TWI784458B - 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 wavelength converting films and to light emitting devices comprising such wavelength converting films.

Photoluminescent substances are materials that emit light after absorbing energy in the form of light or electricity. Depending on the components forming photoluminescent substances and the mechanism of light emission, photoluminescent substances can be classified into inorganic photoluminescent substances (or dyes), organic photoluminescent dyes, nanocrystalline photoluminescent substances, and the like.

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

Quantum dot technology has achieved high levels 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 concerns. In addition, some quantum dots have a much lower efficiency in converting blue LED light to green or red light. quantum efficiency. Furthermore, quantum dots can have low stability when exposed to moisture and oxygen, often requiring expensive packaging processes. Quantum dots can be extremely costly because size uniformity can be extremely difficult to control during their production.

Therefore, there is a need for new photoluminescent films with high quantum efficiency, high color gamut output, and lower cost relative to quantum dots and other existing photoluminescent dye-containing films.

Some embodiments include a wavelength converting film comprising: a polymer matrix; a first photoluminescent dye that absorbs blue wavelength light and emits an emission having a full width at half width of less than 40 nm a spectrum of green wavelength light; a second photoluminescent dye that absorbs blue or green wavelength light and 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; Wherein the first photoluminescent dye, the second photoluminescent dye and the light scattering center are dispersed in the polymer matrix.

及/或

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

and/or

.

，或其任何組合。 In some embodiments, the first photoluminescent dye may comprise a BODIPY group, a linker group, and a naphthalimide group. In some embodiments, the first photoluminescent dye can be selected from:

, or any combination thereof.

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

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

Some embodiments include a light emitting device comprising a photoluminescent wavelength conversion film described herein.

Some embodiments include a backlight having a blue light source comprising a photoluminescent wavelength conversion film described herein.

These and other embodiments are described in more detail below.

10: Equipment

12: Light source

14: Back reflector

16: Membrane/WLC membrane

18: mask

20: Observer

22: BEF

24: Double brightness enhancement film

26: mask

28: Porous PVB w/Dye

30: Waveguide

32: Specular reflector

34:DBEF

36: BEF

38: BEF

40:Optical film

42: OLED EQE

44: Specular reflector

46:LED/Waveguide

48: WLC film

50: mask

52: Detector

54:MCPD Integrated Detector

Figure 1 is a schematic diagram of one embodiment of a display device incorporating the improved WLC film described herein.

Figure 2 is a schematic diagram of one embodiment of a display device incorporating the improved WLC film described herein.

Figure 3 is a schematic illustration of one embodiment of a display device incorporating the improved WLC film described herein picture.

Figure 4 is a schematic diagram of a test setup including film embodiments described herein.

Figure 5 is a schematic diagram of a test setup including film embodiments described herein.

Figure 6 is a schematic diagram of a test setup including film embodiments described herein.

Figure 7 is a schematic diagram of a test setup including film embodiments 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]).

9 is a graph showing light intensity as a function of wavelength for various films created as identified in Table 1. FIG.

10 is a graph showing light intensity as a function of wavelength for various films created as identified in Table 1. FIG.

Figure 11 is a 1931 CIE color chart showing color gamut representations for various films described herein.

Cross References to Related Applications

This application claims the benefit of U.S. Provisional Application No. 63/002,330, filed March 30, 2020, which is hereby incorporated by reference in its entirety.

The present invention relates to novel wavelength converting films comprising photoluminescent compounds (or dyes) 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 comprises a dipyrromethene complexed with a disubstituted boron atom (typically a BF2 unit ₎ . The IUPAC name for the BODIPY core is 4,4-difluoro-4-bora-3a,4a-diaza-s-indoxan.

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

，其中X=NR，其中R可為連接基團或芳基。 The term "naphthalene dicarboxylic acid" or "naphthalene dicarboxylic 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 naphthalene dicarboxylic acid moiety.

Use of the terms "may" or "may" should be construed as shorthand for "is" or "does not", or alternatively "does" or "does not" or "will" or "will not", etc. For example, the expression "the film may comprise scattering centers disposed within a polymer matrix" should be interpreted as, for example, "in some embodiments, the film comprises scattering centers disposed within a polymer matrix", or "in some embodiments, the film Scattering centers disposed within the polymer matrix are not included."

The term ITU-R Recommendation BT.2020 (more commonly known by the acronym Rec.2020 or BT.2020) refers to the color display standard of the color gamut. The RGB primaries used by Rec.2020 are equivalent to monochromatic light sources on the CIE 1931 spectral locus. The wavelengths of the Rec.2020 primary colors are 630nm for the red primary color, 532nm for the green primary color, and 467nm for the blue primary color. The Rec.2020 color space covers 75.8% of the CIE 1931 color space (the area within the defined triangle). The Rec.2020 color space uses the CIE standard illuminant 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 converting film comprising a polymer matrix, a first organic photoluminescent compound, and a second organic photoluminescent compound. in some real In an embodiment, the film may comprise a first organic photoluminescent dye that is green-emitting and has an emission peak with a full width at half width of less than 40 nm. In some embodiments, the film may comprise a second organic photoluminescent dye that is red-emitting and has an emission peak with a full width at half width of less than 40 nm. In some embodiments, the film may contain light scattering centers. In some examples, the first organic photoluminescent dye (green light emitting), the second organic photoluminescent dye (red light emitting), and the scattering centers are disposed within the polymer matrix. In some embodiments, the films provide high quantum yields. In some embodiments, the film provides a wide color gamut greater than 80%. A suitable means for determining the color gamut percentage is to measure the area under the resulting 1931 CIE color space, eg Figure 11. In some embodiments, the film may be between 80% and 99.9% gamut, such as 86%, 90%, 93% and/or 95%, or a range defined by any of the equivalent values. In some embodiments, an LCD backlight is described that includes the aforementioned film.

