps:
A. select beta-dicarbonyl compound II and boron trifluoride diethyl etherate as raw material, be dissolved in anhydrous organic solvent, form solution, the general structure of described beta-dicarbonyl compound II is:
In formula: R representative does not have the aryl replacing or has the aryl of replacement;
B. use on nitrogen purging reaction soln layer of air 2 minutes, form dry indifferent gas environment;
C. in the solution of step a, inject acid binding agent, the raw material boron trifluoride diethyl etherate of reinjecting;
D. the solution in step c is heated to anhydrous organic solvent reflux temperature, carries out complex reaction;
E., after question response finishes, water will react cancellation;
F. extraction merges organic phase, and with desiccant dryness;
G. organic phase vacuum is spin-dried for, obtains thick product;
H. thick product carries out chromatographic column separation in silica gel or neutral alumina column, and eluent is selected from any one or both the above arbitrary combination in sherwood oil, methylene dichloride and chloroform;
I. elutriant vacuum is spin-dried for, obtains finished product.
As preferably, the consumption of described boron trifluoride diethyl etherate and beta-dicarbonyl compound II is 7:1 according to the ratio of mol ratio.
As preferably, described acid binding agent is triethylamine; The consumption of triethylamine and beta-dicarbonyl compound II is 6:1 according to the ratio of mol ratio.
As preferably, described anhydrous organic solvent is methylene dichloride.
Beneficial effect of the present invention is:
O provided by the invention, O bis-flute profile organic boron difluoride fluorescence dyes, are by having O, and the 2-acyl group indone derivative of O bis-flute profile parts reacts and obtains under alkaline anhydrous condition with boron trifluoride diethyl etherate, and as an example of methylene chloride reflux temperature example, its reaction formula is as follows:
The compounds of this invention is dissolved in after chloroform under UV-irradiation, has the fluorescence of different wave length with substituting group difference.It is worth mentioning that, this class O provided by the invention, O bis-flute profile organic boron difluoride fluorescence dyes have equally fluorescent emission under solid state, therefore can be used for preparing laser dyes, information storage medium, luminescent material and sun power sensitizing dye battery, and effect is very good.
O provided by the invention, O bis-flute profile organic boron difluoride fluorescence dyes are new compounds that a class can produce blue solution fluorescence.This O, O bis-flute profile organic boron difluoride fluorescence dye stable chemical natures, thermostability are strong, molar extinction coefficient ε is large, and maximum stokes (Stokes) displacement reaches 79nm.Its solid has advantages of that under 365nm UV-irradiation solid fluorescence is that it is maximum, and having overcome organic boron fluorescence dye solid state does not have the defect of fluorescent emission, widened the range of application of organic boron fluorescence dye.
In addition, O provided by the invention, the preparation method of O bis-flute profile organic boron difluoride fluorescence dyes, compared with other existing organic boron difluoride fluorescence dyes of preparation, its raw material is easy to get, simple to operate, product yield is high, can greatly save man power and material.
Embodiment
Fusing point data are recorded by X-4 digital micro-analysis melting point apparatus.In Bruker Avance II DMX500MHz liquid NMR spectrometer with superconducting magnet, with CDCl
3make solvent, trimethyl silane (TMS) does interior mark, measures respectively
1h NMR spectrogram and
13c NMR spectrogram; Ultraviolet spectrum data is measured on the UV765 of Shanghai Precision Scientific Apparatus Co., Ltd ultraviolet-visible spectrophotometer.Fluorescence data is measured in Hitachi F-2500 type fluorescence spectrophotometer.According to Law of Lambert-Beer, be figure with sample concentration and its absorbance, the slope of gained straight line is the molar absorptivity of this sample; Adopt dilute solution relative method, the fluorescence quantum yield according to following formula calculation sample:
Φ
x=Φ
s(F
x/F
s)(A
s/A
x)(n
x/n
s)
2
X representative sample in formula, S represents reference substance; Φ represents fluorescent quantum yield, and F represents the fluorescence emission peak area integral under a certain excitation wavelength, and A represents the absorbance of a certain excitation wavelength, the refractive index that n is dilute solution.Be reference substance at this with rhodamine B (in methanol solution, fluorescence quantum yield 0.9), measure the fluorescence quantum yield of compound.Stokes (Stokes) displacement is defined as maximum absorption wavelength (UV: λ
ab) and maximum emission wavelength (FL: λ
em) between difference.
