TW202142676A - Improved wavelength conversion film - Google Patents

Abstract

Described herein is an improved wavelength conversion film with composite materials that have improved quantum efficiency and color gamut. The film includes narrow FWHM green and red emitting dyes.

Description

Improved wavelength conversion film

The present invention relates to a wavelength conversion film, and relates to a light emitting device including the wavelength conversion film.

Photoluminescent substances are materials that emit light after absorbing energy in the form of light or electricity. Depending on the composition and luminescence mechanism of the photoluminescence material, the photoluminescence material can be classified into inorganic photoluminescence material (or dye), organic photoluminescence dye, nanocrystal photoluminescence material, and the like.

Recently, various attempts to use this photoluminescent substance to change the spectrum of a light source have been described. The photoluminescent substance absorbs light of a specific wavelength from a light source, converts this light into longer wavelength light in the visible light region, and emits the light. Depending on the light-emitting characteristics of the photoluminescent material, the brightness, color purity, color gamut, etc. of the emitted light can be greatly enhanced. Inorganic photoluminescent materials can be formed from parent compounds (such as sulfides, oxides or nitrides and activator ions), and can be used in high-quality display devices with excellent physical and chemical stability and high color purity reproduction. However, there are disadvantages in that these inorganic photoluminescent materials are extremely expensive, have low luminous efficiency, and light emission in the near ultraviolet or blue region of 400 nm or higher is limited.

Quantum dot technology has achieved a high level of quantum efficiency and color gamut. However, cadmium-based quantum dots can be extremely toxic and are restricted in many countries due to health and safety issues. In addition, some quantum dots have a much lower quantum efficiency in converting blue LED light into green or red light. In addition, when exposed to moisture and oxygen, quantum dots may have low stability and often require expensive packaging processes. The cost of quantum dots can be extremely high because it can be extremely difficult to control size uniformity during their production.

Therefore, compared with quantum dots and other existing films containing photoluminescent dyes, a new type of photoluminescent film with high quantum efficiency, high color gamut output and lower cost is required.

Some embodiments include a wavelength conversion film, the wavelength conversion film comprising: a polymer matrix; a first photoluminescent dye, the first photoluminescent dye absorbs blue wavelength light, and emits a full-width half-width less than 40 nm The green wavelength light of the emission spectrum; a second photoluminescent dye that absorbs blue or green wavelength light and emits red wavelength light having an emission spectrum with a full width half width of less than 40 nm; and light scattering Center; wherein the first photoluminescent dye, the second photoluminescent dye and the light scattering center are scattered in the polymer matrix.

。In some embodiments, the first photoluminescent dye may include a BODIPY group, a linking group, and a perylene group. In some embodiments, the first photoluminescent dye is selected from:

.

，或其任何組合。In some embodiments, the first photoluminescent dye may include a BODIPY group, a linking group, and a naphthalenedimethimide group. In some embodiments, the first photoluminescent dye may be selected from:

, Or any combination thereof.

。In some embodiments, the second photoluminescent dye may include a BODIPY group, a linking group, and a perylene group. In some embodiments, the second photoluminescent dye may include [SD-1]:

.

In some embodiments, the film may have a quantum yield greater than 85%. In some embodiments, the film may have a color gamut of the BT2020 standard that is greater than 85%. In some embodiments, the film may have a thickness of less than 100 microns.

Some embodiments include a light emitting device that includes the photoluminescence wavelength conversion film described herein.

Some embodiments include a backlight device having a blue light source including the photoluminescence wavelength conversion film described herein.

These and other embodiments are described in more detail below.

Cross references to related applications

This application claims the rights and interests of U.S. Provisional Application No. 63/002,330 filed on March 30, 2020, and the entire content of the U.S. Provisional Application is incorporated herein by reference.

The present invention relates to a novel wavelength conversion film, which includes a photoluminescent compound (or dye) with high quantum efficiency, high color gamut output and low cost.

。The term "BODIPY" as used herein refers to a chemical moiety having the following formula:

.

The BODIPY moiety contains a dipyrromethene group complexed with a disubstituted boron atom (usually a BF _{2 unit).} The IUPAC name of BODIPY core is 4,4-difluoro-4-bora-3a,4a-diaza-s-indase.

The term "perylene" as used herein refers to a chemical moiety having the following formula:

，其中X=NR，其中R可為連接基團或芳基。The term "naphthalenedicarboxylic acid" or "naphthalenedicarboxylic acid derivative" as used herein refers to a chemical moiety having the following chemical formula:

, Where X=NR, where R can be a linking group or an aryl group.

In some embodiments, a linking group is used to link the BODIPY moiety to the perylene moiety. In some embodiments, a linking group is used to link the BODIPY moiety to the naphthalenedicarboxylic acid moiety.

The use of the terms "may" or "may be" should be interpreted as a shorthand for "being" or "not being", or alternatively "doing" or "not doing" or "will" or "will not" etc. For example, the expression "the film may include scattering centers disposed in the polymer matrix" should be interpreted as, for example, "in some embodiments, the film includes scattering centers disposed in the polymer matrix", or "in some embodiments, the film Does not include scattering centers placed in the polymer matrix."

The term ITU-R recommendation BT.2020 (more commonly known as the abbreviation Rec. 2020 or BT.2020) refers to the color display standard of the color gamut. The RGB primary colors used in Rec. 2020 are equivalent to the monochromatic light source on the CIE 1931 spectral locus. The wavelength of the Rec. 2020 primary color is 630 nm for the red primary color, 532 nm for the green primary color, and 467 nm for the blue primary color. The Rec. 2020 color space covers 75.8% of the CIE 1931 color space (the area within the determined triangle). Rec. 2020 color space uses CIE standard luminous body D65 as the white point and the following color coordinates: X _w = 0.3127; Y _w = 0.3290; X _R = 0.708, Y _R = 0.292, X _G = 0.17, Y _G = 0.797; X _B = 0.131; Y _B = 0.046.

Some embodiments include a wavelength conversion film that includes a polymer matrix, a first organic photoluminescent compound, and a second organic photoluminescent compound. In some embodiments, the film may include a first organic photoluminescent dye that emits green light and has an emission peak with a full width at half maximum of less than 40 nm. In some embodiments, the film may include a second organic photoluminescent dye that emits red light and has an emission peak with a full width at half maximum of less than 40 nm. In some embodiments, the film may include light scattering centers. In some examples, the first organic photoluminescent dye (emitting green light), the second organic photoluminescent dye (emitting red light), and the scattering center are disposed within the polymer matrix. In some embodiments, the film provides high quantum yield. In some embodiments, the film provides a wide color gamut greater than 80%. A suitable method for determining the percentage of the color gamut is to measure the area under the 1931 CIE color space generated, as shown in Figure 11. In some embodiments, the film may be between 80% and 99.9% color gamut, such as 86%, 90%, 93%, and/or 95%, or a range defined by any of these equivalent values. In some embodiments, an LCD backlight is described that includes the aforementioned film.

In some embodiments, the film may comprise a polymer matrix. In some embodiments, the polymer matrix may have greater than 75% transparency. In some embodiments, the polymer matrix may comprise a hydrophilic polymer. In some embodiments, the polymer matrix may comprise polyvinyl butyral, polyvinyl acetate, polyvinyl alcohol, or polyacrylate. In some embodiments, the polymer matrix may comprise polyvinyl butyral (PVB). In some embodiments, the polyacrylate may be a polyalkyl acrylate. In some embodiments, the polyalkyl acrylate may be polymethylmethacrylate (PMMA).

In some embodiments, the luminescent compound (and/or the photoluminescence wavelength conversion film containing the luminescent compound) has a narrow absorption or emission band, so that a small amount of visible wavelength light is emitted. The absorption or emission band can be characterized by the full width at half maximum (FWHM). In the present invention, FWHM defines the width of the absorption or emission spectrum in nanometers at half of the absorption or emission peak wavelength. In some embodiments, when dispersed in a substantially transparent polymer matrix, the luminescent compound has an absorption with a FWHM value of less than or equal to 50 nm, less than or equal to 40 nm, less than or equal to 35 nm, or less than or equal to 30 nm. belt. In some embodiments, when dispersed in a substantially transparent polymer matrix, the luminescent compound has an emission with a FWHM value of less than or equal to 50 nm, less than or equal to 40 nm, less than or equal to 35 nm, or less than or equal to 30 nm. belt.

，或其任何組合。In some embodiments, the film may include a first organic light-emitting compound (or dye). In some embodiments, the first organic light-emitting dye (and/or the photoluminescence wavelength conversion film containing the first organic light-emitting dye) may have an emission peak (green light) between 510 nm and 560 nm. In some embodiments, the emission spectrum of the first organic light emitting dye and/or the photoluminescence wavelength conversion film may have a full width at half width (FWHM) of less than 50 nm, less than 40 nm, less than 35 nm, or less than 30 nm. In some embodiments, the first organic light-emitting dye may include a BODIPY group, a linking group, and a perylene group. In some embodiments, the BODIPY group is covalently bonded to the linking group. In some embodiments, the linking group is covalently bonded to the perylene group. In some embodiments, the first organic light emitting dye may include a BODIPY group, a linking group, and a naphthalenedicarboxylic acid derivative group. In some embodiments, the naphthalenedicarboxylic acid derivative group may be a naphthalenedimethimide group. In some embodiments, the naphthalimide group is covalently bonded to the linking group. In some embodiments, the first organic light-emitting dye may be selected from FD-1, FD-2, FD-3 or FD-4:

, Or any combination thereof.

。In some embodiments, the wavelength conversion film may include a second organic photoluminescent dye. In some embodiments, the second organic photoluminescence dye (and/or the photoluminescence wavelength conversion film containing the second organic luminescence dye) may have an absorption peak (absorption of blue light) between 400 nm and 470 nm. In some embodiments, the second organic photoluminescent dye (and/or the photoluminescence wavelength conversion film containing the second organic luminescent dye) may have an emission peak (red light) between 600 nm and 660 nm . In some embodiments, the second organic photoluminescence dye (and/or the photoluminescence wavelength conversion film containing the second organic luminescence dye) may have an emission peak between 615 nm and 645 nm. In some embodiments, the emission spectrum of the second organic photoluminescence dye and/or the photoluminescence wavelength conversion film may have a full width at half width (FWHM) of less than 50 nm, less than 40 nm, less than 35 nm, or less than 30 nm . In some embodiments, the second organic photoluminescent dye may include a BODIPY group and a perylene group. In some embodiments, the second organic photoluminescent dye may include SD-1:

.

