CN113321671A - Boron dipyrromethene solid-state luminescent material, preparation method and application thereof, and blue light driven LED - Google Patents
Boron dipyrromethene solid-state luminescent material, preparation method and application thereof, and blue light driven LED Download PDFInfo
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Abstract
The invention belongs to the technical field of fluorescent dyes, and particularly relates to a BODIPY solid-state luminescent material, a preparation method and application thereof, and a blue light-driven LED. The invention provides a BODIPY solid-state luminescent material which has a structure shown in any one of formulas I-1-I-5, wherein the molecular structure of the BODIPY solid-state luminescent material provided by the invention has a certain conjugated structure, and an electron-donating group and an electron-withdrawing group are introduced to modify the molecular structure, so that the strong pi-pi accumulation is avoided while the charge transfer caused by the electron-donating group and the electron-withdrawing group in the molecule is increased, and the luminescence is realized and the luminescent quantum efficiency is higher. Therefore, the BODIPY solid-state luminescent material provided by the invention has good hue, saturation and color rendering property and high luminous efficiency.
Description
Technical Field
The invention belongs to the technical field of fluorescent dyes, and particularly relates to a BODIPY solid-state luminescent material, a preparation method and application thereof, and a blue light-driven LED.
Background
The BODIPY fluorescent dye has stable chemical structure, strong ground state absorption and high fluorescence quantum efficiency, is paid attention to the field of photoelectric functional materials, and is widely applied to the fields of molecular probes, photodynamic therapy, laser dyes, nonlinear optical materials, solar cells and the like. However, the BODIPY fluorescent dye has a large pi-conjugated plane, and can cause strong pi-pi accumulation in a solid state to generate fluorescence quenching, so that the luminous efficiency and the luminous stability of the luminescent material are influenced, and the application of the BODIPY fluorescent dye as a solid luminescent material is limited.
Disclosure of Invention
In view of the above, the present invention provides a BODIPY solid state light emitting material, a preparation method and applications thereof, and a blue light driven LED.
The invention provides a BODIPY solid-state luminescent material which has a structure shown in any one of formulas I-1-I-5:
the invention provides a preparation method of the BODIPY solid luminescent material, which comprises the following steps:
mixing aromatic aldehyde, 2, 4-dimethylpyrrole, trifluoroacetic acid and chloralkane in a protective atmosphere, and carrying out nucleophilic addition reaction to obtain a reaction solution A;
the aromatic aldehyde is 3, 5-bis (3',5' -dimethylphenyl) benzaldehyde, 3, 5-bis (3',5' -dimethoxyphenyl) benzaldehyde, 3, 5-bis (3',5' -di-tert-butylphenyl) benzaldehyde, 3, 5-bis (3',5' -difluorophenyl) benzaldehyde or 3, 5-bis (3',5' -bistrifluoromethylphenyl) benzaldehyde;
mixing the reaction solution A and dichloro dicyano benzoquinone, and carrying out oxidation reaction to obtain a reaction solution B;
and mixing the reaction solution B, triethylamine and boron trifluoride-diethyl ether for coordination reaction to obtain the BODIPY solid luminescent material.
Preferably, the mass ratio of the aromatic aldehyde to the 2, 4-dimethylpyrrole is 1 (2-4).
Preferably, the ratio of the amount of the substance of the aromatic aldehyde, the volume of the triethylamine and the volume of the boron trifluoride-diethyl ether is 1 mol: (8-20) L: (8-20) L.
Preferably, the temperature of the nucleophilic addition reaction is 10-30 ℃, and the time is 24-36 h; the protective atmosphere comprises nitrogen or argon.
Preferably, the temperature of the oxidation reaction and the temperature of the coordination reaction are independently 20-35 ℃, and the time is independently 5-36 h.
Preferably, the chloroalkane is dichloromethane, chloroform or 1, 2-dichloroethane.
The invention provides the application of the BODIPY solid-state luminescent material prepared by the preparation method in the technical scheme or the application of the BODIPY solid-state luminescent material prepared by the preparation method in fluorescent dye.
The invention provides a blue light driven LED, which comprises a blue LED and a boron dipyrromethene solid-state luminescent material deposited on the surface of the blue LED;
the BODIPY solid-state luminescent material is one or more of the BODIPY solid-state luminescent materials in the technical scheme or one or more of the BODIPY solid-state luminescent materials prepared by the preparation method in the technical scheme.
The invention provides a preparation method of a blue light driven LED (light emitting diode) in the technical scheme, which comprises the following steps:
mixing the BODIPY solid-state luminescent material with a glue solution to obtain a mixture, wherein the mass percentage of the BODIPY solid-state luminescent material in the mixture is 20-50%;
and depositing the mixture on the surface of a blue LED to obtain the LED driven by blue light.
The molecular structure of the solid-state luminescent material of the BODIPY provided by the invention has a certain conjugated structure, and modified molecular structures of electron donating groups (3, 5-dimethylphenyl, 3, 5-dimethoxyphenyl, 3, 5-di-tert-butylphenyl) and electron withdrawing groups (3, 5-difluorophenyl and 3, 5-bistrifluoromethylphenyl) are introduced, so that the strong pi-pi accumulation is avoided while the charge transfer caused by the electron donating groups and the electron withdrawing groups in the molecules is increased, and the luminescence is realized and the luminescent quantum efficiency is higher. Therefore, the BODIPY solid-state luminescent material provided by the invention has good hue, saturation and color rendering property and high luminous efficiency.
