WO2021202536A1

WO2021202536A1 - Improved wavelength conversion film

Info

Publication number: WO2021202536A1
Application number: PCT/US2021/024896
Authority: WO
Inventors: Jie Cai; Shijun Zheng; Jeffrey R. Hammaker; Hiep Luu; Jan SASKA; Guang Pan; Peng Wang
Original assignee: Nitto Denko Corporation
Priority date: 2020-03-30
Filing date: 2021-03-30
Publication date: 2021-10-07
Also published as: JP2023522304A; TWI784458B; WO2021202536A9; TW202142676A; CN115485352A; KR20220137075A

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

CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Application No. 63/002,330, filed

March 30, 2020, which is incorporated by reference herein in its entirety.

FIELD

The present disclosure relates to wavelength conversion films and light-emitting devices including the same.

BACKGROUND

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.

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.

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.

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 Some embodiments include a wavelength converting film comprising: a polymer matrix; a first photoluminescent dye that: absorbs a blue wavelength light, and emits green wavelength light with an emission spectrum having a full width half maximum of less than 40 nm; a second photoluminescent dye that: absorbs a blue orgreen wavelength light, and emits red wavelength light with an emission spectrum having a full width half maximum of less than 40 nm; and light scattering centers; wherein the first photoluminescent dye, second photoluminescent dye and the light scattering centers are dispersed within the polymer matrix.

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

In some embodiments, the first photoluminescent dye may comprise a BODIPY group, a linking group and a naphthalimide group. In some embodiments, the first photoluminescent dye may be selected from:

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

In some embodiments, the film may have a quantum yield of greater than 85%. In some embodiments, the film may have a color gamut of greater than 85% of 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 backlit device having a blue light source comprising a photoluminescent wavelength conversion film described herein.

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.

FIG. 5 is a schematic of a testing configuration including film embodiments described herein.

FIG. 6 is a schematic of a testing configuration including film embodiments described herein.

FIG. 7 is a schematic of a testing configuration including film embodiments described herein.

FIG. 8 is a graph showing the light intensity as a function of wavelength for an embodiments (Film Ex-1 and Ex-2 [FD-1:SD-1]) described herein.

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

FIG. 10 is a graph showing the light intensity as a function of wavelength for the various films created as identified in Table 1. FIG. 11 is a 1931 CIE color chart exhibiting color gamut representations of various films described herein.

DETAILED DESCRIPTION

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

The term "BODIPY" as used herein, refers to a chemical moiety with the formula:

The BODIPY moiety comprises a dipyrromethene complexed with a di-substituted boron atom, typically a BF2 unit. The lUPAC name for the BODIPY core is 4,4-difluoro-4-bora- 3a,4a-diaza-s-indacene.

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

The term "naphthalic acid" or "naphthalic acid derivative" as used herein, refers to a chemical moiety with the formula:

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

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 acid moiety with a linking group.

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."

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: X_w = 0.3127; Y_w = 0.3290; X_R = 0.708, YR = 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 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 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 40 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 80%. Suitable means to determine the percent color gamut is to measure the area under the generated 1931 CIE color space, e.g., Fig. 11. In some embodiments, the film may be between 80 % and 99.9 % color gamut, e.g., 86% , 90%, 93 %, and /or 95%, or a range bounded by any of these values. In some embodiments, a LCD backlight is described, the LCD backlight comprising the aforementioned film.

In some embodiments, the film may comprise a polymer matrix. In some embodiments, the polymer matrix may have a transparency of greater than 75%. In some embodiments, the polymer matrix may comprise a hydrophilic polymer. In some embodiments, the polymer matrix may comprise polyvinyl butyral, polyvinyl acetate, polyvinyl alcohol, or a polyacrylate. In some embodiments the polymer matric may comprise polyvinyl butyral (PVB). In some embodiments, the polyacrylate may be a polyalkylacrylate. In some embodiments, the polyalkyacrylate may be a 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. 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 luminescent 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, or less than or equal to 30 nm when dispersed in the substantially transparent polymer matrix. In some embodiments, the luminescent 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. In some embodiments, the film may comprise a first organic luminescent compound (or dye). In some embodiments, the first organic luminescent dye (and/or the photoluminescent wavelength conversion film comprising the first organic luminescent dye) may have an emissive peak between 510 and 560 nm (green light emitting). In some embodiments, the emissive spectrum of the first organic luminescent dye and/or the photoluminescent wavelength conversion film may have a full width half maximum (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 comprise a BODIPY group, a linking group, and a perylene 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 some embodiments, the first organic luminescent dye may comprise a BODIPY group, a linking group and a naphthalic acid derivative group. In some embodiments, the naphthalic acid derivative group may be a naphthalimide group. In some examples, the naphthalimide group may be covalently bonded to the linking group. In some embodiments, the first organic luminescent dye may be selected from FD-1, FD-2, FD-3, or FD-4:

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 conversion film comprising the second organic luminescent 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 conversion film comprising the second organic luminescent dye) may have an emissive peak between 600 and 660 nm (red light emitting). In some embodiments, the second organic photoluminescent dye (and/or the photoluminescent wavelength conversion film comprising the second organic luminescent dye) may have an emissive peak between 615 and 645 nm. In some embodiments, the emissive spectrum of the second organic photoluminescent dye and/or the photoluminescent wavelength conversion film may have a full width half maximum (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 comprise a BODIPY group and a perylene group. In some embodiments, the second organic photoluminescent dye may comprise SD-1:

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.

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

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.

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 materials 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.

A photoluminescent wavelength conversion 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 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.

In some embodiments, a photoluminescent wavelength conversion 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 conversion 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.

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

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, such as light source 12. In some embodiments, the display device may comprise a back reflector, such as back reflector 14. In some embodiments, the display device may comprise a wavelength converting (WLC) film, such as film 16. In some embodiments, the display device may comprise a mask, such as mask 18. In some embodiments, the WLC film may be in optical communication with the light source, enabling an increased efficacy in transmitting the generated light from the light source to the viewer, 20.