Embodiment 1:
The first O, O bis-flute profile organic boron difluoride fluorescence dyes, this kind of fluorescence dye is expressed as compound 1 in the present embodiment 1, and the structural formula of compound 1 is:
The method of preparing this compound 1 is as follows: at room temperature, 2-benzoyl indone (5mmol, 1.18g) is dropped in 50mL two-mouth bottle, add anhydrous methylene chloride (5mL) solution.After nitrogen purging 2 minutes, use 10mL syringe respectively triethylamine (30mmol, 5mL) and boron trifluoride diethyl etherate (35mmol, 5mL) to be injected to reaction soln.Water cancellation reaction react 2h at methylene chloride reflux temperature after.With dichloromethane extraction 2～3 times, merge organic phase.Use again anhydrous Mg
2sO
4dry organic phase.Finally, after organic phase vacuum is spin-dried for by thick gained product the chromatographic column separating-purifying with the silica gel of 30 times of its weight, the mixed solution being mixed with taking the ratio of methylene dichloride and sherwood oil as 4:1, as eluent, is collected R
fvalue is 0.45 elutriant.Vacuum is spin-dried for and obtains yellow solid compound, is compound 1 finished product of said structure formula, and the productive rate of the method is 83.3%.
The character of this compound 1 is as follows:
Fusing point: 214-215 DEG C.
Under 365nm UV-irradiation, the solid fluorescence effect of compound 1 is yellow.
UV (CHCl
3): λ
ab=373nm(ε=3.7 × 10
4m
-1cm
-1, ε is molar absorptivity).
FL (CHCl
3): λ
em=425nm, Φ=0.46(Φ represents fluorescent quantum yield)
1H?NMR(500MHz,CDCl
3,ppm):δ4.11(s,2H,CH
2),7.51-7.60(m,3H,Ar-H),7.64-7.69(m,2H,Ar-H),7.72-775(m,1H,Ar-H),8.02(d,J=7.8HZ1H,Ar-H),8.03-8.08(m,2H,Ar-H).
13C?NMR(125MHz,CDCl
3,ppm):δ33.4,110.4,124.8,125.6,128.5,129.1,129.8,132.9,134.0,134.2,135.5,149.7,176.3,187.7.
Mass spectrum calculated value: 284.0, measured value: 284.0.
Embodiment 2
The second O, O bis-flute profile organic boron difluoride fluorescence dyes, this kind of fluorescence dye is expressed as compound 2 in the present embodiment, and the structural formula of compound 2 is:
The method of preparing this compound 2 is as follows: under room temperature, 2-Thenoyl indone (5mmol, 1.21g) is dropped in 50mL two-mouth bottle, add anhydrous methylene chloride (5mL) solution.After nitrogen purging 2 minutes, use 10mL syringe respectively triethylamine (30mmol, 5mL) and boron trifluoride diethyl etherate (35mmol, 5mL) to be injected to reaction soln.Water cancellation reaction react 2h at methylene chloride reflux temperature after.With dichloromethane extraction 2～3 times, merge organic phase.Use again anhydrous Mg
2sO
4dry organic phase.Finally, after organic phase vacuum is spin-dried for by thick gained product the chromatographic column separating-purifying with the silica gel of 30 times of its weight, the mixed solution being mixed with taking the ratio of methylene dichloride and sherwood oil as 4:1, as eluent, is collected R
fvalue is 0.38 elutriant.Vacuum is spin-dried for and obtains yellow solid compound 2 finished products, and the productive rate of the method is 89.0%.
The character of this compound 2 is as follows:
Fusing point: 250-251 DEG C
Under 365nm UV-irradiation, the solid fluorescence effect of compound 2 is yellow.
UV (CHCl
3): λ
ab=391nm(ε=4.0 × 10
4m
-1cm
-1, ε is molar absorptivity)
FL (CHCl
3): λ
em=458nm, Φ=0.75(Φ represents fluorescent quantum yield)
1H?NMR(500MHz,CDCl
3,ppm):δ4.04(s,2H,CH
2),7.33(t,J=4.2Hz1H,Thiophene-H),7.55(d,J=7.4Hz1H,Ar-H),7.65(d,J=7.5Hz1H,Ar-H),7.72(t,J=7.4Hz1H,Ar-H),7.93(d,J=4.6Hz1H,Thiophene-H),7.99(d,J=7.5Hz1H,Ar-H),8.15(d,J=3.5Hz1H,Thiophene-H).
13C?NMR(125MHz,CDCl
3,ppm):δ32.7,108.9,124.6,125.6,128.4,129.3,134.5,135.1,135.7,136.8,137.0,148.8,169.6,186.5.
Mass spectrum calculated value: 290.0, measured value: 290.0.
