Blue light absorbing compounds, films, and display devices including the same

Abstract

Blue light absorbing compounds which may exhibit increased durability are disclosed herein.

Description

[0001] BLUE LIGHT ABSORBING COMPOUNDS, FILMS, AND DISPLAY DEVICES INCLUDING THE SAME

[0002] Inventors: Shijun Zheng, Jeffrey R. Hammaker

[0003] CROSS-REFERENCE TO RELATED APPLICATIONS

[0004] This application claims priority to U.S. Provisional Application No. 63 / 654,899, filed May 31, 2024, U.S. Provisional Application No. 63 / 698,496, filed September 24, 2024, and U.S. Provisional Application No. 63 / 698,497, filed September 24, 2024; all of which are incorporated by reference in their entirety.

[0005] BACKGROUND

[0006] Unless otherwise indicated in the present disclosure, the details described in the present disclosure are not prior art to the claims in the present application and are not admitted to be prior art by inclusion in this section.

[0007] 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 their light emission mechanism.

[0008] 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, these inorganic photoluminescent substances are cost intensive, have low light emission efficiency, and the emission of light in a near ultraviolet or blue region of 400 nm or higher is limited.

[0009] Quantum dot technology has been used to achieve a high level of quantum efficiency and color gamut. However, cadmium-based quantum dots may 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 may 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 may be difficult to control size uniformity during their production.

[0010] Fluorescent inks or toners have been described (e.g., in United States Patent Number 5,681 ,381 and United States Patent Publication Number 2003 / 00841). However, their use with a source light arising from plural pixelated sources of different colors, e.g., blue, green and red, raises additional problems arising from the different colored light sources. Some toners or inks have included fluorescence resonance energy transfer (FRET) technology, but the quantum yield has not always been at the desired level.

[0011] Isoquinoline compounds are described in United States Patent No. 9,969,932 for use in a white film context. Other examples of isoquinoline embodiments may include a blue absorber element and an emitter element, where the blue absorber compound is covalently linked to the emitter element (FRET) (See e.g., PCT / US2024 / 02237, filed March 29, 2024). However, in the context of some pixel formulations, the concentration of the blue absorber compound may be much greater than in the white film context, e.g., about 100 times greater. Covalent linkage or linkage between the blue absorbing compound and the green / red light emitting compound, e.g., a FRET compound, may not be required but the high concentration of the blue absorbing compound may lead to increased and more rapid deterioration of the blue emitting compound.

[0012] Therefore, there is a need for a blue absorbing chromophore compound having increased durability, including for example increased durability in pixelated media and / or printer inks for use with pixelated light sources.

[0013] SUMMARY

[0014] The present disclosure relates to blue light absorbing compounds, and to films and light-emitting display devices including the same. The compounds may be according to the following formula: wherein:

[0015] Ri is a C1-C5 alkyl substituted aryl ; and each of R2, R3, R4, Rs and Re is independently selected from H and an aryl substituted with at least one trihaloalkyl provided that at least one of R2, R3, R4, Rs and Re is an aryl substituted with at least one trihaloalkyl.

[0016] In some forms, R1 may be where each of R7 and Rs is a C1-C5 alky. In some forms, R1 may some forms, R2 Rs,R4, Rs and Re may independently be one some forms, the blue light absorbing compound may have one of the following structures:

[0017]

[0018]

[0019] In some forms, one or more of the aforementioned blue light absorbing compounds may display an at least 15% durability increase in T80% @150mW / cm2relative to a compound which does not include at least one of R2, R3, R4, Rs and Re as an aryl substituted with at least one trihaloalkyl.

[0020] In one embodiment, a blue light absorption media may include a blue light absorbing compound described herein and a polymer matrix. The blue light absorbing compound may be disposed within the polymer matrix, and the absorption media may absorb light between about 400 nm to about 500 nm. In some forms, the optical density of the light absorption media may be about 0.5 to about 2.

[0021] In a further embodiment, a wavelength converting media mixture may include a blue light absorbing compound and a photoluminescent dye where the photoluminescent dye includes a narrowly emitting moiety. In one form, the blue light absorbing compound and the photoluminescent dye may be disposed within an ink media.

[0022] These and other embodiments are described in greater detail below.

[0023] DETAILED DESCRIPTION

[0024] The present disclosure relates to blue light absorbing compounds, and to films and media containing same. In some aspects, the blue light absorbing compounds, films and / or media may exhibit increased photostability. For example, the provision of at least one trihaloalkyl aryl, such as a trifluoromethyl aryl, on an isoquinoline structure of the blue light absorbing compound may significantly improve the photostability of the blue light absorbing compound.

[0025] In some embodiments, a blue light absorbing compound may include a isoquinoline, isoquinoline derivative, or xanthenoisoquinoline derivative. In some embodiments, the blue light absorbing compound may be a compound according to the following formula: may be a substituted aryl group, and where Y may be a hydrogen group or an aryl substituted with at least one trihalogen group.

[0026] In some embodiments, a blue light absorbing compound may include a naphthalimide or naphthalimide derivative. In some forms, the blue light absorbing compound may include a naphthalic imide group. In some forms, the blue light absorbing compound may be a compound according to the following formula: substituted aryl ; and each of R2,

[0027] R3, R4, Rs, and Re is selected from H and an aryl with at least one trihaloalkyl (e.g., a -

[0028] CF3) substitution provided that at least one of R2, R3, R4, Rs, and Re is an aryl with at least one trihaloalkyl (e.g., a -CF3) substitution. In some forms, the C1-C5 alkyl substituted aryl alkyl may some aspects, the presence of the isopropyl group(s) in these structures may improve solubility and stability. In some forms, each of R2, R3, R4, Rs, and Re may independently be selected from one of H, some forms, when the blue light absorbing compound is included in a matrix polymer, inclusion of the -CF3 group on the phenyl substitution of the blue light absorbing compound may lead to increased solubility in the matrix polymer to prevent aggregation, which results in significant improvement of photostability.