In some embodiments, the first photoluminescent compound can absorb light from the ultraviolet/blue light absorption spectrum and emit light in the green emission spectrum, thereby enhancing the perceived green light emitted. In other embodiments, the second photoluminescent compound can absorb light from the green/blue absorption spectrum and emit light in the red emission spectrum, thereby enhancing the perceived emitted red light. In some embodiments, the first photoluminescent dye and the second photoluminescent dye can absorb light from the ultraviolet/blue absorption spectrum and emit light of other wavelengths, wherein the combined light can be perceived as white light. In some examples, the perceived white light may have a color temperature described as cold. In some examples, the perceived white light may have a color temperature described as warm.

The ratio of the amounts of the first photoluminescence dye and the second photoluminescence dye can be adjusted to tune the color characteristics of the photoluminescence wavelength conversion film. For example, the weight ratio of the first photoluminescent dye to the second photoluminescent dye may be about 0.01-100 (the ratio of 1 mg of the first photoluminescent dye to 100 mg of the second photoluminescent dye is 0.01), About 0.01-0.2, about 0.2-0.4, about 0.4-0.6, about 0.6-0.8, about 0.8-1, about 1-2, about 2-3, about 3-4, about 4-5, about 5-6, About 6-7, about 7-8, about 8-9, about 9-10, about 10-20, about 20-40, about 40-70, about 70-100, about 0.43, about 0.91, about 1.8, or About 3.0.

In some embodiments, the film may include scattering centers disposed within the polymer matrix. In some embodiments, the scattering center may be a solid particle comprising a material having a refractive index different from that of the polymer matrix material. The scattering material may be a material whose refractive index (RI) is different from the RI of the polymer matrix. Scattering materials can be used to increase the external quantum yield, for example by reducing total internal reflection. Material RI PMMA 1.49 PVB 1.49 Silicon 1.42 Air pockets or voids 1.00

In some embodiments, the RI difference between the polymer matrix material and the light scattering material may be at least 0.05, 0.1, at least 0.2, at least 0.3, at least 0.4, or at least 0.5, up to 1 or 2.

In some embodiments, the scattering material may be silicone beads. In some embodiments, the scattering center may comprise air pockets defined within the polymer matrix. In some embodiments, the average diameter of the scattering material may be between 1 micrometer (µm) and 10 micrometers (µm), about 1-2 µm, about 2-3 µm, about 3-4 µm, about 4-5 µm, about 5-6 µm, about 6-7 µm, about 7-8 µm, about 8-9 µm, about 9-10 µm, or approximately any value within the range defined by any of these equivalent values value. In some embodiments, the scattering centers may be substantially uniformly dispersed within the polymer matrix. In some embodiments, the top layer portion of the film, for example, the side away from the blue light emitting source, may have a scattering center greater than 50%. In some embodiments, the scattering centers may be uniformly distributed within the polymer matrix.

The photoluminescence wavelength conversion film may have any suitable thickness, such as less than about 500 µm, less than about 200 µm, or less than about 100 µm, such as about 1-20 µm, about 20-30 µm, about 30-40 µm, about 40-50 µm, about 50-80 µm, about 80-120 µm, about 120-200 µm, about 200-300 µm, or about 300-500 µm.

In some embodiments, the photoluminescence wavelength conversion film can have at least about 70%, at least about 80%, or at least about 90% at the maximum of red or green luminescence; and/or up to about 80%, up to about 90%, up to about 100% internal quantum yield (IQE). In some embodiments, the photoluminescence wavelength conversion film may have at least about 50%, at least about 60%, at least about 70%, at least about 80%, or at least about 90% at the maximum of red or green luminescence; And/or up to about 80%, up to about 90%, up to about 100% of external quantum yield (EQE).

In some embodiments, the display device may be represented by a device such as device 10. As shown in FIG. 1, the device 10 may include a light source, such as a light source 12 . In some embodiments, the display device may include a wavelength converting (WLC) film, such as the film 16 . In some embodiments, the WLC film may be in optical communication with the light source, thereby enabling the efficiency of transmitting the generated light from the light source to the observer 20 to be improved.

In some embodiments, the display device may be schematically represented by FIG. 2. As shown in FIG. 2, the display device, such as the device 10 , may include a light source, such as a light source 12 . In some embodiments, the display device may include a back reflector, such as the back reflector 14 . In some embodiments, the display device may include a wavelength converting (WLC) film, such as the film 16 . In some embodiments, the display device may include a mask, such as mask 18 . In some embodiments, the WLC film may be in optical communication with the light source, thereby enabling the efficiency of transmitting the generated light from the light source to the observer 20 to be improved.

In some embodiments, the display device may be schematically represented by FIG. 3. As shown in FIG. 3, a display device is described. The device, for example, the device 10 , may include a light source, for example, the light source 12 . In some embodiments, the display device may include a back reflector, such as the back reflector 14 . In some embodiments, the display device may include a wavelength conversion (WLC) film, such as WLC film 16 . In some embodiments, the display device may include a mask, such as mask 18 . In some embodiments, the WLC film, such as the WLC film 16 , may be in optical communication with the light source, and/or be interposed between the light source and the observer 20 and/or a shield (such as the shield 18 ), thereby making it possible to improve the The efficiency with which the generated light is transmitted from the light source to the observer. In some embodiments, the display device may include one or more brightness enhancement films (BEF), such as BEF 22 , such as Vikuiti brand BEF (3M Minneapolis, MN, USA). In some embodiments, the display device may include one or more polarizers and/or brightness enhancement films, such as dual brightness enhancement films (DBEF) 24 , such as DBEF II (3M Minneapolis, MN, USA). In some embodiments, the use of one or more brightness enhancement films may be referred to as an optical film stack.

Some embodiments include a method for preparing an LED light source. In some embodiments, the method may include using an organic solvent and the photoluminescent dyes described herein to produce an undried wavelength-shifting polymer layer. In some embodiments, the method may include mixing the polymer and/or monomer with an organic solvent. In some embodiments, the polymer and/or monomer precursor may be dispersed, dissolved in a solvent, and/or mixed with a solvent. In some embodiments, solvents can be used to make the material layer. In some embodiments, the solvent may be a non-polar solvent. In some embodiments, the non-polar solvent may include, but is not limited to, xylene, cyclohexanone, acetone, toluene, methyl ethyl ketone, or any combination thereof. In some embodiments, the solvent may be a polar solvent. In some embodiments, the polar solvent may include ethanol, dimethylformamide (DMF), or a combination thereof. In some embodiments, the solvent may be a combination of a non-polar solvent and a polar solvent.

In some embodiments, the method may include immersing the undried polymer photocatalytic WLC layer in an aqueous solution. In some embodiments, the aqueous solution may include water. In some embodiments, the aqueous solution may contain at least 90% water. In some embodiments, the water may be deionized water. In some embodiments, the undried polymer photocatalytic WLC layer may be immersed in the aqueous solution for between 5 minutes to about 1 hour.

In some embodiments, the method may include removing the undried polymer photocatalytic WLC layer from the aqueous solution. In some embodiments, the method may include drying the undried polymer photocatalytic WLC layer. It is believed that fabricating the polymer photocatalytic WLC layer in this manner provides multiple air pockets defined in the emitting or distal surface of the polymer photocatalytic WLC layer. In some embodiments, the air pockets are substantially completely within about 1 micrometer to about 5 micrometers from the emitting surface of the polymer photocatalytic WLC layer.

In some embodiments, the polymer material comprises about 2% to about 50% by weight of polymer, about 2 to 5% by weight, about 5 to 10% by weight, about 10 to 15% by weight, and about 15 to 20% by weight. , About 20-25% by weight, about 25-30% by weight, about 30-35% by weight, about 35-40% by weight, about 40-45% by weight, about 45-50% by weight, about 2.5% by weight to 30% by weight %, about 5-15% by weight, about 15-25% by weight, about 25-35% by weight, or about 30% by weight or about any value within the range defined by any of these equivalent values Aqueous solution.

Examples Example 1. A film, the film comprising: a polymer matrix; a first photoluminescent dye, the first photoluminescent dye absorbs blue wavelength light and has a narrow emission with a full-width half-width emission spectrum of less than 40 nm Green wavelength light; a second photoluminescent dye that absorbs blue or green wavelength light and narrowly emits red wavelength light having an emission spectrum with a full width at half width of less than 40 nm; and a light scattering center , The first photoluminescence dye, the second photoluminescence dye and the light scattering center are arranged in the polymer matrix.

Embodiment 2. The film of embodiment 1, wherein the first photoluminescent dye comprises a BODIPY group, a linking group, and a perylene group.

。 Embodiment 3. The film of embodiment 2, wherein the first photoluminescent dye is selected from:

.

Embodiment 4. The film of embodiment 1, wherein the first photoluminescent dye comprises a BODIPY group, a linking group, and a naphthalenedimethimide group.

。 Embodiment 5. The film of embodiment 2, wherein the first photoluminescent dye is selected from:

.

Embodiment 6. The film of embodiment 1, wherein the second photoluminescent dye comprises a BODIPY group, a linking group, and a perylene group.

。 Embodiment 7. The film of embodiment 6, wherein the second photoluminescent dye comprises

.

Embodiment 8. The film of embodiments 1 to 7, wherein the quantum yield of the film is greater than 85%.

Embodiment 9. The film of embodiments 1 to 7, wherein the film has a color gamut of greater than 85% of the BT2020 standard.

Embodiment 10. The film of embodiments 1 to 7, wherein the thickness of the film is less than 100 microns.

Embodiment 11. A light emitting device comprising the film according to Embodiments 1 to 10.

Embodiment 12. A backlight device having a blue light source, the device including the film according to Embodiments 1-10.

It has been found that the embodiments of the film comprising the photoluminescent composite described herein have improved performance compared to other forms of color conversion films. These benefits are further demonstrated by the following examples, which are only intended to illustrate the present invention and are not intended to limit the scope or basic principles in any way.

