WO2023158509A2

WO2023158509A2 - Wavelength conversion film and display device including the same

Info

Publication number: WO2023158509A2
Application number: PCT/US2022/079751
Authority: WO
Inventors: Jie Cai; Shijun Zheng; Jeffrey R. HAMMAKER; Hiep Luu; Xinliang DING; Tissa Sajoto; Jan SASKA; Peng Wang
Original assignee: Nitto Denko Corporation
Priority date: 2021-11-12
Filing date: 2022-11-11
Publication date: 2023-08-24
Also published as: CN118251979A; WO2023158509A3; TW202334720A

Abstract

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

Description

WAVELENGTH CONVERSION FILM AND DISPLAY DEVICE INCLUDING THE SAME

Inventors: Jie Cai, Shijun Zheng, Jeffrey Fl. Hammaker, Hiep Luu, Xinliang Ding, Tissa Sajoto, Jan Saska, and Peng Wang

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Application No. 63/278,923, filed November 12, 2021 , which is incorporated by reference herein in its entirety.

FIELD

[0002] The present disclosure relates to wavelength converting films and lightemitting display devices including the same.

BACKGROUND

[0003] Photoluminescent substances are materials that emit light after absorbing energy in the form of light or electricity. Photoluminescent substances may be classified as inorganic photoluminescent substances (or dyes), organic photoluminescent dyes, nanocrystal photoluminescent substances, and the like, depending on the components forming the photoluminescent substance and light emission mechanism.

[0004] Recently, a variety of attempts to modify the spectrum of a light source using such photoluminescent substances have been described. Photoluminescent substances absorb specific wavelengths of light from a light source, convert this to light of a longer wavelength in a visible region, and emit the light. Depending on the light emission properties of the photoluminescent substance, the brightness, color purity, color gamut, etc., of the emitted light may be greatly enhanced. An inorganic photoluminescent substance may be formed with a parent compound such as a sulfide, an oxide or a nitride, and activator ions, and may be used in high-quality display apparatuses having excellent physical and chemical stability and high reproduction of color purity. However, there are disadvantages in that these inorganic photoluminescent substances are very high-priced, have low light emission efficiency, and the emission of light in a near ultraviolet or blue region of 400 nm or higher is limited. [0005] Quantum dot technology has achieved a high level of quantum efficiency and color gamut. However, cadmium-based quantum dots can be very toxic and are restricted in many countries due to health safety issues. In addition, some quantum dots have much lower quantum efficiency in converting blue LED light to green or red light. Furthermore, quantum dots can have a low stability when exposed to moisture and oxygen, often requiring expensive encapsulation processes. The cost of quantum dots may be high because it can be difficult to control the size uniformity during their production.

[0006] Therefore, there is a need for new photoluminescent films having a high quantum efficiency, high color gamut output, and lower cost relative to quantum dot and other existing photoluminescent dye containing films.

SUMMARY

[0007] Some embodiments include a wavelength converting film comprising: a polymer matrix; a first photoluminescent dye, the first photoluminescent dye absorbing blue wavelength light and narrowly emitting green wavelength light with an emission spectrum having a full width half maximum of less than 40 nm; a second photoluminescent, the second photoluminescent dye absorbing blue or green wavelength light and narrowly emitting a red wavelength light with an emission spectrum having a full width half maximum of less than 55 nm; and light scattering centers; wherein the first photoluminescent dye, the second photoluminescent dye, and the light scattering centers are disposed within the polymer matrix.

[0008] In some embodiments, the first photoluminescent dye may comprise an optionally substituted BODIPY group, a linking group, and an optionally substituted isoquinoline group. In some embodiments, the first photoluminescent dye can be:

Chemical Formula: C55H₄₈BF₂N₃O9 Exact Mass: 943.35 Molecular Weight: 943.81 (FD-1), and/or

Chemical Formula: C60H47BF5NaO9 Exact Mass: 1059.33 Molecular Weight: 1059.85 (FD-3).

[0009] In some embodiments, the first photoluminescent dye may comprise an optionally substituted BODIPY group, a linking group, and an optionally substituted naphthalic imide group. In some embodiments, the first photoluminescent dye may

Chemical Formula: C₆7H59BF2N4O₈ Exact Mass: 1096.44 Molecular Weight: 1097.04

(FD-2).

[0010] In some embodiments, the second photoluminescent dye may comprise an optionally substituted BODIPY group, a linking group, and an optionally substituted isoquinoline group. In some embodiments, the second photoluminescent dye may be:

[0011] In some embodiments, the second photoluminescent dye may comprise an optionally substituted BODIPY group, a linking group, and an optionally substituted naphthalimide group. In some embodiments, the second photoluminescent dye may be:

[0012] In some embodiments, the second photoluminescent dye may comprise an optionally substituted BODIPY group, a linking group, and an optionally substituted perylene group. In some embodiments, the second photoluminescent dye may comprise:

[0013] In some embodiments, the film may have an internal quantum yield of greater than 80%. In some embodiments, the film may have an external quantum yield of greater than 50%. In some embodiments, the film may have a color gamut of greater than 90% of BT.2020 standard or Rec. 2020 standard. In some embodiments, the film may have a thickness of less than 50 microns.

[0014] Some embodiments include a light emitting device comprising a photoluminescent wavelength converting film described herein.

[0015] Some embodiments include a backlit device having a blue light source, the device comprising a photoluminescent wavelength converting film described herein.

[0016] These and other embodiments are described in greater detail below.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic of an embodiment of a display device incorporating the improved WLC film described herein.

FIG. 2 is a schematic of an embodiment of a display device incorporating the improved WLC film described herein.

FIG. 3 is a schematic of an embodiment of a display device incorporating the improved WLC film described herein.

FIG. 4 is a schematic of a testing configuration including film embodiments described herein. DETAILED DESCRIPTION

[0017] The present disclosure relates to wavelength converting films comprising photoluminescent compounds (or dyes) having a high quantum efficiency, high color gamut output, and low cost.

[0018] The term “BODIPY” as used herein, refers to an optionally substituted chemical moiety with the formula:

wherein the rings indicated by dashed lines are optional.

[0019] 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-indacene.

[0020] The term “perylene” or “perylene derivative” as used herein, refers to an optionally substituted chemical moiety with the formula:

[0021] The term “naphthalic imide” or “naphthalic acid derivative” or as used herein, refers to an optionally substituted chemical moiety with the formula:

wherein X = NR, wherein R may be a linking group or an aryl group.

[0022] The term “isoquinoline” or “isoquinoline derivative” or “xanthenoisoquinoline derivative” as used herein, refers to an optionally substituted chemical moiety with the formula:

wherein X = NR, wherein R may be a linking group or an aryl group, and Y may be a hydrogen group, C1-C3 alkyl, or an aryl group, e.g., a benzyl group.

[0023] The term “naphthalimide” or “naphthalimide derivative” as used herein, refers to an optionally substituted chemical moiety with the formula:

wherein R° may be a hydrogen (H), a substituted or unsubstituted aryl, or a CF3, wherein X may be an oxygen (O) or a sulfur (S), wherein R¹ can be a hydrogen, a substituted or unsubstituted aryl (such as phenyl, fluoroalkylphenyl (e.g., 4-trifluoromethylphenyl), etc.), or a C1-C5 alkyl. [0024] In some embodiments, the BODIPY moiety is connected to a perylene moiety with a linking group. In some embodiments, the BODIPY moiety is connected to a naphthalic imide moiety with a linking group. In some embodiments, the BODIPY moiety is connected to an isoquinoline moiety with a linking group. In some embodiments, the BODIPY moiety is connected to a naphthalimide moiety with a linking group.

[0025] Use of the term “may” or “may be” should be construed as shorthand for “is” or “is not” or, alternatively, “does” or “does not” or “will” or “will not,” etc. For example, the statement “the film may comprise scattering centers disposed within the polymer matrix” should be interpreted as, for example, “In some embodiments, the film comprises scattering centers disposed within the polymer matrix,” or “In some embodiments, the film does not comprise scattering centers disposed within the polymer matrix.”

[0026] The term ITU-R Recommendation BT.2020 (more commonly known by the abbreviations Rec. 2020 or BT.2020) refers to a 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 wavelength of the Rec. 2020 primary colors 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% (area within the determined triangle) of the CIE 1931 color space. Rec. 2020 uses CIE Standard llluminant D65 as the white point and the following color coordinates: Xw = 0.3127; Yw = 0.3290; XR = 0.708, YR = 0.292, XG = 0.17, YG = 0.797; XB = 0.131 ; YB = 0.046.

[0027] Some embodiments include a wavelength converting film comprising a polymer matrix, a first organic photoluminescent compound, and a second organic photoluminescent compound. In some embodiments, the film may comprise a first organic photoluminescent dye that is green-emitting and has an emissive peak with a full width half maximum of less than 30 nm or 40 nm. In some embodiments, the film may comprise a second organic photoluminescent dye that is a red-emitting and has an emissive peak with a full width half maximum of less than 55 nm. In some embodiments, the film may comprise 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 centers are disposed within the polymer matrix. In some embodiments, the film provides a high quantum yield. In some embodiments, the film provides a broad color gamut of greater than 90%. Suitable means to determine the percent color gamut is to measure the area under the generated 1931 CIE color space. In some embodiments, the film may be between 89% and 99.9% color gamut, e.g., 91 -92%, 92-93%, 93-94%, 98-99.9%, 89- 93%, 93-96%, and or 96-99.9%, or a range bounded by any of these values. Some embodiments include an LCD backlight comprising the aforementioned film.

[0028] In some embodiments, the film may comprise a polymer matrix. In some embodiments, the polymer matrix may have a transparency of greater than 75%, greater than 80%, greater than 90%, or greater than 95%. In some embodiments, the polymer matrix may comprise a hydrophilic or a hydrophobic polymer. In some embodiments, the polymer matrix may comprise polyvinyl butyral, polyvinyl acetate, polyvinyl alcohol, or a polyacrylate. In some embodiments the polymer matrix may comprise polyvinyl butyral (PVB). In some embodiments, the polyacrylate may be a polyalkylacrylate. In some embodiments, the polyalkylacrylate may be a polymethylmethacrylate (PMMA).