Embodiment 3:
The third O, O bis-flute profile organic boron difluoride fluorescence dyes, this kind of fluorescence dye is expressed as compound 3 in the present embodiment, and the structural formula of compound 3 is:
The method of preparing this compound 3 is as follows: under room temperature, 2-naphthoyl indone (5mmol, 1.43g) is dropped in 50mL two-mouth bottle, add anhydrous methylene chloride (5mL) solution.After nitrogen purging 2 minutes, use 10mL syringe respectively triethylamine (30mmol, 5mL) and boron trifluoride diethyl etherate (35mmol, 5mL) to be injected to reaction soln.Water cancellation reaction react 2h at methylene chloride reflux temperature after.With dichloromethane extraction 2～3 times, merge organic phase.Use again anhydrous Na
2sO
4dry organic phase.Finally, after organic phase vacuum is spin-dried for by thick gained product the chromatographic column separating-purifying with the silica gel of 30 times of its weight, the mixed solution being mixed with taking the ratio of methylene dichloride and sherwood oil as 2:1, as eluent, is collected R
fvalue is 0.48 elutriant.Vacuum is spin-dried for and obtains yellow solid compound 3, and the productive rate of the method is 80.7%.
The character of this compound 3 is as follows:
Fusing point: 275-277 DEG C.
Under 365nm UV-irradiation, the solid fluorescence effect of compound 3 is orange.
UV (CHCl
3): λ
ab=384nm(ε=3.9 × 10
4m
-1cm
-1, ε is molar absorptivity).
FL (CHCl
3): λ
em=463nm, Φ=0.31(Φ represents fluorescent quantum yield)
1H?NMR(500MHz,CDCl
3,ppm):δ4.24(s,2H,CH
2),7.58(t,J=7.5Hz1H,Ar-H),7.64(t,J=7.4Hz1H,Ar-H),7.70(t,J=6.5Hz2H,Ar-H),7.76(t,J=7.5Hz1H,Ar-H),7.94(d,J=8.0Hz1H,Ar-H),8.01(d,J=7.6Hz1H,Ar-H),8.05(d,J=7.6Hz2H,Ar-H),8.19(dd,J=1.6,8.7Hz1H,Ar-H),8.78(s,1H,Ar-H).
13C?NMR(125MHz,CDCl
3,ppm):33.5,110.0,115.1,123.2,124.5,125.0,125.6,127.3,127.7,1128.5,128.9,129.6,129.9,132.5,135.4,135.6,136.2.
Mass spectrum calculated value: 334.1, measured value: 334.1.
Embodiment 4:
The 4th kind of O, O bis-flute profile organic boron difluoride fluorescence dyes, this kind of fluorescence dye is expressed as compound 4 in the present embodiment, and the structural formula of compound 4 is:
The method of preparing this compound 4 is as follows: under room temperature, 2-(4-bromophenyl) formyl radical indone (5mmol, 1.57g) is dropped in 50mL two-mouth bottle, add anhydrous methylene chloride (5mL) solution.After nitrogen purging 2 minutes, use 10mL syringe respectively triethylamine (30mmol, 5mL) and boron trifluoride diethyl etherate (35mmol, 5mL) to be injected to reaction soln.Water cancellation reaction react 2h at methylene chloride reflux temperature after.With dichloromethane extraction 2～3 times, merge organic phase.Use again anhydrous Na
2sO
4dry organic phase.Finally, after organic phase vacuum is spin-dried for by thick gained product the chromatographic column separating-purifying with the silica gel of 30 times of its weight, the mixed solution being mixed with taking the ratio of methylene dichloride and sherwood oil as 2:1, as eluent, is collected R
fvalue is 0.49 elutriant.Vacuum is spin-dried for and obtains yellow solid compound 4, and the productive rate of the method is 79.6%.
The character of this compound 4 is as follows:
Fusing point: 243-244 DEG C.
Under 365nm UV-irradiation, the solid fluorescence effect of compound 4 is yellow.
UV (CHCl
3): λ
ab=359nm(ε=3.5 × 10
4m
-1cm
-1, ε is molar absorptivity).
FL (CHCl
3): λ
em=410nm, Φ=0.40(Φ represents fluorescent quantum yield)
1H?NMR(500MHz,CDCl
3,ppm):δ4.10(s,2H,CH
2),7.55(t,J=7.5HZ1H,Ar-H),7.66(d,J=7.6HZ1H,Ar-H),7.66-7.77(m,3H,Ar-H),8.02-8.04(m,3H,Ar-H).
13C?NMR(125MHz,CDCl
3,ppm):δ33.3,110.4,125.0,125.6,128.6,129.7,131.1,131.7,132.5,133.9,135.8,149.6,174.9,188.2.
Mass spectrum calculated value: 362.0, measured value: 362.0.