In some embodiments, the membrane may comprise a polymer matrix. In some embodiments, the polymer matrix can have a transparency greater than 75%. In some embodiments, the polymer matrix can 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 photoluminescent wavelength conversion film comprising the luminescent compound) has a narrow absorption or emission band such that a small amount of visible wavelength light is emitted. Absorption or emission bands can be characterized by full width at half maximum (FWHM). In the present invention, FWHM defines the width in nanometers of the absorption or emission spectrum at half the absorption or emission peak wavelength. In some embodiments, when dispersed in a substantially transparent poly When in a compound matrix, the luminescent compound has an absorption band 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. In some embodiments, the luminescent compound has an emission band with a FWHM value 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 when dispersed in a substantially transparent polymer matrix.

，或其任何組合。 In some embodiments, the film can include a first organic emissive compound (or dye). In some embodiments, the first organic luminescent dye (and/or the photoluminescent wavelength conversion film including the first organic luminescent dye) may have an emission peak (green light emission) between 510 nm and 560 nm. In some embodiments, the emission spectrum of the first organic light emitting dye and/or photoluminescent wavelength conversion film can have a full width at half half (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 luminescent 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 luminescent dye may include a BODIPY group, a linking group, and a naphthalene dicarboxylic acid derivative group. In some embodiments, the naphthalene dicarboxylic acid derivative group may be a naphthalimide group. In some embodiments, the naphthalimide group is covalently bonded to the linking group. In some embodiments, the first organic luminescent dye can be selected from FD-1, FD-2, FD-3 or FD-4:

, or any combination thereof.

In some embodiments, the wavelength converting film can include a second organic photoluminescent dye. In some embodiments, the second organic photoluminescent dye (and/or the photoluminescent wavelength conversion film including the second organic photoluminescent dye) may have an absorption peak (absorbs blue light) between 400 nm and 470 nm. In some embodiments, the second organic luminescent dye (and/or the photoluminescent wavelength conversion film comprising the second organic luminescent dye) may have an emission peak (emits red light) between 600 nm and 660 nm. In some embodiments, the second organic luminescent dye (and/or the photoluminescent wavelength conversion film comprising the second organic luminescent dye) may have an emission peak between 615 nm and 645 nm. In some embodiments, the emission spectrum of the second organic photoluminescent dye and/or photoluminescent wavelength conversion film can have a full width at half half (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 BODIPY groups and perylene groups. In some embodiments, the second organic photoluminescent dye can comprise SD-1:

In some embodiments, the first photoluminescent compound can absorb light from within the ultraviolet/blue absorption spectrum and emit light within the green emission spectrum, thereby enhancing the perceived emitted green light. In other embodiments, the second photoluminescent compound may absorb light from within the green/blue absorption spectrum and emit light within 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 within the ultraviolet/blue light absorption spectrum and emit light at other wavelengths, wherein the resulting light combined can Take perception as white light. In some examples, perceived white light may have a color temperature described as cool. In some examples, perceived white light may have a color temperature described as warm.

The ratio of the amounts of the first photoluminescent dye and the second photoluminescent dye can be adjusted to tune the color characteristics of the photoluminescent wavelength conversion film. For example, the weight ratio of the first photoluminescent dye to the second photoluminescent dye can 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 comprise scattering centers disposed within the polymer matrix. In some embodiments, the scattering centers may be solid particles comprising a material having a different refractive index than the polymeric matrix material. The scattering material may be a material having a refractive index (RI) different from that of the polymer matrix. Scattering materials can be used to increase external quantum yield, for example by reducing total internal reflection.

In some embodiments, the difference in RI between the polymeric matrix material and the light scattering material can 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 can be silicone beads. In some embodiments, the scattering centers 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 -6μm, about 6-7μm, about 7-8μm, about 8-9 μm, about 9-10 μm, or approximately any value within the range defined by any of these equivalents. In some embodiments, the scattering centers can be substantially uniformly dispersed within the polymer matrix. In some embodiments, the top portion of the film, eg, the side away from the blue light emitting source, may have greater than 50% scattering centers. In some embodiments, the scattering centers may be uniformly distributed within the polymer matrix.

The photoluminescent wavelength conversion film can 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 μm -80 μm, about 80-120 μm, about 120-200 μm, about 200-300 μm, or about 300-500 μm.

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

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

In some embodiments, a display device may be schematically represented by FIG. 2 . As shown in FIG. 2 , a display device, such as device 10 , may include a light source, such as light source 12 . In some embodiments, a display device may include a back reflector, such as back reflector 14 . In some embodiments, the display device may include a wavelength converting (WLC) film, such as 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 increased efficiency in transmitting the generated light from the light source to the observer 20 .

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

Some embodiments include a method for making an LED light source. In some embodiments, the method can include fabricating an undried wavelength-shifting polymer layer with an organic solvent and a photoluminescent dye as described herein. In some embodiments, the method can include mixing the polymer and/or monomer with an organic solvent. In some embodiments, polymer and/or monomer precursors may be dispersed, dissolved in, and/or mixed with a solvent. In some embodiments, solvents may be used to fabricate the material layers. In some embodiments, the solvent can be a non-polar solvent. In some embodiments, nonpolar Reactive solvents may include, but are not limited to, xylene, cyclohexanone, acetone, toluene, methyl ethyl ketone, or any combination thereof. In some embodiments, the solvent can be a polar solvent. In some embodiments, the polar solvent may include ethanol, dimethylformamide (DMF), or combinations thereof. In some embodiments, the solvent can be a combination of non-polar and polar solvents.