In addition, the boron-fluoride dipyrrole solid luminescent material with the formulas I-1 to I-5 has diversified luminescent properties due to different electron-donating and electron-withdrawing group modification groups in the molecular structure. The results of the embodiments of the invention show that the BODIPY solid-state luminescent material provided by the invention has the chromaticity coordinate of (0.19-0.29, 0.26-0.38), the color rendering index of 33-66, the color temperature of 1136-83060 and the luminous efficiency of 1.09-34.13 lm/W.
The preparation method provided by the invention adopts a one-pot reaction, has high yield and simple operation, and is suitable for industrial production.
Drawings
FIG. 1 is a diagram showing an ultraviolet-visible absorption spectrum of a fluoroboric dipyrrole solid state light-emitting material methylene chloride solution prepared in example 1;
FIG. 2 is a solid powder of a BODIPY-based solid state light emitting material prepared in example 1 and a fluorescence emission spectrum in a dichloromethane solution;
FIG. 3 is a graph showing the luminous effect of a blue LED prepared by applying the solid-state luminescent material of BODIPY prepared in example 1;
FIG. 4 is a photograph of an energized LED driven by blue light prepared in application example 1;
FIG. 5 is a diagram showing an ultraviolet-visible absorption spectrum of a fluoroboric dipyrrole solid state light-emitting material methylene chloride solution prepared in example 2;
FIG. 6 shows fluorescence emission spectra of solid powder and dichloromethane solution of solid-state phosphor of BODIPY prepared in example 2;
fig. 7 is a graph showing the luminous effect of a blue LED prepared from the solid state luminescent material of BODIPY prepared in application example 2;
FIG. 8 is a photograph of an energized blue-light driven LED prepared in application example 2;
FIG. 9 is a diagram showing an ultraviolet-visible absorption spectrum of a fluoroboric dipyrrole solid-state light-emitting material methylene chloride solution prepared in example 3;
FIG. 10 is a solid powder of a BODIPY-based solid state light-emitting material prepared in example 3 and a fluorescence emission spectrum in a dichloromethane solution;
fig. 11 is a graph showing the light emitting effect of a blue LED prepared from the solid state luminescent material of BODIPY prepared in application example 3;
FIG. 12 is a photograph of an energized blue-light driven LED prepared in application example 3;
FIG. 13 is a diagram showing an ultraviolet-visible absorption spectrum of a fluoroboric dipyrrole solid-state light-emitting material methylene chloride solution prepared in example 4;
FIG. 14 shows fluorescence emission spectra of solid powder of a BODIPY-based solid state light emitting material prepared in example 4 and in a dichloromethane solution;
fig. 15 is a graph showing the luminous effect of a blue LED prepared from the diboron fluoride solid state luminescent material prepared in application example 4;
fig. 16 is a photograph of the blue-light-driven LED prepared in application example 4 after being energized;
FIG. 17 is a diagram showing an ultraviolet-visible absorption spectrum of a fluoroboric dipyrrole solid-state light-emitting material methylene chloride solution prepared in example 5;
FIG. 18 is a solid powder of a BODIPY-based solid state light-emitting material prepared in example 5 and a fluorescence emission spectrum in a dichloromethane solution;
fig. 19 is a graph showing the luminous effect of a blue LED prepared from the diboron fluoride solid-state luminescent material prepared in application example 5;
fig. 20 is a photograph of the blue-light-driven LED prepared in application example 5 after energization.
Detailed Description
The invention provides a boron dipyrromethene solid-state luminescent material which has a structure shown in formulas I-1-I-5:
the invention provides a BODIPY solid-state luminescent material which has a structure shown in formulas I-1-I-5, wherein in the BODIPY solid-state luminescent material with the structure shown in formulas I-1-I-5, 3, 5-dimethylphenyl, 3, 5-dimethoxyphenyl and 3, 5-di-tert-butylphenyl are used as electron-donating groups, and 3, 5-difluorophenyl and 3, 5-ditrifluoromethylphenyl are used as electron-withdrawing groups. The BODIPY solid-state luminescent material with the structure shown in the formulas I-1-I-5 has a strong absorption peak at a position of 410-520 nm, the excitation level is high, the luminescent color in a solution is green, and the emission wavelength is about 530 nm; under the solid condition, the maximum reflection wavelength range is 589-638 nm, the range is in a visible light region, and the light-emitting color covers orange to red.
The invention provides a preparation method of the BODIPY solid luminescent material, which comprises the following steps:
mixing aromatic aldehyde, 2, 4-dimethylpyrrole, trifluoroacetic acid and chloralkane in a protective atmosphere, and carrying out nucleophilic addition reaction to obtain a reaction solution A;
the aromatic aldehyde is 3, 5-bis (3',5' -dimethylphenyl) benzaldehyde, 3, 5-bis (3',5' -dimethoxyphenyl) benzaldehyde, 3, 5-bis (3',5' -di-tert-butylphenyl) benzaldehyde, 3, 5-bis (3',5' -difluorophenyl) benzaldehyde or 3, 5-bis (3',5' -bistrifluoromethylphenyl) benzaldehyde;
mixing the reaction solution A and dichloro dicyano benzoquinone, and carrying out oxidation reaction to obtain a reaction solution B;
and mixing the reaction solution B, triethylamine and boron trifluoride-diethyl ether, and performing coordination reaction to obtain the BODIPY solid luminescent material.
In the present invention, the starting materials are all commercially available products well known to those skilled in the art, unless otherwise specified.