Embodiment 5:
The 5th kind of O, O bis-flute profile organic boron difluoride fluorescence dyes, this kind of fluorescence dye is expressed as compound 5 in the present embodiment, and the structural formula of compound 5 is:
The method of preparing this compound 5 is as follows: under room temperature, 2-(4-bromophenyl) formyl radical indone (5mmol, 1.25g) is dropped in 50mL two-mouth bottle, add anhydrous methylene chloride (5mL) solution.After nitrogen purging 2 minutes, use 10mL syringe respectively triethylamine (30mmol, 5mL) and boron trifluoride diethyl etherate (35mmol, 5mL) to be injected to reaction soln.Water cancellation reaction react 2h at methylene chloride reflux temperature after.With dichloromethane extraction 2～3 times, merge organic phase.Use again anhydrous Na
2sO
4dry organic phase.Finally, after organic phase vacuum is spin-dried for by thick gained product the chromatographic column separating-purifying with the silica gel of 30 times of its weight, the mixed solution being mixed with taking the ratio of methylene dichloride and sherwood oil as 2:1, as eluent, is collected R
fvalue is 0.52 elutriant.Vacuum is spin-dried for and obtains yellow solid compound 5, and the productive rate of the method is 89.3%.
The character of this compound 5 is as follows:
Fusing point: 214-216 DEG C.
Under 365nm UV-irradiation, the solid fluorescence effect of compound 4 is yellow.
UV (CHCl
3): λ
ab=379nm(ε=4.0 × 10
4m
-1cm
-1, ε is molar absorptivity).
FL (CHCl
3): λ
em=437nm, Φ=0.59(Φ represents fluorescent quantum yield)
1H?NMR(500MHz,CDCl
3,ppm):δ2.49(s,3H,CH
3),4.10(s,2H,CH
2),7.38(d,J=8.2HZ2H,Ar-H),7.55(t,J=7.6HZ1H,Ar-H),7.64(d,J=7.7HZ1H,Ar-H),7.71-7.74(m,1H,Ar-H),7.73(d,J=7.7HZ1H,Ar-1),8.09(d,J=8.2HZ2H,Ar-H).
13C?NMR(125MHz,CDCl
3,ppm):δ21.9,33.5,110.0,124.7,125.5,128.4,129.9,130.0,130.1,134.4,135.2,145.8,149.4,176.4,187.0.
Mass spectrum calculated value: 298.1, measured value: 298.1.
Embodiment 6:
The 6th kind of O, O bis-flute profile organic boron difluoride fluorescence dyes, this kind of fluorescence dye is expressed as compound 6 in the present embodiment, and the structural formula of compound 6 is:
The method of preparing this compound 5 is as follows: under room temperature, 2-(4-bromophenyl) formyl radical indone (5mmol, 1.33g) is dropped in 50mL two-mouth bottle, add anhydrous methylene chloride (5mL) solution.After nitrogen purging 2 minutes, use 10mL syringe respectively triethylamine (30mmol, 5mL) and boron trifluoride diethyl etherate (35mmol, 5mL) to be injected to reaction soln.Water cancellation reaction react 2h at methylene chloride reflux temperature after.With dichloromethane extraction 2～3 times, merge organic phase.Use again anhydrous Na
2sO
4dry organic phase.Finally, after organic phase vacuum is spin-dried for by thick gained product the chromatographic column separating-purifying with the silica gel of 30 times of its weight, the mixed solution being mixed with taking the ratio of methylene dichloride and sherwood oil as 1:1, as eluent, is collected R
fvalue is 0.58 elutriant.Vacuum is spin-dried for and obtains yellow-green colour solid chemical compound 6, and the productive rate of the method is 91.3%.
The character of this compound 6 is as follows:
Fusing point: 239-240 DEG C.
Under 365nm UV-irradiation, the solid fluorescence effect of compound 4 is yellow-green colour.
UV (CHCl
3): λ
ab=389nm(ε=4.2 × 10
4m
-1cm
-1, ε is molar absorptivity).
FL (CHCl
3): λ
em=451nm, Φ=0.64(Φ represents fluorescent quantum yield)
1H?NMR(500MHz,CDCl
3,ppm):δ3.95(s,3H,CH
3),4.10(s,2H,CH
2),7.06(d,J=7.6Hz2H,Ar-H),7.54-7.70(m,3H,Ar-H),8.00(d,J=8.7Hz1H,Ar-H),8.21(d,J=7.7Hz2H,Ar-H).
13C?NMR(125MHz,CDCl
3,ppm):δ33.7,55.7,114.6,124.5,125.3,128.3,132.6,
134.8,149.0.