化合物 6.5 ： 步驟 1 ： 將4-羥基-2,6-二甲基苯甲醛(0.75 g，5 mmol)、2,4-二甲基吡咯(1.04 g，11 mmol)在100 mL無水二氯甲烷中的溶液脫氣30 min，隨後加入一滴三氟乙酸。將該溶液在氬氣下在室溫下攪拌隔夜。向所得溶液中加入DDQ(2.0 g，8.8 mmol)，且在室溫下攪拌隔夜。將所得混合物過濾，且用二氯甲烷徹底洗滌，得到褐色固體，為所需化合物6.4(1.6 g，100%產率)。LCMS (APCI+)：C₂₁ H₂₅ N₂ O (M+H)的計算值= 321；實驗值為321。 Example Synthesis of the first photoluminescent dye. Synthesis of compound FD-1 :

Compound 6.5 : Step 1 : Combine 4-hydroxy-2,6-dimethylbenzaldehyde (0.75 g, 5 mmol), 2,4-dimethylpyrrole (1.04 g, 11 mmol) in 100 mL of anhydrous dichloromethane The solution was degassed for 30 min, and then one drop of trifluoroacetic acid was added. The solution was stirred overnight at room temperature under argon. DDQ (2.0 g, 8.8 mmol) was added to the resulting solution and stirred at room temperature overnight. The resulting mixture was filtered and washed thoroughly with dichloromethane to obtain a brown solid as the desired compound 6.4 (1.6 g, 100% yield). LCMS (APCI+): _{Calculated value for C 21} H ₂₅ N ₂ O (M+H)=321; experimental value is 321.

Step 2 : Add 5 mL of trimethylamine to a solution of dipyrromethene and compound 6.4 (1.0 g) in 60 mL THF. The solution was degassed for 10 min, and then trifluoroboron-diethyl ether (5 mL) was slowly added. Next, the solution was heated at 70°C for 30 min. The resulting solution was subjected to flash chromatography (silica gel) using dichloromethane as the eluent. The desired fractions were collected and dried under reduced pressure to obtain compound 6.5 as an orange solid (0.9 g, yield 76%). LCMS (APCI+): _{calculated value of C 21} H ₂₄ BF ₂ N ₂ O (M+H)=369; experimental value: 369. ¹ H NMR (400 MHz, chloroform-d) δ 6.64 (s, 2H), 5.97 (s, 2H), 4.73 (s, 1H), 2.56 (s, 6H), 2.09 (s, 6H), 1.43 (s , 6H).

Compound 10.1 (2,5-Di(tert-butyl)perylene): Under the protection of nitrogen atmosphere, 5 g of perylene (19.81 mmol) was dissolved in 300 ml of anhydrous o-pyrene in a three-necked round bottom flask. In dichlorobenzene. The resulting yellow solution was cooled to 0°C. 2.64 g of AlCl ₃ (19.81 mmol) was added in small portions via a powder distribution funnel within 45 minutes, after which 50 mL of tertiary butyl chloride (458 mmol) was added dropwise. The resulting green solution was stirred at room temperature for 24 hours. The reaction mixture was poured into 100 mL of ice water. The organic layer was separated and concentrated to dryness using a rotary evaporator, where the water bath of the rotary evaporator was set to 70°C. Redisperse the residue in 450 mL of hot hexane. The yellow solution was cooled and left overnight at room temperature. The insoluble material was filtered and detected by LCMS as a tetra(tertiary butyl) analogue (M+H=477), and the filtrate was bis(tertiary butyl) perylene and tris(tertiary butyl) ) A mixture of perylene, which is loaded on a silica gel column. Chromatographic separation was performed using hexane:EtOAc (9:1) to obtain 3.75 g of a light yellow solid product compound 10.1, namely 2,5-di(tert-butyl)perylene, with a yield of 52%. The calculated value of LCMS (APCI+) for C ₂₈ H ₂₉ (M+H)=365; the experimental value is 365. 1H NMR (400 MHz, chloroform-d) δ 8.30-8.21 (m, 4H), 7.72-7.63 (m , 4H), 7.50 (t, J = 7.8 Hz, 2H), 1.50 (s, 18H).

Compound 12.1 (4-(8,11-bis(tert-butyl)perylene-3-yl)-4-oxobutyric acid methyl ester): under the protection of nitrogen atmosphere, at 0℃ at 15 2.63 g AlCl ₃ (19.97 mmol) was added to a suspension of 2.45 mL methyl 4-chloro-4-oxobutyrate (19.97 mmol) in 175 mL anhydrous DCM in small portions via a powder dispersion funnel within minutes middle. The resulting solution was stirred at 0°C for 1 hour. Next, a solution of 5.77 g of compound 10.1 [2,5-di(tert-butyl)perylene] (15.85 mmol) dissolved in anhydrous DCM was added dropwise while maintaining the temperature at 0°C. The resulting dark purple solution was stirred overnight at room temperature under a nitrogen atmosphere. The next day, the solution was poured into a mixture of 150 mL ice water and 300 mL DCM. The organic layer was separated; the aqueous layer was re-extracted with 100 mL ethyl acetate. The organic layers were combined, dried with MgSO ₄ and concentrated. Load the residue on the silica column. Chromatographic separation was performed with hexane:ethyl acetate (9:1) as the eluent to obtain 2.7 g of compound 12.1 as an orange solid product with a yield of 35%. LCMS (APCI+): _{calculated value of C 33} H ₃₅ O ₃ (M+H)=479; experimental value: 479; ¹ H NMR (400 MHz, chloroform-d) δ 8.58 (d, J = 8.6 Hz, 1H) , 8.34-8.27 (m, 3H), 8.23 (d, J = 8.0 Hz, 1H), 7.98 (d, J = 7.9 Hz, 1H), 7.73 (s, 1H), 7.68 (s, 1H), 7.60 ( t, J = 8.0 Hz, 1H), 3.75 (s, 3H), 3.41 (t, J = 6.5 Hz, 2H), 2.86 (t, J = 6.6 Hz, 2H), 1.49 (d, J = 3.5 Hz, 18H).

Compound 12.2 (4-(8,11-bis(tertiary butyl)perylene-3-yl)butyric acid): 470.5 mg of compound 12.1 [4-(8,11-bis(tertiary butyl) Perylene-3-yl)-4-oxobutyric acid methyl ester) (0.983 mmol) and 150 μL of 98% hydrazine monohydrate (2.949 mmol) dissolved in 2 mL of diethylene glycol Microwave the vial and stir at room temperature. To the solution was added 275 mg KOH (powder) (4.91 mmol), and stirred at 80°C for 15 min. Subsequently, the solution was heated to 140° C. and bubbled with a slow flow of argon for 2 hours. The vial containing the solution was sealed with a septum, an argon atmosphere was maintained with a balloon, and the temperature was increased to 190°C. The resulting solution was stirred for 16 hours while maintaining the temperature at 190°C. The solution was then cooled to room temperature and diluted with 20 mL of water, acidified with 6N HCl. The resulting green solid was collected by filtration and purified by SiO2 column chromatography using DCM:EtOAc (1:1) as the eluent to obtain 110 mg of compound 12.2 as a green solid product with a yield of 88%. LCMS (APCI+): _{calculated value of C 32} H ₃₅ O ₂ (M+H)=451; experimental value: 451; 1H NMR (400 MHz, chloroform-d) δ 8.27-8.19 (m, 3H), 8.15 (d , J = 7.7 Hz, 1H), 7.88 (d, J = 8.4 Hz, 1H), 7.62 (d, J = 5.2 Hz, 2H), 7.53 (t, J = 8.0 Hz, 1H), 7.34 (d, J = 7.7 Hz, 1H), 5.30 (s, 1H), 3.09 (t, J = 7.7 Hz, 2H), 2.48 (t, J = 7.2 Hz, 2H), 2.11 (p, J = 7.4 Hz, 2H), 1.47 (s, 18H).

Compound FD-1 under the protection of nitrogen, 74.27 mg of DCC (0.36 mmol) was added to the compound containing 66 mg of 6.5 [4-(5,5-difluoro-1,3,7,9-tetramethyl-5H- 4l4,5l4-Dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborocyclo-10-yl)-3,5-dimethylphenol] (0.18 mmol), 100 mg of compound 12.2 [4-(8,11-bis(tert-butyl)perylene-3-yl)butyric acid] (0.22 mmol), 43.6 mg DMAP (0.36 mmol) dissolved in 2.0 mL of anhydrous THF solution. The resulting solution was stirred at room temperature for 16 hours. Water was added, followed by 50 mL ethyl acetate. The solution was then passed through diatomaceous earth. The organic layer was separated and concentrated. The crude product was purified by silica gel column chromatography using hexane: ethyl acetate (9:1) as the eluent to obtain 43 mg of FD-1 as an orange-red solid product with a yield of 24%. LCMS (APCI+): C ₅₃ H ₅₆ BF ₂ N ₂ O ₂ (M+H) calculated value = 801; experimental value: 801.1H NMR (400 MHz, chloroform-d) δ 8.26 (d, J = 7.4 Hz , 1H), 8.24 (s, 1H), 8.22 (s, 1H), 8.18 (d, J = 7.7 Hz, 1H), 7.93 (d, J = 8.3 Hz, 1H), 7.63 (s, 1H), 7.62 (s, 1H), 7.53 (t, J = 7.9 Hz, 1H), 7.4 (d, J = 7.4 Hz, 1H), 6.85 (s, 2H), 5.96 (s, 2H), 3.18 (t, J = 7.3 Hz, 2H), 2.69(t, J = 7.4 Hz, 2H), 2.55 (s, 6H), 2.25 (t, J = 7.4 Hz, 2H), 2.1 (s, 6H), 1.48 (s, 9H) , 1.47 (s, 9H), 1.38 (s, 6H).