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

In some embodiments, the method can include removing the undried polymeric photocatalytic WLC layer from the aqueous solution. In some embodiments, the method can include drying the undried polymeric photocatalytic WLC layer. It is believed that fabricating a polymeric photocatalytic WLC layer in this manner provides multiple air pockets defined in the emitting or distal surface of the polymeric photocatalytic WLC layer. In some embodiments, the air pockets are substantially entirely within about 1 micron to about 5 microns from the emitting surface of the polymeric photocatalytic WLC layer.

In some embodiments, the polymeric material comprises about 2% to about 50% by weight polymer, about 2-5% by weight, about 5-10% by weight, about 10-15% by weight, about 15-20% 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 values aqueous solution.

Example

Embodiment 1. A film comprising: a polymer matrix; a first photoluminescent dye that absorbs blue wavelength light and narrowly emits a green wavelength having an emission spectrum with a full width at half width of less than 40 nm 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 that the first A photoluminescent dye, a second photoluminescent dye, and light scattering centers are disposed within 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.

或

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

or

Embodiment 4. The film of embodiment 1, wherein the first photoluminescent dye comprises a BODIPY group, a linking group, and a naphthalimide 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 membrane of embodiments 1-7, wherein the quantum yield of the membrane 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 1-7, wherein the film has a thickness of 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 comprising the film according to embodiments 1-10.

Embodiments of films comprising the photoluminescent composites described herein have been found to have improved performance compared to other forms of color converting films. These benefits are further demonstrated by the following examples, which are intended to illustrate the invention only and are not intended to limit the scope or rationale in any way.

example Synthesis of the first photoluminescent dye.

Synthetic compound FD-1:

Compound 6.5:

Step 1: Degas a solution of 4-hydroxy-2,6-dimethylbenzaldehyde (0.75 g, 5 mmol), 2,4-dimethylpyrrole (1.04 g, 11 mmol) in 100 mL of dry dichloromethane for 30 min , followed by the addition of a drop of trifluoroacetic acid. The solution was stirred overnight at room temperature under argon. To the resulting solution was added DDQ (2.0 g, 8.8 mmol) and stirred at room temperature overnight. The resulting mixture was filtered and washed thoroughly with dichloromethane to give a brown solid as desired compound 6.4 (1.6 g, 100% yield). LCMS (APCI+): Calcd. for _C21H25N2O (M ₊ H) = ₃₂₁ ; found 321.

Step 2: 5 mL of trimethylamine was added to a solution of dipyrromethane, compound 6.4 (1.0 g) in 60 mL of THF. The solution was degassed for 10 min, then trifluoroboron-diethyl ether (5 mL) was added slowly. Next, the solution was heated at 70 °C for 30 min. The resulting solution was subjected to flash chromatography (silica gel) using dichloromethane as eluent. The desired fractions were collected and dried under reduced pressure to afford compound 6.5 as an orange solid (0.9 g, 76% yield). LCMS (APCI ₊ ): Calcd. for _C2iH24BF2N2O ( _{M +} H) = 369; found: 369. ¹ H NMR (400MHz, 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-dichlorobenzene in a three-neck round bottom flask. The resulting yellow solution was cooled to 0 °C. 2.64 g _of AlCl3 (19.81 mmol) was added in small portions via a powder distribution funnel over 45 minutes, followed by the dropwise addition of 50 mL of tert-butyl chloride (458 mmol). 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 with a water bath set at 70 °C. The residue was redispersed into 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 the tetra(tert-butyl) analog (M+H=477), while the filtrate was bis(tert-butyl)perylene and tri(tert-butyl) ) a mixture of perylenes, loading the mixture onto a silica gel column. Chromatographic separation was performed using hexane:EtOAc (9:1) to obtain 3.75 g of light yellow solid product compound 10.1, namely 2,5-di(tert-butyl)perylene, with a yield of 52%. LCMS (APCI+) calcd for C ₂₈ H ₂₉ (M+H) = 365; found 365. 1H NMR (400MHz, chloroform-d) δ 8.30-8.21(m, 4H), 7.72-7.63(m, 4H), 7.50(t, J=7.8Hz, 2H), 1.50(s, 18H).

Compound 12.1 (methyl 4-(8,11-di(tert-butyl)perylene-3-yl)-4-oxobutanoate):

Under a nitrogen atmosphere, 2.63 g of AlCl ₃ (19.97 mmol) was added in small portions to 2.45 mL of methyl 4-chloro-4-oxobutyrate ( 19.97 mmol) in suspension in 175 mL of anhydrous DCM. The resulting solution was stirred at 0 °C for 1 hour. Next, a solution of 5.77 g of compound 10.1[2,5-bis(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 of ethyl acetate. The organic layers were combined, dried over MgSO ₄ and concentrated. The residue was loaded onto a silica gel column. Chromatographic separation was performed using hexane:ethyl acetate (9:1) as eluent to obtain 2.7 g of compound 12.1 as an orange solid product with a yield of 35%. LCMS (APCI+): calcd for C ₃₃ H ₃₅ O ₃ (M+H) = 479; found: 479; ¹ H NMR (400 MHz, chloroform-d) δ 8.58 (d, J = 8.6 Hz, 1 H), 8.34-8.27(m,3H),8.23(d,J=8.0Hz,1H),7.98(d,J=7.9Hz,1H),7.73(s,1H),7.68(s,1H),7.60(t ,J=8.0Hz,1H),3.75(s,3H),3.41(t,J=6.5Hz,2H),2.86(t,J=6.6Hz,2H),1.49(d,J=3.5Hz,18H ).