[0029] In some forms, the blue light absorbing compound may be one of the following compounds:

[0030]

[0031] In one embodiment, a blue light absorbing compound described herein may absorb visible light between about 350 nm, about 400 nm, or about 450 nm to about 475 nm, about 500 nm, or about 550 nm, or any permutation of these values, e.g., from about

[0032] 400 nm to about 500 nm. In some forms, the optical density of a light absorption media including a compound described herein may be between about 0.1 , about 0.25, about 0.5, about 0.75, or about 1.0 to about 1.5, about 2.0, or about 2.5 and / or any permutations of these values.

[0033] In some embodiments, one or more blue light absorbing compounds described herein may exhibit increased durability. For example, in some embodiments, one or more blue light absorbing compounds described may display at least about a 5%, about a 10%, about a 15%, about a 20%, or about a 25% durability increase in T80% @150mW / cm2relative to a comparative example that is similar but does not include at least one trihaloalkyl substituted aryl as described herein. For example, in some aspects the T80% may be increased from 27 hours of the comparative example to at least 33 hours and / or 35 hours at the concentration of 0.5 mM in matrix polymer, although other variations in the increase are possible and contemplated. In some forms, the durability in T80% @ 150 mW / cm2of one or more blue light absorbing compounds may be increased from 30 hours of a comparative example that does include at least one trihaloalkyl substituted aryl as described herein to 69 and / or 92 hours at the concentration of 5 mM in matrix polymer, although other variations in the increase are possible and contemplated.

[0034] In one embodiment, a film includes a blue light absorbing compound described herein. In some forms, the film may include a polymer matrix, and the polymer matrix may have a transparency greater than about 75%. In some forms, the polymer matrix may include a hydrophilic polymer. In some forms, the polymer matrix may include Polyethylene terephthalate glycol (PETG), polyvinyl butyral, polyvinyl acetate, polyvinyl alcohol, or a polyacrylate. In some forms, the polyacrylate may be a polyalkylacrylate such as polymethylmethacrylate (PMMA). In some forms, the polymer matrix may include ethyl cellulose and / or polyester or copolymers including the same. In some forms, the blue light absorbing compound is disposed within the polymer matrix. In one embodiment, a display device may include the film and / or a compound described herein.

[0035] In some forms, the film may further include a transparent substrate. In forms where the film includes a transparent substrate, the wavelength converting media may include scattering centers disposed within an ink media. In some forms, the film may include scattering centers disposed within the polymer matrix. In some forms, the scattering centers may be solid particles including scattering materials having a refractive index (Rl) different than the refractive index of the polymer matrix material. Scattering material(s) may be useful in increasing external quantum yield, e.g., by reducing total internal reflection. Non-limiting examples of scattering materials and their respective Rl values include:

[0036] In some forms, the difference in Rl between the polymer matrix and the scattering material may be at least about 0.05, at least about 0.1 , at least about 0.2, at least about 0.3, at least about 0.4, or at least about 0.5, or up to about 1 or about 2, although other variations are possible and contemplated.

[0037] In some forms, the scattering material may include silicone beads. In some forms, the scattering centers may include air voids defined within the polymer matrix. In some forms, the scattering centers may have an average diameter of between about 1 nm, about 5 nm and / or about 10 nm to about 150 nm, about 175 nm, about 200 nm and / or about 250 nm, or any average diameter in a range bounded by any of these values. In some forms, the scattering centers may be substantially uniformly dispersed within the polymer matrix. In some forms, the top-level portion of the film, for example, the side configured to be positioned distal to a blue light emitting source, may include greater than 50% of the scattering centers. In some forms, the scattering centers may be uniformly distributed throughout the polymer matrix.

[0038] Hereinafter, embodiments and methods will be described in more detail.

[0039] EXAMPLES

[0040] Various benefits, including improved performance, of the subject matter disclosed herein 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.

[0041] Synthesis of blue absorber compound

[0042] 1.1 Synthesis of Compound BAC2-1

[0043] Compound BAC2-1.1 (5,11-dibromo-1 H,3H-isochromeno[6,5,4-mna]xanthene-1,3- dione): A 2L 2N round bottom flask was charged with a stir bar and fitted with a long- finned condenser. 1 H,3H-isochromeno[6, 5, 4-mna]xanthene-1 , 3-dione (synthesized according to literature: RSC Adv., 2014, 4, 53072-53078) (34.688 mmol, 10.00 g) was added to the flask, followed by the addition of ortho-dichlorobenzene (ODCB)(1000 mL). The reaction mixture was stirred at room temperature and Br2 (416.26 mmol, 21.3 mL) was added. The second neck was stoppered and the reaction mixture was heated at 75 °C open to air over the weekend. The reaction mixture was cooled to room temperature and a solid was filtered off. The filtrate was diluted with hexanes (-20% of volume) and a second precipitate was filtered off. Both of these precipitates were dried in vacuo at 100 °C. Orangish solids (BAC2-1.1), 10.866 g total (69.9% yield) were obtained. Both had similar LCMS and NMR. MS (APCI): calculated for Chemical Formula: CisHeB^Ot (M+H) = 445; found: 445.

[0044] 1 H NMR (400 MHz, TCE) 5 9.47 (dd, J = 8.4, 1.5 Hz, 1 H), 8.76 (d, J = 14.2 Hz, 2H), 7.72 - 7.63 (m, 1 H), 7.56 (dd, J = 8.3, 1 .4 Hz, 1 H), 7.46 (ddd, J = 8.5, 6.7, 1.9 Hz, 1 H).

[0045] Compound BAC2-1.2: A mixture of compound BAC2-1.1 (2.066 g, 4.6 mmol), and 2,6- diisopropylaniline (3.26 g, 18 mmol) in 40 mL propionic acid was heated at 165 °C for 48 hours under inert atmosphere. After being cooled to room temperature, the mixture was diluted with 300 mL DCM, and stirred for 5 min. The resultant mixture was filtered, and a yellow solid was collected and dried in vacuum to afford 1.57 g of desired product. The filtrate solution was washed with water (200 mL) and 5% Na2COs aqueous solution (150 mL x 3). The organic phase was collected, dried over MgSC>4, loaded on silica gel and purified by flash chromatography using eluents of hexanes / DCM (0% to 100% DCM). The first main peak was collected as the desired product. Removal of solvents gave a yellow solid, which combined with the solid collected from filtration (total: 2.4 g, in 86% yield).