[0029] In some embodiments, the photoluminescent compound (and/or the photoluminescent wavelength converting film comprising the photoluminescent compound) has a narrow absorption or emission band, such that a small amount of visible wavelength light is emitted. The absorption or emission band may be characterized by the full width at half maximum (FWHM). In the present disclosure, FWHM defines the width, in nanometers, of the absorption or emission spectrum at half the absorption or emission peak wavelength. In some embodiments, the photoluminescent compound has an absorption band with a FWHM value that is less than or equal to 50 nm, less than or equal to 40 nm, less than or equal to 35 nm, less than or equal to 30 nm, or less than or equal to 25 nm when dispersed in the substantially transparent polymer matrix. In some embodiments, the photoluminescent compound has an emission band with a FWHM value that is 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 the substantially transparent polymer matrix. [0030] In some embodiments, the film may comprise a first organic photoluminescent compound (or dye). In some embodiments, the first organic photoluminescent dye (and/or the photoluminescent wavelength converting film comprising the first organic photoluminescent dye) may have an emissive peak between 510 and 520 nm, or 520 and 530 nm, or a range bounded by any of these values (green light emitting). In some embodiments, the emissive spectrum of the first organic photoluminescent dye and/or the photoluminescent wavelength converting film may have a full width half maximum (FWHM) of less than 35 nm, less than 30 nm, or less than 20 nm.

[0031] In some embodiments, the first organic photoluminescent dye may comprise an optionally substituted BODIPY group, a linking group, and an optionally substituted isoquinoline group. In some embodiments, the optionally substituted isoquinoline group may be an optionally substituted isoquinoline derivative group. In some embodiments, the optionally substituted isoquinoline group may be an optionally substituted xanthenoisoquinoline derivative group. In some embodiments, the optionally substituted BODIPY group is covalently bonded to the linking group. In other embodiments, the linking group is covalently bonded to the optionally substituted isoquinoline group. In other embodiments, the linking group is covalently bonded to the optionally substituted isoquinoline derivative group. In other embodiments, the linking group is covalently bonded to the optionally substituted xanthenoisoquinoline derivative group.

[0032] In some embodiments, the first organic photoluminescent dye may comprise an optionally substituted BODIPY group, a linking group and an optionally substituted naphthalic imide group. In some embodiments, the optionally substituted naphthalic imide group may be an optionally substituted naphthalic acid derivative group. In some embodiments, the optionally substituted BODIPY group is covalently bonded to the linking group. In other embodiments, the linking group is covalently bonded to the optionally substituted naphthalic imide group. In other embodiments, the linking group is covalently bonded to the optionally substituted naphthalic acid derivative group.

[0033] In some embodiments, the first organic photoluminescent dye can be selected from the photoluminescent dyes described in co-pending U.S. Provisional Application No. 63/152,309, filed February 22, 2021 , which is incorporated herein by reference for its discussion of photoluminescent dyes and to U.S. Provisional Application No. 63/278,904, filed November 12, 2021 , Attorney Docket No. N3253.10133US02, which is incorporated herein by reference.

[0034] In some embodiments, the first organic photoluminescent dye may be selected from FD-1 , FD-2, or FD-3:

Chemical Formula: C55H₄₈BF₂N3O9 Exact Mass: 943.35 Molecular Weight: 943.81 (FD-1 ),

Chemical Formula: C₆₇H59BF2N₄O₈ Exact Mass: 1096.44 Molecular Weight: 1097 04 (FD-2),

Chemical Formula: C60H47BF5NaO9 Exact Mass: 1059.33 Molecular Weight: 1059.85

(FD-3), or any combination thereof.

[0035] In some embodiments, the wavelength converting film may comprise a second organic photoluminescent dye. In some embodiments, the second organic photoluminescent dye (and/or the photoluminescent wavelength converting film comprising the second organic photoluminescent dye) may have an absorption peak between 400 and 470 nm (blue light absorbing). In some embodiments, the second organic photoluminescent dye (and/or the photoluminescent wavelength converting film comprising the second organic photoluminescent dye) may have an emissive peak between 610 and 620 nm, or 620 and 630 nm, or a range bounded by any of these values (red light emitting). In some embodiments, the emissive spectrum of the second organic photoluminescent dye and/or the photoluminescent wavelength converting film may have a full width half maximum (FWHM) of less than 65nm, 55 nm, 50 nm, 45 nm, less than 40 nm, or less than 35 nm.

[0036] In some embodiments, the second organic photoluminescent dye may comprise a BODIPY group, a linking group and a perylene group. In some embodiments, the perylene group may be a perylene derivative group. In some embodiments, the BODIPY group is covalently bonded to the linking group. In other embodiments, the linking group is covalently bonded to the perylene group. In other embodiments, the linking group is covalently bonded to the perylene derivative group.

[0037] In some embodiments, the second organic photoluminescent dye may comprise a BODIPY group, a linking group and an isoquinoline group. In some embodiments, the isoquinoline group may be an isoquinoline derivative group. In some embodiments, the BODIPY group is covalently bonded to the linking group. In other embodiments, the linking group is covalently bonded to the isoquinoline group. In other embodiments, the linking group is covalently bonded to the isoquinoline derivative group.

[0038] In some embodiments, the second organic photoluminescent dye may comprise a BODIPY group, a linking group and a naphthalimide group. In some embodiments, the naphthalimide group may be an naphthalimide derivative group. In some embodiments, the BODIPY group is covalently bonded to the linking group. In other embodiments, the linking group is covalently bonded to the naphthalimide group. In other embodiments, the linking group is covalently bonded to the naphthalimide derivative group.

[0039] In some embodiments, the first organic photoluminescent dye can be selected from the photoluminescent dyes described in co-pending U.S. Provisional Application No. 63/248,863, filed September 27, 2021 , which is incorporated herein by reference for its discussion of photoluminescent dyes, to U.S. Provisional Application No. 63/278,904, filed November 19, 2021 , Attorney Docket No. N3252.10147US02, which is incorporated herein by reference, and to PCT Patent Publication W02020/210761 , which is incorporated herein by reference. In some embodiments, the second organic photoluminescent dye may be selected from SD-1 , SD-2, SD-3, SD-4, or SD-5:

Chemical Formula: C₆₁ H42BCl2F₂N₃O₅

Molecular Weight: 1016.73

(SD-4),

any combination thereof.

[0040] In some embodiments, the first photoluminescent compound may absorb light from within the UV/blue absorption spectrum and emit light within the green emission spectrum, enhancing the perceived emitted green light. In other embodiments, the second photoluminescent compound may absorb light from within the green and/or blue absorption spectrum and emit light within the red emission spectrum, enhancing the perceived emitted red light. In some embodiments, the first and second photoluminescent dyes may absorb light from within the UV/blue absorption spectrum and emit light in other wavelengths, wherein the combined resultant light may be perceived as white light. In some examples, the perceived white light may have a color temperature described as cool. In some embodiments, the perceived white light may have a color temperature described as warm.

[0041] In some embodiments, first photoluminescent dye and second photoluminescent dye may absorb about 60-70% of a light source emitting light within the blue spectrum. In some embodiments, the resultant white light comprises 30-50% blue light, 20-30% red light emitted from the wavelength converting film, and 20-30% green light emitted from the wavelength converting film. The thickness of the film may be adjusted to tune the percentage of blue light absorbed by the wavelength converting film and the percentage of blue light that passes through the wavelength converting film to comprise the resultant white light. In some embodiments, the photoluminescent wavelength converting film may have any suitable thickness, such as less than about 500 pm, less than about 200 pm, or less than about 100 pm, such as about 1 -20 pm, about 10-40 pm, about 20-30 pm, about 30-40 pm, about 40-50 pm, about 50-80 pm, about 80-120 pm, about 120-200 pm, about 200-300 pm, or about 300-500 pm.

[0042] In some embodiments, the thickness of the wavelength converting film may be reduced or increased according to the Beer-Lambert law. In particular, the Beer-Lambert law may be used to derive the relationships between the thickness of the film and the concentration of the first photoluminescent dye and second photoluminescent dye to achieve 60-70% of blue light emitting from a light source. In some embodiments, the dye concentration may be decreased, and the thickness may be increased to permit absorption of 60-70% of the blue light. In some embodiments, the dye concentration may be increased, and the thickness may be decreased to permit absorption of 60-70% of the blue light. In some embodiments, the photoluminescent wavelength converting film may have a suitable thickness of greater than 20 pm and less than 30 pm for most dye concentrations as shown in Table 1 of the Examples section below.

[0043] In some embodiments, the length of the linking group can be tuned to optimize the solubility of the first photoluminescent dye and the second photoluminescent dye. In some embodiments, the solubility of the first photoluminescent dye and the second photoluminescent dye may be greater than 0.15%. In some embodiments, the solubility of the first photoluminescent dye and the second photoluminescent dye may be about .03%-0.8%, about 0.8%-2%, or about 2%-3%, or a solubility in a range bounded by any of the values above.

[0044] The ratio of the amounts of the first photoluminescent dye and the second photoluminescent dye may be adjusted to tune the color properties of the photoluminescent wavelength converting film. For example the weight ratio of the first photoluminescent dye to the second photoluminescent dye may be about 0.01 - 100 (1 mg of the first photoluminescent dye and 100 mg of the second photoluminescent dye is a ratio of 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.

[0045] 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 scattering materials having a refractive index (Rl) different than the refractive index of the polymer matrix material. Scattering material may be materials whose refractive index is different from Rl of polymer matrix. Scattering material may be useful in increasing external quantum yield, e.g., by reducing total internal reflection.

[0046] In some embodiments, the difference in Rl 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.

[0047] In some embodiments, the scattering material may be silicone beads. In some embodiments, the scattering centers may comprise air voids defined within the polymer matrix. In some embodiments, the scattering centers may have an average diameter of between 1 micron (pm) and 10 microns (pm), about 1 -2 pm, about 2-3 pm, about 3-4 pm, about 4-5 pm, about 5-6 pm, about 6-7 pm, about 7-8 pm, about 8-9 pm, about 9-10 pm, or about any value in a ranged bounded by any of these values. In some embodiments, the scattering centers may be substantially uniformly dispersed within the polymer matrix. In some embodiments, the top-level portion of the film, for example, the side distal to the blue light emitting source, may have greater than 50% of the scattering centers. In some embodiments, the scattering centers may be uniformly distributed throughout the polymer matrix.

[0048] In some embodiments, a photoluminescent wavelength converting film may have an internal quantum yield (IQE) that is at least about 70%, at least about 80%, or at least about 90%; and/or up to about 80%, up to about 90%, up to about 100%, at the red or the green emission maximum. In some embodiments, a photoluminescent wavelength converting film may have an external quantum yield (EQE) that is at least about 50%, at least about 60%, at least about 70%, at least about 80%, or at least about 90%; and/or up to about 80%, up to about 90%, or up to about 100%, at the red or the green emission maximum.

