CN103172650A - Strong fluorescence fluoro-boron dipyrrole compound containing triphenylamine structure as well as preparation method and application thereof - Google Patents
Strong fluorescence fluoro-boron dipyrrole compound containing triphenylamine structure as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a strong fluorescence fluoro-boron dipyrrole compound containing a triphenylamine structure as well as a preparation method and an application thereof, belonging to the technical fields of organic chemical industry and fine chemical industry. The preparation method comprises the following steps of: weighing and dissolving formyl substituted triphenylamine and 2,4-dimethyl pyrrolo in a dry dissolvent under the protection of inert atmosphere; adding a catalyst; reacting at a room temperature in a dark place for 6-10 hours; then adding an oxidant; reacting at room temperature for 20-40 minutes; and finally adding organic amine and a boron triflouride complex compound and reacting for 3-8 hours, thus obtaining the strong fluorescence fluoro-boron dipyrrole compound containing a triphenylamine structure. The synthetic method is simple and convenient, and the synthetic compound serves as a laser dye and has relatively high solution pumping laser efficiency, narrowed ultraviolet and visible absorption spectrum and fluorescence emission spectrum, high fluorescence quantum efficiency and good light stability.
Description
Technical field
The present invention relates to a kind of hyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds that contain fluorine-triphenylamine structure and preparation method thereof and application, belong to organic chemical industry and fine chemical technology field.
Background technology
In prior art, laser apparatus mainly is divided into two kinds, a kind of is the laser apparatus that can only produce specific wavelength, as: He-Cd optical maser wavelength is that 325 nanometers, argon laser optical maser wavelength are 488.5 nanometers, Yttrium-Aluminium-Garnet laser apparatus (YAG) optical maser wavelength is 1060 nanometers, these laser apparatus make the application of laser apparatus be subject to many restrictions because optical maser wavelength is certain; Another kind of laser apparatus is the laser of the required wavelength of continuous wave output within the specific limits, as, Sorokin made dye laser with the Rhodamine6G dyestuff in 1967, and this class laser apparatus has obtained broad research due to superior performance.
Laser dyes is a kind of fluorescence dye of high quantum production rate of dye laser special use, and it can produce the adjustable laser of wavelength within the specific limits under the effect of LASER Light Source (optical pumping).
Fluorine boron two azoles (BODIPY) are fluorochromes that occurs in recent years, and it is the mixture that is formed by two pyrroles's methylene radical and boron trifluoride.Such dye molecule synthesizes owing to being easy to, have that higher light stability and quantum yield, long service life, uptake factor are large, absorption and emission band width, luminous efficiency advantages of higher, all has potential application prospect in fields such as bioprobe, solar cells, in recent years, be subject to research widely, as: Arbeloa T.L. study group has reported the BODIPY dyestuff of four kind of 2,6 bit substituent in 1999; Chinese patent 200910011731.5 discloses hyperfluorescenceCeng Yongminggaoyingguang fluorine boron two pyrroles's dyestuffs that a class contains carbazole structure, is that to adopt fluorine boron two pyrroles be raw material with being with substituent carbazole aldehyde, generates fluorine boron two pyrrole derivative; Chinese patent 200810012180.X discloses long wavelength boron dipyrromethene dye and preparation method thereof, and it adopts bromine or iodine is raw material for fluorine boron two pyrroles and substituted alkenyl boric acid, generates two keys and grips altogether fluorine boron two pyrrole derivative of connection.But in prior art, also there is no fluorine boron two azoles as the applied research of laser dyes.
Summary of the invention
The object of the present invention is to provide a kind of hyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds that contain fluorine-triphenylamine structure and preparation method thereof and application, hyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds that contain fluorine-triphenylamine structure of the present invention are used as laser dyes, have higher solution pumping lasing efficiency, the ultraviolet-visible absorption spectroscopy that narrows.
The invention provides a kind of hyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds that contain fluorine-triphenylamine structure, its structural formula is formula (П) or formula (Ш):
Formula (П) formula (Ш).