[0046] 1H NMR (400 MHz, CDCI3) 6 9.54 (dd, J = 8.4, 1.5 Hz, 1 H), 8.87 (d, J = 14.7 Hz, 2H), 7.66 (ddd, J = 8.4, 7.1 , 1.5 Hz, 1 H), 7.61 - 7.41 (m, 3H), 7.36 (d, J = 7.8 Hz, 2H), 2.69 (p, J = 6.9 Hz, 2H), 1.18 (dd, J = 6.8, 1.5 Hz, 12H).

[0047] Compound BAC2-1 : A mixture of compound BAC2-1.2 (0.37 g, 0.61 mmol), (3,5- bis(trifluoromethyl)phenyl)boronic acid (0.37 g, 1.8 mmol), Pd(PPh3)4 (140 mg, 0.12 mmol), and K2CO3 (248 mg, 1.8 mmol) in dioxane / water (25 mL / 5 mL) was heated at 100 °C under argon atmosphere overnight. After being cooled to room temperature, the mixture was loaded on silica gel and purified by flash chromatography using eluents of hexanes / DCM (0% to 100 % DCM). The main peak was collected, and removal of solvents gave a yellow solid (0.45 g, in 84% yield).

[0048] LCMS (APCI-): Calcd for C46H29F12NO3 (M-) = 871.2; Found: 871.

[0049] 1H NMR (400 MHz, CDCI3) 6 8.81 (s, 1 H), 8.56 (s, 1 H), 8.29 (s, 2H), 8.06 (d, J = 10.0 Hz, 4H), 7.57 - 7.45 (m, 2H), 7.37 (d, J = 7.7 Hz, 2H), 7.26 (d, J = 1.2 Hz, 1 H), 7.07 - 6.95 (m, 2H), 2.86 - 2.65 (m, 2H), 1.21 (dd, J = 6.9, 3.6 Hz, 12H).

[0050] 1.2 Synthesis of Compound BAC2-2

[0051] Compound BAC2-2: A mixture of compound BAC2-1.2 (0.37g, 0.61 mmol), (4- (trifluoromethyl)phenyl)boronic acid (0.342 g, 1.8 mmol), Pd(PPh3)4 (140 mg, 0.12 mmol), and K2CO3 (248 mg, 1.8 mmol) in dioxane / water (9 mL / 1 mL) was heated at 100 °C under argon atmosphere overnight. The resultant mixture was loaded on silica gel after being cooled to room temperature, then purified by flash chromatography using eluents of hexanes / DCM (0% to 100% DCM). The main peak was collected, and removal of solvents gave a yellow solid, which was washed with MeOH, then filtered and dried in air to give a bright yellow solid (BAC2-2) (0.38 g, in 85% yield).

[0052] LCMS (APCI-): Calcd for C44H31F6NO3 (M-) = 735.22; Found: 735.1H NMR (400 MHz, CDCI3) 6 8.77 (s, 1 H), 8.54 (s, 1 H), 7.94 (d, J = 8.1 Hz, 2H), 7.89 - 7.80 (m, 4H), 7.70 (d, J = 8.0 Hz, 2H), 7.55 - 7.46 (m, 1 H), 7.42 (ddd, J = 8.5, 7.2, 1 .5 Hz, 1 H), 7.36 (d, J = 7.8 Hz, 2H), 7.30 (d, J = 1.3 Hz, 1 H), 7.16 (dd, J = 8.3, 1.5 Hz, 1 H), 6.95 (ddd, J = 8.3, 7.1 , 1.4 Hz, 1 H), 2.77 (p, J = 6.8 Hz, 2H), 1.20 (dd, J = 6.8, 3.7 Hz, 12H).

[0053] 1.3 Synthesis of BAC2-3: Compound BAC2-3.1 : A mixture of 4-bromo-1 ,8-naphthalic anhydride (2.77g, 10 mmol) and 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 °C overnight under argon atmosphere. After being cooled down to room temperature 50 mL of 20% hydrochloride acid aqueous solution was added dropwise to the solution, followed by the addition of 50 mL of water. 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 of crude product. The crude product was dispersed in 30 mL of acetone and stirred overnight at room temperature to dissolve the impurities. Filtration and drying in vacuum gave a brown yellow solid as desired product (3.3g, in 80% yield). LCMS (APCI+): calcd for Ci8H9BrNO6(M+H) = 413.95; Found: 414.

[0054] 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).

[0055] Compound BAC2-3.2: A mixture of compound BAC2-3.1 (1.5 g, 3.6 mmol) and iron powder (0.60 g, 10.8 mmol) in acetic acid (50 mL) was heated at 125 °C for 30 min. After being cooled to room temperature, 100 mL of water was added to the mixture while stirring. The resulting mixture was filtered and washed with water, dried in air and vacuumed to give a solid (1.35 g, in 82% yield). LCMS (APCI-): calcd for CisHwBrNCL = 382.98; Found: 383.

[0056] 1H NMR (400 MHz, DMSO-cfe) 6 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).

[0057] Compound BAC2-3.3: Compound BAC2-3.2 (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 of water was added dropwise at 0 °C. The whole was stirred for one hour at 0 °C, then it was transferred into an additional funnel, and dropped into a copper sulfate solution (12g, 47 mmol, in 140 mL water) over a one hour period at 130 °C. After being cooled to room temperature, the precipitate was collected by filtration, washed with water (100mL x 3), then stirred in 50 mL of acetone at 40 °C for 30 min. Filtration and drying in air then in vacuum gave a brown yellow solid (1.76g, in 70% yield). LCMS (APCI+): calcd for Ci8H8BrO4(M+H) = 366.95; Found: 367.

[0058] 1H NMR (400 MHz, d2-TCE) 5 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).