[0049] In some embodiments, a display device may be represented by a device 10. As shown in Fig. 1 , the device 10 may comprise a light source 12. In some embodiments, the display device 10 may comprise a wavelength converting (WLC) film 16. In some embodiments, the WLC film 16 may be in optical communication with the light source 12, enabling an increased efficacy in transmitting the generated light from the light source 12 to a viewer 20.

[0050] In some embodiments, a display device may be represented schematically by Fig. 2. As shown in Fig. 2, a display device, such as device 10, may comprise a light source 12. In some embodiments, the display device 10 may comprise a back reflector 14. In some embodiments, the display device 10 may comprise a wavelength converting (WLC) film 16. In some embodiments, the display device 10 may comprise a mask 18. In some embodiments, the WLC film 16 may be in optical communication with the light source 12, enabling an increased efficacy in transmitting the generated light from the light source 12 to a viewer 20.

[0051] In some embodiments, a display device may be represented schematically by Fig. 3. As shown in Fig. 3, a display device is described, the device 10, may comprise a light source 12. In some embodiments, the display device 10 may comprise a back reflector 14. In some embodiments, the display device 10 may comprise a wavelength converting (WLC) film 16. In some embodiments, the display device may comprise a mask 18. In some embodiments, the WLC film 16, may be in optical communication with the light source 12, and/or interposed between the light source 12 and a viewer 20, and/or the mask 18, enabling an increased efficacy in transmitting the generated light from the light source 12 to the viewer 20.

[0052] As shown in Fig. 3 and Fig. 4, in some embodiments, the display device 10 may comprise one or more brightness enhancement films (BEF) 22, e.g., Vikuiti brand BEF (3M Minneapolis, MN, USA). In some embodiments, the display device 10 may comprise one or more polarizer and/or brightness enhancement films, e.g., dual brightness enhancement film (DBEF) 24, e.g., DBEF II (3M Minneapolis, MN, USA). In some embodiments, the use of one or more brightness enhancement films may be termed an optical film stack.

[0053] Some embodiments include a method for making an LED light source. In some embodiments, the method may comprise making an undried wavelength shifting polymeric layer with an organic solvent and the photoluminescent dye described herein. In some embodiments, the method may include mixing a polymer and/or a monomer with an organic solvent. In some embodiments, the polymer and/or monomer precursor may be dispersed, dissolved and/or mixed with a solvent. In some embodiments, solvents may be used in manufacture of material layers. 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, xylenes, 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 comprise ethanol, dimethylformamide (DMF), or a combination thereof. In some embodiments, the solvent may be a combination of non-polar and polar solvents.

[0054] In some embodiments, the method may comprise submerging 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 may comprise at least 90% water. In some embodiments, the water may be deionized water. In some embodiments, the undried polymeric photocatalytic WLC layer may be submerged in an aqueous solution for between 5 minutes to about 1 hour.

[0055] In some embodiments, the method may comprise withdrawing the undried polymeric photocatalytic WLC layer from the aqueous solution. In some embodiments, the method may comprise drying the undried polymeric photocatalytic WLC layer. It is believed that making the polymeric photocatalytic WLC layer in this manner provides a plurality of air voids defined in the emissive or distal surface of the polymeric photocatalytic WLC layer. In some embodiments, the air voids are substantially entirely within about 1 micron to about 5 microns from the emissive surface of the polymeric photocatalytic WLC layer. [0056] In some embodiments, the polymer material comprises an aqueous solution of about 2 wt% to about 50 wt% polymer, about 2-5 wt%, about 5-10 wt%, about 10-15 wt%, about 15-20 wt%, about 20-25 wt%, about 25-30 wt%, about 30-35 wt%, about 35-40 wt%, about 40-45 wt%, about 45-50 wt%, about 2.5 to 30 wt%, about 5-15 wt%, about 15-25 wt%, about 25-35 wt%, or about 30 wt% polymer, or about any value in a range bounded by any of these values.

EMBODIMENTS

Embodiment 1. A wavelength converting film comprising: a polymer matrix; a first photoluminescent dye, the first photoluminescent dye absorbing blue wavelength light and narrowly emitting green wavelength light with an emission spectrum having a full width half maximum of less than 30 nm; a second photoluminescent dye, the second photoluminescent dye absorbing blue or green wavelength light and narrowly emitting a red wavelength light with an emission spectrum having a full width half maximum of less than 55 nm; and light scattering centers, wherein the first photoluminescent dye, the second photoluminescent dye, and the light scattering centers are disposed within the polymer matrix.

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

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

Chemical Formula: C55H₄₈BF₂N₃O9 Exact Mass: 943 35 Molecular Weight: 943.81 (FD-1), or

Chemical Formula: C60H47BF5N3O9 Exact Mass: 1059.33 Molecular Weight: 1059.85 (FD-3).

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

Embodiment 5. The wavelength converting film of embodiment 4, wherein the first photoluminescent dye is selected from:

Chemical Formula: C₆7H59BF2N4O₈ Exact Mass: 1096.44 Molecular Weight: 1097.04 (FD-2).

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

Embodiment 7. The wavelength converting film of embodiment 6, wherein the second photoluminescent dye is selected from:

Chemical Formula: C67H46BCI2F2N3O5 Exact Mass: 1091.29 Molecular Weight: 1092.83 (SD-2), or

Chemical Formula: C₆₁H42BCl2F2N₃O₅

Molecular Weight: 1016.73 (SD-4)

Embodiment 8. The wavelength converting film of embodiment 1 , wherein the second photoluminescent dye comprises a BODIPY group, a linking group, and a naphthalimide group.

Embodiment 9. The wavelength converting film of embodiment 8, wherein the second photoluminescent dye is selected from:

Embodiment 10. The wavelength converting film of embodiment 1 , wherein the second photoluminescent dye comprises a BODIPY group, a linking group, and a perylene group.

Embodiment 11. The wavelength converting film of embodiment 8, wherein the second photoluminescent dye is selected from:

Embodiment 12. The wavelength converting film of embodiments 1-11 , wherein the wavelength converting film has an internal quantum yield of greater than 80%.

Embodiment 13. The wavelength converting film of embodiments 1-11 , wherein the wavelength converting film has an external quantum yield of greater than 50%.

Embodiment 14. The wavelength converting film of embodiments 1-11 , wherein the wavelength converting film has a color gamut of greater than 90% of BT.2020 standard

Embodiment 15. The wavelength converting film of embodiments 1-11 , wherein the wavelength converting film has a thickness between 10 gm and 40 gm.

Embodiment 16. A light emitting device comprising the wavelength converting film of embodiments 1 -15.

Embodiment 17. A backlit device having a blue light source, the device comprising the wavelength converting film of embodiments 1 -15.

Examples

[0057] It has been discovered that embodiments of the film including photoluminescent complexes described herein have improved performance as compared to other forms of color conversion films. These benefits are further demonstrated by the following examples, which are intended to be illustrative of the disclosure only but are not intended to limit the scope or underlying principles in any way.

Synthesis of first photoluminescent dyes

Synthesis procedure for Compound FD-1

[0058] A mixture of ethyl 2,4-dimethyl-1 H-pyrrole-3-carboxylate (1.0g, 6.0 mmol), 4-hydroxy-2,6-dimethylbenzaldehyde (0.449 g, 3.0 mmol) and tosylic acid (50 mg, 0.29mmol) in 50 mL 1 ,2-dichloroethane was degassed and stirred at room temperature overnight. LCMS analysis shows that one main peak with m/e+ = 467.

[0059] To the resulting solution, DDQ (0.817g, 3.6 mmol) was added then stirred for 30 min at room temperature. LCMS analysis shows that all starting material was converted to desired product with m/e+ =465.

[0060] With ice-bath cooling, 1 .7 mL triethylamine and 2.2 mL BF3-diethy I ether were added sequentially to the mixture from step 2. The whole was heated at 50 -C for one hour. LCMS analysis shows -30% conversion. To the mixture, additional 1 mL triethylamine and 1 mL BF3-diethyl ether was added, the whole was heated at 50 ^ºC for additional one hour. LCMS analysis shows that all stating materials were converted to desired BODIPY product with m/e-i- = 513, m/e- = 512. The reaction mixture was submitted directly to silica gel and purified by flash chromatography using eluents of hexanes/ethyl acetate (0% -> 30% ethyl acetate). The main desired peak was collected, and removal of solvents gave an orange solid (1.0 g, in 65% yield). LCMS (APCI): calculated for C27H32BF2N2O5 (M+H): 513.2; Found: 513. 1 H NMR (400 MHz, Chloroform-d) 5 7.26 (s, 3H), 6.68 (s, 2H), 4.29 (q, J = 7.1 Hz, 4H), 2.84 (s, 6H), 2.05 (s, 6H), 1.34 (t, J = 7.1 Hz, 6H).

Compound FD-1.2:

[0061] A mixture of 2-nitrophenol (6.6g, 48 mmol), KOH powder (2.4g, 43 mmol) was mixed and stirred under vacuum for 30 min, then copper powder (0.4 g) was added, followed by 100 mL anhydrous DMF. The mixture was stirred for 5 min, then 4-chloronaphthalic anhydride (5.1 g, 22 mmol) was added. The whole was degassed then heated at reflux for 1.5 hr. After cooled to room temperature, 100mL 20% hydrochloride acid was added dropwise into the resulted reaction mixture, which was allowed to sit for 2 hrs. The precipitate was collected by filtration, then was dried under vacuum overnight to give yellow brown solid (4.6 g). It was further purified by stirred in refluxed acetic acid (50 mL) for 2 hrs, then cooled to room temperature. Filtration and dried in air gave a yellow solid (3.0g, in 41% yield). Confirmed by LCMS (APCI): calculated for C18H10NO6 (M+H): 336.0; Found: 336. ¹H NMR (400 MHz, Chloroform- d) 5 8.80 (dd, J = 8.5, 1 .2 Hz, 1 H), 8.72 (dd, J = 7.3, 1 .2 Hz, 1 H), 8.50 (d, J = 8.2 Hz, 1 H), 8.19 (dd, J = 8.2, 1 .7 Hz, 1 H), 7.90 (dd, J = 8.5, 7.3 Hz, 1 H), 7.79 (td, J = 7.9, 1 .7 Hz, 1 H), 7.54 (td, J = 8.0, 1 .3 Hz, 1 H), 7.39 (dd, J = 8.3, 1 .2 Hz, 1 H), 6.89 (d, J = 8.2 Hz, 1 H).