The present invention also provides a kind of preparation method who contains hyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds of fluorine-triphenylamine structure, comprises the following steps:
(1) under inert atmosphere protection, take triphenylamine and 2, the 4-dimethyl pyrrole of formyl radical replacement and be dissolved in dry solvent, adding catalyzer, room temperature lucifuge reaction 6 ~ 10 hours obtains purplish red solution;
The triphenylamine that described formyl radical replaces is two (4-formylphenyl) aniline or three-(4-formylphenyl) amine;
(2) take oxygenant and being dissolved in dry solvent, join in the purplish red solution that step (1) obtains, room temperature reaction 20 ~ 40 minutes obtains dark solution;
(3) add organic amine and boron trifluoride complex in dark solution, reacted 3 ~ 8 hours, obtain containing hyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds of fluorine-triphenylamine structure;
Described boron trifluoride complex is boron trifluoride methyl ether complex compound, boron trifluoride ethyl ether complex or boron trifluoride ether complex.
Preferably, the triphenylamine that described formyl radical replaces is by taking with stoichiometric reaction institute expense, and is described 2, and the 4-dimethyl pyrrole is by taking with 1 ~ 1.2 times of stoichiometric reaction institute expense.
Preferably, described solvent is methylene dichloride (DCM) or chloroform.
Preferably, described catalyzer is trifluoroacetic acid (TFA) or propionic acid.
Preferably, described oxygenant is tetrachlorobenzoquinone (p-chloranil) or DDQ (DDQ).
Preferably, described oxygenant doubly takes by the 1-1.2 with stoichiometric reaction institute expense.
Preferably, described organic amine is triethylamine, triisopropylamine or diisopropylethylamine.
The present invention also provides the application as laser dyes of hyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds that contain fluorine-triphenylamine structure, the described structural formula that contains hyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds of fluorine-triphenylamine structure is formula (I), formula (П) or formula (Ш):
Formula (I)
Formula (П) formula (Ш).
The invention has the beneficial effects as follows:
The present invention builds up to the BODIPY fluorophore of different numbers in the triphenylamine parent respectively, better symmetric fluorine boron two azole compounds have been obtained having, simple synthetic method of the present invention, the compound that makes is used as laser dyes, have higher solution pumping lasing efficiency, the ultraviolet-visible absorption spectroscopy that narrows and fluorescence emission spectrum, high fluorescence quantum efficiency and good light stability, its maximum fluorescence quantum yield in toluene solution reaches 0.94, and Laser output efficient reaches more than 30%.
Description of drawings
Fig. 1 is laser emission spectrum and the fluorescence spectrum of dye molecule TPABO1 in toluene solution of the embodiment of the present invention 1;
Fig. 2 is that the dye molecule TPABO1 of the embodiment of the present invention 1 is at CDCl
3In (deuterochloroform)
1HNMR NMR (Nuclear Magnetic Resonance) spectrum spectrogram;
Fig. 3 is laser emission spectrum and the fluorescence spectrum of dye molecule TPABO2 in toluene solution of the embodiment of the present invention 2;
Fig. 4 is that the dye molecule TPABO2 of the embodiment of the present invention 2 is at CDCl
3In
1H nuclear magnetic resonance, spectrum spectrogram;
Fig. 5 is the mass spectrogram of the dye molecule TPABO2 of the embodiment of the present invention 2;
Fig. 6 is laser emission spectrum and the fluorescence spectrum of dye molecule TPABO3 in toluene solution of the embodiment of the present invention 3;
Fig. 7 is the Laser emission image of toluene solution under laser pumping of the dye molecule TPABO3 of the embodiment of the present invention 3;
Fig. 8 is that the dye molecule TPABO3 of the embodiment of the present invention 3 is at CDCl
3In
1H nuclear magnetic resonance, spectrum spectrogram;
Fig. 9 is the mass spectrogram of the dye molecule TPABO3 of the embodiment of the present invention 3.
Embodiment
Contain hyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds of fluorine-triphenylamine structure, it is divided into V-type and Y type take trianilino group as core, and structural formula is formula (П) or formula (Ш):
Formula (П) formula (Ш).
Contain the preparation method of hyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds of fluorine-triphenylamine structure, comprise the following steps:
(1) under inert atmosphere protection, take triphenylamine and 2, the 4-dimethyl pyrrole of formyl radical replacement and be dissolved in dry solvent, adding catalyzer, room temperature lucifuge stirring reaction 6 ~ 10 hours obtains purplish red solution;
The triphenylamine that described formyl radical replaces is two (4-formylphenyl) aniline or three-(4-formylphenyl) amine;
(2) take oxygenant and being dissolved in dry solvent, join in the purplish red solution that step (1) obtains, stirring at room reaction 20 ~ 40 minutes obtains dark solution;
(3) add triethylamine in dark solution, stirring at room 5 ~ 10 minutes, add boron trifluoride complex, under ice bath, stirring reaction is 3 ~ 8 hours, obtain reaction solution, reaction solution obtains containing hyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds of fluorine-triphenylamine structure after extracting and separating, underpressure distillation, chromatographic column are separated;
Described boron trifluoride complex is boron trifluoride methyl ether complex compound, boron trifluoride ethyl ether complex or boron trifluoride ether complex.