In a protective atmosphere, mixing aromatic aldehyde, 2, 4-dimethylpyrrole, trifluoroacetic acid and chloralkane, and carrying out nucleophilic addition reaction to obtain a reaction solution A; the aromatic aldehyde is 3, 5-bis (3',5' -dimethylphenyl) benzaldehyde, 3, 5-bis (3',5' -dimethoxyphenyl) benzaldehyde, 3, 5-bis (3',5' -di-tert-butylphenyl) benzaldehyde, 3, 5-bis (3',5' -difluorophenyl) benzaldehyde or 3, 5-bis (3',5' -bistrifluoromethylphenyl) benzaldehyde.
In the present invention, the ratio of the amount of the aromatic aldehyde to the amount of the 2, 4-dimethylpyrrole is preferably 1 (2 to 4), more preferably 1 (2.5 to 3.5); in the present invention, the chloroalkane is preferably dichloromethane, chloroform or 1, 2-dichloroethane, more preferably dichloromethane; the method has no special requirement on the dosage of the chloralkane, and can realize the complete dissolution of the aromatic aldehyde and the 2, 4-dimethylpyrrole; the invention has no special requirement on the dosage of the trifluoroacetic acid, and the reaction system is maintained in an acidic environment. In the invention, the volume ratio of the trifluoroacetic acid to the chloralkane is preferably (1-2): 100, more preferably (1.2 to 1.5): 100. in the present invention, the trifluoroacetic acid is a catalyst, providing an acidic environment for the nucleophilic addition reaction.
In the invention, the aromatic aldehyde, the 2, 4-dimethylpyrrole, the trifluoroacetic acid and the chloralkane are preferably mixed by adding the aromatic aldehyde and the 2, 4-dimethyl into the chloralkane for dissolving to obtain a mixed solution, and then adding the trifluoroacetic acid into the mixed solution; the order of addition of the aromatic aldehyde and 2, 4-dimethyl is not required.
In the invention, the nucleophilic addition reaction is carried out in a protective atmosphere, wherein the protective atmosphere is preferably nitrogen or argon, and the temperature of the nucleophilic addition reaction is preferably 10-30 ℃, and more preferably 15-28 ℃; the time of the nucleophilic addition reaction is preferably 24-36 h, and more preferably 28-34 h. In the present invention, the nucleophilic addition reaction is preferably carried out under stirring, and the present invention has no special requirement for the specific implementation process of the stirring.
In an embodiment of the present invention, the equation for the affinity addition reaction is:
after the reaction solution A is obtained, the reaction solution A and dichloro dicyano benzoquinone are mixed for oxidation reaction to obtain a reaction solution B.
In the present invention, the ratio of the amounts of the aromatic aldehyde and dichlorodicyanobenzoquinone is preferably 1: (1-2), more preferably 1: (1.2-1.5). In the present invention, the dichlorodicyanobenzoquinone participates in the oxidation reaction as an oxidizing agent.
In the present invention, the reaction solution a and dichlorodicyanobenzoquinone are preferably mixed by adding dichlorodicyanobenzoquinone to the reaction solution a.
In the invention, the temperature of the oxidation reaction is preferably 20-35 ℃, more preferably 25-33 ℃, and the time of the oxidation reaction is preferably 5-36 h, more preferably 6-32 h. In the present invention, the oxidation reaction is preferably carried out under the condition of stirring, and the condition of stirring is preferably the same as the nucleophilic addition reaction.
In an embodiment of the present invention, the equation for the oxidation reaction is:
after the reaction solution B is obtained, the reaction solution B, triethylamine and boron trifluoride-diethyl ether are mixed for coordination reaction to obtain the BODIPY solid luminescent material.
In the present invention, the ratio of the volume of triethylamine, the volume of boron trifluoride-diethyl ether, and the amount of the substance of aromatic aldehyde is preferably (8 to 20) L: (8-20) L: 1 mol; more preferably (10 to 16.5) L: (10-18) L: 1 mol. In the present invention, the mixing of the reaction solution B, triethylamine and boron trifluoride-diethyl ether is preferably performed by adding the triethylamine and boron trifluoride-diethyl ether to the reaction solution B, and in the present invention, the addition order of the triethylamine and boron trifluoride-diethyl ether is preferably performed by adding the triethylamine first and then the boron trifluoride-diethyl ether.
In the invention, the temperature of the coordination reaction is preferably 20-35 ℃, more preferably 23-30 ℃, and the time of the coordination reaction is preferably 5-36 h, more preferably 8-30 h. In the present invention, the coordination reaction is preferably carried out under the condition of stirring, and the condition of stirring is preferably the same as the nucleophilic addition reaction.
In an embodiment of the present invention, the equation for the coordination reaction is:
the invention preferably carries out post-treatment on the reaction liquid of the coordination reaction to obtain the BODIPY solid luminescent material. In the present invention, the post-treatment preferably comprises:
extracting the reaction liquid obtained by the coordination reaction to obtain an organic phase;
washing the organic phase and concentrating to obtain a crude product;
separating and purifying the crude product to obtain a purified solution;
and drying the purified solution to obtain the BODIPY solid luminescent material.
In the invention, the extraction agent for extraction is preferably a mixed solvent of chloralkane and water, and the volume ratio of the chloralkane solvent to the water in the mixed solvent is preferably (1.6-2.4): 1, and more preferably 2: 1; the chloroalkane solvent preferably comprises dichloromethane, chloroform or 1, 2-dichloroethane, more preferably dichloromethane. In the invention, the extraction solvent is preferably a mixed solvent of a chloroalkane solvent and water, and the loss of the reaction liquid during transfer can be effectively avoided.