Compound 12.2 (4-(8,11-di(tert-butyl)perylene-3-yl)butanoic acid):

470.5 mg of compound 12.1 [4-(8,11-di(tert-butyl) perylene-3-yl)-4-oxobutyric acid methyl ester] (0.983 mmol) and 150 μL of 98% A solution of hydrazine monohydrate (2.949 mmol) dissolved in 2 mL of diethylene glycol was placed in a microwave vial and stirred at room temperature. 275 mg KOH (powder) (4.91 mmol) was added to the solution 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, a balloon was used to maintain an argon atmosphere and the temperature was raised 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 eluent to afford 110 mg of compound 12.2 as a green solid product in 88% yield. LCMS (APCI+): Calcd. for C ₃₂ H ₃₅ O ₂ (M+H) = 451; found: 451; 1H NMR (400 MHz, chloroform-d) δ 8.27-8.19 (m, 3H), 8.15 (d, J=7.7Hz,1H),7.88(d,J=8.4Hz,1H),7.62(d,J=5.2Hz,2H),7.53(t,J=8.0Hz,1H),7.34(d,J= 7.7Hz,1H),5.30(s,1H),3.09(t,J=7.7Hz,2H),2.48(t,J=7.2Hz,2H),2.11(p,J=7.4Hz,2H),1.47 (s,18H).

Compound FD-1

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

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]diazaborine-2,8-dicarboxylate dibenzyl ester):

To a 250 mL round bottom flask was added 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 cooling bath was removed, and the mixture was stirred at room temperature for 3.5 h. The insolubles were filtered off to obtain a crude solution of the oxime 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 and heated to 60 °C in an oil bath. The solidified tert-butyl 2-(hydroxyimino-3-oxobutyrate solution was added slowly. The temperature was then raised to 75° C. and stirred for 1 hour. Then, the reaction mixture was poured into water (4 L). The precipitate was collected and filtered to give benzyl 2,4-dimethyl-1H-pyrrole-3-carboxylate, which was recrystallized from MeOH as a white solid to give 15 g, yield based on 3-oxobutane Benzyl ester is 65% ^.1 H NMR (400MHz, 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 benzyl 2,4-dimethyl-1H-pyrrole- ₃ -carboxylate, 0.524 g (4.36 mmol) of MgSO was dissolved in 8 mL of anhydrous DCE , and stirred at room temperature for 15 minutes in the presence of argon. 0.327 g of 2,6-dimethyl-4-hydroxybenzaldehyde (2.18 mmol) was added in small portions; the vial was closed with a Teflon cap. The resulting mixture was purged with argon for 15 min, and TFA (3 drops, catalytic amount) was added. The reaction mixture was stirred at 65 °C for 16 hours. TLC and LCMS showed the starting material was 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 the starting material was consumed. The resulting mixture was filtered through short path Celite; the filtrate was concentrated to dryness, the residue was redissolved in 50 mL DCE, stirred with triethylamine (1.4 mL, 19 mmol) at room temperature for 15 min, then cooled to 0 °C. 3 mL of _BF3 (18.36 mmol) was slowly added. 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 , the solvent was removed by rotary evaporation. The residue was chromatographically separated on a silica gel column using CH ₂ Cl ₂ /EtOAc as eluent to obtain 1 g of pure compound 44.2, namely 5,5-difluoro-10-(4-hydroxy-2,6-dimethyl phenyl)-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diaze Borhene-2,8-dibenzyl dicarboxylate) as an orange-red solid in a 72% yield based on 2,6-dimethyl 4-hydroxybenzaldehyde. LCMS ( _APCI- ), M _{- calcd} for _{C37H35BF2N2O5} : _636.26 ; found: 636. ¹ H NMR (400MHz, chloroform-d) δ 7.42-7.28(m,4H),6.66(d,J=0.7Hz,1H),5.29(d,J=11.3Hz,2H),2.82(s,3H) ,2.04(d,J=5.4Hz,3H),1.72(s,3H).

Compound 4-(perylene-3-yl)butyric acid methyl ester

Step 1: In a 1 L two-necked flask equipped with a magnetic stir bar, powder distributor funnel, a yellow suspension mixture of perylene (5.22 g, 20.68 mmol) in anhydrous DCM (500 mL) was stirred in an ice-water bath and bubbled with argon for 15 minutes; slowly added methyl 4-chloro-4-oxobutanoate (3.425 g, 22.75 mmol) via 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 the powder distributor funnel. The resulting dark purple mixture was stirred at room temperature under argon for 16 hours. TLC and LCMS showed almost complete consumption of starting material. The reaction mixture was diluted with 500 mL DCM, then poured into ice-water (150 mL water), the organic layer was separated, concentrated to dryness with _MgSO4 . The residue was triturated with toluene. The solid was filtered and washed with 50 mL of toluene. The combined filtrate and washings were then concentrated to a volume of 50 mL, then loaded onto a column (330 g) and eluted with toluene/EtOAc (100:0)→(4.1) to give 1.25 g of the desired product. The product from column chromatography and the solid product from workup were combined and recrystallized using hexane:EtOAc (9:1 ) to give 4.24 g of a yellow solid, 56% yield. LCMS (APCI-), calculated for (M-) for C25H18O3: 366.13; found: 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=8.1Hz,1H),7.78(d,J=8.1Hz,1H),7.73(d,J=8.1Hz,1H),7.64-7.48(m,3H ), 3.75(s, 3H), 3.41(t, J=6.5Hz, 2H), 2.86(t, J=6.5Hz, 2H).