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, such as device 10, may comprise a light source, such as light source 12. In some embodiments, the display device may comprise a back reflector, such as back reflector 14. In some embodiments, the display device may comprise a wavelength converting (WLC) film, such as WLC film 16. In some embodiments, the display device may comprise a mask, such as mask 18. In some embodiments, the 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 the mask, such as mask 18, enabling an increased efficacy in transmitting the generated light from the light source to the viewer. In some embodiments, the display device may comprise one or more brightness enhancement films (BEF), such as BEF 22, e.g., Vikuiti brand BEF (3M Minneapolis, MN, USA). In some embodiments, the display device 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.

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.

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.

In some embodiments, the method may comprise withdrawing the undried polymeric photocatalytic WLC layerfrom 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.

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%, or about any value in a range bounded by any of these values.

EMBODIMENTS Embodiment 1. A 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 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 40 nm, and light scattering centers, the first photoluminescent dye, second photoluminescent dye and light scattering centers 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

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

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

Embodiment 8. The film of embodiments 1-7, wherein the film has a quantum yield of greater than 85%.

Embodiment 9. The film of embodiments 1-7, wherein the film has a color gamut of greater than 85% of 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 of embodiments 1- 10.

Embodiment 12. A backlit device having a blue light source, the device comprising the film of embodiments 1-10.

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. Examples

Synthesis of first photoluminescent dyes. Synthesis of compound FD-1:

Compound 6.5:

Step 1: A solution of 4-hydroxyl-2,6-dimethylbenzaldehyde (0.75 g, 5 mmol), 2,4- dimethylpyrrole (1.04 g, 11 mmol) in 100 mL anhydrous dichloromethane was degassed for 30 min, then a drop of trifluoroacetic acid was added. The solution was stirred overnight at room temperature while under argon gas. To the resulting solution, DDQ (2.0 g, 8.8 mmol) was added and stirred at room temperature overnight. The resulting mixture was filtered and washed with dichloromethane extensively to give a brown solid as desired compound 6.4 (1.6g, 100% yield). LCMS (APCI+): calculated for C21H25N2O (M+H) = 321; found 321.

Step 2: 5 mL of trimethylamine was added to a solution of dipyrrolomethane, compound 6.4, (l.Og) in 60 mL THF. The solution was degassed for 10 min, then trifluoroboron-diethylether (5 mL) was added slowly. Next the solution was heated at 70 ^°C for 30 min. The resulting solution was submitted to flash chromatography (silica gel) using dichloromethane as the eluent. The desired fraction was collected and dried under reduced pressure to give compound 6.5 as an orange solid (0.9 g, in 76% yield). LCMS (APCI+): calculated for C₂₁H₂₄BF₂N₂O (M+H) = 369; found: 369. Y NMR (400 MHz, Chloroform-d) d 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-butylperylene):

Under protection of nitrogen atmosphere, 5 g of perylene (19.81 mmol) was dissolved in 300 ml ortho-dichlorobenzene anhydrous in a three neck round bottle flask. The resulting yellow solution was cooled to 0 °C. 2.64 g of AICI3 (19.81 mmol) was added in small portions via a powder dispensing funnel over 45 minutes following by dropwise addition of 50 mL of tert- butylchloride (458 mmol). The resulting green color solution was stirred 24 hrs. at room temperature. The reaction mixture was poured into 100 mL of ice- water. The organic layer was separated, concentrated to dryness with a rotavapor with its water bath was set at 70 °C. The residue was re-dispersed into 450 mL of hot hexanes. The yellow solution was cooled and stood at room temperature overnight. The insoluble material was filtered and detected by LCMS as the tetra-tert-butyl analog (M+H= 477), while the filtrate was a mixture of di- and tri- tert-butyl perylene which was loaded onto silica gel column. Chromatography was run with Hexanes: EtOAc (9:1) to gain 3.75 g pale yellow color solid product of compound 10.1, 2,5-di- tert-butylperylene, yield 52%. LCMS (APCI+) calculated for C28H29 (M+H) =365; found 365. 1H NMR (400 MHz, Chloroform-d) d 8.30 - 8.21 (m, 4H), 7.72 - 7.63 (m, 4H), 7.50 (t, J = 7.8 Hz, 2H), 1.50 (s, 18H).

Compound 12.1 (Methyl 4-(8,ll-di-tert-butylperylen-3-yl)-4-oxobutanoate):

Under protection of nitrogen atmosphere, 2.63 g of AICI3 (19.97 mmol) was added in small portions via a powder dispersion funnel to a suspension of 2.45 mL methyl 4-chloro-4- oxobutanoate (19.97 mmol) in 175 mL of DCM anhydrous at 0 °C over 15 minutes. The resulting solution was stirred at 0 °C over 1 hr. Next, a solution of 5.77 g of compound 10.1 [2,5-di-tert-butylperylene], (15.85 mmol) dissolved in DCM anhydrous was dropwise while maintaining the temperature at 0 °C. The resulting dark purple solution was stirred overnight at room temperature under nitrogen atmosphere. The next day the solution was poured into a mixture of 150 mL of ice water and 300 mL DCM. The organic layer was separated; the water layer was reextracted with 100 mL of ethyl acetate. The organic layers were combined, dried with MgSC>4 and concentrated. The residue was loaded onto silica gel column. Chromatography was run with hexanes: ethyl acetate (9:1) as the eluents, resulting in 2.7 g of compound 12.1 as an orange color solid product, yield 35%. LCMS (APCI+): calculated for C33H35O3 (M+H) =479; found: 479; *H NMR (400 MHz, Chloroform-d) d 8.58 (d, J = 8.6 Hz, 1H), 8.34 - 8.27 (m, 3H), 8.23 (d, J = 8.0 Hz, 1H), 7.98 (d, J = 7.9 Hz, 1H), 7.73 (s, 1H), 7.68 (s, 1H), 7.60 (t, J = 8.0 Hz, 1H), 3.75 (s, 3H), 3.41 (t, J =6.5 Hz, 2H), 2.86 (t, J = 6.6 Hz, 2H), 1.49 (d, J = 3.5 Hz, 18H).