The organic phase obtained by the extraction is preferably washed, in the invention, the washing solvent is preferably saturated sodium chloride solution, and the water-soluble impurities in the organic phase are further removed by washing.
The concentration of the solvent may be carried out by a method known to those skilled in the art, and in the present invention, the concentration is preferably distillation, and the conditions of the distillation are not particularly limited, and the solvent may be removed.
In the invention, the separation and purification is preferably column chromatography separation and purification, the eluent used for the column chromatography separation and purification is preferably a mixed eluent of dichloromethane and petroleum ether, and the volume ratio of dichloromethane to petroleum ether in the mixed eluent is preferably (1-6): 1, more preferably (3-5): 1, and most preferably 4: 1.
The invention has no special requirements on the specific implementation process of the drying, and the eluent is removed completely.
The invention provides an application of the BODIPY solid-state luminescent material prepared by the technical scheme or the BODIPY solid-state luminescent material prepared by the preparation method in a fluorescent dye.
The boron-dipyrromethene solid luminescent material provided by the invention can be directly used as a fluorescent dye. The invention has no special requirements on the specific method for applying the BODIPY solid-state luminescent material in the fluorescent dye, and the method which is well known by the technicians in the field can be adopted.
The invention provides a blue light driven LED, which comprises a blue LED and a boron dipyrromethene solid-state luminescent material deposited on the surface of the blue LED;
the BODIPY solid-state luminescent material is one or more of the BODIPY solid-state luminescent materials described in the technical scheme or one or more of the BODIPY solid-state luminescent materials prepared by the preparation method described in the technical scheme.
In the invention, when the BODIPY solid-state luminescent materials are more than two of the BODIPY solid-state luminescent materials in the technical scheme, the specific mass ratio of the BODIPY solid-state luminescent materials has no special requirement, so that the luminescent color can be realized.
The source of the blue LED is not particularly limited in the invention, and a commercially available blue LED well known to those skilled in the art can be adopted, and in the invention, the commercially available blue LED preferably consists of a packaged complete depilatory chip which emits blue light of 400-480 nm at 350 milliampere current. The invention has no special requirement on the deposition thickness of the BODIPY solid-state luminescent material, and in the specific embodiment of the invention, the deposition thickness is preferably 2-5 mm.
In the invention, the wavelength of the blue light-driven LED is preferably 400-480 nm, and more preferably 460 nm.
The invention provides a preparation method of a blue light driven LED, which comprises the following steps:
mixing the BODIPY solid luminescent material with the glue solution to obtain a mixture;
depositing the mixture on the surface of a blue LED to obtain a blue light-driven LED;
the mass percentage of the BODIPY solid luminescent material in the mixture is 20-50%.
The invention mixes the BODIPY solid luminescent material and the glue solution to obtain a mixture. In the invention, the glue solution preferably comprises A/B glue. In the specific embodiment of the invention, in the A/B glue, A is Polydimethylsiloxane (PDMS), B is vinyltriethoxysilane; in the invention, the mass ratio of A to B in the A/B glue is preferably 10: 1. In the invention, the mass percentage of the BODIPY solid-state luminescent material in the mixture is preferably 20-50%, more preferably 22-28%, and most preferably 25-27%. The invention has no special requirements on the specific implementation process of mixing the BODIPY solid-state luminescent material and the glue solution.
After the mixture is obtained, the mixture is deposited on the surface of the blue LED, and the blue LED is obtained after drying.
The present invention is not particularly limited with respect to the specific implementation of the deposition and drying, and deposition procedures known to those skilled in the art may be employed. The range of the blue LED is the same as above, and is not described herein again.
In order to further illustrate the present invention, the following embodiments are described in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Under a nitrogen atmosphere, 2, 4-dimethylpyrrole (1.29g,13.55mmol) and 3, 5-bis (3',5' -dimethylphenyl) benzaldehyde (1.7g,5.4mmol) were dissolved in 100mL of anhydrous dichloromethane, followed by the addition of 2mL of trifluoroacetic acid. After the dropwise addition, the reaction was stirred at room temperature for 12 hours. Dichloro-dicyanoquinone (1.35g,5.94mmol) was then added and the reaction was continued at room temperature for 12 h. 10mL of triethylamine and 10mL of boron trifluoride-diethyl ether were added thereto and the reaction was stirred for 10 hours. Then, the obtained reaction solution was extracted with a mixed solvent of dichloromethane and water (the volume ratio of dichloromethane to water was 2:1), the obtained organic phase was washed successively with a saturated sodium chloride solution, dichloromethane was distilled off, and the obtained concentrated solution was subjected to column chromatography separation and purification, the eluent was a mixed eluent of petroleum ether and dichloromethane, and the volume ratio of petroleum ether and dichloromethane was 1:2, to obtain a fluoroboric dipyrrole solid luminescent material having a structure represented by formula I-1 (abbreviated as 1a, red solid, yield 62%).
The 1a is shown as a formula I-1,
nuclear magnetic data for 1 a:1H NMR(400MHZ,CDCl3):δ7.91(s,1H),7.51(s,2H),7.04(s,2H),6.01(s,2H),2.57(s,6H),2.39(s,12H),1.52(s,6H).19F NMR(376MHz,CDCl3)δ-146.22(q,JB,F＝67.68Hz)。
test example 1
The boron-dipyrromethene solid-state luminescent material prepared in example 1 was subjected to ultraviolet-visible absorption spectrum testing, under room temperature conditions, a proeutectoid TU1900 type ultraviolet-visible spectrophotometer was used to perform ultraviolet absorption spectrum scanning at a wavelength of 200-800 nm, and the ultraviolet-visible absorption spectrum of 1a in a dichloromethane solution was measured, with the test results shown in fig. 1. As shown in FIG. 1, 1a has a strong absorption peak at 410-520 nm, which indicates that 1a has a high excitation level and a light-emitting range substantially in a visible light region.