Compound FD-1.3:

[0062] A mixture of compound FD-1.2 4-(2-nitrophenoxyl)-1 ,8-naphthalic anhydride (2.0g, 6 mmol) and iron powder (<1 Oum, 0.91 g, 16 mmol) in acetic acid (75 mL) was heated to reflux for 30 min. The resulting solution was poured into water (220mL). The resulted precipitate was collected by filtration and washed with water and dried thoroughly in air then under vacuum to afford a yellow solid (1 .65g, in 90% yield). Confirmed by LCMS (APCI): calculated for C18H12NO4 (M+H): 306.1 ; Found: 306.

Compound FD-1.4:

[0063] Compound FD-1.3 4-(2-aminophnoxy)-1 ,8-naphthalic anhydride (1.5g, 4.9mmol), was dispersed in acetic acid (35mL) and cooled to 0 ^ºC. While being stirred, precooled hydrochloric acid (3mL, 37 mmol) was added, then sodium nitrite solution (3.29g, 46 mmol) in 12 mL water was added dropwise at 0 ^ºC. The whole was stirred for one hour at 0 -C, then was transferred into additional funnel, and dropped into a refluxed copper sulfate solution (5.08g, 20 mmol, in 50 mL water) over one-hour period. After cooled to room temperature, the precipitate was collected by filtration, washed with water, then dried in air then in vacuum to give a yellow solid (0.92g, in 65% yield). Confirmed by LCMS (APCI): calculated for C18H8O4 (M-): 288.0; Found: 288. ¹H NMR (400 MHz, Chloroform-d) 5 8.61 (dd, J = 17.1 , 8.1 Hz, 2H), 8.09 (d, J = 8.0 Hz, 1 H), 7.97 (d, J = 7.9 Hz, 1 H), 7.59 (t, J = 7.7 Hz, 1 H), 7.40 (t, J = 8.1 Hz, 2H), 7.33 (d, J = 8.4 Hz, 1 H).

Compound FD-1.5:

[0064] A mixture of compound FD-1.4 1 H,3H-isochromeno[6,5,4- mna]xanthene-1 ,3-dione (100mg, 0.347 mmol), 4-(4-aminophenyl)butanoic acid (125 mg, 0.7 mmol) in 5 mL DMF was heated at 165 ^ºC for 2.5 hrs in microwave reactor. To the mixture, 15 mL acetone was added, the resulted precipitate was collected by filtration and dried in air to give a yellow solid (120 mg, in 77% yield). Confirmed by LCMS (APCI): calculated for C28H19NO5 (M-): 449.1 ; Found: 449. ¹H NMR (400 MHz, DMS0-d6) 5 8.38 (d, J = 41 .6 Hz, 4H), 7.81 - 6.97 (m, 8H), 2.69 - 2.64 (m, 2H), 2.26 (t, J = 7.2 Hz, 2H), 1 .87 (p, J = 7.2 Hz, 2H).

Compound FD-1 :

[0065] A mixture of compound FD-1.5 (45mg, 0.1 mmol), compound FD-1.1 (40 mg, 0.078 mmol), DMAP/TsOH salt (59mg, 0.2 mmol) and DIG (0.1 mL, 0.63 mmol) in 5 mL DOM was stirred room temperature overnight, then at 45 ^ºC for 2 hrs. The reaction mixture was submitted to silica gel and purified by flash chromatography using eluents of DCM/ethyl acetate (0% to 10% ethyl acetate). The desired product peak was collected and concentrated under reduced pressure. The resulting solid was further washed with methanol and dried in air to give an orange solid (46 mg, in 62% yield). Confirmed by LCMS (APCI): calculated for C55H49BF2N3O9 (M+H): 944.3; Found: 944. ¹ H NMR (400 MHz, d2-TCE) 6 8.54 (dd, J = 18.7, 8.1 Hz, 2H), 7.40 - 7.25 (m, 5H), 7.20 (d, J = 8.3 Hz, 2H), 6.93 (s, 2H), 4.19 (q, J = 7.1 Hz, 4H), 2.80 (t, J = 7.6 Hz, 2H), 2.75 (s, 6H), 2.62 (t, J = 7.4 Hz, 2H), 2.10 (t, J = 7.6 Hz, 2H), 2.06 (s, 6H), 1.65 (s, 6H), 1.25 (t, J = 7.1 Hz, 6H).

Synthesis procedure for Compound FD-2

Compound FD-2.1 :

[0066] A mixture of ethyl 2,4-dimethyl-1 H-pyrrole-3-carboxylate (1.0g, 6.0 mmol), 4-hydroxy-2,6-dimethylbenzaldehyde (0.449g, 3.0 mmol) and p- toluenesulfonic acid (p-TsOH) (50 mg, 0.29mmol) in 50 mL dichloroethane (DCE) was degassed and stirred at room temperature overnight. Liquid chromatography-Mass spectroscopy (LCMS) analysis shows that reaction completed with main peak of m/e⁺ = 467. To the mixture obtained above, 2,3-Dichloro-5,6-dicyano-1 ,4-benzoquinone (DDQ) (0.817g, 3.6 mmol) was added and the whole was stirred at room temperature for 30 min. LCMS analysis indicates that reaction completed with main peak of m/e⁺ = 465. With ice-batch cooling, to the mixture obtained above, triethylamine (1.7 mL, 12 mmol) and BFs-diethyl ether (2.2 mL, 18 mmol) was added, and the resulting mixture was stirred at 50 °C for one hour. Additional 1 mL triethylamine and 1 mL BFs-diethyl ether were added, and the whole was heated for additional one hour. LCMS analysis indicates that all dipyrrolemethine starting material was converted to BODIPY product with m/e⁺ = 513. After cooled to room temperature, the reaction mixture was submitted to silica gel and purified by flash chromatography using eluents of hexanes/ethyl acetate (0% to 30% ethyl acetate). The desired fraction was collected. After removal of solvents, the desired product was obtained as orange solid (1 .0g, in 65% yield). ¹ H NMR (400 MHz, Chloroform-d) 5 6.68 (s, 2H), 4.29 (q, J = 7.1 Hz, 4H), 2.84 (s, 6H), 2.05 (s, 6H), 1 .34 (t, J = 7.1 Hz, 6H). LCMS (APCI+): calculated for C27H32BF2N2O5 (M+H) = 513.2; Found: 513.

Compound FD-2:

[0067] A mixture of Compound FD-2.1 (100mg, 0.195mmol), FD-2.2 (4-(4-(6- (4-(diphenylamino)phenyl)-1 ,3-dioxo-1 H-benzo[de]isoquinolin-2(3H)- yl)phenyl)butanoic acid) (132 mg, 0.22 mmol), diisopropylcarbodiimide (DIG) (0.1 mL, 0.63 mmol) and dimethylaminopyridine (DMAP)Zp-TsOH (1 18 mg, 0.4 mmol) in dichloromethane (DCM) (6mL) was stirred at room temperature overnight, then loaded on silica gel, and purified by flash chromatography using eluents of DCM/ethyl acetate (0% to 5% ethyl acetate). The desired main orange color faction was collected. After removal of solvents, the resulting solid was reprecipitated in DCM/MeOH. The desired product was obtained after filtration and dried in air as orange solid (145 mg, 68% yield). ¹H NMR (400 MHz, d2-TCE) 6 8.56 (dd, J = 7.4, 4.7 Hz, 2H), 8.43 (d, J = 8.3 Hz, 1 H), 7.79 - 7.64 (m, 2H), 7.41 - 7.18 (m, 10H), 7.18 - 7.12 (m, 6H), 7.03 (t, J = 7.3 Hz, 2H), 6.93 (s, 2H), 4.19 (q, J = 7.1 Hz, 4H), 2.81 (t, J = 7.6 Hz, 2H), 2.75 (s, 6H), 2.62 (t, J = 7.4 Hz, 2H), 2.1 1 (t, J = 7.5 Hz, 2H), 2.06 (s, 6H), 1 .65 (s, 6H), 1 .25 (t, J = 7.1 Hz, 6H). LCMS (APCI-): calculated for C67H59BF2N4O8 (M-) = 1096.4; Found: 1096.

Synthesis procedure for Compound FD-3

Procedure of FD-3.1 synthesis - 2-(4-(9-bromo-1 ,3-dioxo-1 H-xantheno[2,1 ,9- def] isoquinolin-2(3H)-yl)phenyl)acetic acid:

[0068] A mixture of SD-2.6 (400.0 mg, 1.1 mmol), 4-aminophenylacetic acid (329.4 mg, 2.2 mmol) and DMAP (9.3 mg, 0.080 mmol) in DMF (8 mL) was degassed at room temperature. Then the mixture was heated up to 165 -C and has been kept at this temperature for 3 hrs. TLC and LCMS showed -95% conversion without observable side-reaction. The mixture was cooled down to 50 ^ºC. Then it was poured into an acetone solution (40 mL), which has been pre-chilled by water-ice bath. The mixture was kept at 0 -C for 2 hrs and was been kept stirring at room temperature overnight. The solid was collected through vacuum filtration and washed by acetone (4 mL). And it was dried by vacuum oven at 100 ^ºC for 3 hrs to provide the pure compound FD-3.1 as a yellow brown solid 395.0 mg, 73% yield. MS (APCI): calculated for C₂6Hi4BrNO₅ ([M+H]+) = 500 found: 500. ¹H NMR (400 MHz, CDCI2CDCI2) 6 8.65 (d, J = 8.0 Hz, 1 H), 8.62 (d, J = 8.0 Hz, 1 H), 8.21 (dd, J = 6.4 Hz, 2.4 Hz, 1 H), 7.99 (bs, 1 H), 7.95 (t, J = 7.6 Hz, 1 H), 7.67 (dd, J = 8.4 Hz, 2.4 Hz, 1 H), 7.53 (d, J = 8.0 Hz, 2H), 7.37 (d, J = 8.4 Hz, 1 H), 7.32 (m, 3H), 2.94 (s, 2H).