[0059] Compound BAC2-3.4 (5,9,11 -tribromo-1 H,3H-isochromeno[6,5,4-mna]xanthene- 1 ,3-dione): 9-bromo-1 H,3H-isochromeno[6, 5, 4-mna]xanthene-1 , 3-dione (1576-104) (5.000 mmol, 1836 mg) and NBS (10.50 mmol, 1869 mg) were combined in 96% sulfuric acid and stirred at 60 °C for 40 minutes, then cooled to room temperature. The mixture was poured into -500 mL of water and crushed ice with stirring for 15 minutes, then the resulting precipitate was filtered off and washed with water. The precipitate was dried in a vacuum oven at 80 °C to give a brownish solid (assume 100%), and taken directly to the next step. LCMS shows a mixture of tri-bromo and tetra-bromo isomers that was too insoluble for NMR.

[0060] Compound BAC2-3.5 (5,7,9,11-tetrabromo-2-(2,6-diisopropylphenyl)-1 H- xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione): Compound BAC2-3.4 (assume 100% yield, 5.000 mmol, 2625 mg) was stirred with 2,6-diisopropylaniline (50.00 mmol, 9.4 mL) in propionic acid (50 mL) under argon overnight at 150 °C. The mixture was cooled to room temperature, diluted with water, acidified to pH -1 with 6N HCI, and more water was added (-300 mL) to precipitate the product. The precipitate was taken up in methanol, added -25% v / v water, and the resulting precipitate was filtered off again, and dried in a vacuum oven at 80 °C to give a mixture of tri-bromoimides and tetra-bromoimides with the same ratio as in the previous step. It was used in the next step without further purification. Assume 100% yield.

[0061] Compound BAC2-3 (5,9,11-tris(3,5-bis(trifluoromethyl)phenyl)-2-(2,6- diisopropylphenyl)-1 H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione): Compound

[0062] BAC2-3.5 (5.000 mmol, 3421 mg), (3,5-bis(trifluoromethyl)phenyl)boronic acid (30.00 mmol, 7737 mg), potassium carbonate (50.00 mmol, 6911 mg), and Pd(dppf)Cl2 (0.7500 mmol, 549 mg) were stirred in dry THF (120 mL) and water (30 mL) under argon at 80 °C for 90 minutes. LCMS shows loss of most of tetra-bromo (dehydrohalogenation), giving -10% di-, 20% tetra-, and tri-. The reaction mixture was cooled to room temperature, the THF removed in vacuo, and the residue taken up in DCM / water with filtering through a polypropylene frit to retain water, and eluting with DCM. To the DCM was added ~45g of flash silica gel, the solvent removed in vacuo, the silica packed into a loading tube, and purified by flash chromatography on silica gel (220g, 30% DCM / hexanes (2 CV) 50% (10 CV), stopping the gradient at 35.0% and eluting isocratic for the rest of the run). Fractions containing product were evaporated to dryness in vacuo to give a yellow solid, which NMR showed is a mixture of isomers. The yellow residue was dissolved in hot methanol and allowed to cool and crystallize overnight. The resulting crystals were filtered off, washing with a small volume of methanol. The crystals were dried under high vacuum at 100 °C to give a yellow solid, 1531 mg (24% yield from mono-bromo-anhydride). MS (APCI): calculated for Chemical Formula: Chemical Formula: C54H31F18NO3 (M+H) 1084; found: 1084. 1 H NMR (400 MHz, TCE) 5 8.79 (s, 1 H), 8.55 (s, 1 H), 8.32 - 8.27 (m, 2H), 8.16 (s, 1 H), 8.12 (d, J = 1.6 Hz, 2H), 8.06 (s, 1 H), 7.84 (s, 1 H), 7.75 (dd, J = 8.6, 2.2 Hz, 1 H), 7.49 (t, J = 7.8 Hz, 1 H), 7.44 - 7.37 (m, 3H), 7.34 (d, J = 7.8 Hz, 2H), 7.28 (d, J = 2.2 Hz, 1 H), 3.46 (s, 4H), 2.71 (h, J = 6.8 Hz, 2H), 1.18 (dd, J = 6.9, 3.6 Hz, 12H). 1.4 Synthesis of Compound BAC2-4

[0063] Exact Mass: 599.25

[0064] Molecular Weight: 599.73

[0065] CE-1

[0066] Compound CE-1 : A mixture of compound BAC2-1.2 (0.4g, 0.66 mmol), (phenyl)boronic acid (0.244 g, 2.0 mmol), Pd(PPhs)4 (58 mg, 0.05 mmol), and K2CO3 (276 mg, 2.0 mmol) in dioxane / water (9 mL / 1 mL) was heated at 100 °C under argon atmosphere overnight.

[0067] The resultant mixture was loaded on silica gel after being cooled to room temperature, then purified by flash chromatography using eluents of hexanes / DCM (0% to 100% DCM). The main peak was collected, and removal of solvents gave a yellow solid, which was washed with MeOH, then filtered and dried in air to give a bright yellow solid (0.37 g, in 93% yield). Compound CE-1 is disclosed in U.S. Patent No. 9,969,932.

[0068] LCMS (APCI-): Calcd for C42H33NO3 (M-) = 599.25; Found: 599.

[0069] 1H NMR (400 MHz, CDCI3) 5 8.77 (s, 1 H), 8.56 (s, 1 H), 7.88 - 7.75 (m, 2H), 7.63 - 7.43 (m, 9H), 7.42 - 7.32 (m, 3H), 7.26 - 7.18 (m, 2H), 6.93 - 6.80 (m, 1 H), 2.79 (p, J = 6.8 Hz, 2H), 1.20 (dd, J = 6.8, 2.7 Hz, 12H).

[0070] Chemical Formula: C30H22Br3NO3 Chemical Formula: C51H34F9NO3 Exact Mass: 680.91 Exact Mass: 879.24 Molecular Weight: 684.22 Molecular Weight: 879.82

[0071] BAC2-4.2 BAC2-4

[0072] Compound BAC2-4.1 : To a solution of compound BAC2-1.1 (1.0 g, 2.23 mmol) in 6 mL of 96% concentrated sulfuric acid, NBS (0.5 g, 2.8 mmol) was added, and the mixture was stirred at 50 °C for 2 hours. The resulting mixture was poured into water (150 mL) while stirring, and a yellow precipitate formed. The yellow precipitate was collected by filtration then dried in vacuum to give a yellow solid (1.16 g, in quantitative yield).