Test example 2
Fluorescence emission spectrum test was performed on the boron-dipyrromethene solid-state light-emitting material prepared in example 1: dissolving 1a in a dichloromethane solution at room temperature using a Hitachi F4600 fluorometer to obtain a dichloromethane solution of 1a (the concentration of 1a is 1X 10)-5mol/L) was excited at a wavelength of 502nm to obtain fluorescence emission spectra of a dichloromethane solution of 1a and a solid powder of 1a, respectively, as shown in FIG. 2. As can be seen from FIG. 2, the dichloromethane solution of 1a has a large emission peak at 500-600 nm, while the solid powder of 1a has a large emission peak at 525-800 nm, which indicates that 1a shows different fluorescence in the solution and in the solid state, because the light emission sources of 1a in the solution and in the solid state are different.
Application example 1
Mixing the 1a and the A/B glue, and depositing the obtained mixture on the surface of a commercial blue LED to obtain a blue light-driven LED which is marked as a 1 a-LED; wherein, the commercial blue LED is composed of a packaged and integrated depilatory chip which emits 460nm blue light at 350 milliampere current; the mass ratio of a to B to 1a in the mixed solution was 100:10:40, the light emission results of the blue-light driven LED are shown in fig. 3, and the actual photograph of the blue-light driven LED after energization is shown in fig. 4. As can be seen from fig. 3, the chromaticity coordinates of the blue-light-driven LED are (0.29,0.37), the color rendering index is 33, the color temperature is 2150, and the luminous efficiency is 16.46lm/W, which indicates that the luminous efficiency of 1a is high; as can be seen from fig. 4, the emission color of the blue-light-driven LED prepared in example 1 was orange-yellow light visible to the naked eye.
Example 2
Under a nitrogen atmosphere, 2, 4-dimethylpyrrole (1.29g,13.55mmol) and 3, 5-bis (3',5' -dimethoxyphenyl) benzaldehyde (2.0g,5.4mmol) were dissolved in 100mL of anhydrous dichloromethane, followed by the addition of 1mL of trifluoroacetic acid. After the dropwise addition, the reaction was stirred at room temperature for 12 hours. Dichloro-dicyanoquinone (1.35g,5.94mmol) was then added and the reaction was continued at room temperature for 12 h. 10mL of triethylamine and 10mL of boron trifluoride-diethyl ether were added thereto and the reaction was stirred for 10 hours. Then extracting the obtained reaction liquid by using a mixed solvent of dichloromethane and water (the volume ratio of dichloromethane to water is 2:1), washing and drying the obtained organic phase by using a saturated sodium chloride solution in sequence, distilling to remove dichloromethane, carrying out column chromatography separation and purification on the obtained concentrated solution, wherein an eluent is a mixed eluent of petroleum ether and dichloromethane, the volume ratio of the petroleum ether to the dichloromethane is 1:2, and obtaining the BODIPY solid luminescent material (abbreviated as 1b, red solid and yield of 75%) with the structure shown in formula I-2,
the 1b is shown as a formula I-2,
nuclear magnetic data of 1 b:1H NMR(400MHZ,CDCl3)δ7.90(s,1H),7.52(d,J＝4.0,2H),6.77(d,J＝4.0,4H),6.51(t,J＝4.0,2H),6.01(s,1H),3.86(s,12H),2.58(s,6H),1.51(s,6H).19F NMR(376MHz,CDCl3)δ-146.23(q,JB,F＝60.16Hz)。
test example 3
The boron-dipyrromethene solid-state luminescent material prepared in example 2 was subjected to ultraviolet-visible absorption spectrum testing, under room temperature conditions, a proeutectoid TU1900 type ultraviolet-visible spectrophotometer was used to perform ultraviolet absorption spectrum scanning at a wavelength of 200-800 nm, and the ultraviolet-visible absorption spectrum of 1b in a dichloromethane solution was measured, with the test results shown in fig. 5. As shown in FIG. 5, 1b has a strong absorption peak at 410-520 nm, which indicates that 1b has a high excitation level and a light-emitting range substantially in the visible light region.
Test example 4
Fluorescence emission spectrum test was performed on the diboron fluoride solid state luminescent material prepared in example 2: dissolving 1b in a dichloromethane solution at room temperature using a Hitachi F4600 fluorometer to obtain a dichloromethane solution of 1b (1b concentration 1X 10)-5mol/L) was excited at a wavelength of 502nm to obtain fluorescence emission spectra of a dichloromethane solution of 1b and a solid powder of 1b, respectively, as shown in FIG. 6. As can be seen from FIG. 6, the dichloromethane solution of 1b has a large emission peak at 500-600 nm, while the solid powder of 1b has a large emission peak at 525-720 nm, which indicates that 1b shows different fluorescence in the solution and in the solid state, because the light emission sources of 1b are different in the solution and the solid state.