Compound 12.2 (4-(8,ll-di-tert-butylperylen-3-yl) butanoic acid): A solution of 470.5 mg of compound 12.1 [methyl 4-(8,ll-di-tert-butylperylen-3-yl)-4- oxobutanoate], (0.983 mmol) and 150 pL of 98% 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 of KOH (powder) (4.91 mmol) was added to the solution and stirred for 15 min at 80 °C. Next, the solution was heated to 140 °C and bubbled with a slow stream of argon gas for 2 hours. The vial containing the solution was sealed a septum, an argon atmosphere was maintained with a balloon and the temperature was raised to 190 °C. The resulting solution was stirred over 16 hrs. 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 HCI. The resulting green color solid was collected by filtering and purified with SiCh column chromatography, using DCM: EtOAc (1:1) as the eluent, resulting in 110 mg of compound 12.2 as a green color solid product, yield 88%. LCMS (APCI+): calculated for C32H35O2 (M+H) =451; found: 451; 1H NMR (400 MHz, Chloroform-d) d 8.27 - 8.19 (m, 3H), 8.15 (d, J = 7.7 Hz, 1H), 7.88 (d, J = 8.4 Hz, 1H), 7.62 (d, J = 5.2 Hz, 2H), 7.53 (t, J = 8.0 Hz, 1H), 7.34 (d, J = 7.7 Hz, 1H), 5.30 (s, 1H), 3.09 (t, J = 7.7 Hz, 2H), 2.48 (t, J = 7.2 Hz, 2H), 2.11 (p, J = 7.4 Hz, 2H), 1.47 (s, 18H).

Compound FD-1

Under protection of nitrogen atmosphere, 74.27 mg of DCC (0.36 mmol) was added to a solution comprised of 66 mg of compound 6.5 [4-(5,5-difluoro-l,3,7,9-tetramethyl-5H- 414, 5l4-dipyrrolo[l, 2-c:2',l'-f][l,3,2]diazaborinin-10-yl)-3, 5-dimethyl phenol], (0.18 mmol), 100 mg of compound 12.2 [4-(8,ll-di-tert-butylperylen-3-yl)butanoic acid], (0.22 mmol), 43.6 mg of DMAP (0.36 mmol) dissolved in 2.0 mL of THF anhydrous. The resulting solution was stirred for 16 hrs. at room temperature. Water was added follow by 50 mL of ethyl acetate. The solution was next passed through Celite. The organic layer was separated and concentrated. The crude product was purified by silica gel column chromatography, using Hexanes: ethyl acetate (9:1) as the eluents, resulting 43 mg of FD-1 as a red orange color solid product, yield 24%. LCMS (APCI+): calculated for C53H56BF2N2O2 (M+H) =801; found: 801. 1H NMR (400 MHz, Chloroform-d) d 8.26 (d, J = 7.4 Hz, 1H), 8.24 (s, 1H), 8.22 (s, 1H), 8.18 (d, J = 7.7 Hz, 1H), 7.93 (d, J = 8.3 Hz, 1H), 7.63 (s, 1H), 7.62 (s, 1H), 7.53 (t, J = 7.9 Hz, 1H), 7.4 (d, J = 7.4 Hz, 1H), 6.85 (s, 2H), 5.96 (s, 2H), 3.18 (t, J = 7.3 Hz, 2H), 2.69(t, J = 7.4 Hz, 2H), 2.55 (s, 6H), 2.25 (t, J = 7.4 Hz, 2H), 2.1 (s, 6H), 1.48 (s, 9H), 1.47 (s, 9H), 1.38 (s, 6H). Synthesis of compound FD-2:

Compound 44.2: (Dibenzyl 5,5-difluoro-10-(4-hydroxy-2,6-dimethylphenyl)-l,3,7,9- tetramethyl-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-2,8-dicarboxylatel: To a 250 mL round bottom flask 40 mL (241 mmol) of tert-butyl-3-oxobutanoate was dissolved in 80 mL of acetic acid. The mixture was cooled in an ice water bath to about 10 °C. Sodium nitrite (18 g, 262 mmol) was added over 1 h while the temperature was kept under 15 °C. The cold bath was removed and the mixture was stirred for 3.5 h at room temperature. The un-soluble material was filtered off to give a crude solution of oxime, which was used without further purification in the next step. Next, 50 g of zinc dust (0.76 mol) was added portion-wise to a mixture of 13.7 mL (79 mmol) benzyl-3-oxobutyrate and 100 mL of acetic acid. The resulting mixture was stirred in an oil bath and heated to 60 °C. The cured tert- butyl-2-(hydroxyimino-3-oxobutanoate solution was added slowly. The temperature was then increased to 75 °C and stirred for 1 h. Next, the reaction mixture was poured into water (4 L). The precipitate was collected and filtered to yield benzyl 2,4-dimethyl-lH-pyrrole-3- carboxylate, which was recrystallized from MeOH as a white solid, gained 15 g, yield 65%, based on benzyl 3-oxobutyrate. ¹H NMR (400 MHz, CDCI3): 8.88 (br, s, 1H, NH), 7.47-7.33 (m, 5H, C=CH), 5.29 (s, 2H, CH₂), 2.53, 2.48 (2s, 6H, 2CH₃), 1.56 (s, 9H, 3CH₃).

Next, in a 25 mL vial, a mixture of 1 g (4.36 mmol) of benzyl 2,4-dimethyl-lH-pyrrole- 3-carboxylate, 0.524 g (4.36 mmol) of MgSC , was dissolved in 8 mL of anhydrous DCE and stirred at room temperature in the presence of argon gas, for 15 min. 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 h. TLC and LCMS showed starting materials were consumed. To the crude product, 0.544 g (2.398 mmol) of DDQ was added in one portion. The resulting mixture was stirred at room temperature for ½ h. TLC and LCMS showed the starting materials were consumed. The resulting mixture was filtered through a short path of celite, the filtrate was concentrated to dryness, and the residue was re-dissolved into 50 mL of 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 added slowly. The resulting mixture was stirred at room temperature for ½ h the heated to 86 °C for 45 min. The reaction mixture was then diluted with 150 mL of CHCI3, quenched with 50 mL brine. The organic layers were separated and dried over MgSC>4, the solvents were removed by rotary evaporation. The residue was chromatographed on a column of silica gel using CF^Ch/EtOAc as eluent to afford a 1 g of pure compound 44.2, dibenzyl 5,5-difluoro-10-(4-hydroxy-2,6- dimethyl phenyl)-l, 3,7, 9-tetramethyl-5H-4l4, 514-dipy rrolo[l,2-c:2',l'-f] [1,3, 2]diazaborinine-