Procedure of compound SD-5.1 synthesis - 2-(4-(1,3-dioxo-9-(4- (trifluoromethyl)phenyl)-1 H-xantheno[2,1 ,9-def]isoquinolin-2(3H)- yl)phenyl)acetic acid:

[0069] A 100 mL vial was fitted with a stir bar. To the vial, compound FD-3.1 (400.0 mg, 0.80 mmol), 4-(trifluoromethyl)phenylboronic acid (262.2 mg, 1.6 mmol), Pd(dppf)CI₂ (41 .0 mg, 0.056 mmol) and K2CO3 (298.0 mg, 2.2 mmol) in THF/DMF/H2O (22 ml/ 4.4 ml/ 2.2 ml) was degassed at room temperature. The reaction mixture was heated up to 80 ^ºC and the reaction has been kept at this temperature overnight. TLC was used to monitor the reaction. After the completion, the reaction was worked up by the addition of 0.1 N HCI (150 ml) and EtOAc (150 ml). The aqueous phase was further extracted by THF (150 ml*3). The combined organic phases were dried over anhydrous Na2SO4, concentrated under rotavapor and purified by flash chromatography, using DCM in EtOAc (0-40%, with 0.1 % TFA) as an eluent to provide the pure RL-naphthalimide derivative SD-5.1 as a yellow/yellow brown solid. 363.0 mg, 80% yield. MS (APCI): calculated for C33H18F3NO5 ([M+H]+) = 566 found: 566. ¹ H NMR (400 MHz, DMSO-d6) 8.76 (m, 1 H), 8.56 (m, 2H), 8.52 (dd, J = 8.0 Hz, J = 3.2 Hz, 1 H), 8.15 (m, 2H), 8.06 (m, 1 H), 7.94 (d, J = 8.0 Hz, 2H), 7.66 (dd, J = 8.0 Hz, J = 4.0 Hz, 1 H), 7.53 (m, 1 H), 7.45 (d, J = 8.0 Hz, 2H), 7.33 (d, J = 8.0 Hz, 2H), 3.72 (s, 2H).

Procedure for Compound FD-3:

[0070] A mixture of compound SD-5.1 (50 mg, 0.089 mmol), compound FD-2.1 (30 mg, 0.059 mmol), DMAP/TsOH salt (15 mg, 0.051 mmol) and EDC-HCI (60 mg, 0.31 mmol) in 5 mL DCM was stirred at room temperature overnight. The reaction mixture was submitted to silica gel and purified by flash chromatography using eluents of DCM/ethyl acetate (0% to 10% ethyl acetate). The desired product peak was collected and concentrated under reduced pressure. The resulting solid was re precipitated with ethyl acetate/methanol and dried in air to give an orange solid (45mg, in 72%). LCMS (APCI-): calculated for C60H47BF5N3O9: 1059.33; Found: 1059. ¹ H NMR (400 MHz, Methylene Chloride-d2) 6 8.73 (d, J = 7.9 Hz, 1 H), 8.66 (d, J = 8.3 Hz, 1 H), 8.39 (d, J = 2.2 Hz, 1 H), 8.17 (d, J = 8.0 Hz, 1 H), 7.86 (dt, J = 11 .4, 8.4 Hz, 5H), 7.64 (d, J = 8.3 Hz, 2H), 7.57 (d, J = 8.6 Hz, 1 H), 7.43 (d, J = 8.3 Hz, 1 H), 7.41 - 7.35 (m, 2H), 7.09 (s, 2H), 4.30 (q, J = 7.1 Hz, 4H), 4.05 (s, 2H), 2.84 (s, 6H), 2.18 (s, 6H), 1 .77 (s, 6H), 1 .36 (t, J = 7.1 Hz, 6H).

Synthesis Procedures of Second Photoluminescent Dyes

Synthesis Procedure of Compound SD-1

Compound SD-1.1 (2-(4-bromophenyl)-4-phenyl-1 H-pyrrole): was synthesized according to literature procedure: Synlett, 2016, 27(1 1 ), 1738-1742.

Compound SD-1 .2:

[0071] A mixture of SD-1.1 (2-(4-bromophenyl)-4-phenyl-1 H-pyrrole) (1.0g, 3.36 mmol), 2,4,6-trimethylbenzaldehyde (0.249 g, 1 .68 mmol) and tosylic acid (50mg) in 1 ,2-dichloroethane (80 mL) was heated at 50 ^ºC for 24 hrs. LCMS analysis shows that the main peak is desired product with m/e⁺ = 727.To the mixture, DDQ (454 mg, 2 mmol) was added, and stirred for one hour at room temperature. LCMS analysis shows that the reaction completed with one main peak of m/e- = 724. To the mixture, triethylamine (0.85 mL, 6 mmol), BFs-diethyl ether (1.1 mL, 9mmol) were added at 0 °C. The whole was heated at 50 ^ºC for one hour. Another potion of triethylamine (0.5 mL) and B F3-d iethy I ether (0.5 mL) were added, and the mixture was heated at 50 ^ºC for additional one hour. LCMS shows that the reaction completed with main peak of m/e- = 772. The mixture was diluted with 50 mL DCM, then washed with water twice, brine once, then concentrated to 100 mL and loaded onto silica gel, purified by flash chromatography using eluents of hexanes/DCM (40% to 100% DCM). The main desired peak was collected, after removal of solvent under reduced pressure, desired product was obtained as a purple solid (1.06g, in 81.6% yield). Confirmed by LCMS (APCI): calculated for C42H₃₁BBr₂F₂N₂ (M-): 770.1 ; Found: 770. ¹ H NMR (400 MHz, Chloroform-d) 5 7.81 - 7.73 (m, 4H), 7.61 - 7.53 (m, 4H), 6.99 - 6.90 (m, 2H), 6.85 (dd, J = 8.3, 6.9 Hz, 4H), 6.78 - 6.71 (m, 4H), 6.42 (s, 2H), 6.00 (s, 2H), 1 .98 (s, 6H), 1.85 (s, 3H).

Compound SD-1 .3:

[0072] A mixture of compound SD-1.2 (160 mg, 0.207 mmol), 4-(4, 4,5,5- tetramethyl-1 ,3,2-dioxaborolan-2-yl)phenol (184 mg, 0.828 mmol), Pd(dppf)CI₂ (16 mg, 0.022mol), potassium carbonate (140 mg, 1.01 mmol) in THF/water (8mL/1 mL) was degassed then heated at 80 ^ºC for 120 min. The resulted mixture was diluted with 20 mL DCM, loaded on silica gel and purified by flash chromatography using eluents of DCM/Ethyl acetate (0% to 20% ethyl acetate). The desired main peak was collected, after removal of solvent under reduced pressure, the desired product was obtained as a dark solid (130 mg, in 79% yield). ¹H NMR (400 MHz, TCE-d2) 5 7.98 - 7.91 (m, 4H), 7.62 - 7.54 (m, 4H), 7.54 - 7.46 (m, 4H), 6.92 - 6.85 (m, 4H), 6.84 (d, J = 2.1 Hz, 2H), 6.82 - 6.74 (m, 4H), 6.73 - 6.66 (m, 4H), 6.46 (s, 2H), 5.92 (s, 2H), 4.88 (s, 2H), 1.92 (s, 6H), 1.78 (s, 3H).

Compound SD-1 :

[0073] A mixture of compound SD-1.3(80mg, 0.1 mmol), compound SD-1.4 (100 mg, 0.222 mmol), DMAP/TsOH salt (59 mg, 0.2 mmol), DIG (0.15 mL) in 6 mL DCM was stirred at room temperature overnight, then at 45 ^ºC for 2 hrs. The resulted mixture was loaded on silica gel and purified by flash chromatography using eluents of DCM/ethyl acetate (0% to 10% ethyl acetate). The desired di-coupled product was collected as the 2nd main peak. After removal of solvents, washed with methanol and dried in air, the desired product was obtained as a dark solid (100 mg, in 60% yield). Confirmed by ¹ H NMR. ¹H NMR (400 MHz, d2-TCE) 0 8.49 (dd, J = 16.0, 8.1 Hz, 4H), 7.99 (d, J = 8.2 Hz, 6H), 7.85 (d, J = 8.0 Hz, 2H), 7.63 (dd, J = 8.5, 3.7 Hz, 8H), 7.50 (t, J = 7.8 Hz, 2H), 7.42 - 7.25 (m, 8H), 7.25 - 7.08 (m, 10H), 6.84 (dt, J = 36.5, 7.3 Hz, 6H), 6.70 (d, J = 7.5 Hz, 4H), 6.48 (s, 2H), 5.93 (s, 2H) ^º, 2.80 (t, J = 7.7 Hz, 4H), 2.63 (t, J = 7.4 Hz, 4H), 2.1 1 (t, J = 7.7 Hz, 4H), 1 .92 (s, 6H), 1 .78 (s, 3H).

Synthesis procedure of Compound SD-2

General procedure for preparation of compounds SD-2.1 , SD-2.2 and SD-2.3

Compound SD-2.1 :

[0074] To a solution of 1 -benzosuberone (10.0 mmol, 1.46 mL) in 3:1 , H2O/EtOH (32.5 mL) at room temperature were added NH2OH-HCI (15.0 mmol, 1.04 g) and sodium acetate (25.0 mmol, 2.05 g) and the reaction mixture was stirred at 95 °C for 1 h. It was then cooled to room temperature, filtered, washed with water (150 mL) and lyophilized for 16 h to give 1 .64 g of 6,7,8,9-tetrahydro-5H-benzo[7]annulen- 5-one oxime (94% yield) as a colorless solid which was used in the subsequent synthetic step without further purification.

[0075] To a solution of 6,7,8,9-tetrahydro-5H-benzo[7]annulen-5-one oxime (5.71 mmol, 1.00 g) in DMSO (9.00 mL) at room temperature was added KOH (17.1 mmol, 959 mg) and the reaction mixture was heated to 140 °C before 1 ,2- dichloroethane (1 1.4 mmol, 897 pL) in DMSO (2.00 mL) was added over 3 h via a syringe pump. The mixture was then cooled to room temperature, quenched with 1 M aqueous NH4CI solution (30.0 mL) and extracted with CH2CI2 (3 x 30.0 mL). The combined organics were dried (MgSO4) and concentrated under reduced pressure. Flash chromatography (hexanes 9:1 , hexanes/EtOAc) gave 262 mg of SD-2.1 (25% yield) as a yellow solid. ¹ H NMR (400 MHz, Chloroform-d) 5 8.18 (br s, 1 H), 7.34 (dd, J = 7.8, 1.3 Hz, 1 H), 7.25 - 7.19 (m, 1 H), 7.16 (dd, J = 7.6, 1.6 Hz, 1 H), 7.13 - 7.07 (m, 1 H), 6.84 (t, J = 2.8 Hz, 1 H), 6.17 (t, J = 2.8 Hz, 1 H), 2.91 (t, J = 6.8 Hz, 2H), 2.86 - 2.80 (m, 2H), 2.07 - 1 .98 (m, 2H); ¹³C NMR (101 MHz, Chloroform-d) 0 140.4, 131 .8, 129.3, 126.8, 125.9, 125.2, 123.2, 121.8, 1 18.3, 1 1 1.1 , 34.9, 27.8, 26.7.