In step of the present invention (1), the structural formula of described two (4-formylphenyl) aniline or three-(4-formylphenyl) amine is respectively:
Two (4-formylphenyl) aniline (S2) and three-(4-formylphenyl) amine (S3) is prior art, can prepare by approach well known, and its reaction formula is:
In formula, TPA is triphenylamine, POCl
3Be phosphorus oxychloride, DMF is DMF, and r.t. is room temperature.
In the present invention, usually take by stoichiometric ratio the triphenylamine and 2 that formyl radical replaces, the 4-dimethyl pyrrole, two (4-formylphenyl) aniline and 2, the stoichiometric ratio of 4-dimethyl pyrrole reaction is 1:4, the stoichiometric ratio of three-(4-formylphenyl) amine and the reaction of 2,4-dimethyl pyrrole is 1:6; For the triphenylamine complete reaction that formyl radical is replaced, can make 2, the 4-dimethyl pyrrole is excessive, the triphenylamine that preferred described formyl radical replaces is by taking with stoichiometric reaction institute expense, described 2, the 4-dimethyl pyrrole is by taking with 1 ~ 1.2 times of stoichiometric reaction institute expense, namely by molar ratio 1:(4 ~ 4.8) take two (4-formylphenyl) aniline and 2, the 4-dimethyl pyrrole, by molar ratio 1:(6 ~ 7.2) take three-(4-formylphenyl) amine and 2,4-dimethyl pyrrole; More preferably, take two (4-formylphenyl) aniline and 2,4-dimethyl pyrrole by molar ratio 1:4.4, take three-(4-formylphenyl) amine and 2,4-dimethyl pyrrole by molar ratio 1:6.6.
In step of the present invention (1) and step (2), described solvent phase is same, is methylene dichloride or chloroform.
In step of the present invention (1), described catalyzer is trifluoroacetic acid (TFA) or propionic acid.
In step of the present invention (1); the consumption of described catalyzer can adopt the known consumption of those skilled in the art to add; preferably add with catalytic amount, more preferably, the amount of substance of catalyzer be the triphenylamine that replaces of formyl radical amount of substance 0.01-0.1 doubly.
In step of the present invention (2), described oxygenant is tetrachlorobenzoquinone or DDQ.
In step of the present invention (2), oxygenant doubly takes by the 1-1.2 with stoichiometric reaction institute expense, the amount of substance of the oxygenant that namely takes be 2,4-dimethyl pyrrole amount of substance 0.5-0.6 doubly.
In step of the present invention (3), described organic amine is triethylamine, triisopropylamine or diisopropylethylamine.
In step of the present invention (3), the consumption of described organic amine is 20 ~ 30 times by stoichiometric reaction institute expense.
In step of the present invention (3), the consumption of described boron trifluoride complex is for by 20 ~ 30 times of stoichiometric reaction institute expense, and namely the amount of substance of boron trifluoride complex is 2, and the 10-15 of the amount of substance of 4-dimethyl pyrrole doubly.
In step of the present invention (3), preferably reaction solution is poured into water, add methylene chloride or the chloroform extraction separation, decompression evaporates methylene dichloride or chloroform, chromatographic column is separated, and eluent is sherwood oil: ethyl acetate=1: 10 (volume ratio), collect the green fluorescence part, decompression is the evaporate to dryness eluent down, obtains containing hyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds of fluorine-triphenylamine structure.
In step of the present invention (1), (2) and (3), magnetic agitation is all adopted in described stirring, and the magnetic agitation motor speed is preferably 400 ~ 500rpm.
The reaction formula of hyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds that contain fluorine-triphenylamine structure of formula (П) structure is:
The reaction formula of hyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds that contain fluorine-triphenylamine structure of formula (Ш) structure is:
The present invention also provides the application as laser dyes of hyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds that contain fluorine-triphenylamine structure, the described structural formula that contains hyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds of fluorine-triphenylamine structure is formula (I), formula (П) or formula (Ш):
Formula (I)
Formula (П) formula (Ш).