2,8-dicarboxylate), as a red orange solid, 72% yield based on 2,6-dimethyl 4- hydroxybenzaldehyde. LCMS (APCI-), calcd M- for C37H35BF2N2O5: 636.26; found: 636. ¹H NMR (400 MHz, Chloroform-d) d 7.42 - 7.28 (m, 4H), 6.66 (d, J = 0.7 Hz, 1H), 5.29 (d, J = 11.3 Hz, 2H), 2.82 (s, 3H), 2.04 (d, J = 5.4 Hz, 3H), 1.72 (s, 3H). Compound methyl 4-(perylen-3-yl) butanoate

Step 1: In 1 L two-neck flask equipped with magnetic stirring bar, powder dispenser funnel, a yellow suspension mixture of perylene (5.22 g, 20.68 mmol) in DCM anhydrous (500 mL) was stirred and bubbled with argon 15 minutes in an ice-water bath; methyl 4-chloro-4- oxo butanoate (3.425 g, 22.75 mmol) was added slowly via syringe. The cooling bath was removed to allow the mixture stirring at RT for 15 minutes. The mixture was cooled again with an ice-water bath; AICI₃ (3.3 g, 24.74 mmol) was added in small portion via the powder dispenser funnel. The resulting dark purple color mixture was stirred at RT for 16 hours under the protection of Argon. TLC and LCMS shown starting materials were almost consumed. The reaction mixture was diluted with 500 mL DCM then poured to ice-water (150 ml water), the organic layer was separated, dried with MgS04, concentrated to dryness. The residue was triturated with toluene. The solid was filtered, washed with toluene 50 mL. The filtrate and washed were combined and then concentrated to the volume of 50 mL then loaded on to column (330 g), eluting with toluene/ EtOAc (100:0) - (4.1) gained 1.25 g of desired product. The product from column chromatography and the solid product from work up were combined and re-crystallized using hexanes: EtOAc (9:1), gained 4.24 gyellow solid, yield 56%. LCMS (APCI-), calcd (M-) for C25H1803 :366.13; found: 366. 1H NMR (400 MHz, Chloroform- d) d 8.57 (dd, J = 8.6, 1.0 Hz, 1H), 8.30 - 8.17 (m, 4H), 7.97 (d, J = 8.1 Hz, 1H), 7.78 (d, J = 8.1 Hz, 1H), 7.73 (d, J = 8.1 Hz, 1H), 7.64 - 7.48 (m, 3H), 3.75 (s, 3H), 3.41 (t, J = 6.5 Hz, 2H), 2.86 (t, J = 6.5 Hz, 2H).

Step 2: In a 250 ml round bottom flask, a yellow mixture of the product of above step (4.24 g, 11.58 mmol) in DCM anhydrous (100 mL) was stirred and bubbled with Argon 15 minutes on a cooling ice+ water bath; TFA (25 mL) was added slowly. Cooling bath was removed to allow the mixture stirring at RT for 15 minutes; triethylsilane (15 mL) was added in at once. The resulting dark color mixture was stirred at RT for 16 hours underthe protection of argon. TLC and LCMS shown starting materials were consumed. The reaction mixture was diluted with 200 mL DCM then put on the rotary evaporator. TFA and DCM were removed. The residue was re-dissolved into DCM (50 ml) and the mixture was concentrated to dryness. The dark color crude product was loaded onto S1O2 column, eluting with hexanes/ EtOAc (95:5), affording 4.00 g of methyl 4-(perylen-3-yl) butanoate as a yellow solid product, yield 98%. LCMS (APCI+), calcd M+ for C25H20O2: 353.15; found: 353. Methyl 4-(4,9,10-tribromoperylen-3-yl) butanoate / methyl 4-(4,10-dibromo-4,12b- dihydroperylen-3-yl) butanoate / methyl 4-(5,9,10-tribromoperylen-3-yl) butanoate:

A mixture of methyl 4-(perylen-3-yl) butanoate (1.00 g, 2.837 mmol, 1 eq), in anhydrous chloroform (20 mL) was placed in a two neck flask and protected from light. The mixture was purged with argon for 15 minutes, and NBS (1.767 g, 9.929 mmol, 3.5 eq) was added in small portions then stirred at room temperature for 15 min. DMF anhydrous (10 mL) was added. The resulting mixture was stirred at room temperature under protection of argon for 4 hours. TLC and LCMS showed starting materials were consumed. 25 mL water was added and the organic layer was separated; the water layer was re-extracted with ethyl acetate, washed several times with water, dried with MgSC and concentrated. The crude product was purified by SiCh column chromatography, eluted with Hexanes/ DCM (9:1) to (1:4) resulting in 0.655 g of a mixture of three isomers (tribromo-perylene derivatives, dibromo-perylene derivatives, and tetrabromo-perylene derivatives (7:1:05)). The products were used without any further purification. Yield 38%. LCMS (APCI+), calculated for Formula: C25H17Br302; found: 589.

Methyl 4-(4,9,10-tris(trifluoromethyl)perylen-3-yl)butanoate: A 40 mL screw cap vial was charged with a stir bar and fitted with a screw cap septum. The vial was flushed with argon. To this vial was added methyl 4-(4,9,10-tribromoperylen-3- yl)butanoate (mixture of isomers (0.496 mmol, 292 mg), Cul (4.96 mmol, 944 mg), followed by anhydrous dimethylacetamide (10 mL). With stirring at room temperature was added methyl 2,2-difluoro-2-(fluorosulfonyl)acetate (4.96 mmol, 0.631 mL) via syringe at room temperature. The reaction was placed in a heat block set to 160 °C and stirred for 3 hours. Additional portions of Cul (4.96 mmol, 944 mg) and methyl 2,2-difluoro-2- (fluorosulfonyl)acetate (4.96 mmol, 0.631 mL) were added and the reaction stirred for an additional hour. The reaction mixture was cooled to room temperature and diluted to 100 mL total volume with water. The product was filtered off, washing with water. The precipitate was dried and washed with dichloromethane until the dichloromethane washes where colorless. The combined organic washings were evaporated to dryness and purified by flash chromatography on silica gel (50% toluene/hexanes (1 CV) - 100% toluene (10 CV)). Fractions containing the desired product (as a mixture of isomers) were evaporated to dryness to give 90 mg (33% yield). MS (APCI): calculated for Chemical Formula: C28H17F902 (M-) = 556; found: 556.