[0073] LCMS (APCI-): calcd for Ci8H5Br3O4 = 521.77; found: 521.7.

[0074] 1H NMR (400 MHz, CDCI3) 6 9.69 (d, J = 2.2 Hz, 1 H), 8.88 - 8.76 (m, 2H), 7.77 (dd, J = 8.7, 2.3 Hz, 1 H), 7.72 - 7.50 (m, 1 H), 7.44 (d, J = 8.7 Hz, 1 H).

[0075] Compound BAC2-4.2: A mixture of compound BAC2-4.1 (1.16 g, 2.2 mmol) and 2,6- diisopropylaniline (3 mL, 15.6 mmol) in propionic acid (25 mL) was heated at 170 °C overnight. The resulting mixture was diluted with 200 mL of DCM, then washed with water (200 mL x 2) and 5% NaHCO3 (100 mL x 2), then dried over MgSC>4, loaded on silica gel and purified by flash chromatography using eluents of hexanes / DCM (0% to 60% DCM). The 1stmain peak was collected, then removal of the solvents gave a yellow solid (1.0 g, in 66.4% yield).

[0076] LCMS (APCI-): calcd for C3oH22Br3N03 = 680.91 ; Found: 680.8.

[0077] 1H NMR (400 MHz, CDCI3) 6 9.90 - 9.46 (m, 1 H), 8.98 - 8.77 (m, 2H), 7.90 - 7.64 (m, 1 H), 7.62 - 7.41 (m, 2H), 7.36 (d, J = 7.7 Hz, 2H), 2.67 (p, J = 6.7 Hz, 2H), 1.18 (dd, J = 6.9, 1.9 Hz, 12H). Compound BAC2-4: A mixture of compound BAC2-4.2 (0.52 g, 0.76 mmol), 4- trifluoromethylphenylboronic acid (1.444 g, 7.6 mmol), Pd(PPh3)4 (0.14 g, 0.12 mmol), and K2CO3 (0.69 g, 5 mmol) in 1 ,4-dioxane / water (15 mL / 1.5 mL) was degassed then heated at 100 °C under argon for 16 hours. The resulting mixture was diluted with 200 mL of DCM, washed with water and brine, dried over MgSC>4, then loaded on silica gel, and purified by flash chromatography using eluents of hexanes / DCM (0% to 30% DCM). The main fractions were collected then submitted for another chromatography separation using eluents of hexanes / toluene (0% to 80% toluene). The 1stmain peak was collected as the desired product. Removal of solvents gave a yellow solid (0.48 g, in 77.8% yield). LCMS (APCI-): Calcd for C51H34F9NO3 = 879.24; Found: 879.1.

[0078] 1H NMR (400 MHz, TCE) 5 8.64 (s, 1 H), 8.44 (s, 1H), 7.86 (dd, J = 8.2, 6.2 Hz, 4H), 7.78 (d, J = 8.3 Hz, 2H), 7.69 (d, J = 7.9 Hz, 2H), 7.57 (dd, J = 8.6, 2.2 Hz, 1 H), 7.50 - 7.36 (m, 4H), 7.31 (d, J = 8.6 Hz, 1 H), 7.28 - 7.22 (m, 3H), 7.01 (d, J = 8.0 Hz, 2H), 2.65 (p, J = 6.8 Hz, 2H), 1.08 (dd, J = 6.9, 3.1 Hz, 12H).

[0079] 1.5 Synthesis of BAC2-5

[0080] Compound BAC2-5.1 : To a solution of 5, 11 -dibromoisochromenoxanthene- 1 , 3-dione (1.0 g, 2.23 mmol) in 6 mL of 96% concentrated sulfuric acid NBS (1.1 g, 6.18 mmol) was added and the mixture was stirred at 50 °C for 2 hours. The resulting mixture was poured into water (150 mL) while stirring, and a yellow precipitate formed. The yellow precipitate was collected by filtration then dried in vacuum to give a yellow solid (1 .3 g, in 94% yield). LCMS (APCI-): Calcd for Ci8H4Br4O4 (M-) = 599.68; Found: 600. 1H NMR (400 MHz, CDCI3) 6 9.79 (d, J = 4.2 Hz, 1 H), 8.82 - 8.76 (m, 3H).

[0081] Compound BAC2-5.2: A mixture of compound BAC2-5.1 (1.3 g, 2.15 mmol) and 2,6- diisopropylaniline (3 mL, 15.6 mmol) in propionic acid (25 mL) was heated at 170 °C overnight. The resulting mixture was diluted with 200 mL DCM, then washed with water (200 mL x 2) and 5% NaHCCh (100 mL x 2), then dried over MgSCL, loaded on silica gel and purified by flash chromatography using eluents of hexanes / DCM (0% to 100% DCM). The main peak was collected and concentrated, then submitted to chromatography again using eluents of hexanes / toluene (0% to 100% toluene). The desired fractions were collected, and removal of the solvents gave a yellow solid (0.68 g, in 41% yield).

[0082] LCMS (APCI-): calcd for C3oH2iBr4N03 = 758.83; Found: 759.

[0083] Compound BAC2-5: A mixture of compound BAC2-5.2 (0.68 g, 0.89 mmol), 4- trifluoromethylphenylboronic acid (1.709 g, 9 mmol), Pd(PPhs)4 (0.20 g, 0.17 mmol), and K2CO3 (1.38 g, 10 mmol) in 1 ,4-dioxane / water (20 mL / 2 mL) was degassed then heated at 100 °C under argon for 16 hours. The resulting mixture was diluted with 200 mL DCM, washed with water and brine, dried over MgSO4, then loaded on silica gel, and purified by flash chromatography using eluents of hexanes / DCM (0% to 30% DCM). The main fractions were collected then submitted for another chromatography separation using eluents of hexanes / toluene (0% to 60% toluene). The 1stmain peak was collected as the desired product. Removal of solvents gave a yellow solid (0.50 g, in 55% yield).