Step 2: In a 250 mL round bottom flask, a yellow mixture of the product from the above step (4.24 g, 11.58 mmol) in anhydrous DCM (100 mL) was stirred and bubbled with argon for 15 min on a cooled ice+water bath; slowly TFA (25 mL) was added. 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 under argon for 16 hours. TLC and LCMS showed the starting material was consumed. The reaction mixture was diluted with 200 mL of DCM and then placed on a rotavap. Remove TFA and DCM. The residue was redissolved in DCM (50ml), and the mixture was concentrated to dryness. The dark crude product was loaded onto a _SiO2 column and eluted with hexane/EtAcO (95:5) to give 4.00 g of methyl 4-(perylene-3-yl)butanoate as a yellow solid product. The yield was 98%. LCMS (APCI+), calculated for M+ for C25H20O2: 353.15; found: 353.

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

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

Methyl 4-(4,9,10-tris(trifluoromethyl)perylene-3-yl)butanoate:

A 40 mL screw cap vial was filled with a stir bar and fitted with a screw cap septum. Flush the vial with argon. To the vial was added methyl 4-(4,9,10-tribromoperylene-3-yl)butanoate (mixture of isomers (0.496 mmol, 292 mg), CuI (4.96 mmol, 944 mg), Anhydrous dimethylacetamide (10 mL) was then added. Under stirring at room temperature, methyl 2,2-difluoro-2-(fluorosulfonyl)acetate (4.96 mmol, 0.631 mL was added via syringe at room temperature ). The reaction was placed in a heating block set at 160° C. and stirred for 3 hours. An additional portion of CuI (4.96 mmol, 944 mg) and methyl 2,2-difluoro-2-(fluorosulfonyl)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 washed with dichloromethane , until dichloromethane was washed to colorless. The combined organic washes were evaporated to dryness and separated by flash chromatography on silica gel (50% toluene/hexane (1 CV) → 100% toluene (10 CV)) Purification. Fractions containing the desired product (as a mixture of isomers) were evaporated to dryness to give 90 mg (33% yield). MS (APCI): Calcd for formula C28H17F9O2 (M-) = 556; 556.

Compound 46.1: 4-(4,9,10-tris(trifluoromethyl)perylene-3-yl)butanoic acid:

A 250 mL 2-necked round bottom flask was charged with a stir bar and flushed with argon. 4-(4,9,10-tris(trifluoromethyl)perylene-3-yl)butanoic acid (3.00mmol, 1.141g) and KOH (30.0mmol, 1.683g) were added to the flask, followed by Add ethanol (200 proof, 200 mL). The flask was fitted with a finned air condenser and heated with stirring in a heating block at 95° C. under argon for two hours. 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 shrinkage to give a crude precipitate in quantitative yield. MS (APCI): calcd for formula C27H15F9O2 (M-) = 542; found: 542.

FD-2(10-(2,6-Dimethyl-4-((4-(4,9,10-tris(trifluoromethyl)perylene-3-yl)butyryl)oxy)benzene base)-5,5-difluoro-1,3,7,9-tetramethyl-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2 ]diazaborine-2,8-dibenzyl dicarboxylate):

In a 40 mL screw-cap vial, add a stir bar, compound 46.1 [4-(4,9,10-tris(trifluoromethyl)perylene-3-yl)butanoic acid] (0.164mmol, 89mg) 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]diazaborine-2,8-dibenzyl dicarboxylate] and DMAP: pTsOH 1:1 salt (0.200mmol, 59mg) . 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 THF (10 mL) was added and sonicated for 30 sec. An additional portion of compound 46.1 (0.150 mmol, 51 mg) was added and stirred overnight at 50 °C under argon. The crude product was purified by flash chromatography on silica gel (100% toluene (2 CV)→10% EtOAc/toluene (10 CV)). Fractions containing the product (as a mixture of isomers) were evaporated to dryness to afford 128 mg (67% yield) of FD-2. MS (APCI): calcd for formula C64H48BF11N2O6 (M-) = 1160; found: 1160.

Synthetic compound FD-3:

10-(4-((4-(4-(6-(4-(diphenylamino)phenyl)-1,3-dipentoxy-1H-benzo[de]isoquinoline-2 (3H)-yl)phenyl)butyryl)oxy)-2,6-dimethylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4λ4,5λ4- Dibenzyl dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborine-2,8-dicarboxylate:

To compound 44.2[5,5-difluoro-10-(4-hydroxyl-2,6-dimethylphenyl)-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo [1,2-c:2',1'-f][1,3,2]diazaborine-2,8-dibenzyl dicarboxylate] (1.18mmol, 750mg), compound 13.3. 2 (see the following synthesis, 1.30mmol, 780mg) and DMAP. To a solution of pTsOH salt (2.36 mmol, 694 mg) in anhydrous _{CH2Cl2 (} 6.00 mL) was added DIC (7.08 mmol, 1.11 mL), and the reaction mixture was stirred at room temperature 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) afforded 1.10 g of compound FD-3 (76% yield) as an orange solid. 1H NMR (400MHz, chloroform-d) δ 8.68(dd, J=7.2,2.4Hz,2H),8.48(d,J=8.5Hz,1H),7.77(dd,J=9.3,7.4Hz,2H), 7.44-7.27(m,20H),7.24-7.20(m,6H),7.11(t,J=7.3Hz,2H),6.97(s,2H),5.27(s,4H),2.85(d,J= 13.9Hz, 8H), 2.67(t, J=7.4Hz, 2H), 2.22-2.06(m, 8H), 1.72(s, 6H); 19F NMR(376MHz, chloroform-d) δ-142.72--143.09( m); 13C NMR (101MHz, 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, 121.7, 15 , 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-4:

Compound 13.3.1:

[4-(4-(6-bromo-1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl)phenyl)butanoic acid]: to 6-bromo- 1H,3H-Benzo[de]isochromene-1,3-dione (18.4 mmol, 3.30 g) in EtOH (200 proof, 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. It was then cooled to room temperature, diluted with EtOH (200 proof, 50.0 mL), filtered and washed with more EtOH (200 proof, 100 mL) and hexane (100 mL) to afford 5.02 g of compound 13.3.3. 1 (72% yield) as an off-white solid. 1H NMR (400MHz, DMSO-d6) δ 12.15(s,1H),8.63-8.55(m,2H),8.34(d,J=7.8Hz,1H),8.25(d,J=7.9Hz,1H),8.03(dd,J=8.5,7.3 Hz,1H),7.34(d,J=8.3Hz,2H),7.29(d,J=8.2Hz,2H),2.68(t,J=7.3Hz,2H),2.29(t,J=7.3Hz, 2H), 1.87 (p, J=7.5Hz, 2H); 13C NMR (101MHz, 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-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl) Phenyl)butyric acid]: To a suspension of 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) under Ar atmosphere Pd(PPh ₃ ) ₄ (0.562mmol, 649mg) and (4-(diphenylamino)phenyl)boronic acid (11.8mmol, 3.41g) were added to the solution, and the reaction mixture was stirred at 80°C for 16 hours. It was then filtered and washed with EtOH (200 proof, 200 mL). The filter cake was partitioned between 1M HCl (300 mL) and _CH2Cl2 (300 mL), and the mixture was extracted with _{CH2Cl2 ( 3} x 300 mL). The combined organics were dried ( _MgSO4 ) and concentrated under reduced pressure to afford 6.50 g of compound 13.3.2 (96% yield) as an orange/red solid. 1H NMR (400MHz, chloroform-d) δ 8.67(dd, J=7.5,2.5Hz,2H),8.47(d,J=8.5Hz,1H),7.79-7.71(m,2H),7.42-7.36(m ,4H),7.33(apparent t,J=7.8Hz,4H),7.28-7.19(m,8H),7.10(apparent t,J=7.3Hz,2H),2.79(t,J=7.6Hz, 2H), 2.46 (t, J=7.3Hz, 2H), 2.06 (apparent p, J=7.6Hz, 2H); ¹³ C NMR (101MHz, 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-formyl-3,5-dimethylphenyl-4-(4-(6-(4-(diphenylamino)phenyl)-1,3-dioxo-1H- Benzo[de]isoquinolin-2(3H)-yl)phenyl)butyrate]:

To 4-hydroxy-2,6-dimethylbenzaldehyde (5.97mmol, 897mg), compound 13.3.2 (4.98mmol, 3.00g) and DMAP. To a solution of pTsOH salt (9.96 mmol, 2.93 g) in anhydrous _{CH2Cl2 (} 25.0 mL) was added DIC (29.9 mmol, 4.68 mL) and the reaction was stirred at room temperature for 80 min. 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 (400MHz, chloroform-d) δ 10.57(s,1H),8.70-8.64(m,2H),8.48(dd,J=8.5,1.2Hz,1H),7.76(dd,J=9.1,7.4Hz ,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=7.6Hz,2H),2.69-2.59(m,8H),2.16(p,J=7.5Hz,2H);13C NMR(101MHz,chloroform-d)δ 192.3,171.4,164.6,164.4,148.4, 147.3,147.2,141.5,133.5,133.2,131.6,131.3,130.8,130.1,129.5,129.2,127.7,123.0, 122.0, 122.0, 122.0, 122.02.02.02.0222.0222.0222.0222.0 33.6, 26.1, 20.7.

FD-4:

To ethyl 2-methyl-1H-pyrrole-3-carboxylate (61mg, 0.4mmol), compound 13.3[4-(4-(6-(4-(diphenylamino)phenyl)-1, 3-Dioxo-1H-benzo[de]isoquinolin-2(3H)-yl)phenyl)butanoic acid 4-formyl-3,5-dimethylphenyl] (100mg, 0.136 mmol), _MgSO4 (120 mg, 1.0 mmol) in dichloroethane (5 mL) was added 3 drops of TFA, followed by heating at 65 °C for 3 days. Triethylamine (0.13 mL, 0.9 mmol), BF ₃ -etherate (0.09 mL, 0.5 mmol) were added to the resulting mixture, followed by heating at 60° C. for 30 minutes. After cooling to room temperature, the mixture was loaded onto 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 give compound FD-4 as an orange-red solid (40 mg, 27% overall yield). LCMS (APCI): Calcd. for C65H55BF2N4O8 (M-): 1068; found: 1068. 1H NMR (400MHz, 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=8.3Hz,2H),7.36-7.30(m,2H),7.24(dt,J=13.8,8.1Hz,6H),7.15 (d,J=8.6Hz,6H),7.08-6.99(m,4H),6.91(s,2H),4.17(q,J=7.1Hz,4H),2.84(s,6H),2.80(m, 2H), 2.65(t, J=7.4Hz, 2H), 2.13(m, 2H), 2.08(s, 6H), 1.24(t, J=7.1Hz, 6H).