The laser emission spectrum of hyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds that contain fluorine-triphenylamine structure of the present invention's preparation and fluorescence spectrum test are all carried out under room temperature, fluorescence spectrum test concentrations: 1.0 * 10
-5M, laser property test concentrations: 1.0 * 10
-2M。
For making those skilled in the art further understand the present invention, further illustrate the present invention below in conjunction with embodiment and accompanying drawing.
The preparation of hyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds that contain fluorine-triphenylamine structure of formula (I) structure:
(1) take 4-pentanoic benzaldehyde 0.274 gram, 2,4-dimethyl pyrrole, 0.19 gram is dissolved in 20 milliliters of anhydrous methylene chlorides, adds 2 (10ul) trifluoroacetic acids, and under nitrogen protection, room temperature magnetic agitation 6 hours obtains purplish red solution;
(2) 0.3 gram tetrachlorobenzoquinone is dissolved in 10 milliliters of methylene dichloride, is added in above-mentioned purplish red solution, stirring at room 30 minutes obtains dark solution;
(3) add 3 milliliters of triethylamines and 3 milliliters of boron trifluoride ether solutions in above-mentioned dark solution, stirring at room 6 hours adds 100 ml water cancellation reactions, dichloromethane extraction, the anhydrous magnesium sulfate drying organic phase, concentrating under reduced pressure, crude product are through the silica gel column chromatography separating-purifying, with the mixing solutions wash-out of petrol ether/ethyl acetate, evaporating solvent, drying obtains red needle-like crystal, is hyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds that contain fluorine-triphenylamine structure, is denoted as: dye molecule TPABO1.
HyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds that contain fluorine-triphenylamine structure that embodiment 1 is obtained carry out laser emission spectrum and fluorescent spectroscopy; Fig. 1 is laser emission spectrum and the fluorescence spectrum of dye molecule TPABO1 in toluene solution, curve 1 is the fluorescence spectrum of dye molecule TPABO1, can find out that dye molecule TPABO1 reaches maximum intensity value at the 516nm place, curve 2 is the laser emission spectrum of dye molecule TPABO1, can find out that dye molecule TPABO1 maximum intensity value occurs at the 543nm place; Fig. 1 shows that the spectrum peak of dye molecule TPABO1 is moved before and after laser pumping, peak width at half height narrows gradually, the Laser emission intensity enhancing.Fig. 1 confirmation has hyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds that contain fluorine-triphenylamine structure of formula (I) structure and can use as laser dyes.
HyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds that contain fluorine-triphenylamine structure that embodiment 1 is obtained carry out nuclear magnetic resonance spectroscopy, and Fig. 2 is that dye molecule TPABO1 is at CDCl
3In
1H nuclear magnetic resonance, spectrum spectrogram; Record
1H NMR (400MHz, CDCl
3) δ 7.30 (d, J=7.6Hz, 5H), 7.22-7.01 (m, 11H), 6.01 (s, 2H), 2.56 (s, 6H), 1.59 (s, 6H);
13C NMR (100MHz, CDCl
3) δ 155.36,148.68,147.54,129.68,129.07,128.38,124.94,123.59,121.37,14.85; IR (KBr, cm – 1): ν=2913,2675,2360,1590,1543,1496,1375,1307,1152,1075,972,808,693,472; The peak of chemical displacement value 1 ~ 3 is pyrroles's methyl hydrogen of dye molecule, and chemical displacement value 4 ~ 6 unimodal is the hydrogen on the dye molecule pyrroles, and chemical displacement value is fragrant hydrogen on the triphenylamine phenyl ring greater than 7 peak.
The preparation of hyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds that contain fluorine-triphenylamine structure of formula (П) structure:
(1) take two (4-formylphenyl) aniline 0.301 grams, 2,4-dimethyl pyrrole, 0.38 gram is dissolved in 40 milliliters of anhydrous methylene chlorides, add 2 (10ul) trifluoroacetic acids as catalyzer, under nitrogen protection, room temperature magnetic agitation 8 hours obtains purplish red solution;
(2) 0.455 gram tetrachlorobenzoquinone is dissolved in 20 milliliters of methylene dichloride, is added in above-mentioned purplish red solution, stirring at room 30 minutes obtains dark solution;
(3) add 5 milliliters of triethylamines and 5 milliliters of boron trifluoride ether solutions toward above-mentioned dark solution, stirring at room 8 hours adds 200 ml water cancellation reactions, dichloromethane extraction, the anhydrous magnesium sulfate drying organic phase, concentrating under reduced pressure, crude product are through the silica gel column chromatography separating-purifying, with the mixing solutions wash-out of petrol ether/ethyl acetate, evaporating solvent, drying obtains red powder, namely contains hyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds of fluorine-triphenylamine structure, is denoted as: dye molecule TPABO2.
HyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds that contain fluorine-triphenylamine structure that embodiment 2 is obtained carry out laser emission spectrum and fluorescent spectroscopy; Fig. 3 is laser emission spectrum and the fluorescence spectrum of dye molecule TPABO2 in toluene solution, curve 1 is the fluorescence spectrum of dye molecule TPABO2, can find out that dye molecule TPABO2 reaches maximum intensity value at the 519nm place, curve 2 is the laser emission spectrum of dye molecule TPABO2, can find out that dye molecule TPABO2 maximum intensity value occurs at the 535nm place; Fig. 3 shows that dye molecule TPABO2 spectrum peak is moved before and after laser pumping, peak width at half height narrows gradually, the Laser emission intensity enhancing.Fig. 3 confirmation has hyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds that contain fluorine-triphenylamine structure of formula (П) structure and can use as laser dyes.
HyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds that contain fluorine-triphenylamine structure that embodiment 2 is obtained carry out magnetic resonance detection, and Fig. 4 is that dye molecule TPABO2 is at CDCl
3In
1H nuclear magnetic resonance, spectrum spectrogram; Record
1H NMR (300MHz, CDCl
3) δ 7.37-7.30 (m, 3H), 7.16 (dd, J=16.5,7.8Hz, 10H), 6.01 (s, 4H), 2.56 (s, 12H), 1.59 (s, 12H);
13C NMR (75MHz, CDCl
3) δ 155.49,148.11,142.82,131.70,129.77,129.29,125.30,124.30,123.93,121.27,14.53; IR (KBr, cm
-1): ν=2937,2739,2677,2491,1596,1544,1471,1401,1308,1155,1037,981,804,696,527,474.ESI-MS:m/z=783.3; The peak of chemical displacement value 1 ~ 3 is pyrroles's methyl hydrogen of dye molecule, and chemical displacement value 4 ~ 6 unimodal is the hydrogen on the dye molecule pyrroles, and chemical displacement value is fragrant hydrogen on the triphenylamine phenyl ring greater than 7 peak.
HyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds that contain fluorine-triphenylamine structure that embodiment 2 is obtained carry out mass spectroscopy; Fig. 5 is the mass spectrogram of dye molecule TPABO2, can find out, molecular weight is 738.3 to be molecular ion peaks of TPABO2.
Fig. 4 and Fig. 5 show, the present invention has prepared hyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds that contain fluorine-triphenylamine structure of formula (П) structure really.
The preparation of hyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds that contain fluorine-triphenylamine structure of formula (Ш) structure:
(1) take three-(4-formylphenyl) amine 0.329 grams, 2,4-dimethyl pyrrole, 0.57 gram is dissolved in 50 milliliters of anhydrous chloroforms, adds 2 (10ul) trifluoroacetic acids, and under nitrogen protection, room temperature magnetic agitation 10 hours obtains purplish red solution;
(2) 0.738 gram tetrachlorobenzoquinone is dissolved in 30 milliliters of chloroforms, is added in above-mentioned purplish red solution, stirring at room 40 minutes obtains dark solution;
(3) add 6 milliliters of triethylamines and 8 milliliters of boron trifluoride ether solutions in above-mentioned dark solution, stirring at room 4 hours adds 200 ml water cancellation reactions, chloroform extraction, use the anhydrous magnesium sulfate drying organic phase, concentrating under reduced pressure, crude product are through the silica gel column chromatography separating-purifying, with the mixing solutions wash-out of petrol ether/ethyl acetate, evaporating solvent, drying obtains red powder, namely contains hyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds of fluorine-triphenylamine structure, is denoted as: dye molecule TPABO3.
HyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds that contain fluorine-triphenylamine structure that embodiment 3 is obtained carry out laser emission spectrum and fluorescent spectroscopy; Fig. 6 is laser emission spectrum and the fluorescence spectrum of dye molecule TPABO3 in toluene solution, curve 1 is the fluorescence spectrum of dye molecule TPABO3, can find out that dye molecule TPABO3 reaches maximum intensity value at the 519nm place, curve 2 is the laser emission spectrum of dye molecule TPABO3, can find out that dye molecule TPABO3 maximum intensity value occurs at the 548nm place; Fig. 6 illustrates that dye molecule TPABO3 spectrum peak is moved before and after laser pumping, peak width at half height narrows gradually, the Laser emission intensity enhancing.
Fig. 7 is the Laser emission image of toluene solution under 355 nanometer laser pumpings of TPABO3, can find out the toluene solution of dye molecule TPABO3 under 355 nanometer laser pumpings, and vertical surface produces the green laser hot spot.
Fig. 6 and Fig. 7 illustrate that hyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds that contain fluorine-triphenylamine structure of the embodiment of the present invention 3 preparation can use as laser dyes.
HyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds that contain fluorine-triphenylamine structure that embodiment 3 is obtained carry out magnetic resonance detection, and Fig. 8 is that dye molecule TPABO3 is at CDCl
3In
1H nuclear magnetic resonance, spectrum spectrogram; Record
1H NMR (300MHz, CDCl
3) δ 7.23 (s, 12H), 6.02 (s, 6H), 2.56 (s, 18H), 1.59 (s, 18H);
13C NMR (75MHz, CDCl
3) δ 155.70,147.64,143.79,141.04,131.58,142.67,130.16,129.64,124.50,121.38,14.55; IR (KBr, cm
-1): ν=2920,2852,1600,1545,1511,1440,1372,1308,1194,1154,1077,1050,975,829,709,475.ESI-MS:m/z=984.5; The peak of chemical displacement value 1 ~ 3 is pyrroles's methyl hydrogen of dye molecule, and chemical displacement value 4 ~ 6 unimodal is the hydrogen on the dye molecule pyrroles, and chemical displacement value is fragrant hydrogen on the triphenylamine phenyl ring greater than 7 peak.
HyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds that contain fluorine-triphenylamine structure that embodiment 3 is obtained carry out mass spectroscopy, and Fig. 9 is the mass spectrogram of dye molecule TPABO3, can find out, molecular weight is 984.5 to be molecular ion peaks of TPABO3.
Fig. 8 and Fig. 9 show, the present invention has prepared hyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds that contain fluorine-triphenylamine structure of formula (Ш) structure really.
Claims (9)
1. contain hyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds of fluorine-triphenylamine structure, it is characterized in that, its structural formula is formula (П) or formula (Ш):
Formula (П) formula (Ш).
2. contain the preparation method of hyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds of fluorine-triphenylamine structure, it is characterized in that, comprise the following steps:
(1) under inert atmosphere protection, take triphenylamine and 2, the 4-dimethyl pyrrole of formyl radical replacement and be dissolved in dry solvent, adding catalyzer, room temperature lucifuge reaction 6 ~ 10 hours obtains purplish red solution;
The triphenylamine that described formyl radical replaces is two (4-formylphenyl) aniline or three-(4-formylphenyl) amine;
(2) take oxygenant and being dissolved in dry solvent, join in the purplish red solution that step (1) obtains, room temperature reaction 20 ~ 40 minutes obtains dark solution;
(3) add organic amine and boron trifluoride complex in dark solution, reacted 3 ~ 8 hours, obtain containing hyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds of fluorine-triphenylamine structure;
Described boron trifluoride complex is boron trifluoride methyl ether complex compound, boron trifluoride ethyl ether complex or boron trifluoride ether complex.
3. the preparation method who contains hyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds of fluorine-triphenylamine structure according to claim 2; it is characterized in that; the triphenylamine that described formyl radical replaces is by taking with stoichiometric reaction institute expense; described 2, the 4-dimethyl pyrrole is by taking with 1 ~ 1.2 times of stoichiometric reaction institute expense.
4. the preparation method who contains hyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds of fluorine-triphenylamine structure according to claim 2, is characterized in that, described solvent is methylene dichloride or chloroform.
5. the preparation method who contains hyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds of fluorine-triphenylamine structure according to claim 2, is characterized in that, described catalyzer is trifluoroacetic acid or propionic acid.
6. the preparation method who contains hyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds of fluorine-triphenylamine structure according to claim 2, is characterized in that, described oxygenant is tetrachlorobenzoquinone or DDQ.