[0084] LCMS (APCI-): calcd for C58H37F12NO3 = 1023.26; Found: 1023.

[0085] 1H NMR (400 MHz, CDCI3) 6 8.83 - 8.52 (m, 2H), 8.02 - 7.69 (m, 7H), 7.68 - 7.45 (m, 4H), 7.45 - 7.29 (m, 5H), 7.22 - 6.98 (m, 3H), 6.90 - 6.57 (m, 2H), 2.75 (q, J = 6.8 Hz, 2H), 1.18 (dd, J = 7.0, 3.7 Hz, 12H).

[0086] 1.6 Synthesis of BAC2-6

[0087] Compound BAC2-6: A mixture of compound BAC2-6-1 (0.37g, 0.61 mmol), (3-

[0088] (trifluoromethyl)phenyl)boronic acid (0.342 g, 1.8 mmol), Pd(PPhs)4 (140 mg, 0.12 mmol), and K2CO3 (248 mg, 1.8 mmol) in dioxane / water (9 mL / 1 mL) was heated at 100 °C under argon atmosphere overnight. The resulting mixture was loaded on silica gel after being cooled to room temperature, then purified by flash chromatography using eluents of hexanes / EA (0% to 10% EA). The main peak was collected, and removal of solvents gave a yellow solid, which was washed with MeOH, and after filtration and drying in air it gave a bright yellow solid (0.35 g, in 78% yield).

[0089] LCMS (APCI-): Calcd for C44H31F6NO3 (M-) = 735.22; Found: 735.

[0090] 1H NMR (400 MHz, TCE) 58.63 (s, 1 H), 8.41 (s, 1H), 8.02 (s, 1H), 7.91 (d, J= 7.5 Hz, 1H), 7.76-7.58 (m, 6H), 7.42-7.29 (m, 2H), 7.27-7.14 (m, 3H), 6.98 (dd, J= 8.3, 1.5

[0091] Hz, 1H), 6.84 (ddd, J=8.4, 7.1, 1.4 Hz, 1H), ,2.64 (p, J = 6.8Hz, 2H), 1.08 (dd, J = 6.9, 3.0 Hz, 12H).

[0092] Synthesis of BAC2-7, BAC2-10, and BAC2-13:

[0093] BAC2-7-3

[0094]

[0095] Compound BAC2-7-1 (6-(4-bromo-2-nitrophenoxy)-1 H,3H-benzo[de]isochromene- 1, 3-dione): A mixture of 4-bromo-1 ,8-naphthalic anhydride (2.77 g, 10 mmol), and 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 °C overnight under argon atmosphere. After being cooled down to room temperature, 50mL of 20% hydrochloride acid aqueous solution was added dropwise to the solution, followed by the addition of 50 mL of water. The resulting mixture was allowed to stand for 3 hrs, then it was filtered to collect the precipitate, which was dried in vacuum to afford 4.6 g of crude product. The crude product was dispersed in 30 mL of acetone and stirred overnight at room temperature to dissolve the impurities. Filtration and drying in vacuum gave a yellow brown solid as the desired product (3.3 g, in 80% yield). LCMS (APCI+): calcd for Ci8H9BrNO6(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 BAC2-7-2 (6-(2-amino-4-bromophenoxy)-1 H,3H- benzo[de]isochromene-1, 3-dione): A mixture of compound BAC2-7-1 (1.5 g, 3.6 mmol) and iron powder (0.60 g, 10.8 mmol) in acetic acid (50 mL) was heated at 125 °C for 30 min. After being cooled to room temperature, 100 mL of water was added to the mixture while stirring. The resulting mixture was filtered and washed with water, and dried in air and vacuum to give a solid (1.35 g, in 82% yield). LCMS (APCI-): calcd for CisHwBrNCL = 382.98; Found: 383.1H NMR (400 MHz, DMSO-cfe) 6 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).

[0096] Compound BAC2-7-3 (9-bromo-1 H,3H-isochromeno[6,5,4-mna]xanthene-1,3- dione): Compound BAC2-7-2 (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 °C. The whole was stirred for one hour at 0 °C, then it was transferred into an addition funnel, and dropped into a copper sulfate solution (12g, 47 mmol, in 140 mL water) over a one hour period at 130 °C. After being cooled to room temperature, the precipitate was collected by filtration, washed with water (100mL x 3), and then stirred in 50 mL of acetone at 40 °C for 30 min. Filtration and drying in air then in vacuum gave a brown yellow solid (1.76g, in 70% yield). LCMS (APCI+): calcd for C18H8BrO4 (M+H) = 366.95; Found: 367.1H NMR (400 MHz, d2-TCE) 5 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).

[0097] Compound BAC2-7-4 (5,9,11-tribromo-1 H,3H-isochromeno[6,5,4-mna]xanthene- 1 ,3-dione): Compound BAC2-7-3 (20.00 mmol, 7434 mg) was physically mixed with NBS (42.00 mmol, 7476 mg) in a round bottom flask with a stir bar. To the flask was added 96% sulfuric acid (60 mL) and the resulting slurry was stirred and heated to 60 °C for 30 minutes, then additional NBS was added (30.00 mmol, 5340 mg) and the slurry stirred at 60 °C for an additional 20 minutes. The mixture was then cooled to room temperature. The slurry was poured into 300 mL of stirred water, using acetone to help transfer (small volumes). The resulting slurry was stirred over the weekend, then filtered off, washing with water. The resulting precipitate was suspended in hot methanol, cooled to room temperature, filtered, suspended in acetone, the precipitate filtered again, and then the residue was dried in vacuo to give a yellowish solid, 10800 mg, quantitative yield. LCMS shows a mixture of tri-, tetra-, and penta-bromo isomers, with penta-bromo being the predominant species, along with other impurities. Not soluble enough for NMR. Used in next step as-is.