Application example 2
Mixing the 1B and the A/B glue, and depositing the obtained mixture on the surface of a commercial blue LED to obtain a blue light-driven LED which is marked as a 1B-LED; wherein, the commercial blue LED is composed of a packaged and integrated depilatory chip which emits 460nm blue light at 350 milliampere current; the mass ratio of a to B to 1B in the mixed solution was 100:10:40, the light emission results of the blue-light driven LED are shown in fig. 7, and the actual photograph of the blue-light driven LED after energization is shown in fig. 8. As can be seen from fig. 7, the chromaticity coordinates of the blue-light-driven LED are (0.42,0.36), the color rendering index is 48, the color temperature is 1136, and the luminous efficiency is 1.09lm/W, which indicates that the luminous efficiency of 1b is high; as can be seen from fig. 8, the emission color of the blue-light-driven LED prepared in example 2 was red visible to the naked eye.
Example 3
Under a nitrogen atmosphere, 2, 4-dimethylpyrrole (1.29g,13.55mmol) and 3, 5-bis (3',5' -di-tert-butylphenyl) benzaldehyde (2.6g,5.4mmol) were dissolved in 100mL of an anhydrous dichloromethane solution, followed by addition of 1mL of trifluoroacetic acid. After the dropwise addition, the reaction was stirred at room temperature for 12 hours. Dichloro-dicyanoquinone (1.35g,5.94mmol) was then added and the reaction was continued at room temperature for 12 h. 10mL of triethylamine and 10mL of boron trifluoride-diethyl ether were added thereto and the reaction was stirred for 10 hours. Then extracting the obtained reaction liquid by using a mixed solvent of dichloromethane and water (the volume ratio of dichloromethane to water is 2:1), washing and drying the obtained organic phase by using a saturated sodium chloride solution in sequence, distilling to remove dichloromethane, carrying out column chromatography separation and purification on the obtained concentrated solution, wherein an eluent is a mixed eluent of petroleum ether and dichloromethane, the volume ratio of the petroleum ether to the dichloromethane is 1:2, and obtaining the BODIPY solid luminescent material (abbreviated as 1c, red solid and yield of 72%) with the structure shown in formula I-3,
the 1c is shown as a formula I-3,
nuclear magnetic data of 1 c:1H NMR(400MHZ,CDCl3)δ7.97(s,1H),7.53(d,J＝4.0,2H),7.51(s,6H),6.02(s,2H),2.59(s,6H),1.55(s,6H),1.39(s,12H).19F NMR(376MHz,CDCl3)δ-146.17(q,JB,F＝67.68Hz).
test example 5
The boron-dipyrromethene solid-state luminescent material prepared in example 3 was subjected to ultraviolet-visible absorption spectrum testing, under room temperature conditions, a proeutectoid TU1900 type ultraviolet-visible spectrophotometer was used to perform ultraviolet absorption spectrum scanning at a wavelength of 200 to 800nm, and the ultraviolet-visible absorption spectrum of 1c in a dichloromethane solution was measured, with the test results shown in fig. 10. As shown in FIG. 10, 1c shows a strong absorption peak at 410-520 nm, which indicates that the excitation level of 1c is higher and the light-emitting range is substantially in the visible light region.
Test example 6
The boron-containing dipyrromethene solid-state luminescent material prepared in example 3 was subjected to fluorescenceAnd (3) emission spectrum testing: the solution of 1c in methylene chloride was dissolved at room temperature using a Hitachi F4600 fluorometer to obtain a methylene chloride solution of 1c (the concentration of 1c was 1X 10)-5mol/L) of the solid powder, and fluorescence emission spectra of the dichloromethane solution of 1c and the solid powder of 1c were obtained by excitation at a wavelength of 501nm, respectively, and the results are shown in FIG. 11. As can be seen from FIG. 11, the dichloromethane solution of 1c has a large emission peak at 500-600 nm, while the solid powder of 1c has a large emission peak at 525-775 nm, which shows that 1c shows different fluorescence in the solution and in the solid state, because the light emission sources of 1c are different in the solution and the solid state.
Application example 3
Mixing the 1c and the A/B glue, and depositing the obtained mixture on the surface of a commercial blue LED to obtain a blue light-driven LED which is marked as a 1 c-LED; wherein, the commercial blue LED is composed of a packaged and integrated depilatory chip which emits 460nm blue light at 350 milliampere current; the mass ratio of a to B to 1c in the mixed solution was 100 to 10 to 40, the emission result of the blue-driven LED is shown in fig. 12, and the photograph of the blue-driven LED after energization is shown in fig. 13. As can be seen from fig. 12, the chromaticity coordinates of the blue-light-driven LED are (0.23,0.38), the color rendering index is 33, the color temperature is 3163, and the luminous efficiency is 21.19lm/W, indicating that the luminous efficiency of 1c is high; as can be seen from fig. 13, the emission color of the blue-light-driven LED prepared in example 3 is orange light visible to the naked eye.
Example 4
Under a nitrogen atmosphere, 2, 4-dimethylpyrrole (1.29g,13.55mmol) and 3, 5-bis (3',5' -difluorophenyl) benzaldehyde (1.78g,5.4mmol) were dissolved in 100mL of anhydrous dichloromethane followed by the addition of 2mL of trifluoroacetic acid. After the dropwise addition, the reaction was stirred at room temperature for 12 hours. Dichloro-dicyanoquinone (1.35g,5.94mmol) was then added and the reaction was continued at room temperature for 12 h. 10mL of triethylamine and 10mL of boron trifluoride-diethyl ether were added thereto and the reaction was stirred for 10 hours. Then, the obtained reaction solution is extracted by using a mixed solvent of dichloromethane and water (the volume ratio of dichloromethane to water is 2:1), the obtained organic phase is washed and dried by saturated sodium chloride solution in sequence, dichloromethane is distilled to remove, and the obtained concentrated solution is subjected to column chromatography separation and purification, wherein an eluent is a mixed eluent of petroleum ether and dichloromethane, and the volume ratio of the petroleum ether to the dichloromethane is 1:2, so that the diboron fluoride solid luminescent material with the structure shown in the formula I-4 is obtained (the abbreviation is 1d, red solid and the yield is 79%).