7. the preparation method who contains hyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds of fluorine-triphenylamine structure according to claim 2, is characterized in that, described oxygenant doubly takes by the 1-1.2 with stoichiometric reaction institute expense.
8. the preparation method who contains hyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds of fluorine-triphenylamine structure according to claim 2, is characterized in that, described organic amine is triethylamine, triisopropylamine or diisopropylethylamine.
9. contain hyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds of fluorine-triphenylamine structure as the application of laser dyes, the described structural formula that contains hyperfluorescenceCeng Yongminggaoyingguang fluorine boron two azole compounds of fluorine-triphenylamine structure is formula (I), formula (П) or formula (Ш):
Formula (I)
Formula (П) formula (Ш).
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN104628753A (en) * | 2014-12-30 | 2015-05-20 | 东莞理工学院 | Meso-triphenylamine-substituted 3,5-aryl-modified boron dipyrromethene fluorophore derivatives and preparation method thereof |
| WO2015119039A1 (en) * | 2014-02-05 | 2015-08-13 | 東レ株式会社 | Photoelectric conversion element and image sensor |
| CN105647220A (en) * | 2016-01-20 | 2016-06-08 | 三峡大学 | D-pi-A structure boron fluorine dye and preparation method and application |
| CN105669734A (en) * | 2016-03-16 | 2016-06-15 | 东南大学 | BCPA-BODIPY fluorescent molecules and preparation method and application thereof |
| CN106987152A (en) * | 2017-03-08 | 2017-07-28 | 三峡大学 | One class fluorine boron near infrared fluorescent dye and the application in non-protonic solvent in the detection of minor amount of water |
| CN108047259A (en) * | 2017-12-28 | 2018-05-18 | 江苏大学 | A kind of 2,2 '-bithiophene -5,5 '-boron difluoride dipyrromethane compound and its preparation method and use |
| CN108409765A (en) * | 2018-03-27 | 2018-08-17 | 南京林业大学 | Nopinane base beta-diketon boron difluoride complex compound and its preparation method and application |
| CN108912152A (en) * | 2018-06-20 | 2018-11-30 | 中国科学院理化技术研究所 | β -dicarbonyl boron fluoride compound and preparation method and application thereof |
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| CN117164609A (en) * | 2023-10-20 | 2023-12-05 | 蚌埠学院 | D-A aggregation-induced photovoltaic material based on boron fluoride-triphenylamine-benzyl cyanide and preparation method and application thereof |
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| US9842884B2 (en) | 2014-02-05 | 2017-12-12 | Toray Industries, Inc. | Photoelectric conversion element and image sensor |
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| CN108409765A (en) * | 2018-03-27 | 2018-08-17 | 南京林业大学 | Nopinane base beta-diketon boron difluoride complex compound and its preparation method and application |
| CN108912152A (en) * | 2018-06-20 | 2018-11-30 | 中国科学院理化技术研究所 | β -dicarbonyl boron fluoride compound and preparation method and application thereof |
| CN108912152B (en) * | 2018-06-20 | 2020-11-24 | 中国科学院理化技术研究所 | Beta-dicarbonyl boron fluoride compound and preparation method and application thereof |
| CN109734738A (en) * | 2019-02-21 | 2019-05-10 | 南京林业大学 | A kind of fluorescence probe and the preparation method and application thereof that can quickly detect sulfurous acid hydrogen radical ion |
| CN109734738B (en) * | 2019-02-21 | 2021-01-08 | 南京林业大学 | Fluorescent probe capable of rapidly detecting bisulfite ions and preparation method and application thereof |
| CN112851699A (en) * | 2019-11-28 | 2021-05-28 | 乐金显示有限公司 | Organic compound, organic light emitting diode including the same, and device including the same |
| CN112500715A (en) * | 2020-12-08 | 2021-03-16 | 湖南航天磁电有限责任公司 | Fluorine boron dye molecule with donor and acceptor, quaternary ammonium salt thereof and preparation method |
| CN117164609A (en) * | 2023-10-20 | 2023-12-05 | 蚌埠学院 | D-A aggregation-induced photovoltaic material based on boron fluoride-triphenylamine-benzyl cyanide and preparation method and application thereof |
| CN117164609B (en) * | 2023-10-20 | 2024-06-07 | 蚌埠学院 | D-A aggregation-induced photovoltaic material based on boron fluoride-triphenylamine-benzyl cyanide and preparation method and application thereof |
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