化合物 44.2 ： (5,5- 二氟 -10-(4- 羥基 -2,6- 二甲基苯基 )-1,3,7,9- 四甲基 -5H-4l4,5l4- 二吡咯并 [1,2-c:2',1'-f][1,3,2] 二氮雜硼雜環 -2,8- 二羧酸二苄酯 ) ： 向250 mL的圓底燒瓶中加入溶於80 mL的乙酸中的40 mL(241 mmol)的3-側氧基丁酸第三丁酯。將混合物在冰水浴中冷卻至約10℃。在1小時內加入亞硝酸鈉(18 g，262 mmol)，同時將溫度保持低於15℃。移除冷浴，且將混合物在室溫下攪拌3.5 h。將不溶物濾除，得到肟的粗製溶液，該粗製溶液無需進一步純化即用於下一步驟。接著，將50 g鋅粉(0.76 mol)分批加入至13.7 mL(79 mmol)的3-側氧基丁酸苄酯及100 mL乙酸的混合物中。將所得混合物在油浴中攪拌且加熱至60℃。緩慢加入固化的2-(羥基亞胺基-3-側氧基丁酸第三丁酯溶液。隨後將溫度升至75℃且攪拌1小時。接著，將反應混合物倒入水(4 L)中。將沈澱物收集且過濾，得到2,4-二甲基-1H-吡咯-3-羧酸苄酯，將其自MeOH中再結晶為白色固體，得到15 g，產率基於3-側氧基丁酸苄酯為65%。¹ H NMR (400 MHz, CDCl₃ ): 8.88 (br, s, 1H, NH), 7.47-7.33 (m, 5H, C=CH), 5.29 (s, 2H, CH₂ ), 2.53, 2.48 (2s, 6H, 2CH₃ ), 1.56 (s, 9H, 3CH₃ )。 Synthesis of compound FD-2 :

Compound 44.2 : (5,5 -Difluoro- 10-(4- hydroxy- 2,6 -dimethylphenyl )-1,3,7,9 -tetramethyl- 5H-4l4,5l4 -dipyrrolo [1,2-c:2',1'-f][1,3,2] diazepine- 2,8 -dicarboxylic acid dibenzyl ester ) : add to a 250 mL round bottom flask 40 mL (241 mmol) of tert-butyl 3-oxobutyrate dissolved in 80 mL of acetic acid. The mixture was cooled to about 10°C in an ice water bath. Sodium nitrite (18 g, 262 mmol) was added over 1 hour while keeping the temperature below 15°C. The cold bath was removed, and the mixture was stirred at room temperature for 3.5 h. The insoluble matter was filtered off to obtain a crude oxime solution, which was used in the next step without further purification. Next, 50 g of zinc powder (0.76 mol) was added in batches to a mixture of 13.7 mL (79 mmol) of benzyl 3-oxobutyrate and 100 mL of acetic acid. The resulting mixture was stirred in an oil bath and heated to 60°C. Slowly add the solidified solution of tert-butyl 2-(hydroxyimino-3-oxobutyrate. The temperature is then raised to 75°C and stirred for 1 hour. Then, the reaction mixture is poured into water (4 L) The precipitate was collected and filtered to obtain 2,4-dimethyl-1H-pyrrole-3-carboxylic acid benzyl ester, which was recrystallized from MeOH as a white solid to obtain 15 g, and the yield was based on 3-oxo Benzyl butyrate is 65%. ¹ H NMR (400 MHz, CDCl ₃ ): 8.88 (br, s, 1H, NH), 7.47-7.33 (m, 5H, C=CH), 5.29 (s, 2H, CH ₂ ), 2.53, 2.48 (2s, 6H, 2CH ₃ ), 1.56 (s, 9H, 3CH ₃ ).

Next, in a 25 mL vial, a mixture of 1 g (4.36 mmol) of 2,4-dimethyl-1H-pyrrole-3-carboxylic acid benzyl ester and 0.524 g (4.36 mmol) of MgSO ₄ was dissolved in 8 mL of anhydrous DCE, and stirred for 15 minutes at room temperature in the presence of argon. 0.327 g of 2,6-dimethyl-4-hydroxybenzaldehyde (2.18 mmol) was added in multiple small portions; the vial was closed with a Teflon cap. The resulting mixture was purged with argon for 15 minutes, and TFA (3 drops, catalytic amount) was added. The reaction mixture was stirred at 65°C for 16 hours. TLC and LCMS showed that the starting material has been consumed. To the crude product was added 0.544 g (2.398 mmol) of DDQ in one portion. The resulting mixture was stirred at room temperature for ½ hour. TLC and LCMS showed that the starting material has been consumed. The resulting mixture was filtered through short-path diatomaceous earth; the filtrate was concentrated to dryness, the residue was re-dissolved in 50 mL of DCE, stirred with triethylamine (1.4 mL, 19 mmol) at room temperature for 15 min, and then cooled to 0°C. Slowly add 3 mL of BF ₃ (18.36 mmol). The resulting mixture was stirred at room temperature for ½ h and heated to 86°C for 45 min. The reaction mixture was then _{diluted with 150 mL of CHCl 3} and quenched with 50 mL of brine. The organic layer was separated and dried over MgSO ₄ and the solvent was removed by rotary evaporation. The residue was chromatographed on a silica gel column using CH ₂ Cl ₂ /EtOAc as the eluent to obtain 1 g of pure compound 44.2, which is 5,5-difluoro-10-(4-hydroxy-2,6-di Methylphenyl)-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]二Azaborole-2,8-dicarboxylic acid dibenzyl ester) is an orange-red solid, and the yield based on 2,6-dimethyl 4-hydroxybenzaldehyde is 72%. LCMS (APCI-), _{calculated value of M- for C 37} H ₃₅ BF ₂ N ₂ O ₅ : 636.26; experimental value: 636. ¹ H NMR (400 MHz, chloroform-d) δ 7.42-7.28 (m, 4H), 6.66 (d, J = 0.7 Hz, 1H), 5.29 (d, J = 11.3 Hz, 2H), 2.82 (s, 3H ), 2.04 (d, J = 5.4 Hz, 3H), 1.72 (s, 3H).

步驟1：在配備有磁力攪拌棒、粉末分配器漏斗的1 L雙頸燒瓶中，在冰水浴中將二萘嵌苯(5.22 g，20.68 mmol)在無水DCM(500 mL)中的黃色懸浮混合物進行攪拌且用氬氣鼓泡15分鐘；經由注射器緩慢加入4-氯-4-側氧基丁酸甲酯(3.425 g，22.75 mmol)。移除冷卻浴，以讓混合物在室溫下攪拌15分鐘。將混合物再次用冰水浴冷卻；經由粉末分配器漏斗分多個小部分加入加入AlCl3(3.3 g，24.74 mmol)。將所得深紫色混合物在氬氣保護下在室溫下攪拌16小時。TLC及LCMS顯示起始材料幾乎均消耗完。將反應混合物用500 mL DCM稀釋，隨後倒入冰-水(150 ml水)中，分離有機層，用MgSO₄ ，濃縮至乾。將殘餘物用甲苯研磨。將固體過濾，用50 mL甲苯洗滌。合併濾液及洗滌物，隨後濃縮至50 mL的體積，隨後加載至柱(330 g)上，用甲苯/EtOAc(100:0)à(4.1)溶離，得到1.25 g所需產物。將來自柱層析法的產物及來自後處理的固體產物合併，且使用己烷:EtOAc(9:1)再結晶，得到4.24 g黃色固體，產率為56%。LCMS (APCI-)，針對C25H18O3的(M-)的計算值：366.13；實驗值：366。1H NMR (400 MHz, 氯仿-d) δ 8.57 (dd, J = 8.6, 1.0 Hz, 1H), 8.30-8.17 (m, 4H), 7.97 (d, J = 8.1 Hz, 1H), 7.78 (d, J = 8.1 Hz, 1H), 7.73 (d, J = 8.1 Hz, 1H), 7.64-7.48 (m, 3H), 3.75 (s, 3H), 3.41 (t, J = 6.5 Hz, 2H), 2.86 (t, J = 6.5 Hz, 2H)。 Compound Methyl 4-( Perylene- 3 -yl ) butyrate

Step 1: In a 1 L double-necked flask equipped with a magnetic stir bar and a powder distributor funnel, a yellow suspension mixture of perylene (5.22 g, 20.68 mmol) in anhydrous DCM (500 mL) in an ice-water bath Stir and bubble with argon for 15 minutes; methyl 4-chloro-4-oxobutanoate (3.425 g, 22.75 mmol) was slowly added via a syringe. The cooling bath was removed to allow the mixture to stir at room temperature for 15 minutes. The mixture was cooled again with an ice-water bath; AlCl3 (3.3 g, 24.74 mmol) was added in small portions via a powder distributor funnel. The resulting dark purple mixture was stirred at room temperature for 16 hours under the protection of argon. TLC and LCMS showed that the starting materials were almost consumed. The reaction mixture was diluted with 500 mL DCM, then poured into ice-water (150 ml water), the organic layer was separated, and concentrated to dryness _{with MgSO 4.} The residue was triturated with toluene. The solid was filtered and washed with 50 mL of toluene. The filtrate and washings were combined, then concentrated to a volume of 50 mL, and then loaded on a column (330 g), and eluted with toluene/EtOAc (100:0)→(4.1) to obtain 1.25 g of the desired product. The product from the column chromatography and the solid product from the post-treatment were combined and recrystallized using hexane:EtOAc (9:1) to obtain 4.24 g of a yellow solid with a yield of 56%. LCMS (APCI-), calculated value of (M-) for C25H18O3: 366.13; experimental value: 366.1H NMR (400 MHz, chloroform-d) δ 8.57 (dd, J = 8.6, 1.0 Hz, 1H), 8.30 -8.17 (m, 4H), 7.97 (d, J = 8.1 Hz, 1H), 7.78 (d, J = 8.1 Hz, 1H), 7.73 (d, J = 8.1 Hz, 1H), 7.64-7.48 (m, 3H), 3.75 (s, 3H), 3.41 (t, J = 6.5 Hz, 2H), 2.86 (t, J = 6.5 Hz, 2H).

Step 2: In a 250 mL round bottom flask, a yellow mixture of the product of the above step (4.24 g, 11.58 mmol) in anhydrous DCM (100 mL) was stirred on a cooling ice + water bath and bubbling with argon for 15 minutes ; Slowly add TFA (25 mL). The cooling bath was removed to allow the mixture to stir at room temperature for 15 minutes; triethylsilane (15 mL) was added immediately. The resulting dark mixture was stirred at room temperature for 16 hours under argon protection. TLC and LCMS showed that the starting material has been consumed. The reaction mixture was diluted with 200 mL DCM and then placed on a rotary evaporator. Remove TFA and DCM. The residue was re-dissolved in DCM (50 ml), and the mixture was concentrated to dryness. The dark crude product was loaded on a SiO ₂ column and dissolved with hexane/EtAcO (95:5) to obtain 4.00 g of methyl 4-(perylene-3-yl)butyrate as a yellow solid product. The yield was 98%. LCMS (APCI+), calculated value of M+ for C25H20O2: 353.15; experimental value: 353.