1d is shown as a formula I-4,
nuclear magnetic data for 1 d:1H NMR(400MHZ,CDCl3)δ7.84(s,1H),7.56(d,J＝4.0,2H),7.15(dd,J＝8.0,4H),6.84-6.89(m,J＝4.0,2H),6.03(s,2H),2.58(s,6H),1.48(s,6H).19F NMR(376MHz,CDCl3)δ-146.22(q,JB,F＝67.68Hz),-108.61(s)。
test example 7
The boron-dipyrromethene solid-state luminescent material prepared in example 4 was subjected to ultraviolet-visible absorption spectrum testing, under room temperature conditions, a proeutectoid TU1900 type ultraviolet-visible spectrophotometer was used to scan the ultraviolet absorption spectrum at a wavelength of 200-800 nm, and the ultraviolet-visible absorption spectrum of 1d in dichloromethane solution was measured, with the test results shown in fig. 13. As shown in FIG. 13, 1d shows a strong absorption peak at 410-520 nm, which indicates that the 1d has a high excitation level and the light-emitting range is substantially in the visible light region.
Test example 8
Fluorescence emission spectrum test was performed on the diboron fluoride solid state light emitting material prepared in example 4: the obtained 1d solution was dissolved in a dichloromethane solution at room temperature using a Hitachi F4600 fluorometer to obtain a 1d dichloromethane solution (1d concentration: 1X 10)-5mol/L) of the solid powder, and fluorescence emission spectra of the dichloromethane solution of 1d and the solid powder of 1d were obtained respectively by excitation at a wavelength of 503nm, and the results are shown in FIG. 14. As can be seen from FIG. 14, the dichloromethane solution of 1d has a large emission peak at 500-600 nm, while the solid powder of 1d has a large emission peak at 550-750 nm, which indicates that 1d shows different fluorescence in the solution and in the solid state, because 1d shows different fluorescence in the solution and the solid stateThe light emission sources of the states are different.
Application example 4
Mixing the 1d and the A/B glue, and depositing the obtained mixture on the surface of a commercial blue LED to obtain a blue light-driven LED which is marked as a 1 d-LED; wherein, the commercial blue LED is composed of a packaged and integrated depilatory chip which emits 460nm blue light at 350 milliampere current; the mass ratio of a to B to 1d in the mixed solution was 100:10:40, the light emission results of the blue-driven LED are shown in fig. 15, and the actual photograph of the blue-driven LED after energization is shown in fig. 16. As can be seen from fig. 15, the chromaticity coordinates of the blue-light-driven LED are (0.19,0.36), the color rendering index is 43, the color temperature is 4423, the luminous efficiency is 34.13lm/W, and it is shown that the luminous efficiency of 1d is high; as can be seen from fig. 16, the emission color of the blue-light-driven LED prepared in example 4 is yellow light visible to the naked eye.
Example 5
Under a nitrogen atmosphere, 2, 4-dimethylpyrrole (1.29g,13.55mmol) and 3, 5-bis (3',5' -bistrifluoromethylphenyl) benzaldehyde (2.86g,5.4mmol) were dissolved in 100mL of anhydrous dichloromethane solution, followed by the addition of 2mL of trifluoroacetic acid. After the dropwise addition, the reaction was stirred at room temperature for 12 hours. Dichloro-dicyanoquinone (1.35g,5.94mmol) was then added and the reaction was continued at room temperature for 12 h. 10mL of triethylamine and 10mL of boron trifluoride-diethyl ether were added thereto and the reaction was stirred for 10 hours. Then extracting the obtained reaction liquid by using a mixed solvent of dichloromethane and water (the volume ratio of dichloromethane to water is 2:1), washing and drying the obtained organic phase by using a saturated sodium chloride solution in sequence, distilling to remove dichloromethane, carrying out column chromatography separation and purification on the obtained concentrated solution, wherein an eluent is a mixed eluent of petroleum ether and dichloromethane, the volume ratio of the petroleum ether to the dichloromethane is 1:2, and obtaining the BODIPY solid luminescent material (abbreviated as 1e, red solid and yield of 75%) with the structure shown in formula I-5,
the 1e is shown as a formula I-5,
nuclear magnetic data of 1 e:1H NMR(400MHZ,CDCl3)δ8.06(s,4H),7.96(s,2H),7.93(s,1H),7.70(s,2H),6.06(s,2H),2.59(s,6H),1.51(s,6H).19F NMR(376MHz,CDCl3)δ-146.20(q,JB,F＝63.92Hz),-62.66(s).
test example 9
The boron-dipyrromethene solid-state luminescent material prepared in example 5 was subjected to ultraviolet-visible absorption spectrum testing, under room temperature conditions, a proeutectoid TU1900 type ultraviolet-visible spectrophotometer was used to scan the ultraviolet absorption spectrum at a wavelength of 200-800 nm, and the ultraviolet-visible absorption spectrum of 1e in a dichloromethane solution was measured, with the test results shown in fig. 17. As shown in FIG. 17, 1e shows a strong absorption peak at 410-520 nm, indicating that 1e has a high excitation level and a luminescence range substantially in the visible light range.