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

A 250 mL 2-neck round bottomed flask was charged with a stir bar and flushed with argon. To this flask was added 4-(4,9,10-tris(trifluoromethyl)perylen-3-yl)butanoic acid (3.00 mmol, 1.141 g) and KOH (30.0 mmol, 1.683 g), followed by ethanol (200 proof, 200 mL). The flask was fitted with a finned air condenser and heated in a heat block at 95 °C under argon with stirringfortwo hours. The reaction mixture was cooled to room temperature and diluted with water (to 500 mL total volume) in an Erlenmeyer flask and quenched with aqueous 6N HCI (5 mL). The resulting precipitate was collected and concentrated in vacuo to give a crude precipitate in quantitative yield. MS (APCI): calculated for Chemical Formula: C27H15F902 (M-) = 542; found: 542.

FD-2 _ (Dibenzyl _ 10-(2.6-dimethyl-4-((4-(4.9.10-tris(trifluoromethyl)perylen-3- ynbutanoynoxyiphenyn-S.S-difluoro-l.B.T.Sl-tetramethyl-SH-AIA.SIA-dipyrrolori^-c^'. f1fl.3.2ldiazaborinine-2.8-dicarboxylate): A 40 mL screw cap vial was charged with a stir bar, compound 46.1 [4-(4,9,10- tris(trifluoromethyl)perylen-3-yl)butanoic acid] (0.164 mmol, 89 mg) and compound 44.2 [dibenzyl 5, 5-dif luoro-10-(4-hyd roxy-2, 6-dimethyl phenyl)-l, 3, 7,9-tetramethyl-5H-4l4, 514- dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-2,8-dicarboxylate] , and DMAP:pTsOH 1:1 salt (0.200 mmol, 59 mg). The vial was flushed with argon and anhydrous dichloromethane (20 mL) was added. Diisopropylcarbodiimide (0.300 mmol, 47 pL) was added and the reaction was stirred under argon at room temperature overnight. The next morning, added anhydrous tetrahydrofuran (10 mL) and sonicated for 30 seconds. Added an additional portion of compound 46.1 (0.150 mmol, 51 mg) and stirred at 50 °C under argon overnight. The crude product was purified by flash chromatography on silica gel (100% toluene (2 CV) - 10% EtOAc/toluene (10 CV)). Fractions containing product (as a mixture of isomers) were evaporated to dryness to give 128 mg (67% yield) of FD-2. MS (APCI): calculated for Chemical Formula: C64H48BF11N206 (M-) = 1160; found: 1160.

Synthesis of compound FD-3:

Dibenzyl 10-(4-((4-(4-(6-(4-(diphenylamino)phenyl)-l,3-dioxo-lH- benzo[de]isoquinolin-2(3H)-yl)phenyl)butanoyl)oxy)-2,6-dimethylphenyl)-5,5-difluoro- l,3,7,9-tetramethyl-5H-4A4,5A4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine-2,8- dicarboxylate: To a solution of compound 44.2 [dibenzyl 5,5-difluoro-10-(4-hydroxy-2,6- dimethylphenyl)-l,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[l,2-c:2',l'-f][l,3,2]diazaborinine- 2,8-dicarboxylate] (1.18 mmol, 750 mg), compound 13.3.2 (see synthesis below, 1.30 mmol, 780 mg) and DMAP-pTsOH salt (2.36 mmol, 694 mg) in anhydrous CH₂CI₂ (6.00 mL) was added DIC (7.08 mmol, 1.11 mL) and the reaction mixture was stirred at r.t. for 16 h. It was then filtered through celite and concentrated under reduced pressure. Flash chromatography (7:3, hexanes/EtOAc -> 3:2, hexanes/EtOAc) gave 1.10 g of compound FD-3 (76% yield) as an orange solid. 1H NMR (400 MHz, Chloroform-d) d 8.68 (dd, J = 7.2, 2.4 Hz, 2H), 8.48 (d, J = 8.5 Hz, 1H), 7.77 (dd, J = 9.3, 7.4 Hz, 2H), 7.44 - 7.27 (m, 20H), 7.24 - 7.20 (m, 6H), 7.11 (t, J = 7.3 Hz, 2H), 6.97 (s, 2H), 5.27 (s, 4H), 2.85 (d, J = 13.9 Hz, 8H), 2.67 (t, J = 7.4 Hz, 2H), 2.22 - 2.06 (m, 8H), 1.72 (s, 6H); 19F NMR (376 MHz, Chloroform-d) d -142.72 - -143.09 (m); 13C NMR (101 MHz, Chloroform-d) d 171.5, 164.0, 159.9, 148.4, 147.3, 147.2, 146.9, 136.7, 135.8, 131.6, 131.3, 130.8, 129.5, 128.6, 128.4, 128.3, 127.8, 126.7, 125.1, 123.7, 122.5, 121.8,

121.3, 66.2, 34.8, 33.6, 26.1, 19.7, 15.1, 12.6.