， 將4-(二萘嵌苯-3-基)丁酸甲酯(1.00 g，2.837 mmol，1當量)在無水氯仿(20 mL)中的混合物置於雙頸燒瓶中，且避光。將混合物用氬氣吹掃15分鐘，且將NBS(1.767 g，9.929 mmol，3.5當量)以多個小部分加入，隨後在室溫下攪拌15 min。加入無水DMF(10 mL)。將所得混合物在氬氣保護下在室溫下攪拌4小時。TLC及LCMS顯示原料已消耗。加入25 mL水，且分離有機層；將水層用乙酸乙酯再萃取，用水洗滌幾次，用MgSO₄ 乾燥且濃縮。將粗產物藉由SiO₂ 柱層析法純化，用己烷/DCM(9:1)至(1:4)溶離，得到0.655 g的三種異構體的混合物(三溴二萘嵌苯衍生物、二溴二萘嵌苯衍生物及四溴二萘嵌苯衍生物(7:1:05))。產物無需進一步純化即使用。產率為38%。LCMS (APCI+)：式C25H17Br3O2的計算值；實驗值：589。

Methyl 4-(4,9,10 -tribromoperylene- 3 -yl ) butyrate /4-(4,10 -dibromo- 4,12b -dihydroperylene- 3 -yl ) Methyl butyrate /4-(5,9,10 -tribromoperylene- 3 -yl ) methyl butyrate:

, A mixture of methyl 4-(perylene-3-yl)butyrate (1.00 g, 2.837 mmol, 1 equivalent) in anhydrous chloroform (20 mL) was placed in a double-necked flask, protected from light. The mixture was purged with argon for 15 minutes, and NBS (1.767 g, 9.929 mmol, 3.5 equivalents) was added in small portions, followed by stirring at room temperature for 15 minutes. Add dry DMF (10 mL). The resulting mixture was stirred at room temperature for 4 hours under argon protection. TLC and LCMS showed that the starting material has been consumed. 25 mL of water was added, and the organic layer was separated; the aqueous layer was re-extracted with ethyl acetate, washed with water several times, dried with MgSO ₄ and concentrated. The crude product was purified by SiO ₂ column chromatography and eluted with hexane/DCM (9:1) to (1:4) to obtain 0.655 g of a mixture of three isomers (tribromoperylene derivative , Dibromoperylene derivatives and tetrabromoperylene derivatives (7:1:05)). The product was used without further purification. The yield was 38%. LCMS (APCI+): calculated value of formula C25H17Br3O2; experimental value: 589.

Methyl 4-(4,9,10-tris(trifluoromethyl)perylene-3-yl)butyrate: Fill a 40 mL screw cap vial with a stirring rod and install a screw cap septum. Flush the vial with argon. To the vial was added methyl 4-(4,9,10-tribromoperylene-3-yl)butyrate (a mixture of isomers (0.496 mmol, 292 mg), CuI (4.96 mmol, 944 mg) ), followed by the addition of anhydrous dimethylacetamide (10 mL). Under stirring at room temperature, methyl 2,2-difluoro-2-(fluorosulfonyl)acetate (4.96 mmol) was added via a syringe at room temperature. , 0.631 mL). Place the reaction in a heating block set at 160°C and stir for 3 hours. Add an additional portion of CuI (4.96 mmol, 944 mg) and 2,2-difluoro-2-(fluorosulfonyl) Methyl acetate (4.96 mmol, 0.631 mL), and the reaction was stirred for another hour. The reaction mixture was cooled to room temperature and diluted with water to a total volume of 100 mL. The product was filtered off, washed with water. The precipitate was dried and Wash with dichloromethane until the dichloromethane washes to colorless. The combined organic washings are evaporated to dryness and flash chromatography on silica gel (50% toluene/hexane (1 CV)→100% toluene ( 10 CV)) Purification. The fraction containing the desired product (as a mixture of isomers) was evaporated to dryness to obtain 90 mg (33% yield). MS (APCI): calculated value of chemical formula C28H17F9O2 (M-)= 556; experimental value: 556.

Compound 46.1: 4-(4,9,10-Tris(trifluoromethyl)perylene-3-yl)butyric acid: A 250 mL 2-neck round bottom flask was charged with a stir bar and flushed with argon. 4-(4,9,10-tris(trifluoromethyl)perylene-3-yl)butyric acid (3.00 mmol, 1.141 g) and KOH (30.0 mmol, 1.683 g) were added to the flask, followed by Add ethanol (200 standard alcohol content, 200 mL). The flask was equipped with a finned air condenser, and was stirred and heated in a heating block at 95°C for two hours under argon. The reaction mixture was cooled to room temperature, and diluted with water in an Erlenmeyer flask (to a total volume of 500 mL), and quenched with 6N aqueous HCl (5 mL). The resulting precipitate was collected and concentrated in vacuo to obtain a crude precipitate in a quantitative yield. MS (APCI): calculated value of chemical formula C27H15F9O2 (M-)=542; experimental value: 542.

FD-2(10-(2,6 -Dimethyl- 4-((4-(4,9,10- tris ( trifluoromethyl ) perylene- 3 -yl ) butyryl ) oxy ) benzene yl) -5,5-difluoro--1,3,7,9- tetramethyl -5H-414,514- two-pyrrolo [1,2-c: 2 ', 1'-f] [1,3,2 ] diazepine boron heterocycles as 2,8-dicarboxylic acid dibenzyl ester): added in 40 mL screwcap vial stir bar, compound 46.1 [4- (4,9, 10-tris (trifluoromethyl )Perylene-3-yl)butyric acid] (0.164 mmol, 89 mg) and compound 44.2 [5,5-difluoro-10-(4-hydroxy-2,6-dimethylphenyl)-1 ,3,7,9-Tetramethyl-5H-414,514-Dipyrrolo[1,2-c:2',1'-f][1,3,2]diazepine-2,8 -Dibenzyl dicarboxylate] and DMAP:pTsOH 1:1 salt (0.200 mmol, 59 mg). The vial was flushed with argon, and anhydrous dichloromethane (20 mL) was added. Diisopropylcarbodiimide (0.300 mmol, 47 µL) was added, and the reaction was stirred at room temperature under argon overnight. The next morning, anhydrous tetrahydrofuran (10 mL) was added and ultrasonic treatment was performed for 30 seconds. An additional portion of compound 46.1 (0.150 mmol, 51 mg) was added and stirred at 50°C overnight under argon. The crude product was purified by flash chromatography on silica gel (100% toluene (2 CV) à 10% EtOAc/toluene (10 CV)). The fraction containing the product (as a mixture of isomers) was evaporated to dryness to obtain 128 mg (67% yield) of FD-2. MS (APCI): calculated value of chemical formula C64H48BF11N2O6 (M-)=1160; experimental value: 1160.

10-(4-((4-(4-(6-(4-(二苯基胺基)苯基)-1,3-二側氧基-1H-苯并[de]異喹啉-2(3H)-基)苯基)丁醯基)氧)-2,6-二甲基苯基)-5,5-二氟-1,3,7,9-四甲基-5H-4λ4,5λ4-二吡咯并[1,2-c:2',1'-f][1,3,2]二氮雜硼雜環-2,8-二羧酸二苄酯： 向化合物44.2 [5,5-二氟-10-(4-羥基-2,6-二甲基苯基)-1,3,7,9-四甲基-5H-4l4,5l4-二吡咯并[1,2-c:2',1'-f][1,3,2]二氮雜硼雜環-2,8-二羧酸二苄酯](1.18 mmol，750 mg)、化合物13.3.2(參見以下合成，1.30 mmol，780 mg)及DMAP·pTsOH鹽(2.36 mmol，694 mg)在無水CH₂ Cl₂ (6.00 mL)中的溶液中加入DIC(7.08 mmol，1.11 mL)，且將反應混合物在室溫下攪拌16小時。隨後將反應混合物濾過矽藻土且減壓濃縮。急驟層析法(7:3，己烷/EtOAc→3:2，己烷/EtOAc)得到1.10 g的化合物FD-3(產率為76%)，為橙色固體。1H NMR (400 MHz, 氯仿-d) δ 8.68 (dd, J = 7.2, 2.4 Hz, 2H), 8.48 (d, J = 8.5 Hz, 1H), 7.77 (dd, J = 9.3, 7.4 Hz, 2H), 7.44-7.27 (m, 20H), 7.24-7.20 (m, 6H), 7.11 (t, J = 7.3 Hz, 2H), 6.97 (s, 2H), 5.27 (s, 4H), 2.85 (d, J = 13.9 Hz, 8H), 2.67 (t, J = 7.4 Hz, 2H), 2.22-2.06 (m, 8H), 1.72 (s, 6H); 19F NMR (376 MHz, 氯仿-d) δ -142.72 - -143.09 (m); 13C NMR (101 MHz, 氯仿-d) δ 171.5, 164.0, 159.9, 148.4, 147.3, 147.2, 146.9, 136.7, 135.8, 131.6, 131.3, 130.8, 129.5, 128.6, 128.4, 128.3, 127.8, 126.7, 125.1, 123.7, 122.5, 121.8, 121.3, 66.2, 34.8, 33.6, 26.1, 19.7, 15.1, 12.6。 Synthesis of compound FD-3 :

10-(4-((4-(4-(6-(4-(diphenylamino)phenyl)-1,3-dioxy-1H-benzo[de]isoquinoline-2 (3H)-yl)phenyl)butyryl)oxy)-2,6-dimethylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4λ4,5λ4- Dipyrrolo[1,2-c:2',1'-f][1,3,2]diazepine-2,8-dicarboxylic acid dibenzyl ester: To compound 44.2 [5,5 -Difluoro-10-(4-hydroxy-2,6-dimethylphenyl)-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c: 2',1'-f][1,3,2]diazepine-2,8-dicarboxylic acid dibenzyl ester] (1.18 mmol, 750 mg), compound 13.3.2 (see synthesis below, To a solution of 1.30 mmol, 780 mg) and DMAP·pTsOH salt (2.36 mmol, 694 mg) in anhydrous CH ₂ Cl ₂ (6.00 mL) was added DIC (7.08 mmol, 1.11 mL), and the reaction mixture was kept at room temperature Stir for 16 hours. The reaction mixture was then filtered through Celite and concentrated under reduced pressure. Flash chromatography (7:3, hexane/EtOAc→3:2, hexane/EtOAc) gave 1.10 g of compound FD-3 (yield 76%) as an orange solid. 1H NMR (400 MHz, chloroform-d) δ 8.68 (dd, J = 7.2, 2.4 Hz, 2H), 8.48 (d, J = 8.5 Hz, 1H), 7.77 (dd, J = 9.3, 7.4 Hz, 2H) , 7.44-7.27 (m, 20H), 7.24-7.20 (m, 6H), 7.11 (t, J = 7.3 Hz, 2H), 6.97 (s, 2H), 5.27 (s, 4H), 2.85 (d, J = 13.9 Hz, 8H), 2.67 (t, J = 7.4 Hz, 2H), 2.22-2.06 (m, 8H), 1.72 (s, 6H); 19F NMR (376 MHz, chloroform-d) δ -142.72-- 143.09 (m); 13C NMR (101 MHz, chloroform-d) δ 171.5, 164.0, 159.9, 148.4, 147.3, 147.2, 146.9, 136.7, 135.8, 131.6, 131.3, 130.8, 129.5, 128.6, 128.4, 128.3, 127.8, 126.7, 125.1, 123.7, 122.5, 121.8, 121.3, 66.2, 34.8, 33.6, 26.1, 19.7, 15.1, 12.6.