[0098] Compound BAC2-7-5 (1,3,5-triisopropyl-2-nitrobenzene): 1 ,3,5-triisopropylbenzene (209.4 mmol, 42800 mg) was stirred in acetic acid (200 mL) and acetic anhydride (150 mL) at room temperature with a large stir bar and treated with 90% nitric acid (18.1 mL) over a period of about 5 minutes with vigorous stirring. The stirring was continued for another 20 minutes, then the mixture was poured into 1 L of water and stirred, then diluted to 1.8L with water and stirred for about 10 minutes. The resulting waxy precipitate was filtered off, washed with water, dissolved in DCM, separated from water, dried over magnesium sulfate, filtered, and evaporated to dryness in vacuo. The residue was taken up in a small volume of hot methanol, then placed in a -20 °C freezer overnight, along with a portion of pure methanol. In the morning, the resulting solid was filtered off quickly, washing with a small volume of the cold methanol, the crystals dissolved in methanol, and evaporated to dryness in vacuo to give a light yellow solid, 43950 mg (84% yield). MS (APCI): calculated for Chemical Formula: C15H23NO2 (M+H) = 250; found: 250.1H NMR (400 MHz, DMSO) 5 6.36 (s, 2H), 2.15 (hept, J = 6.9 Hz, 1 H), 1 .94 (hept, J = 6.8 Hz, 2H), 0.46 (d, J = 6.9 Hz, 6H), 0.43 (d, J = 7.0 Hz, 12H).

[0099] Compound BAC2-7-6 (2,4,6-triisopropylaniline): Compound BAC2-7-5 (72.19 mmol, 18000 mg) was suspended in acetic acid (300 mL) and concentrated hydrochloric acid (80 mL) and heated and stirred to 100 °C, then treated, in portions, with zinc dust (599.2 mmol, 39179 mg), keeping the addition slow enough to prevent the reaction mixture from bubbling over. The mixture was stirred for a few minutes, then cooled to 0 °C and very carefully quenched with solid KOH until the pH was ~8. The resulting aqueous solution was extracted with ether (3 X 250 mL), the ether layers washed with brine, dried over magnesium sulfate, filtered, and evaporated to dryness in vacuo to give a light yellow oil, 9672 mg (61 % yield). Low yield due to spillage of some of product. MS (APCI): calculated for Chemical Formula: C15H25N (M+H) = 220; found: 220.1H NMR (400 MHz, DMSO) 5 6.03 (s, 2H), 2.21 (hept, J = 6.8 Hz, 2H), 1.96 (hept, J = 7.0 Hz, 1 H), 0.43 (d, J = 6.8 Hz, 12H), 0.38 (d, J = 6.9 Hz, 6H). The compound was pure enough for the next step with no purification.

[0100] Compound BAC2-7-7 (5,9,11 -tribromo-2-(2,4,6-triisopropylphenyl)-1 H- xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione): Compound BAC2-7-6 (44.09 mmol, 9672 mg) and Compound BAC2-7-4 (assume 100%, 20.00 mmol, 10800 mg) were stirred in propionic acid (150 mL) at 165 °C under argon overnight. The mixture was cooled to room temperature and poured into -1.5L of stirred water. The resulting precipitate was filtered off, then partitioned between hot toluene (1 L) and a 30% potassium carbonate in water solution (300 mL). THF (300 mL) was added to help solubilize product and the mixture stirred at room temperature overnight. The layers were separated, and the organic layer dried over magnesium sulfate, filtered, and evaporated to dryness in vacuo to give a yellow solid, 18.17 g (over 100% yield). LCMS again shows clear evidence of tri-, tetra-, and penta-bromo-isomers, this time fairly clean. NMR data was indiscernible. Divided into 3 portions and taken to Suzuki reaction with three different boronic acids.

[0101] Compound BAC2-7 (5,9,11-tris(4-(trifluoromethyl)phenyl)-2-(2,4,6- triisopropylphenyl)-1 H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione): Compound BAC2-7-7 (8.261 mmol, 6000 mg), (4-(trifluoromethyl)phenyl)boronic acid (74.35 mmol, 14119 mg), potassium carbonate (82.61 mmol, 11418 mg), and Pd(dppf)Ch (1 .652 mmol, 1209 mg) were stirred in dry THF (150 mL) and water (20 mL) under argon at 80 °C for 90 minutes, then cooled to room temperature. The mixture was diluted with ethyl acetate (up to 500 mL), transferred to a separatory funnel, diluted with water (100 mL), the layers separated, the organic layer washed with brine (100 mL), the organic layer dried over magnesium sulfate, filtered, and evaporated to dryness in vacuo. The residue was evaporated onto ~40g of flash silica gel, packed into a loader, and purified by flash chromatography on silica gel (220g, 0% toluene / hexanes (2 CV) 20% (10 CV)-> 40% (5 C) -> 60% (5 CV) - 80% (5 CV), stop at 62.8%, isocratic)). Fractions containing mostly the first peak (overlapping) were collected separately from the second peak and both evaporated to dryness in vacuo. The first peak was evaporated onto ~40g of flash silica gel, packed into a loader, and purified by flash chromatography on silica gel (120g, 0% EtOAc / hexanes (2 CV) - 10% (10 CV), stop at 2.5%, one peak elutes, - 10%, second peak elutes)). Fractions were collected separately and evaporated to dryness in vacuo. The first peak is a single isomer of the triphenyl product (BAC2-7). The second peak is an inseparable mixture of two isomers of the tetraphenyl product (BAC2-10). The second peak was chromatographed similarly, 40g / 120g, 0% EtOAc / hexanes (2 CV) 10% (10 15% (5 CV), major peak eluting after 10%. This peak was evaporated to dryness in vacuo and shown to be a single isomer of the pentaphenyl product (BAC2-13). BAC2- 7 was isolated as a yellow solid, 869 mg (11.4% yield). MS (APCI): calculated for Chemical Formula: C54H40F9NO3 (M+H) = 922; found: 922.1H NMR (400 MHz, DMSO) 5 8.61 (s, 1 H), 8.39 (s, 1 H), 8.12 (d, J = 8.1 Hz, 2H), 8.05 (d, J = 8.1 Hz, 2H), 7.97 (d, J = 8.2 Hz, 2H), 7.95 - 7.87 (m, 3H), 7.60 (d, J = 8.2 Hz, 2H), 7.52 (d, J = 8.6 Hz, 1 H), 7.31 - 7.22 (m, 3H), 7.20 (s, 2H), 2.97 (h, J = 6.9 Hz, 1 H), 2.66 (p, J = 6.8 Hz, 2H), 1.29 (d, J = 6.9 Hz, 6H), 1.08 (dd, J = 6.8, 3.7 Hz, 12H).