Synthesis of compound FD-4:

Compound 13.3

Compound 13.3.1: [4-(4-(6-bromo-l,3-dioxo-lH-benzo[de]isoquinolin-2(3H)-yl)phenyl)butanoic acid]:

To a solution of 6-bromo-lH,3H-benzo[de]isochromene-l,3-dione (18.4 mmol, 3.30 g) in

EtOH (200 proof, 80.0 mL) was added 4-(4-aminophenyl)butanoic acid (16.0 mmol, 4.43 g) and the reaction mixture was heated to reflux for 16 h. It was then cooled to r.t., diluted with EtOH (200 proof, 50.0 mL), filtered and washed with more EtOH (200 proof, 100 mL) and hexanes (100 mL) to give 5.02 g of Compound 13.3.1 (72% yield) as an off-white solid. 1H NMR (400 MHz, DMSO-d6) d 12.15 (s, 1H), 8.63 - 8.55 (m, 2H), 8.34 (d, J = 7.8 Hz, 1H), 8.25 (d, J = 7.9 Hz, 1H), 8.03 (dd, J = 8.5, 7.3 Hz, 1H), 7.34 (d, J = 8.3 Hz, 2H), 7.29 (d, J = 8.2 Hz, 2H), 2.68 (t, J = 7.3 Hz, 2H), 2.29 (t, J = 7.3 Hz, 2H), 1.87 (p, J = 7.5 Hz, 2H); 13C NMR (101 MHz, DMSO-d6) d 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)-l,3-dioxo-lH-benzo[de]isoquinolin-2(3H)- yl)phenyl)butanoic acid]: To a suspension of compound 13.3.1 (11.2 mmol, 4.93 g) and K2CO3 (16.8 mmol, 2.32 g) in 20:1 EtOH/H₂0 (115 mL) under Ar atmosphere were added Pd(PPh3)4 (0.562 mmol, 649 mg) and (4-(diphenylamino)phenyl)boronic acid (11.8 mmol, 3.41 g) and the reaction mixture was stirred at 80 °C for 16 h. It was then filtered and washed with EtOH (200 proof, 200 mL). The filter cake was partitioned between 1 M HCI (300 mL) and CH2CI2 (300 mL) and the mixture was extracted with CH2CI2 (3 x 300 mL). The combined organics were dried (MgS04) and concentrated under reduced pressure to give 6.50 g of compound 13.3.2 (96% yield) as an orange/red solid. 1H NMR (400 MHz, Chloroform-d) d 8.67 (dd, J =

7.5, 2.5 Hz, 2H), 8.47 (d, J = 8.5 Hz, 1H), 7.79 - 7.71 (m, 2H), 7.42 - 7.36 (m, 4H), 7.33 (apparent t, J = 7.8 Hz, 4H), 7.28 - 7.19 (m, 8H), 7.10 (apparent t, J = 7.3 Hz, 2H), 2.79 (t, J = 7.6 Hz, 2H), 2.46 (t, J = 7.3 Hz, 2H), 2.06 (apparent p, J = 7.6 Hz, 2H); 13C NMR (101 MHz, Chloroform-d) d

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-dimethyl phenyl-4-(4-(6-(4-(dipheny la mino)phenyl)-l,3-dioxo-lH- benzo[de]isoquinolin-2(3H)-yl)phenyl)butanoate]:

To a solution of 4-hydroxy-2,6-dimethylbenzaldehyde (5.97 mmol, 897 mg), compound 13.3.2 (4.98 mmol, 3.00 g) and DMAP-pTsOH salt (9.96 mmol, 2.93 g) in anhydrous CH2CI2 (25.0 mL) was added DIC (29.9 mmol, 4.68 mL) and the reaction was stirred at r.t. for 80 min. It was then filtered through celite and concentrated under reduced pressure. Flash chromatography (toluene -> 9:1, toluene/EtOAc) gave 3.05 g of compound 13.3 (83% yield) as a yellow solid. 1H NMR (400 MHz, Chloroform-d) d 10.57 (s, 1H), 8.70 - 8.64 (m, 2H), 8.48 (dd, J = 8.5, 1.2 Hz, 1H), 7.76 (dd, J = 9.1, 7.4 Hz, 2H), 7.44 - 7.37 (m, 4H), 7.37 - 7.26 (m, 6H), 7.25 - 7.19 (m, 6H), 7.14 - 7.08 (m, 2H), 6.87 (s, 2H), 2.85 (t, J = 7.6 Hz, 2H), 2.69 - 2.59 (m, 8H), 2.16 (p, J = 7.5 Hz, 2H); 13C NMR (101 MHz, Chloroform-d) d 192.3, 171.4, 164.6, 164.4,

148.4, 147.3, 147.2, 143.6, 141.5, 133.5, 133.2, 131.8, 131.6, 131.3, 130.8, 130.2, 130.1,

129.5, 129.5, 129.2, 128.6, 127.7, 126.7, 125.0, 123.7, 123.0, 122.6, 122.4, 121.3, 34.7, 33.6, 26.1, 20.7.

FD-4:

To a mixture of ethyl 2-methyl-lH-pyrrole-3-carboxylate (61 mg, 0.4 mmol), compound 13.3 [4-formyl-3,5-dimethylphenyl 4-(4-(6-(4-(diphenylamino)phenyl)-l,3-dioxo- lH-benzo[de]isoquinolin-2(3H)-yl)phenyl)butanoate] (lOOmg, 0.136mmol), MgS04 (120mg, l.Ommol) in dichloroethane (5 mL), was added 3 drops TFA, then heated at 65 °C for 3 days. To the resulting mixture, was added triethylamine (0.13 mL, 0.9 mmol), BF3-etherate (0.09 mL, 0.5 mmol), then heated at 60 °C for 30 min. After cooled to rt., the mixture was loaded on silica gel, and purified by flash chromatography using eluents of DCM/Ethyl acetate (0% - 10% ethyl acetate). The main fraction was collected, and removal of solvents gave compound FD-4 as an orange-red solid (40 mg, in 27% overall yield). LCMS (APCI): calcd for C65H55BF2N408 (M-): 1068; found: 1068. 1H NMR (400 MHz, d2-TCE) d 8.60 - 8.53 (m, 2H),

8.43 (dd, J = 8.6, 1.2 Hz, 1H), 7.75 - 7.67 (m, 2H), 7.39 (d, J = 8.3 Hz, 2H), 7.36 - 7.30 (m, 2H), 7.24 (dt, J = 13.8, 8.1 Hz, 6H), 7.15 (d, J = 8.6 Hz, 6H), 7.08 - 6.99 (m, 4H), 6.91 (s, 2H), 4.17 (q, J = 7.1 Hz, 4H), 2.84 (s, 6H), 2.80 (m, 2H), 2.65 (t, J = 7.4 Hz, 2H), 2.13 (m, 2H), 2.08 (s, 6H),

1.24 (t, J = 7.1 Hz, 6H).