Synthesis of the second photoluminescent dye (SD-1)

((T-4)-[2-[(4,5-Dihydro-3-methyl-2H-benzo[g]indole-2-ylidene-κN)(3,5-dimethyl- 4-((4-(4,9,10-tris(trifluoromethyl)perylene-3-yl)butyryl)oxy)phenyl)methyl]-4,5-dihydro-3-methanol base-1H-benzo[g]indole-κN]boron difluoride):

Compound 9.1 (ethyl 3-methyl-4,5-dihydro-1H-benzo[g]indole-2-carboxylate):

A 250 mL 2-necked round bottom flask was charged with a stir bar and placed in a 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 with stirring open to air. To a 40 mL screw cap vial was added ethyl 2-(hydroxyimino)-3-oxobutanoate (2.50 mmol, 398 mg) and Zn (powder, <10 μm) (12.5 mmol, 818 mg). These were slurried in acetic acid (12.5 mL) and added portionwise to the stirred reaction containing the ketone over a period of about 5 minutes. This procedure was repeated 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, then cooled to room temperature. The reaction was quenched by pouring into water (600 mL) with stirring. The volume was brought up to 900 mL with water, followed by extraction with dichloromethane (4 x 160 mL). The combined organic layers were washed with water (100 mL), brine (100 mL), dried over MgSO ₄ , filtered and evaporated to dryness. Most of the excess 1-tetralone was removed under high vacuum with heating. The crude product was purified by flash chromatography on silica gel (5% EtOAc/hexane (1 CV)→20% EtOAc/hexane (10 CV)). Fractions containing product were evaporated to dryness to afford 1.417 g (55% yield) of compound 9.1. MS (APCI): Calculated value of chemical formula C16H17NO2 (M+H) = 256, experimental value: 256. 1H NMR (400MHz) 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=7.1Hz,2H),2.99-2.92(m,2H),2.70-2.64(m,2H),2.31(s,3H), 1.39(t,J=7.1Hz,3H).

Compound 9.2 (3-methyl-44,5-dihydro-1H-benzo[g]indole):

A 250 mL 2-necked round bottom flask was charged with a stirring bar, and fitted with a finned condenser and a 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 (5.0 M in _H2O , 25.03 mmol, 5.01 mL). The reaction was stoppered and heated in a heating block at 100° C. under argon for 90 minutes. Use heat to homogenize the solution. The temperature was raised to 160°C for 30 minutes, followed by cooling 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, then it was acidified with a solution of 2.5M acetic acid/2.5M NaOAc (20 mL). The pH was lowered to about 3.5 using TFA. 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)). Fractions containing product were evaporated to dryness to afford 767 mg (84% yield) of compound 9.2. MS(APCI): Calculated value of chemical formula C13H13N(M+H) = 184, experimental value: 184. 1H NMR (400MHz, acetonitrile-d ₃ ) δ 9.15(s, 1H), 7.24(d, J=7.5Hz, 1H),7.20-7.13(m,2H),7.00(td,J=7.4,1.4Hz,1H),6.52(dd,J=2.3,0.9Hz,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]indole-2-ylidene-κN)(3,5-dimethyl yl-4-hydroxyphenyl)methyl]-4,5-dihydro-3-methyl-1H-benzo[g]indole-κN]boron difluoride):

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) in a similar manner to the synthesis of compound 44.2 above. The crude product was purified by flash chromatography on silica gel (100% toluene (2 CV)→10% EtOAc/toluene (10 CV)). Fractions containing product were evaporated to give 563 mg (52% yield for 3 steps starting from pyrrole) of compound 9.3. MS(APCI): Calculated value of chemical formula C35H31BF2N2O (M+H) = 544, experimental value: 544. 1H NMR (400MHz, DMSO-d ₆ ) δ 9.61(s, 1H), 8.62(d, J=7.9Hz, 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:

From compound 9.3 (0.116 mmol, 63 mg) and compound 46.1 (4,9,10-tris(trifluoromethyl)perylene-3-yl) in a similar manner to the final synthetic procedure of FD-2 (above) SD-1 was synthesized from butyric acid (0.116mmol, 63mg). The crude product was purified by flash chromatography on silica gel (60% toluene/hexane (2 CV)→100% toluene (isocratic)). will contain the product (as isomer mixture) fractions were evaporated to dryness to afford 84 mg of SD-1 (68% yield). MS (APCI): Calcd for formula C62H44BF11N2O2 (M-) = 1068, found: 1068.

Synthetic polymer-dye solution

Membrane Example 1 (PMMA/Silicon Beads)

A 25% PMMA solution was prepared by adding 90.0 mL of cyclopentanone to 30.0 g of polymethylmethacrylate (PMMA) polymer and stirring at 50° C. for several days. Separately, 0.35 mg of the first photoluminescent compound (green emitter) and 0.70 mg of the second photoluminescent compound (red emitter) were added together into a 20 mL vial. 400 microliters were added to 300 mg of silica beads and sonicated for 5 minutes. 5 mL of 25% PMMA solution was added to 400 ml Si/photoluminescent compound solution and sonicated for 10 minutes. The resulting solution was removed from the stir plate and allowed to stand for about 20 minutes to allow the presence of air bubbles to diminish.