Compound SD-2.3:

[0076] A 100 mL 2 neck round bottomed flask was fitted with an air condenser and a stir bar. To the flask, compound SD-2.1 1 ,4,5,6- tetrahydrobenzo[6,7]cyclohepta[1 ,2-b]pyrrole (813.1 mg, 4.4 mmol) and SD-2.2 4- hydroxy-2,6-dichlorobenzaldehyde (424.3 mg, 2.2 mmol) were added, followed by anhydrous dichloroethane (55 ml). The reaction mixture was sparged with Ar for 30 minutes, then TFA (4 drops) was added. The reaction solution was stirred at room temperature overnight. After the reaction was cooled down to 0 C ^º in an ice-water bath, p-chloranil (731 .8 mg, 2.98 mmol) was added. The reaction was kept at 0 ^ºC for 30 minutes. Then BFs*OEt2 (3.0 mL, 24.1 mmol) and EtsN (1.9 mL, 13.3 mmol) were added at 0 C ^º . The reaction mixture was heated up to 50 ^ºC for 3 hours. The reaction mixture was loaded with silica gel and purified by flash chromatography, using DCM in hexane (0-80-90%) as an eluent to provide the pure BODIPY SD-2.3 as a brown golden solid, 476.0 mg, 36% yield. MS (APCI): calculated for C33H24BCI2F2N2O ([M- H]-) = 584 found: 584. ¹ H NMR (400 MHz, CDCI3) 8.09 (dd, J = 4.0 Hz, 2.0 Hz, 2H), .32 (dddd, J = 13.2 Hz, 7.2 Hz, 7.2 Hz, 2.0 Hz, 4H), 7.22 (dd, J = 6.4 Hz, 2.0 Hz, 2H),

6.99 (s, 2H), 6.43 (s, 2H), 5.77 (bs, 1 H), 2.63 (dd, J = 6.8 Hz, 6.8 Hz, 4H), 2.32 (bs, H), 2.03 (ddd, J = 14.0 Hz, 6.8 Hz, 6.8 Hz, 4H).

[0077] A mixture of 4-bromo-1 ,8-naphthalic anhydride (2.77g, 10 mmol), 4- bromo-2-nitrophenol (3.27g, 15 mmol) was degassed under vacuum for 30 min, then anhydrous NMP (50 mL) was added, followed by addition of sodium hydroxide (0.2g, 5mmol) and copper powder (0.318 g, 5 mmol). The mixture was sparged with argon for 20 min, then heated at 180 ^ºC overnight under argon atmosphere. After cooling down to room temperature, to the solution, 50 mL 20% hydrochloride acid aqueous solution was added dropwise, then 50 mL water was added. The resulting mixture was allowed to stand for 3 hrs, then filtered to collect the precipitate, which was dried in vacuum to afford 4.6 g crude product. The crude product was dispersed in 30 mL acetone and stirred overnight at room temperature to dissolve the impurities. Filtration and dried in vacuum gave a brown yellow solid as desired product (3.3g, in 80% yield). LCMS (APCI+): calculated for G18H9BrNO6 (M+H) = 413.95; Found: 414. ¹H NMR (400 MHz, TCE-d2) 5 8.70 (dd, J = 8.4, 1 .2 Hz, 1 H), 8.63 (dd, J = 7.3, 1 .2 Hz, 1 H), 8.41 (d, J = 8.3 Hz, 1 H), 8.24 (d, J = 2.4 Hz, 1 H), 7.89 - 7.79 (m, 2H), 7.20 (d, J = 8.7 Hz, 1 H), 6.82 (d, J = 8.3 Hz, 1 H).

Compound SD-2.5:

[0078] A mixture of compound SD-2.4 (1.5 g, 3.6 mmol), iron powder (0.60 g, 10.8 mmol) in acetic acid (50 mL) was heated at 125 °C for 30 min. After cooling to room temperature, 100 mL water was added to the mixture while stirring. The resulted mixture was filtered and washed with water, dried in air and vacuum to give a solid (1 .35 g, in 82% yield). LCMS (APCI-): calculated for C18H10BrNO4 = 382.98; Found: 383. ¹H NMR (400 MHz, DMSO-d6) 5 9.01 - 8.26 (m, 3H), 7.96 (s, 1 H), 6.93 (dd, J = 85.2, 36.5 Hz, 4H), 5.54 (s, 2H).

Compound SD-2.6:

[0079] Compound SD-2.5 (2.65g, 6.9mmol), was dispersed in acetic acid (50mL)/water (10mL) and cooled to 0 -C. While being stirred, precooled hydrochloric acid (2.8mL, 34.5 mmol) was added, then sodium nitrite solution (3.57g, 52 mmol) in 15 mL water was added dropwise at 0 ^ºC. The whole was stirred for one hour at 0 ^ºC, then was transferred into additional funnel, and dropped into a copper sulfate solution (12g, 47 mmol, in 140 mL water) for over a one hour period at 130 ^ºC. After cooled to room temperature, the precipitate was collected by filtration, washed with water (100mL x 3), then stirred in 50 mL acetone at 40 ^ºC for 30 min. Filtration, dried in air then in vacuum gave a brown yellow solid (1.76g, in 70% yield). LCMS (APCI+): calculated for C18H8BrC4 (M+H) = 366.95; Found: 367. ¹H NMR (400 MHz, d2-TCE) 0 8.51 (dd, J = 12.3, 8.1 Hz, 2H), 8.12 (d, J = 2.3 Hz, 1 H), 7.86 (d, J = 7.9 Hz, 1 H), 7.60 (dd, J = 8.8, 2.3 Hz, 1 H), 7.28 (d, J = 8.3 Hz, 1 H), 7.23 (d, J = 8.8 Hz, 1 H).

Compound SD-2.7:

[0080] A mixture of compound SD-2.6 (550 mg, 1.5 mmol), 4-(4-aminophenyl) butanoic acid (537 mg, 3 mmol) and DMAP (12.2mg, 0.1 mmol) in 10 mL DMF was heated at 165 ^ºC for 2.5 hrs in microwave reactor. The resulted solution was dropped into 50 mL acetone while stirring. Precipitate formed and was filtered and dried in vacuum oven at 60 ^ºC for overnight to afford the desired product as brown yellow solid (0.49g, in 62% yield). LCMS (APCI-): calculated for C28Hi8BrNOs = 527.04; Found: 527. ¹ H NMR (400 MHz, DMSO-d6) 6 8.54 (d, J = 2.3 Hz, 1 H), 8.41 (dd, J = 9.9, 8.0 Hz, 2H), 8.33 (d, J = 7.9 Hz, 1 H), 7.71 (dd, J = 8.8, 2.3 Hz, 1 H), 7.39 (dd, J = 8.6, 4.2 Hz, 2H), 7.25 (d, J = 8.0 Hz, 2H), 7.17 (d, J = 7.9 Hz, 2H), 2.63 - 2.55 (m, 2H), 2.27 - 2.15 (m, 2H), 1 .87 - 1 .73 (m, 2H).

Compound SD-2.8:

[0081] A mixture of compound SD-2.7 (385 mg, 0.729 mmol), phenylboronic acid (178 mg, 1 .45 mmol), Pd(dppf)CI2 (36 mg, 0.05 mmol), potassium carbonate (276 mg, 2 mmol) in cosolvents of THF/DMF/water (20L/4mL/2mL) was degassed, then heated at 80 ^ºC for overnight. The mixture was worked up with 200 mL ethyl acetate and 50 mL 0.6 N hydrochloric acid aqueous solution. The aqueous phase was extracted with ethyl acetate (100 mL x 2). The organic phase was collected and washed with brine (100 mL x 2), dried over sodium sulfate, then dry loaded on silica gel and purified by flash chromatography using eluents of DCM/EA (0% to 40% EA with 0.1 % TFA). The main desired fraction was collected, removal of solvents under reduced pressure gave a yellow solid (250mg, in 65% yield). LCMS (APCI-): calculated for C34H23NO5 = 525.16; Found: 525. ¹H NMR (400 MHz, TCE-d2) 58.55 (dd, J = 19.5, 8.1 Hz, 2H), 8.20 (d, J = 2.1 Hz, 1 H), 8.01 (d, J = 8.1 Hz, 1 H), 7.72 (dd, J = 8.6, 2.1 Hz, 1 H), 7.62 (d, J = 7.3 Hz, 2H), 7.51 - 7.28 (m, 7H), 7.17 (d, J = 8.2 Hz, 2H), 2.72 (t, J = 7.7 Hz, 2H), 2.39 (t, J = 7.3 Hz, 2H), 1 .99 (q, J = 7.2 Hz, 2H).

Compound SD-2: [0082] A mixture of compound SD-2.3 (31 mg, 0.053mmol), compound SD-2.8 (43 mg, 0.082 mmol), EDC’HCI (100 mg, 0.52 mmol) and DMAP/p-TsOH (16 mg, 0.054 mmol) in DCM (8ml_) was stirred at room temperature overnight. The resulted mixture was then loaded on silica gel, purified by flash chromatography using eluents of DCM/ethyl acetate (0%-5% ethyl acetate). The main red fraction was collected and concentrated to ~ 1 mL under reduced pressure, then 10 mL methanol was added. The resulted precipitate was filtered and dried in air to give a dark red solid (41 mg, in 70.8% yield). LCMS (APCI-): calculated for C67H46BCI2F2N3O5 = 1091.29; Found: 1091. ¹ H NMR (400 MHz, d2-TCE) 5 8.56 (dd, J = 19.3, 8.1 Hz, 2H), 8.21 (d, J = 2.2 Hz, 1 H), 8.02 (d, J = 8.1 Hz, 1 H), 7.97 (t, J = 4.7 Hz, 2H), 7.73 (dd, J = 8.6, 2.1 Hz, 1 H), 7.63 (dd, J = 7.2, 1 .7 Hz, 2H), 7.50 - 7.41 (m, 3H), 7.38 (dd, J = 8.0, 2.2 Hz, 3H), 7.34 - 7.25 (m, 7H), 7.25 - 7.18 (m, 4H), 6.40 (s, 2H), 2.82 (t, J = 7.5 Hz, 2H), 2.67 (t, J = 7.4 Hz, 2H), 2.60 - 2.49 (m, 4H), 2.24 (s, 4H), 2.18 - 2.07 (m, 2H), 2.03 - 1 .90 (m, 4H).