化合物13.3.1： [4-(4-(6-溴-1,3-二側氧基-1H-苯并[de]異喹啉-2(3H)-基)苯基)丁酸]：向6-溴-1H,3H-苯并[de]異色烯-1,3-二酮(18.4 mmol，3.30 g)在EtOH(200標準酒精度，80.0 mL)中的溶液中加入4-(4-胺基苯基)丁酸(16.0 mmol，4.43 g)，且將反應混合物加熱至回流達16小時。隨後將其冷卻至室溫，用EtOH(200標準酒精度，50.0 mL)稀釋，過濾且用更多EtOH(200標準酒精度，100 mL)及己烷(100 mL)洗滌，得到5.02 g的化合物13.3.1(產率為72%)，為灰白色固體。1H NMR (400 MHz, DMSO-d6) δ 12.15 (s, 1H), 8.63-8.55 (m, 2H), 8.34 (d, J = 7.8 Hz, 1H), 8.25 (d, J = 7.9 Hz, 1H), 8.03 (dd, J = 8.5, 7.3 Hz, 1H), 7.34 (d, J = 8.3 Hz, 2H), 7.29 (d, J = 8.2 Hz, 2H), 2.68 (t, J = 7.3 Hz, 2H), 2.29 (t, J = 7.3 Hz, 2H), 1.87 (p, J = 7.5 Hz, 2H); 13C NMR (101 MHz, DMSO-d6) δ 174.3, 163.3, 163.2, 141.8, 133.5, 132.7, 131.6, 131.4, 131.0, 130.0, 129.2, 128.9, 128.8, 128.8, 128.7, 123.4, 122.7, 34.1, 33.2, 26.3。 Synthesis of compound FD-4 :

Compound 13.3.1: [4-(4-(6-Bromo-1,3-dioxo-1H-benzo[de]isoquinoline-2(3H)-yl)phenyl)butanoic acid]: To a solution of 6-bromo-1H,3H-benzo[de]isochrome-1,3-dione (18.4 mmol, 3.30 g) in EtOH (200 standard alcohol, 80.0 mL) was added 4-(4 -Aminophenyl)butyric acid (16.0 mmol, 4.43 g), and the reaction mixture was heated to reflux for 16 hours. Then it was cooled to room temperature, diluted with EtOH (200 standard alcohol, 50.0 mL), filtered and washed with more EtOH (200 standard alcohol, 100 mL) and hexane (100 mL) to obtain 5.02 g of the compound 13.3.1 (72% yield), it is an off-white solid. 1H NMR (400 MHz, DMSO-d6) δ 12.15 (s, 1H), 8.63-8.55 (m, 2H), 8.34 (d, J = 7.8 Hz, 1H), 8.25 (d, J = 7.9 Hz, 1H) , 8.03 (dd, J = 8.5, 7.3 Hz, 1H), 7.34 (d, J = 8.3 Hz, 2H), 7.29 (d, J = 8.2 Hz, 2H), 2.68 (t, J = 7.3 Hz, 2H) , 2.29 (t, J = 7.3 Hz, 2H), 1.87 (p, J = 7.5 Hz, 2H); 13C NMR (101 MHz, DMSO-d6) δ 174.3, 163.3, 163.2, 141.8, 133.5, 132.7, 131.6, 131.4, 131.0, 130.0, 129.2, 128.9, 128.8, 128.8, 128.7, 123.4, 122.7, 34.1, 33.2, 26.3.

Compound 13.3.2: [4-(4-(6-(4-(Diphenylamino)phenyl)-1,3-di-side oxy-1H-benzo[de]isoquinoline-2( 3H)-yl)phenyl)butyric acid]: Add compound 13.3.1 (11.2 mmol, 4.93 g) and K ₂ CO ₃ (16.8 mmol, 2.32 g) in 20:1 EtOH/H ₂ O( 115 mL) was added to the suspension in Pd(PPh ₃ ) ₄ (0.562 mmol, 649 mg) and (4-(diphenylamino)phenyl)boronic acid (11.8 mmol, 3.41 g), and the reaction mixture Stir at 80°C for 16 hours. It was then filtered and washed with EtOH (200 standard alcohol, 200 mL). The filter cake was partitioned between 1 M HCl (300 mL) and CH ₂ Cl ₂ (300 mL), and the mixture was extracted with CH ₂ Cl ₂ (3×300 mL). The combined organics were dried (MgSO ₄ ) and concentrated under reduced pressure to obtain 6.50 g of compound 13.3.2 (96% yield) as an orange/red solid. 1H NMR (400 MHz, chloroform-d) δ 8.67 (dd, J = 7.5, 2.5 Hz, 2H), 8.47 (d, J = 8.5 Hz, 1H), 7.79-7.71 (m, 2H), 7.42-7.36 ( m, 4H), 7.33 (apparent t, J = 7.8 Hz, 4H), 7.28-7.19 (m, 8H), 7.10 (apparent t, J = 7.3 Hz, 2H), 2.79 (t, J = 7.6 Hz , 2H), 2.46 (t, J = 7.3 Hz, 2H), 2.06 (apparent p, J = 7.6 Hz, 2H); ¹³ C NMR (101 MHz, chloroform-d) δ 177.9, 164.6, 148.4, 147.3, 147.1, 141.8, 133.3, 133.2, 131.8, 131.6, 131.3, 130.8, 130.2, 129.5, 129.5, 128.5, 127.7, 126.7, 125.0, 123.6, 123.0, 122.5, 34.8, 33.1, 26.0.

Compound 13.3: [4-Methanoyl-3,5-dimethylphenyl-4-(4-(6-(4-(diphenylamino)phenyl)-1,3-diphenyloxy -1H-benzo[de]isoquinoline-2(3H)-yl)phenyl)butyrate]: to 4-hydroxy-2,6-dimethylbenzaldehyde (5.97 mmol, 897 mg), compound 13.3.2 (4.98 mmol, 3.00 g) and DMAP·pTsOH salt (9.96 mmol, 2.93 g) in anhydrous CH ₂ Cl ₂ (25.0 mL) was added DIC (29.9 mmol, 4.68 mL), and the reaction was Stir at room temperature for 80 minutes. The reaction mixture was then filtered through Celite and concentrated under reduced pressure. Flash chromatography (toluene→9:1, toluene/EtOAc) gave 3.05 g of compound 13.3 (83% yield) as a yellow solid. 1H NMR (400 MHz, chloroform-d) δ 10.57 (s, 1H), 8.70-8.64 (m, 2H), 8.48 (dd, J = 8.5, 1.2 Hz, 1H), 7.76 (dd, J = 9.1, 7.4 Hz, 2H), 7.44-7.37 (m, 4H), 7.37-7.26 (m, 6H), 7.25-7.19 (m, 6H), 7.14-7.08 (m, 2H), 6.87 (s, 2H), 2.85 ( t, J = 7.6 Hz, 2H), 2.69-2.59 (m, 8H), 2.16 (p, J = 7.5 Hz, 2H); 13C NMR (101 MHz, chloroform-d) δ 192.3, 171.4, 164.6, 164.4, 148.4, 147.3, 147.2, 143.6, 141.5, 133.5, 133.2, 131.8, 131.6, 131.3, 130.8, 130.2, 130.1, 129.5, 129.5, 129.2, 128.6, 127.7, 126.7, 125.0, 123.7, 123.0, 122.6, 122.4, 121.3, 34.7, 33.6, 26.1, 20.7.

向2-甲基-1H-吡咯-3-羧酸乙酯(61 mg，0.4 mmol)、化合物13.3 [4-(4-(6-(4-(二苯基胺基)苯基)-1,3-二側氧基-1H-苯并[de]異喹啉-2(3H)-基)苯基)丁酸4-甲醯基-3,5-二甲基苯酯](100 mg，0.136 mmol)、MgSO₄ (120 mg，1.0 mmol)在二氯乙烷(5 mL)中的混合物中加入3滴TFA，隨後在65℃加熱3天。向所得混合物中加入三乙胺(0.13 mL，0.9 mmol)、BF₃ -醚合物(0.09 mL，0.5 mmol)，隨後在60℃加熱30分鐘。冷卻至室溫後，將混合物裝載至矽膠上，且藉由使用DCM/乙酸乙酯(0%à10%乙酸乙酯)溶離劑進行急驟層析法來純化。收集主級分，且移除溶劑，得到化合物FD-4，為橙紅色固體(40 mg，總體產率為27%)。LCMS (APCI)：C65H55BF2N4O8 (M-)的計算值：1068；實驗值：1068。1H NMR (400 MHz, d₂ -TCE) δ 8.60-8.53 (m, 2H), 8.43 (dd, J = 8.6, 1.2 Hz, 1H), 7.75-7.67 (m, 2H), 7.39 (d, J = 8.3 Hz, 2H), 7.36-7.30 (m, 2H), 7.24 (dt, J = 13.8, 8.1 Hz, 6H), 7.15 (d, J = 8.6 Hz, 6H), 7.08-6.99 (m, 4H), 6.91 (s, 2H), 4.17 (q, J = 7.1 Hz, 4H), 2.84 (s, 6H), 2.80 (m, 2H), 2.65 (t, J = 7.4 Hz, 2H), 2.13 (m, 2H), 2.08 (s, 6H), 1.24 (t, J = 7.1 Hz, 6H)。 FD-4 :