Mass spectrum calculated value: 314.1, measured value: 314.1.
The spectral quality of compound 1-3 is listed in table 1:
| Compound | λ ab/nm | Molar absorptivity ε/M -1cm -1 | λ em/nm | Φ | Stokes shift/nm |
| 1 | 373 | 3.7×10 4 | 425 | 0.46 | 52 |
| 2 | 391 | 4.0×10 4 | 458 | 0.75 | 67 |
| 3 | 384 | 3.9×10 4 | 463 | 0.31 | 79 |
| 4 | 359 | 3.5×10 4 | 410 | 0.40 | 51 |
| 5 | 379 | 4.0×10 4 | 437 | 0.59 | 58 |
| 6 | 389 | 4.2×10 4 | 451 | 0.64 | 62 |
Note 1: spectral quality is all measured in chloroformic solution at room temperature;
Note 2: fluorescent quantum yield Φ is reference substance with rhodamine B (in methanol solution, fluorescence quantum yield 0.9), adopts 1 × 10
-5the dilute solution of mol/L is measured.
Claims (5)
1. an O, O bis-flute profile organic boron difluoride fluorescence dyes, is characterized in that the general structure of this fluorescent dye compound I is:
In formula: R represents phenyl, thienyl, naphthyl, 4-bromophenyl, 4-aminomethyl phenyl and 4-p-methoxy-phenyl.
2. an O according to claim 1, the preparation method of O bis-flute profile organic boron difluoride fluorescence dyes, is characterized in that this preparation method comprises the steps:
A. select beta-dicarbonyl compound II as raw material, be dissolved in anhydrous organic solvent, form solution, the general structure of described beta-dicarbonyl compound II is:
In formula: R represents phenyl, thienyl, naphthyl, 4-bromophenyl, 4-aminomethyl phenyl and 4-p-methoxy-phenyl;
B. use on nitrogen purging reaction soln layer of air 2 minutes, form dry indifferent gas environment;
C. in the solution of step a, inject acid binding agent, the raw material boron trifluoride diethyl etherate of reinjecting;
D. the solution in step c is heated to anhydrous organic solvent reflux temperature, carries out complex reaction;
E., after question response finishes, water will react cancellation;
F. extraction merges organic phase, and with desiccant dryness;
G. organic phase vacuum is spin-dried for, obtains thick product;
H. thick product carries out chromatographic column separation in silica gel or neutral alumina column, and eluent is selected from any one or both the above arbitrary combination in sherwood oil, methylene dichloride and chloroform;
I. elutriant vacuum is spin-dried for, obtains finished product.
3. preparation method according to claim 2, is characterized in that the consumption of described boron trifluoride diethyl etherate and beta-dicarbonyl compound II is 6～8:1 according to the ratio of mol ratio.
4. preparation method according to claim 2, is characterized in that any one or both that described acid binding agent is selected from diethylamine or triethylamine mix; The consumption of acid binding agent and beta-dicarbonyl compound II is 5～7:1 according to the ratio of mol ratio.
5. according to the preparation method described in claim 2～4 any one, it is characterized in that described anhydrous organic solvent is selected from any one or the two or more arbitrary combination in methylene dichloride, tetrahydrofuran (THF), toluene, dimethylbenzene.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702768A (en) * | 2012-06-04 | 2012-10-03 | 天津理工大学 | Novel red BODIPY fluorescent dye and preparation method and application thereof |
| CN102993224A (en) * | 2012-09-28 | 2013-03-27 | 浙江理工大学 | Organic boron difluoride complex |
| CN102993223A (en) * | 2012-09-28 | 2013-03-27 | 浙江理工大学 | Organic boron difluoride complex containing N,O-bidentate ligand |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702768A (en) * | 2012-06-04 | 2012-10-03 | 天津理工大学 | Novel red BODIPY fluorescent dye and preparation method and application thereof |
| CN102993224A (en) * | 2012-09-28 | 2013-03-27 | 浙江理工大学 | Organic boron difluoride complex |
| CN102993223A (en) * | 2012-09-28 | 2013-03-27 | 浙江理工大学 | Organic boron difluoride complex containing N,O-bidentate ligand |
Non-Patent Citations (2)
| Title |
|---|
| 《Bisdioxaborine polymethines with large third-order nonlinearities for all-optical signal processing》;Joel M. Hales et al.;《J.AM.CHEM.SOC.》;20061231;第128卷(第35期);11362-11363 * |
| Joel M. Hales et al..《Bisdioxaborine polymethines with large third-order nonlinearities for all-optical signal processing》.《J.AM.CHEM.SOC.》.2006,第128卷(第35期),11362-11363. * |
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