Synthesis of Second photoluminescent dye (SD-1) ((T-4)-[2-[(4,5-Dihydro-3-methyl-2H-benz[g]indol-2-ylidene-KN)(3,5-dimethyl-4--((4-(4,9,10- tris(trifluoromethyl)perylen-3-yl)butanoyl)oxy)phenyl)methyl]-4,5-dihydro-3-methyl-lH- benz[g]indolato-KN]difluoroboron):

Compound 9.1 (Ethyl 3-methyl-4,5-dihydro-lH-benzo[g]indole-2-carboxylate):

A 250 mL 2-neck round bottomed flask was charged with a stir bar and placed in a heat block. To this flask was 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. A 40 mL screw cap vial was charged with ethyl 2-(hydroxyimino)-3- oxobutanoate (2.50 mmol, 398 mg) and Zn (dust, < 10 um) (12.5 mmol, 818 mg). These materials were slurried in acetic acid (12.5 mL) and added to the stirred reaction containing the ketone in portions over a period of about 5 minutes. This process was repeated three times for a total of 10.0 mmol 2-(hydroxyimino)-3-oxobutanoate and 50.0 mmol Zn dust. 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, then extracted with dichloromethane (4 X 160 mL). The combined organic layers were washed with water (100 mL), brine (100 mL), dried over MgSC>4, filtered, and evaporated to dryness. Most of the excess 1-tetralone was removed on high vacuum with heating. The crude product was purified by flash chromatography on silica gel (5% EtOAc/hexanes (1 CV) - 20% EtOAc/hexanes (10 CV). Fractions containing product were evaporated to dryness to give 1.417 g (55% yield) of compound 9.1. MS (APCI): calculated for Chemical Formula: C16H17N02 (M + H) = 256; found: 256. 1H NMR (400 MHz) d 8.98 (s, 1H), 7.35 - 7.31 (m, 1H), 7.27 - 7.21 (m, 2H), 7.20 - 7.15 (m, 1H), 4.34 (q, J = 7.1 Hz, 2H), 2.99 - 2.92 (m, 2H), 2.70 - 2.64 (m, 2H), 2.31 (s, 3H), 1.39 (t, J = 7.1 Hz, 3H).

Compound 9.2 (3-methyl-4,5-dihydro-lH-benzo[g]indole):

A 250 mL 2-neck round bottom flask was charged with a stir 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 (5.0M in H2O, 25.03 mmol, 5.01 mL). The reaction was stoppered and heated in a heat block at 100 ⁰ C for 90 minutes under argon. The solution becomes homogenous with heating. The temperature was increased to 160 °Cfor30 minutes, then cooled to 100 °C. The reaction was quenched by pouring into stirred water (300 mL). This was brought up to a total volume of 500 mL with water, then it was acidified with a solution of 2.5 M acetic acid/2.5 M NaOAc (20 mL). The pH was reduced to ~3.5 with TFA. The resulting purple solid was filtered off, dried, and purified by flash chromatography on silica gel (5% EtOAc/hexanes (1 CV) - 20% EtOAc/hexanes (10 CV)). Fractions containing product were evaporated to dryness to give 767 mg (84% yield) of compound 9.2. MS (APCI): calculated for Chemical Formula: C13H13N (M + H) = 184 found: 184. 1H NMR (400 MHz, Acetonitrile-d3) d 9.15 (s, 1H), 7.24 (d, J = 7.5 Hz, 1H), 7.20 - 7.13 (m, 2H), 7.00 (td, J = 7.4, 1.4 Hz, 1H), 6.52 (dd, J = 2.3, 0.9 Hz, 1H), 2.90 - 2.83 (m, 2H), 2.62 - 2.55 (m, 2H), 2.00 (s, 3H). Compound 9.3 ((T-4)-[2-[(4,5-Dihydro-3-methyl-2H-benz[g]indol-2-ylidene-KN)( 3,5- dimethyl-4-hydroxyphenyl)methyl]-4,5-dihydro-3-methyl-lH-benz[g]indolato-

KNJdifluoroboron):

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 manner similar 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 from pyrrole) of compound 9.3. MS (APCI): calculated for Chemical Formula: C35H31BF2N20 (M + H) = 544 found: 544. 1H NMR (400 MHz, DMSO-d6) d 9.61 (s, 1H), 8.62 (d, J = 7.9 Hz, 2H), 7.45 - 7.38 (m, 2H), 7.38 - 7.34 (m, 4H), 6.68 (s, 2H), 2.91 - 2.83 (m, 4H), 2.58 - 2.52 (m, 4H), 2.04 (s, 6H), 1.41 (s, 6H).

SD-1:

SD-1 was synthesized from Compound 9.3 (0.116 mmol, 63 mg) and compound 46.1 (4,9,10-tris(trifluoromethyl)perylen-3-yl) butanoic acid, 0.116 mmol, 63 mg) in a manner similar to the final synthesis step for FD-2 (described above). The crude product was purified by flash chromatography on silica gel (60% toluene/hexanes (2 CV) - 100% toluene (isocratic)). Fractions containing product (as a mixture of isomers) were evaporated to dryness to give 84 mg of SD-1 (68% yield). MS (APCI): calculated for Chemical Formula: C62H44BF11N202 (M-) = 1068 found: 1068.

Synthesis of polymer-dye solution

Film EX-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 for several days at 50 °C. Separately, 0.35 mg of a first photoluminescent compound (green emitter) and 0.70 mg of a second photoluminescent compound (red emitter) were added together in a 20 mL vial. 400 microliters were added to 300 mg of silicon beads and were sonicated for 5 minutes. 5 mL of the 25% PMMA solution was added to the 400 ml Si/photoluminescent compound solution and was sonicated for 10 minutes. The resulting solution was removed from the stir plate and sat for about 20 minutes to allow for the reduction of the presence of bubbles. Film Ex-2 (PVB / air voids)

A 22% PVB-A solution was prepared by dissolving 20 g PVB-A polymer in 70 mL cyclopentanone. Separately, 0.3 mg photoluminescent dye FD-1 and 0.75 mg photoluminescent dye SD-1 were combined in a 20 mL vial. To the vial containing the photoluminescent compounds was added 5 mL of the 22% PVB-A solution.