To 2-methyl-1H-pyrrole-3-carboxylic acid ethyl ester (61 mg, 0.4 mmol), compound 13.3 [4-(4-(6-(4-(diphenylamino)phenyl)-1 ,3-Diposide oxy-1H-benzo[de]isoquinoline-2(3H)-yl)phenyl)butyric acid 4-methanyl-3,5-dimethylphenyl ester) (100 mg , 0.136 mmol), MgSO ₄ (120 mg, 1.0 mmol) in dichloroethane (5 mL) was added 3 drops of TFA, and then heated at 65 ° C for 3 days. To the resulting mixture were added triethylamine (0.13 mL, 0.9 mmol) and BF ₃ -etherate (0.09 mL, 0.5 mmol), followed by heating at 60° C. for 30 minutes. After cooling to room temperature, the mixture was loaded on silica gel and purified by flash chromatography using DCM/ethyl acetate (0%→10% ethyl acetate) eluent. The main fractions were collected and the solvent was removed to obtain compound FD-4 as an orange-red solid (40 mg, overall yield 27%). LCMS (APCI): Calculated value of C65H55BF2N4O8 (M-): 1068; experimental value: 1068. 1H NMR (400 MHz, d ₂ -TCE) δ 8.60-8.53 (m, 2H), 8.43 (dd, J = 8.6, 1.2 Hz, 1H), 7.75-7.67 (m, 2H), 7.39 (d, J = 8.3 Hz, 2H), 7.36-7.30 (m, 2H), 7.24 (dt, J = 13.8, 8.1 Hz, 6H), 7.15 (d, J = 8.6 Hz, 6H), 7.08-6.99 (m, 4H), 6.91 (s, 2H), 4.17 (q, J = 7.1 Hz, 4H), 2.84 (s, 6H), 2.80 (m , 2H), 2.65 (t, J = 7.4 Hz, 2H), 2.13 (m, 2H), 2.08 (s, 6H), 1.24 (t, J = 7.1 Hz, 6H).

化合物9.1(3-甲基-4,5-二氫-1H-苯并[g]吲哚-2-羧酸乙酯)： 在250 mL的2頸圓底燒瓶中加入攪拌棒，且置於加熱塊中。向該燒瓶中加入1-四氫萘酮(100.0 mmol，14.620 g)及丙酸鈉(100.0 mmol，9.610 g)，之後加入乙酸(50 mL)。在敞開至空氣進行攪拌下將反應加熱至145℃。向40 mL螺旋蓋小瓶中加入2-(羥基亞胺基)-3-側氧基丁酸乙酯(2.50 mmol，398 mg)及Zn(粉，＜10 μm)(12.5 mmol，818 mg)。使此等物質在乙酸中成漿(12.5 mL)，且在約5分鐘的時段內分批加入含有酮的經攪拌反應中。對總共10.0 mmol的2-(羥基亞胺基)-3-氧化丁酸酯及50.0 mmol的鋅粉重複該過程三次。將反應在145℃下攪拌2.5小時，隨後冷卻至室溫。將反應藉由在攪拌下倒入水(600 mL)中進行淬滅。用水使體積達到900 mL，隨後用二氯甲烷(4×160 mL)萃取。將合併的有機層用水(100 mL)、鹽水(100 mL)洗滌，經MgSO₄ 乾燥，過濾，且蒸發至乾燥。在加熱下高真空移除大部分過量的1-四氫萘酮。將粗產物藉由在矽膠(5% EtOAc/己烷(1 CV)à20% EtOAc/己烷(10 CV))上進行急驟層析法來純化。將含有產物的級分蒸發至乾，得到1.417 g(產率為55%)的化合物9.1。MS (APCI)：化學式C16H17NO2 (M+H)的計算值=256，實驗值：256。1H NMR (400 MHz) δ 8.98 (s, 1H), 7.35-7.31 (m, 1H), 7.27-7.21 (m, 2H), 7.20-7.15 (m, 1H), 4.34 (q, J = 7.1 Hz, 2H), 2.99-2.92 (m, 2H), 2.70-2.64 (m, 2H), 2.31 (s, 3H), 1.39 (t, J = 7.1 Hz, 3H)。 Synthesis of the second photoluminescent dye (SD-1) ((T-4)-[2-[(4,5-Dihydro-3-methyl-2H-benzo[g]indol-2-ylidene -κN)(3,5-dimethyl-4-((4-(4,9,10-tris(trifluoromethyl)perylene-3-yl)butyryl)oxy)phenyl)methyl ]-4,5-Dihydro-3-methyl-1H-benzo[g]indolato-κN]boron difluoride):

Compound 9.1 (3-methyl-4,5-dihydro-1H-benzo[g]indole-2-carboxylic acid ethyl ester): In a 250 mL 2-neck round bottom flask, add a stir bar and place In the heating block. To the flask were added 1-tetralone (100.0 mmol, 14.620 g) and sodium propionate (100.0 mmol, 9.610 g), followed by acetic acid (50 mL). The reaction was heated to 145°C while opening to air and stirring. Add ethyl 2-(hydroxyimino)-3-oxobutyrate (2.50 mmol, 398 mg) and Zn (powder, <10 μm) (12.5 mmol, 818 mg) to a 40 mL screw cap vial. These materials were slurried in acetic acid (12.5 mL) and added to the ketone-containing stirred reaction in portions over a period of about 5 minutes. Repeat this process three times for a total of 10.0 mmol of 2-(hydroxyimino)-3-oxybutyrate and 50.0 mmol of zinc powder. The reaction was stirred at 145°C for 2.5 hours and then cooled to room temperature. The reaction was quenched by pouring into water (600 mL) with stirring. The volume was brought to 900 mL with water, followed by extraction with dichloromethane (4×160 mL). The combined organic layer was washed with water (100 mL), brine (100 mL), dried over MgSO ₄ , filtered, and evaporated to dryness. Most of the excess 1-tetralone is removed under high vacuum under heating. The crude product was purified by flash chromatography on silica gel (5% EtOAc/hexane (1 CV)→20% EtOAc/hexane (10 CV)). The product-containing fractions were evaporated to dryness, yielding 1.417 g (yield 55%) of compound 9.1. MS (APCI): The calculated value of the chemical formula C16H17NO2 (M+H)=256, the experimental value: 256. 1H NMR (400 MHz) δ 8.98 (s, 1H), 7.35-7.31 (m, 1H), 7.27-7.21 ( m, 2H), 7.20-7.15 (m, 1H), 4.34 (q, J = 7.1 Hz, 2H), 2.99-2.92 (m, 2H), 2.70-2.64 (m, 2H), 2.31 (s, 3H) , 1.39 (t, J = 7.1 Hz, 3H).

Compound 9.2 (3-methyl-44,5-dihydro-1H-benzo[g]indole): A 250 mL 2-neck round-bottomed flask was charged with a stir bar and equipped with a fin condenser and gas adapter . The flask was flushed with argon, and compound 9.1 (5.01 mmol, 1.278 g) was added to the flask, followed by ethylene glycol (50 mL). To the reaction mixture was added KOH (in H ₂ O in 5.0 M, 25.03 mmol, 5.01 mL ). The reaction was stoppered and heated in a heating block at 100°C for 90 minutes under argon. Use heat to make the solution uniform. The temperature was increased to 160°C for 30 minutes and then cooled to 100°C. The reaction was quenched by pouring into stirred water (300 mL). The reaction was brought to a total volume of 500 mL with water, and then it was acidified with a 2.5 M acetic acid/2.5 M NaOAc (20 mL) solution. Use TFA to lower the pH to about 3.5. The resulting purple solid was filtered off, dried, and purified by flash chromatography on silica gel (5% EtOAc/hexane (1 CV)→20% EtOAc/hexane (10 CV)). The product-containing fractions were evaporated to dryness, yielding 767 mg (84% yield) of compound 9.2. MS (APCI): The calculated value of the chemical formula C13H13N (M+H)=184, the experimental value: 184.1H NMR (400 MHz, acetonitrile-d ₃ ) δ 9.15 (s, 1H), 7.24 (d, J = 7.5 Hz , 1H), 7.20-7.13 (m, 2H), 7.00 (td, J = 7.4, 1.4 Hz, 1H), 6.52 (dd, J = 2.3, 0.9 Hz, 1H), 2.90-2.83 (m, 2H), 2.62-2.55 (m, 2H), 2.00 (s, 3H).

Compound 9.3((T-4)-[2-[(4,5-Dihydro-3-methyl-2H-benzo[g]indol-2-ylidene-κN)(3,5-dimethyl 4-hydroxyphenyl)methyl]-4,5-dihydro-3-methyl-1H-benzo[g]indolato-κN]boron difluoride): with the above compound 44.2 In a similar manner, compound 9.3 was synthesized from compound 9.2 (3.97 mmol, 728 mg) and 4-hydroxy-2,6-dimethylbenzaldehyde (2.02 mmol, 304 mg). The crude product was purified by flash chromatography on silica gel (100% toluene (2 CV) à 10% EtOAc/toluene (10 CV)). The product-containing fractions were evaporated to give 563 mg (52% yield for 3 steps starting from pyrrole) of compound 9.3. MS (APCI): The calculated value of the chemical formula C35H31BF2N2O (M+H) = 544, the experimental value: 544. 1H NMR (400 MHz, DMSO-d ₆ ) δ 9.61 (s, 1H), 8.62 (d, J = 7.9 Hz , 2H), 7.45-7.38 (m, 2H), 7.38-7.34 (m, 4H), 6.68 (s, 2H), 2.91-2.83 (m, 4H), 2.58-2.52 (m, 4H), 2.04 (s , 6H), 1.41 (s, 6H).

SD-1: In a similar manner to the final synthesis step of FD-2 (above), compound 9.3 (0.116 mmol, 63 mg) and compound 46.1 (4,9,10-tris(trifluoromethyl)perylene-3-yl) ) SD-1 was synthesized by butyric acid (0.116 mmol, 63 mg). The crude product was purified by flash chromatography on silica gel (60% toluene/hexane (2 CV)→100% toluene (isocratic)). The fraction containing the product (as a mixture of isomers) was evaporated to dryness, yielding 84 mg of SD-1 (68% yield). MS (APCI): calculated value for chemical formula C62H44BF11N2O2 (M-) = 1068, experimental value: 1068.