Synthesis procedure of Compound SD-3

SD-3.1

SD-3.2

[0083] AICI3 (78.0 g, 585 mmol, 31.9 mL, 1.80 eq) was added to anhydrous DCM (1 .50 L) at 0-10 °C. The mixture was stirred at 0 °C for 30 mins. A mixture of compound SD-3.1 A (88.1 g, 585 mmol, 72.2 mL, 1.80 eq) in anhydrous DCM (100 mL) was added to the mixture at 0-10 °C under N2. Compound SD-3.1 (82 g, 325 mmol, 1 .00 eq) was added to the mixture in portions and the mixture was stirred at 25- 30 °C for 30 mins. The mixture was stirred at 50 °C for 12 hrs. Thin Layer Chromatography (TLC) (Petroleum ether/Ethyl acetate = 10/1 ) showed that the reaction was completed. The mixture was cooled to 25-30 °C and poured into water (1 .00 L). The mixture was separated, and the aqueous phase was extracted with DCM (500 mL * 2). The combine organic layer was dried over Na2SC>4 and concentrated. The product was purified by MPLC (100-200 mesh silica gel, DCM). SD-3.2 (82.0 g, 223 mmol, 68.8% yield) was obtained as orange solid. LCMS (APCI+), calculated for C25HI₈O₃=366.1 ; found: 366. ¹H NMR (400 MHz, Chloroform-d) 0 8.57 (dd, J = 8.6,

1.0 Hz, 1 H), 8.30 - 8.17 (m, 4H), 7.97 (d, J = 8.1 Hz, 1 H), 7.78 (d, J = 8.1 Hz, 1 H),

7.73 (d, J = 8.1 Hz, 1 H), 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).

General procedure for preparation of compound SD-3.3

SD-3.2 SD-3.3

[0084] Trifluoroacetic acid (TFA) (231 g, 2.03 mol, 150 mL, 9.90 eq) was added to a mixture of SD-3.2 (75.0 g, 204 mmol, 1 .00 eq) in anhydrous DCM (600 mL) at 0- 10 °C. The mixture was stirred at 0-10°C for 30 mins. Triethylsilane (Et3SiH) (71 .4 g, 614 mmol, 98.1 mL, 3.00 eq) was added to the mixture at 0-10 °C and the mixture was stirred at 25 °C for 16 hrs. TLC (Petroleum ether/Ethyl acetate = 3/1 ) showed that the reaction was completed. The mixture was concentrated to give the crude product. The crude product was triturated with methyl tertiary-butyl ether (MTBE) (400 mL) at 25-30 °C for 30 mins. The mixture was filtered, and the filtrate cake was washed by MTBE (100 mL). The filtrate cake was dried under vacuum. The mother liquid was concentrated and purified by silica gel chromatography (100-200 mesh silica gel, Petroleum ether/Ethyl acetate = 100/1 -2/1 ). Compound SD-3.3 (62.0 g, 176 mmol, 85.9% yield) was obtained as yellow solid. ¹H NMR (400MHz, CDCI3) 6 8.27 - 8.08 (m, 4H), 7.91 (d, J = 8.3 Hz, 1 H), 7.68 (dd, J = 5.5, 7.9 Hz, 2H), 7.53 (t, J = 8.0 Hz, 1 H), 7.48 (dt, J = 1 .5, 7.9 Hz, 2H), 7.34 (d, J = 7.7 Hz, 1 H), 3.71 (s, 3H), 3.07 (t, J =

7.8 Hz, 2H), 2.47 (t, J = 7.2 Hz, 2H), 2.12 (quin, J = 7.5 Hz, 2H)

General procedure for preparation of compound 3.4

SD-3.3 SD-3.4

[0085] n-Bromosuccinimide (NBS) (88.4 g, 496 mmol, 3.40 eq) was added to a mixture of SD-3.3 (51 .5 g, 146 mmol, 1 .00 eq) in CHCI3 (2.00 L) at 25 °C in portions. The mixture was stirred at 25 °C for 16 hrs and keeping in darkness. LCMS (ET39890- 22-P1 A) showed that the reaction was completed. The mixture was washed by Na2SOs (1 N, 1.00 L). The mixture was separated, and the aqueous phase was extracted with DCM (200 mL). The combine organic layer was concentrated to give the crude product. The product was purified by silica gel chromatography (100-200 mesh silica gel, Petroleum ether/Ethyl acetate = 1 /0-1 /1 ). SD-3.4 (69.2 g, 102 mmol, 69.9% yield, 87.0% purity) was obtained as red brown oil. LCMS (APCI+), calculated for C25Hi7BrsO2= 585.88; found: 589.

General procedure for preparation of SD-3.5

SD-3.4 SD-3.5

[0086] SD-3.4A (228 g, 1.19 mol, 151 ml_, 10.0 eq) was added to a mixture of SD-3.4 (70.0 g, 119 mmol, 1 .00 eq) and Cui (1 13 g, 594 mmol, 5.00 eq) in DMA (490 mL) at 25 °C. The mixture was stirred at 160 °C for 3 hrs under N2. LCMS (ET39890- 26-P1 A) showed that the reaction was completed. The mixture was cooled to 25-30 °C and diluted with water (1 .50 L) and ethyl acetate (EtOAc) (1.00 L). The mixture was filtered through a Celite pad. The filtrate cake was washed by EtOAc (500 mL * 2). The combine filtrate was separated, and the aqueous phase was extracted with EtOAc (500 mL * 2). The combine organic layer was concentrated to give the crude product. The product was purified by silica gel chromatography (100-200 mesh silica gel, Petroleum ether/Ethyl acetate = 1/0 to 1/1). SD-3.5 (40.0 g, 71.9 mmol, 60.5% yield) was obtained as red brown oil.

General procedure for preparation of compound SD-3.6

SD-3.5 SD-3.6

[0087] Sodium hydroxide (NaOH) (8.63 g, 215 mmol, 3.00 eq) was added to a mixture of SD-3.5 (40.0 g, 71.9 mmol, 1.00 eq) in tetrahydrofuran (THF) (200 mL), methanol (MeOH) (200 mL) and H2O (200 mL) at 25 °C. The mixture was stirred at 25 °C for 2 hrs. TLC (Petroleum ether/Ethyl acetate = 10/1 ) showed that the reaction was completed. The mixture was acidified to pH = 1 -2 by hydrogen chloride (HCI) solution (1 N). The mixture was concentrated to remove the solvent. The residue was diluted with water (150 mL) and extracted with EtOAc (100 mL * 2). The combined organic layer was concentrated. The crude product was purified by silica gel chromatography (100-200 mesh silica gel, Petroleum ether/Ethyl acetate = 1/0-0/1 ). SD-3.6 (26.2 g, 48.1 mmol, 66.9% yield, 99.6% purity) was obtained as yellow solid. ¹HNMR (400MHz, CDCI3) 0 8.37 - 7.93 (m, 6H), 7.91 - 7.50 (m, 2H), 3.47 - 3.13 (m, 2H), 2.68 - 2.53 (m, 2H), 2.26 - 2.13 (m, 2H).

General procedure for preparation of Compound SD-3

Compound SD-3.7:

[0088] To a solution of 2,6-dichloro-4-hydroxybenzaldehyde (0.335 mmol, 64 mg), 4-(tris(trifluoromethyl)perylen-3-yl)butanoic acid (0.369 mmol, 200 mg) and DMAP-pTsOH salt (0.034 mmol, 10 mg) in CH2CI2 (1.68 mL) was added DIC (1.34 mmol, 210 pL) and the reaction mixture was stirred at room temperature for 2 hrs. It was then filtered through celite and concentrated under reduced pressure. Flash chromatography (toluene) gave 187 mg of SD-3.7 (78% yield) as a yellow solid. ¹H NMR (400 MHz, Chloroform-d) 5 10.50 - 10.33 (m, 1 H), 8.48 - 7.50 (m, 8H), 7.19 - 7.14 (m, 2H), 3.45 - 3.25 (m, 2H), 2.83 - 2.59 (m, 2H), 2.33 - 2.03 (m, 2H).

Compound SD-3:

[0089] To a solution of SD-2.1 (0.461 mmol, 84 mg) and SD-3.7 (0.210 mmol, 150 mg) in CH2CI2 (4.50 mL) was added p-TsOH-H2O (0.021 mmol, 3 mg) and the reaction mixture was stirred at room temperature for 1 h. DDQ (0.252 mmol, 57 mg) was then added and the mixture was stirred at room temperature for 1 h. T riethylamine (TEA)(1 .26 mmol, 175 pL) was added, the mixture was stirred at room temperature for 1 h before BF3-0Et2 (1 .89 mmol, 233 pL) was added and the mixture was stirred room temperature for 2 h. It was then diluted with EtOAc (30.0 mL), washed with 3 M HCI (3 x 30.0 mL), dried (MgSCU) and concentrated under reduced pressure. Flash chromatography (4:1 toluene/hexanes toluene) gave 106 mg of SD-3 (45% yield) as a purple solid. ¹ H NMR (400 MHz, Methylene Chloride-d2) 5 8.61 - 7.60 (m, 10H),

7.39 - 7.11 (m, 8H), 6.54 - 6.40 (m, 2H), 3.46 - 3.30 (m, 2H), 2.90 - 2.55 (m, 6H),

2.39 - 2.09 (m, 6H), 2.08 - 1 .94 (m, 4H).

Synthesis procedure of Compound SD-4

General procedure of compound SD-4 synthesis

[0090] A 10 mL vial was fitted with a stir bar. To the vial, compound SD-2.3 (25.0 mg, 0.043 mmol), FD-1.5 (24.0 mg, 0.053 mmol), EDC’HCI (40.9 mg, 0.21 mmol) and DMAP*TsOH (25.6 mg, 0.085 mmol) were added, followed by anhydrous DCM (1 .5 ml). The reaction mixture was heated up to 40 ^ºC overnight. After the reaction was cooled down room temperature, the reaction mixture was loaded with silica gel and purified by flash chromatography, using DCM in EtOAc (0-5%) as an eluent to provide the pure RL-naphthalimide-BODIPY 1605-23-3 as a dark purple solid. The solid was further triturated with MeOH (10 ml) to deliver RL-naphthalimide-BODIPY SD-4, 21 .0 mg, 48% yield. MS (APCI): calculated for C61H41CI2F2N3O5 ([M-H]-) = 1015 found: 1015. ¹H NMR (400 MHz, CDCI3) 3 8.66 (dd, J = 18.4 Hz, 7.6 Hz, 2H), 8.10 (m, 3H), 7.99 (d, J =8.0 Hz, 1 H), 7.56 (ddd, J = 8.0 Hz, 8.0 Hz, 1 .6 Hz, 1 H), 7.36 (m, 13H), 7.22 (dd, J = 6.8 Hz, 2.0 Hz, 2H), 6.45 (s, 2H) 2.88 (t, J = 7.6 Hz, 2H), 2.72 (t, J = 7.2 Hz, 2H), 2.63 (m, 4H), 2.20 (m, 6H), 2.04 (ddd, J = 6.8 Hz, 6.8 Hz, 6.8 Hz, 4H).