Casting films

Film Ex-1 fPMMA/Bead filml

A glass substrate 4 inches by 4 inches (clean). The resulting substrate solution was cast on a pre-cleaned (washed with soap and water) glass substrate (4 inches by 4 inches by 4 inches) by a casting machine set at casting blade clearance of 200 microns. The casted film was kept under cover for 30 minutes after casting for an additional 30 minutes. The casted glass surface was then placed on a hot plate and baked at 120 °C for about 20 minutes.

Ex-film-2 fPVB/air voidsl

Blade clearance set to 170um, and the solution was cast on a 4 inches by 4 inches pre- cleaned (soap and water) piece of glass as substrate. The final thickness for porous film was about 40-50um. The freshly coated substrate was left to stand in air for 5 minutes, then immersed or submerged completely into a container with water, making sure the whole substrate was immersed. The immersed cast glass was left overnight in water to enable the water to diffuse into the film. After overnight soaking, the submerged cast substrate was taken out and dried at room temperature or up to 50°C in vacuumed oven to evaporate all solvent. Care was taken to prevent exposure to too high a temperature, as T_g of PVB is 70°C, since exposure to that temperature could cause the created air bubbles to collapse.

Additional examples of films were made with varying first photoluminescent emitters and/or polymer matrix materials as set forth in the Table 1 below. Table 1

Brightness measurement system

The wavelength conversion films Ex-1 and Ex-2 were evaluated using an external quantum efficiency measurement system (Model C9920 Hamamatsu Corporation, Bridgewater, NJ, USA) respectively in configurations as depicted in FIG. 6. Photon detector was located at normal angle of the backlight system, only light emitting close to normal angle will be collected. This measurement is good to compare forward scattering property of diffuser film. A brightness of 232 cd/m² was measured for Film Ex-2 (0.3 wt% FD-1: 0.7 wt% SD-1 [PVB/air voids]). A brightness of film Ex-1 was measured as 122 cd/m². FIG. 8. is a graph showing the intensity as a function of wavelength. This shows that backlight + Film Ex-2 was brighter at about 450 nm, 510 nm and 630 nm. Figs. 9 and 10 are graphs showing the intensity as a function of wavelength for the various films created as identified in Table 1.

Backlit film data was generated from the schematic construct described in FIGs. 2 and 3 using a Kindle HDX7 blue backlight (Amazon, Seattle, WA, USA). Data in parentheses used the schematic construct shown in FIG. 3, while data not in parentheses used the schematic construct shown in FIG. 2, as set forth in Table 2 below. Table 2.

Evaluation method of EQE of the emitting device mounted luminescent thin film.

The External quantum yield and other optical characteristics of the improved WLC film compared with other films where tested using the test apparatus configured as set forth in FIG. 7 and test material mounting configurations as shown in FIGs. 4 and 5. BEF used was Vikuiti brand BEF (IBM). DBEF used was DBEFII brand polarizer/enhancement film (3M). A blue light source and various light emitting materials/films (as set forth in the tables below) were compared. The results are shown in the tables below. FIG. 11 depicts a CIE 1931 color chart with the aforementioned results. The comparative color gamut triangles are shown therein.

Table 3: Film Ex-2 compared with commercial QD films using MCPD

Table 4.

Table 5.

Claims

CLAIMS What is claimed is:

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

2. The photoluminescent wavelength conversion film of claim 1, wherein the first photoluminescent dye comprises a BODIPY group, a linking group and a perylene group.

3. The photoluminescent wavelength conversion film of claim 1, wherein the first photoluminescent dye comprises a BODIPY group, a linking group and a naphthalimide group.

4. The photoluminescent wavelength conversion film of claim 1, 2, or 3, wherein the first photoluminescent dye is:

5. The photoluminescent wavelength conversion film of claim 1, 2, or 3, wherein the second photoluminescent dye comprises a BODIPY group, a linking group, and a perylene group.

6. The photoluminescent wavelength conversion film of claim 5, wherein the second

7. The photoluminescent wavelength conversion film of claim 1, 2, 3, 4, 5, or 6, wherein the polymer matrix comprises PMMA, PVB, or a combination thereof.

8. The photoluminescent wavelength conversion film of claim 7 , wherein the polymer matrix comprises PMMA.

9. The photoluminescent wavelength conversion film of claim 7 , wherein the polymer matrix comprises PVB.

10. The photoluminescent wavelength conversion film of claim 1, 2, 3, 4, 5, 6, 1 , 8, or 9, wherein the light scattering centers comprise silica beads, air voids, or a combination thereof.

11. The photoluminescent wavelength conversion film of claim 10, wherein the light scattering centers comprise silica beads.

12. The photoluminescent wavelength conversion film of claim 10, wherein the light scattering centers comprise air voids.

13. The photoluminescent wavelength conversion film of claim 1, 2, 3, 4, 5, 6, 7, 8 ,9, 10, 11, or 12, further comprising one or more brightness enhancement films.

14. The photoluminescent wavelength conversion film of claim 13, comprising two brightness enhancing films and one dual brightness enhancing film.

15. The photoluminescent wavelength conversion film of claim 1, 2, 3, 4, 5, 6, 7, 8 ,9, 10, 11, 12, 13, or 14, wherein the photoluminescent wavelength conversion film has a quantum yield of greater than 85%.

16. The photoluminescent wavelength conversion film of claim 1, 2, 3, 4, 5, 6, 7, 8 ,9, 10, 11, 12, 13, 14, or 15, wherein the photoluminescent wavelength conversion film has a color gamut of greater than 85% of BT2020 standard.

17. The photoluminescent wavelength conversion film of claim 1, 2, 3, 4, 5, 6, 7, 8 ,9, 10, 11, 12, 13, 14, 15, or 16, wherein the photoluminescent wavelength conversion film has a thickness of less than 100 microns.

18. A light emitting device comprising the photoluminescent wavelength conversion film of claim 1, 2, 3, 4, 5, 6, 7, 8 ,9, 10, 11, 12, 13, 14, 15, 16, or 17.

19. A backlit device having a blue light source comprising the photoluminescent wavelength conversion film of claim 1, 2, 3, 4, 5, 6, 7, 8 ,9, 10, 11, 12, 13, 14, 15, 16, or 17.