Synthetic polymer - dye solution membrane example 1 (PMMA/ silica beads ) was achieved by adding 90.0 mL cyclopentanone to 30.0 g polymethylmethacrylate (PMMA) polymer and stirring at 50°C for several days Prepare 25% PMMA solution. Separately, 0.35 mg of the first photoluminescent compound (green light emitter) and 0.70 mg of the second photoluminescent compound (red light emitter) were added together into a 20 mL vial. Add 400 microliters to 300 mg silica beads and ultrasonically treat them for 5 minutes. 5 mL of 25% PMMA solution was added to 400 ml of Si/photoluminescent compound solution, and ultrasonic treatment was performed for 10 minutes. The resulting solution was removed from the stirring plate and allowed to stand for about 20 minutes to allow the presence of air bubbles to be reduced.

Membrane Example 2 (PVB/ cavitation ) A 22% PVB-A solution was prepared by dissolving 20 g of PVB-A polymer in 70 mL of cyclopentanone. Separately, 0.3 mg of photoluminescent dye FD-1 and 0.75 mg of photoluminescent dye SD-1 were compounded in a 20 mL vial. Add 5 mL of 22% PVB-A solution to the vial containing the photoluminescent compound.

Cast Film Example 1 [PMMA/ Bead Film ] Glass substrate 4 inches by 4 inches (clean). The obtained substrate solution was cast on a pre-cleaned (washed with soap and water) glass substrate (4 inches by 4 inches by 4 inches) by a casting machine set at the gap of the casting blade of 200 microns. The cast film was kept under the cover for 30 minutes, after which it was cast for another 30 minutes. Then the cast glass surface was placed on a hot plate and baked at 120°C for about 20 minutes.

Film example 2 [PVB/ cavitation ] The blade gap was set to 170 μm, and the solution was cast on a 4-inch by 4-inch pre-cleaned (soap and water) glass sheet as a substrate. The final thickness of the porous membrane is about 40-50 μm. The freshly coated substrate is allowed to stand in the air for 5 minutes, and then completely immersed or immersed in a container filled with water to ensure that the entire substrate is immersed. The impregnated cast glass was left in water overnight to allow the water to diffuse into the film. After soaking overnight, the immersed cast substrate was taken out and dried in a vacuum oven at room temperature or up to 50°C to evaporate all the solvent. Take care to prevent exposure to excessively high temperatures, because the glass transition temperature of PVB is 70°C, and exposure to this temperature can cause the generated bubbles to burst.

Additional examples of films made with different first photoluminescent emitters and/or polymer matrix materials as shown in Table 1 below. Table 1 membrane polymer Dyes ( × 10 ^-3 M) Film thickness (μm) Membrane example 2 Porous PVB FD-1: SD-1 = 0.3: 0.7 30 Membrane example 1 PMMA+silicon beads Membrane example 3 PMMA+30% 2 µm Si FD-1: 3×10 ^-2 M SD-1=7×10 ^-2 M 40 Membrane Example 4 FD-2: SD-1 = 0.6: 0.66 40 Membrane Example 5 FD-3:SD-1= 0.9:0.5 36 Membrane Example 6 FD-4:SD-1=1:0.33 40

Luminance measurement system: An external quantum efficiency measurement system (model C9920 Hamamatsu Corporation, Bridgewater, NJ, USA) was used to evaluate example 1 and example 2 of the wavelength conversion film in the configuration depicted in FIG. 6. The photon detector is located at the normal angle of the backlight system, so that only the light emitted close to the normal angle is collected. This measurement is useful for comparing the forward scattering characteristics of diffuser films. The measured brightness of film example 2 (0.3% by weight of FD-1: 0.7% by weight of SD-1 [PVB/cavitation]) was measured at 232 cd/m ² . The brightness measurement of Film Example 1 was 122 cd/m ² . Figure 8 is a graph showing intensity as a function of wavelength. This shows that backlight + film example 2 is brighter at about 450 nm, 510 nm, and 630 nm. 9 and 10 are graphs showing the intensity of various films created as identified in Table 1 as a function of wavelength.

The backlight film material was generated using the Kindle HDX7 blue backlight (Amazon, Seattle, WA, USA) from the schematic structure described in Figure 2 and Figure 3. The materials in parentheses use the schematic structure shown in FIG. 3, and the materials not in parentheses use the schematic structure shown in FIG. 2, as shown in Table 2 below. Table 2. membrane λEm green light (w/o& w/op.) FWHM green light (w/o& w/op.) λEm red light (w/o& w/op.) FWHM red light (w/o& w/op.) EQE (MCPD) EQE (W/ Optical Film (MCPD) Membrane example 2 515(519) 23(23) 636(643) 29(66) 68% 41% Perylene 515(518) 25(23) 635(642) 34(67) 65% 41% 5-trifluoro-perylene 519(522) 26(25) 635(642) 36(68) 72% 48% Naphthalene-Perylene 520(524) 31(31) 634(640) 36(67) 61% 44% 530 nm luminescent dye 529(534) 31(29) 632(638) 33( 38 ) 66% 47%

EQE evaluation method for light-emitting films mounted with light-emitting devices. The external quantum yield and other optical characteristics of the improved WLC film were compared with other films. These films were tested using the test device configured as shown in Fig. 7 and the test material installation configuration shown in Figs. 4 and 5. The BEF used is Vikuiti BEF (IBM). The DBEF used is a DBEFII brand polarizer/enhancement film (3M). Compare blue light sources and various luminescent materials/films (as shown in the table below). The results are shown in the table below. Figure 11 depicts the CIE 1931 color table with the above results. The comparative color gamut triangle is shown therein.

Table 3 : Comparison of film example 2 and commercial QD film using MCPD membrane polymer Dye ( × 10 ^-3 M) Film thickness (μm) IQE ( at 450 nm) (Hamamastu) Membrane example 2 Porous PVB FD-1:SD-1=0.3:0.7 30 89% QD kindle source Multi-layer Quantum dots 210 74% QD sdc Quantum dots Cd-free 300 59% QD 3M Quantum dots 210 83% Table 4. membrane Blue light absorption (%) EQE(MCPD) EQE(w/ optical film [MCPD]) Membrane example 2 40% 68% 41% QD Kindle source 26% 67% 35% QD CE 46% 45% 25% QD 3M 36% 61% 38% Table 5. membrane λEm green light (w/o& w/op.) FWHM green light (w/o& w/op.) λEm red light (w/o& w/op.) FWHM red light (w/o& w/op.) Membrane example 2 515(519) 23(23) 636(643) 29(66) QD Kindle source 544(547) 33(33) 609(609) 41(42) QD CE 532(538) 42(40) 628(631) 58(57) QD 3M 526(531) 33(32) 623(625) 36(36)

10: Equipment 12: light source 14: Back reflector 16: film/WLC film 18: Mask 20: Observer 22: BEF 24: Double brightness enhancement film

Figure 1 is a schematic diagram of an embodiment of a display device incorporating the improved WLC film described herein. Figure 2 is a schematic diagram of an embodiment of a display device incorporating the improved WLC film described herein. Fig. 3 is a schematic diagram of an embodiment of a display device incorporating the improved WLC film described herein. Figure 4 is a schematic diagram of a test configuration including an embodiment of the film described herein. Figure 5 is a schematic diagram of a test configuration including an embodiment of the film described herein. Figure 6 is a schematic diagram of a test configuration including the membrane embodiments described herein. Figure 7 is a schematic diagram of a test configuration including an embodiment of the film described herein. Figure 8 is a graph showing the light intensity as a function of wavelength for the embodiments described herein (film example 1 and example 2 [FD-1:SD-1]). FIG. 9 is a graph showing the light intensity of various films created as identified in Table 1 as a function of wavelength. 10 is a graph showing the light intensity of various films created as identified in Table 1 as a function of wavelength. Figure 11 is a 1931 CIE color table, which shows the color gamut representation of the various films described herein.

Claims (19)

A photoluminescence wavelength conversion film, the photoluminescence wavelength conversion film comprising: Polymer matrix A first photoluminescent dye, which absorbs blue wavelength light and emits green wavelength light having an emission spectrum with a full-width half-width less than 40 nm; A second photoluminescent dye that absorbs blue or green wavelength light and emits red wavelength light having an emission spectrum with a full width half width less than 40 nm; and Light scattering center The first photoluminescence dye, the second photoluminescence dye and the light scattering center are scattered in the polymer matrix. The photoluminescence wavelength conversion film of claim 1, wherein the first photoluminescence dye comprises a BODIPY group, a linking group and a perylene group. The photoluminescence wavelength conversion film of claim 1, wherein the first photoluminescence dye includes a BODIPY group, a linking group, and a naphthalenedimethimide group. The photoluminescence wavelength conversion film of 2 or 3, wherein the first photoluminescence dye is:

, Or a combination thereof. The photoluminescence wavelength conversion film of 2 or 3, wherein the second photoluminescence dye comprises a BODIPY group, a linking group and a perylene group. The photoluminescence wavelength conversion film of claim 5, wherein the second photoluminescence dye comprises

. The photoluminescence wavelength conversion film of 2 or 3, wherein the polymer matrix comprises PMMA, PVB, or a combination thereof. The photoluminescence wavelength conversion film of claim 7, wherein the polymer matrix comprises PMMA. The photoluminescence wavelength conversion film of claim 7, wherein the polymer matrix comprises PVB. The photoluminescence wavelength conversion film of 2 or 3, wherein the light scattering center comprises silica beads, air pockets, or a combination thereof. The photoluminescence wavelength conversion film of claim 10, wherein the light scattering center comprises silica beads. The photoluminescence wavelength conversion film of claim 10, wherein the light scattering center contains air pockets. Such as the photoluminescence wavelength conversion film of claim 1, wherein the photoluminescence wavelength conversion film includes one or more brightness enhancement films. For the photoluminescence wavelength conversion film of claim 13, the photoluminescence wavelength conversion film includes two brightness enhancement films and one dual brightness enhancement film. The photoluminescence wavelength conversion film of 2 or 3, wherein the quantum yield of the photoluminescence wavelength conversion film is greater than 85%. The photoluminescence wavelength conversion film of 2 or 3, wherein the photoluminescence wavelength conversion film has a color gamut greater than 85% of the BT2020 standard. The photoluminescence wavelength conversion film of 2 or 3, wherein the thickness of the photoluminescence wavelength conversion film is less than 100 microns. A light emitting device comprising the photoluminescence wavelength conversion film as claimed in claim 1, 2 or 3. A backlight device having a blue light source, the blue light source comprising the photoluminescence wavelength conversion film as claimed in claim 1, 2 or 3.

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