Film Example 2 (PVB/Cavity)

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

Membrane Example 1 [PMMA/Bead Membrane]

Glass substrate 4 inches by 4 inches (clean). By setting at a casting vane gap of 200 microns The resulting substrate solution was cast onto pre-cleaned (washed with soap and water) glass substrates (4 inches by 4 inches by 4 inches) on a casting machine of . The cast film was kept covered for 30 minutes before being cast for an additional 30 minutes. The cast glass surface was then placed on a hot plate and baked at 120°C for about 20 minutes.

Film example 2 [PVB/cavitation]

The blade gap was set at 170 μm and the solution was cast on 4 inch by 4 inch pre-cleaned (soap and water) glass slides as substrates. The final thickness of the porous membrane is about 40-50 μm. The freshly coated substrates were allowed to stand in air for 5 minutes before being fully immersed or submerged into a container of water, ensuring that the entire substrate was immersed. The impregnated cast glass was left in water overnight to allow the water to diffuse into the membrane. After soaking overnight, the submerged cast substrates were removed and dried in a vacuum oven at room temperature or up to 50°C to evaporate all solvent. Care should be taken to prevent exposure to excessively high temperatures, as PVB has a glass transition temperature of 70°C and exposure to this temperature can lead to the collapse of bubbles produced.

Additional examples of films were made with different first photoluminescent emitters and/or polymer matrix materials as shown in Table 1 below.

Brightness measurement system:

Wavelength conversion film Example 1 and Example 2 were respectively evaluated using an external quantum efficiency measurement system (Model C9920 Hamamatsu Corporation, Bridgewater, NJ, USA) in a configuration as depicted in FIG. 6 . The photon detectors are located at the normal corners of the backlight system so that only light emitted close to the normal corners is collected. This measurement facilitates comparison of the forward scattering properties of the diffuser films. The measured brightness of Film Example 2 (0.3 wt. % FD-1 : 0.7 wt. % SD-1 [PVB/cavitation]) was measured at 232 cd/m ² . The brightness of Film Example 1 was measured to be 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.

Backlit film data was generated from the schematic configuration described in Figures 2 and 3 using a Kindle HDX7 blue backlight (Amazon, Seattle, WA, USA). The data in brackets use the schematic structure shown in Figure 3, and the data not in brackets use the schematic structure shown in Figure 2, as shown in Table 2 below.

Evaluation method of EQE of light-emitting film mounted light-emitting devices.

The external quantum yield and other optical characteristics of the improved WLC films were compared to other films tested using the test setup configured as shown in FIG. 7 and the test material setup shown in FIGS. 4 and 5 . The BEF used was Vikuiti brand BEF (IBM). The DBEF series DBEFII brand polarizer/enhancement film (3M) used was used. 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. A comparison gamut triangle is shown therein.

Claims (19)

A photoluminescence wavelength conversion film, the photoluminescence wavelength conversion film comprising: polymer matrix; a first photoluminescent dye that absorbs blue wavelength light and emits green wavelength light having an emission spectrum with a full width at half width of 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 at 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 dispersed in the polymer matrix. The photoluminescent wavelength conversion film according to claim 1, wherein the first photoluminescent dye comprises a BODIPY group, a linking group and a perylene group. The photoluminescent wavelength conversion film according to claim 1, wherein the first photoluminescent dye comprises a BODIPY group, a linking group and a naphthalimide group. The photoluminescent wavelength conversion film according to claim 1, 2 or 3, wherein the first photoluminescent dye is:

, or a combination thereof. The photoluminescent wavelength conversion film according to claim 1, 2 or 3, wherein the second photoluminescent dye comprises a BODIPY group, a linking group and a perylene group. The photoluminescent wavelength conversion film as claimed in item 5, wherein the second photoluminescent dye comprises

. The photoluminescent wavelength conversion film according to claim 1, 2 or 3, wherein the polymer matrix comprises PMMA, PVB, or a combination thereof. The photoluminescent wavelength conversion film according to claim 7, wherein the polymer matrix comprises PMMA. The photoluminescent wavelength conversion film according to claim 7, wherein the polymer matrix comprises PVB. The photoluminescent wavelength conversion film according to claim 1, 2 or 3, wherein the light scattering center comprises silicon dioxide beads, air pockets, or a combination thereof. The photoluminescent wavelength conversion film according to claim 10, wherein the light scattering center comprises silicon dioxide beads. The photoluminescent wavelength conversion film according to claim 10, wherein the light scattering center contains air pockets. According to the photoluminescence wavelength conversion film of claim 1, the photoluminescence wavelength conversion film further includes one or more brightness enhancement films. According to the photoluminescence wavelength conversion film of claim 13, the photoluminescence wavelength conversion film includes two brightness enhancement films and a double brightness enhancement film. The photoluminescence wavelength conversion film according to claim 1, 2 or 3, wherein the quantum yield of the photoluminescence wavelength conversion film is greater than 85%. The photoluminescence wavelength conversion film according to claim 1, 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 according to claim 1, 2 or 3, wherein the thickness of the photoluminescence wavelength conversion film is less than 100 microns. A light emitting device comprising the photoluminescent wavelength conversion film according to claim 1, 2 or 3. A backlight device, the backlight device has a blue light source, and the blue light source includes the photoluminescence wavelength conversion film according to claim 1, 2 or 3.

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