Synthesis procedure of Compound SD-5

General procedure of compound SD-5 synthesis

[0091] A 25 mL vial was fitted with a stir bar. To the vial, compound SD-2.3 (40.0 mg, 0.068 mmol), 1605-99 SD-5.1 (77.5 mg, 0.137 mmol), EDC-HCI (65.2 mg, 0.340 mmol) and DMAP*TsOH (41.1 mg, 0.137 mmol) were added, followed by anhydrous DCM (4 ml). The reaction mixture was heated up to 40 ^ºC overnight. After the reaction was cooled down room temperature, the reaction mixture was loaded with silica gel and purified by flash chromatography, using DCM in EtOAc (0-4%) as an eluent to provide the pure RL-naphthalimide-BODIPY SD-5 as a dark blue solid. The solid was further triturated with MeOH (15 ml) to deliver RL-naphthalimide-BODIPY SD-5, 46.0 mg, 60% yield. MS (APCI): calculated for C66H41 BCI2F5N3O5 ([M-H]-) = 1132 found: 1132. ¹H NMR (400 MHz, CDCI2CDCI2) 0 8.69 (d, J = 8.0 Hz, 1 H), 8.65 (d, J = 8.0 Hz, 1 H), 8.30 (d, J = 2.0 Hz, 1 H), 8.11 (d, J = 8.0 Hz, 1 H), 8.06 (m, 2H), 7.82 (m, 5H), 7.65 (m, 2H), 7.55 (d, J = 8.0 Hz, 1 H), 7.39 (m, 9H), 7.30 (m, 2H), 6.48 (s, 2H), 4.07 (s, 2H), 2.63 (m, 4H), 2.33 (bs, 3H), 2.06 (m, 4H).

Preparation of polymer solution

25% PMMA polymer solution preparation

[0092] Weigh 30 g PMMA polymer (grade unknown), add into a 250 ml_ glass jar. Use volumetric cylinder to measure 90 mL cyclopentanone or Toluene and add into same glass jar. Stir the solution with a stir bar on a stir station and heat at 50 ^ºC until fully dissolved.

Preparation of dve-oolvmer solution

[0093] 0.2 mg FD-1 , 0.16mg compound SD-3 and 150mg silicone particle

(TSR9000, momentive). To the solution, add to 4mL of 25% PMMA solution. Rigorously mix solution by vortex for 1 minutes, followed by 15 minutes sonication, then stir on stir plate with mild speed.

Film fabrication

Individual dye-polymer film

[0094] Basic optical property was evaluated based on a dye-polymer film. Scattering centers (20% silica beads, average size 2-3 pm) and dye with proper weight was dissolved in to 3 mL above 25% PMMA/Toluene solution to make a 2 mmol/L dye- polymer solution. The solution was rigorously mixed by vortex for 1 minutes, followed by 15 minutes sonication. Several 1 ”x1 ” glass substrates were cleaned with soap water and air blown to dry. The glass substrate was then placed on spin coater holder and the dye-polymer solution was poured onto the glass substrate. Spin coat the film with a spin speed set to 1000 RPM for 20 seconds. Wet coating film was then dried at room temperature for 1 hour and heated at 130 -C for 30 minutes.

Green and red dye-polymer film

[0095] In order to convert blue light to white light mixing with R, G, B color, both the green dye and the red dye were mixed into one film. Clean a 2”x2” glass substrate with soap water and air blow to dry. The glass substrate was then placed on a spin coater holder and the dye-polymer solution was poured on the glass substrate. Spin coat the film with a spin speed set to 1000 RPM. Wet coating film was then dry at room temperature for 1 hour and heat at 130 ^ºC for 30 minutes. Once the film is dry, separate film from glass by immerse in water for 5 minutes.

[0096] Additional examples of films were made with varying the weight of the first photoluminescent dye, the second photoluminescent dye, the scattering particles, and/or polymer matrix materials as set forth in the Table 1 below.

Characterization of dye compound

Absorption and emission spectra

Absorbance and emission spectra of individual dye in polymer film were measured by UV-vis (Shimadzu uv-vis 3600 spectrophotometer) and Fluorolog 3 (Horiba) respectively.

Dye absolute quantum yield

[0097] Absolute quantum yield of the dye film was measured by Absolute PL quantum yield spectrometer C11347 (Hamamatsu) at wavelength 450nm.

Characterization of blue light conversion WLC film

External quantum yield of WLC film on LED backlight device

[0098] The external quantum yield and other optical characteristics of WLC film on LED backlight display application where tested using the test apparatus configured as set forth in Fig. 4. BEF stands for brightness enhancement film, Vikuiti BEF (3M). DBEF is polarizer/enhancement film (3M). A blue LED edge lit backlight was part of a kindle device. MCPD stands for multi-channel photon detection (MCPD-9800, Otsuka Electronics)

EQE is calculated based on equation:

Color gamut - BT.2020 ratio

[0099] Color gamut is certain complete subset of colors. It can be represented by a triangle inside a chromaticity diagram. Three corners of the triangle are primary colors. More color a display is capable to show the large the area of the triangle will be, therefore wider gamut. BT.2020 is a gamut standard for UHD projectors and televisions recommended by ITU (International Telecommunication Union).

[0100] Optical spectra measured by setup described in Fig. 4 was converted to the color gamut triangle in the CIE1931 chromaticity diagram, and triangle area was then estimated and divided by area of triangle of BT.2020 to obtain BT.2020 ratio mentioned here. The larger the ratio, the wider the color gamut of the WLC film. In order to fulfill wide color gamut, each primary color emission spectra shape should be as narrow as possible. Narrow spectra shape can be characterized as small FWHM of emission spectra.

Comparative examples

[0101] Table 2 below identifies comparative Examples 1 and 2 which are examples disclosed in U.S. Patent Application 63/001 ,924. The red dye SD-X corresponds to SD-1 in U.S. Patent Application 63/001 ,924. As can be seen in Table 2, Example 1 has large color gamut (94% BT.2020 ratio), however the FWHM of its red emission spectra is 68 nm, not too narrow. Example 2 gives a narrower FWHM of red emission spectra at the cost of smaller color gamut (88% BT.2020 ratio).

Table 2

Examples

[0102] Films in both the examples list in Table 4 below and the comparative examples listed in Table 2 above were fabricated by the method described in the section above titled “Film fabrication.” Examples 3 thru 9 of Table 5 were produced using the dyes identified in Table 2 and Table 3. All green color emitting dyes appeared have a FWHM of less than 25 nm, and most red color emitting dyes have a FWHM of less than 44 nm. All dyes have an internal quantum yield greater than 80%, some have greater than 95% quantum yield.

[0103] Permeance of these Examples 3 thru 1 1 of Table 5 were evaluated by the method described in the section above titled “Characterization of blue light conversion WLC film.” The majority of the examples show an EQE greater than 51%, an average increase of 10% compared to the comparative examples of Table 2. This is mainly contributed by the internal quantum yield of the dyes in Table 3 and Table 4. In addition, all films have a FWHM of green emission spectra less than 33 nm, and a FWHM of red emission spectra less than 63 nm, and a BT.2020 ratio greater than 90%.

Table 3

Table 4

Table 5

Claims

1 . A wavelength converting film comprising: a polymer matrix; a first photoluminescent dye, the first photoluminescent dye absorbing blue wavelength light and emitting green wavelength light with an emission spectrum having a full width at half maximum of less than 40 nm; a second photoluminescent dye, the second photoluminescent dye absorbing blue or green wavelength light and emitting a red wavelength light with an emission spectrum having a full width at half maximum of less than 55 nm; and light scattering centers, wherein the first photoluminescent dye, the second photoluminescent dye, and the light scattering centers are disposed within the polymer matrix.

2. The wavelength converting film of claim 1 , wherein the first photoluminescent dye comprises an optionally substituted BODIPY group, a linking group, and an optionally substituted isoquinoline group

3. The wavelength converting film of claim 2, wherein the first photoluminescent dye is:

4. The wavelength converting film of claim 1 , wherein the first photoluminescent dye comprises an optionally substituted BODIPY group, a linking group, and an optionally substituted naphthalic imide group.

5. The wavelength converting film of claim 4, wherein the first photoluminescent dye is:

6. The wavelength converting film of claim 1 , wherein the second photoluminescent dye comprises an optionally substituted BODIPY group, a linking group, and an optionally substituted isoquinoline group.

7. The wavelength converting film of claim 6, wherein the second photoluminescent dye is:

(SD-4).

8. The wavelength converting film of claim 1 , wherein the second photoluminescent dye comprises an optionally substituted BODIPY group, a linking group, and an optionally substituted naphthalimide group.

9. The wavelength converting film of claim 8, wherein the second photoluminescent dye is:

10. The wavelength converting film of claim 1 , wherein the second photoluminescent dye comprises an optionally substituted BODIPY group, a linking group, and an optionally substituted perylene group.

11 . The wavelength converting film of claim 8, wherein the second photoluminescent dye is:

12. The wavelength converting film of any one of claims 1 -1 1 , wherein the wavelength converting film has an internal quantum yield of greater than 80%.

13. The wavelength converting film of any one of claims 1 -1 1 , wherein the wavelength converting film has an external quantum yield of greater than 50%.

14. The wavelength converting film of any one of claims 1 -1 1 , wherein the wavelength converting film has a color gamut of greater than 90% of BT.2020 standard

15. The wavelength converting film of any one of claims 1 -1 1 , wherein the wavelength converting film has a thickness between 10 pm and 40 urn.

16. A light emitting device comprising the wavelength converting film of any one of claims 1 -15.

17. A backlit device having a blue light source, the device comprising the wavelength converting film of any one of claims 1 -15.