Test example 10
Fluorescence emission spectrum test was performed on the diboron fluoride solid state light emitting material prepared in example 5: 1e was dissolved in a dichloromethane solution at room temperature using a Hitachi F4600 fluorometer to obtain a dichloromethane solution of 1e (1e concentration: 1X 10)-5mol/L) was added, and excitation was performed at a wavelength of 503nm to obtain fluorescence emission spectra of a dichloromethane solution of 1e and a solid powder of 1e, respectively, as shown in FIG. 18. As can be seen from FIG. 18, the dichloromethane solution of 1e has a large emission peak at 500-600 nm, while the solid powder of 1e has a large emission peak at 600-800 nm, which indicates that 1e shows different fluorescence in the solution and in the solid state, because the light emission sources of 1e in the solution and in the solid state are different.
Application example 5
Mixing the 1e and the A/B glue, and depositing the obtained mixture on the surface of a commercial blue LED to obtain a blue light-driven LED which is marked as a 1 e-LED; wherein, the commercial blue LED is composed of a packaged and integrated depilatory chip which emits 460nm blue light at 350 milliampere current; the mass ratio of a: B:1c in the mixed solution was 100:10:40, the light emission results of the blue-driven LED are shown in fig. 19, and the actual photograph of the blue-driven LED after energization is shown in fig. 20. As can be seen from fig. 19, the chromaticity coordinates of the blue-light-driven LED are (0.20,0.26), the color rendering index is 66, the color temperature is 83060, the luminous efficiency is 10.19lm/W, and it is shown that the luminous efficiency of 1e is high; as can be seen from fig. 20, the emission color of the blue-light-driven LED prepared in example 5 was blue light visible to the naked eye.
The light emitting properties of the blue light-driven LEDs prepared in application examples 1-5 are listed in table 1. As shown in Table 1, the invention is expected to be used as a solid luminescent dye in the field of LEDs.
Table 1 luminescence properties of blue light-driven LEDs prepared in application examples 1-5
In conclusion, the boron-fluorine dipyrrole solid luminescent material provided by the invention has a conjugated structure, the electron-donating group and the electron-withdrawing group are introduced to modify a molecular structure, and the electron flow caused by the electron-donating group and the electron-withdrawing group in the molecule avoids strong pi-pi accumulation, so that the luminescent is realized, the luminescent quantum efficiency is higher, the luminescent material has diversified luminescent properties, the color tone, the saturation and the color rendering are good, and the luminescent efficiency is high. In addition, when the solid-state luminescent material of the BODIPY provided by the invention is in a solid state, the luminescent property of the BODIPY complex changes to a certain extent relative to a solution system due to abundant intermolecular forces existing among molecules of the BODIPY complex.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and the embodiments are within the scope of the present invention.
Claims (10)
1. A BODIPY solid-state luminescent material is characterized by having a structure shown in any one of formulas I-1 to I-5:
2. the method for preparing a BODIPY solid-state luminescent material according to claim 1, comprising the steps of:
mixing aromatic aldehyde, 2, 4-dimethylpyrrole, trifluoroacetic acid and chloralkane in a protective atmosphere, and carrying out nucleophilic addition reaction to obtain a reaction solution A;
the aromatic aldehyde is 3, 5-bis (3',5' -dimethylphenyl) benzaldehyde, 3, 5-bis (3',5' -dimethoxyphenyl) benzaldehyde, 3, 5-bis (3',5' -di-tert-butylphenyl) benzaldehyde, 3, 5-bis (3',5' -difluorophenyl) benzaldehyde or 3, 5-bis (3',5' -bistrifluoromethylphenyl) benzaldehyde;
mixing the reaction solution A and dichloro dicyano benzoquinone, and carrying out oxidation reaction to obtain a reaction solution B;
and mixing the reaction solution B, triethylamine and boron trifluoride-diethyl ether for coordination reaction to obtain the BODIPY solid luminescent material.
3. The method according to claim 2, wherein the ratio of the amounts of the aromatic aldehyde and 2, 4-dimethylpyrrole is 1 (2-4).
4. The method according to claim 2, wherein the ratio of the amount of the substance of the aromatic aldehyde, the volume of triethylamine and the volume of boron trifluoride-diethyl ether is 1 mol: (8-20) L: (8-20) L.
5. The preparation method according to claim 2 or 3, wherein the temperature of the nucleophilic addition reaction is 10-30 ℃ and the time is 24-36 h; the protective atmosphere comprises nitrogen or argon.
6. The preparation method according to claim 2 or 3, wherein the temperature of the oxidation reaction and the coordination reaction is 20 to 35 ℃ independently, and the time is 5 to 36 hours independently.
7. The process according to claim 2 or 4, wherein the chlorinated alkane is dichloromethane, chloroform or 1, 2-dichloroethane.
8. The application of the BODIPY solid-state luminescent material according to claim 1 or the BODIPY solid-state luminescent material prepared by the preparation method according to any one of claims 2 to 7 in fluorescent dyes.
9. The blue light-driven LED is characterized by comprising a blue LED and a BODIPY solid-state luminescent material deposited on the surface of the blue LED;
the BODIPY solid-state luminescent material is one or more of BODIPY solid-state luminescent materials described in claim 1 or one or more of BODIPY solid-state luminescent materials prepared by the preparation method described in any one of claims 2 to 8.
10. A method of making a blue light-driven LED according to claim 9, comprising the steps of:
mixing the BODIPY solid-state luminescent material with a glue solution to obtain a mixture, wherein the mass percentage of the BODIPY solid-state luminescent material in the mixture is 20-50%;
and depositing the mixture on the surface of a blue LED to obtain the LED driven by blue light.
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