[0102] BAC2-10 minor

[0103] Compound BAC2-10 (5,7,9,11-tetrakis(4-(trifluoromethyl)phenyl)-2-(2,4,6- triisopropylphenyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione, major isomer, 5,8,9,11-tetrakis(4-(trifluoromethyl)phenyl)-2-(2,4,6-triisopropylphenyl)-1H- xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione, minor isomer): Yellow solid, 891 mg (10.1% yield). ~3:1 mixture of two isomers, NMR too complicated, LCMS one peak. MS (APCI): calculated for Chemical Formula: C61H43F12NO3 (M+H) = 1066; found: 1066.

[0104] Compound BAC2-13 (5,7,8,9,11-pentakis(4-(trifluoromethyl)phenyl)-2-(2,4,6- triisopropylphenyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione): Yellow solid, 758 mg (7.6% yield). MS (APCI): calculated for Chemical Formula: C68H46F15NO3 (M+H) = 1210; found: 1210.1H NMR (400 MHz, DMSO) 6 8.48 (s, 1 H), 8.42 (s, 1 H), 7.95 (t, J = 5.9 Hz, 4H), 7.63 (d, J = 8.1 Hz, 2H), 7.46 (t, J = 8.5 Hz, 4H), 7.38 (dd, J = 8.2, 6.0 Hz, 4H), 7.32 (d, J = 8.0 Hz, 2H), 7.19 (s, 2H), 7.06 (t, J = 4.1 Hz, 3H), 6.87 (d, J = 8.0 Hz, 2H), 2.97 (p, J = 6.9 Hz, 1 H), 2.65 (p, J = 6.8 Hz, 2H), 1.28 (d, J = 6.9 Hz, 6H), 1.07 (dd, J = 6.9, 1.9 Hz, 12H).

[0105] Synthesis of BAC2-9, BAC2-12, and BAC2-15:

[0106] Compound BAC2-9 (5,9,11-tris(3,5-bis(trifluoromethyl)phenyl)-2-(2,4,6- triisopropylphenyl)-1 H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione): Compound BAC2-9-1 (8.261 mmol, 6000 mg), ((3,5-bis(trifluoromethyl)phenyl)boronic acid (74.35 mmol, 19174 mg), potassium carbonate (82.61 mmol, 11418 mg), and Pd(dppf)Ch (1.652 mmol, 1209 mg) were stirred in dry THF (150 mL) and water (20 mL) under argon at 80 °C for 90 minutes, then cooled to room temperature. The mixture was diluted with ethyl acetate (up to 500 mL), transferred to a separatory funnel, diluted with water (100 mL), the layers separated, the organic layer washed with brine (100 mL), the organic layer dried over magnesium sulfate, filtered, and evaporated to dryness in vacuo. The residue was evaporated onto ~40g of flash silica gel, packed into a loader, and purified by flash chromatography on silica gel (220g, 0% EtOAc / hexanes (2 CV) 10% (10 CV), stop at 1.0% isocratic to elute BAC2-9, then - 4.7%, isocratic to elute BAC2-12, then to 9.0%, BAC2-15 elutes). Fractions containing each product were evaporated to dryness in vacuo separately. For BAC2-9, gives a yellow solid, 1064 mg (11.4% yield). MS (APCI): calculated for Chemical Formula: C57H37F18NO3 (M+H) = 1126; found: 1126.1H NMR (400 MHz, DMSO) 5 8.76 (s, 1 H), 8.64 (d, J = 1.7 Hz, 2H), 8.54 (d, J = 1.7 Hz, 2H), 8.52 (s, 1 H), 8.27 (s, 1 H), 8.20 (s, 1 H), 8.11 (dd, J = 8.7, 2.2 Hz, 1 H), 8.07 (s, 1 H), 7.58 (d, J = 1.6 Hz, 2H), 7.43 (s, 1 H), 7.39 (d, J = 8.6 Hz, 1 H), 7.34 (d, J = 1.5 Hz, 1 H), 7.32 (d, J = 2.2 Hz, 1 H), 7.20 (s, 2H), 2.98 (hept, J = 7.0 Hz, 1 H), 2.65 (hept, J = 6.8 Hz, 2H), 1.29 (d, J = 6.9 Hz, 6H), 1.08 (dd, J = 6.8, 4.4 Hz, 12H). - m nor Compound BAC2-12 (5,7,9,11-tetrakis(3,5-bis(trifluoromethyl)phenyl)-2-(2,4,6- triisopropylphenyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione, major isomer; 5,8,9,11-tetrakis(3,5-bis(trifluoromethyl)phenyl)-2-(2,4,6- triisopropylphenyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione, minor isomer): Gives a yellow solid, 1635 mg (15% yield). NMR too complicated. MS (APCI): calculated for Chemical Formula: C65H39F24NO3 (M+H) = 1338; found: 1338.

[0107] Compound BAC2-15 (5,7,8,9,11-pentakis(3,5-bis(trifluoromethyl)phenyl)-2-(2,4,6- triisopropylphenyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione): Gives a yellow solid, 546 mg (4.3% yield). MS (APCI): calculated for Chemical Formula: C73H41F30NO3 (M+H) = 1550; found: 1550.1H NMR (400 MHz, TCE) 5 8.77 - 8.70 (m, 1 H), 8.66 - 8.55 (m, 1 H), 8.34 - 8.21 (m, 2H), 8.17 (d, J = 13.9 Hz, 1 H), 8.10 (d, J = 8.0 Hz, 1 H), 8.00 (d, J = 22.9 Hz, 1 H), 7.85 - 7.75 (m, 2H), 7.72 - 7.58 (m, 1 H), 7.46 - 7.36 (m, 1 H), 7.36 - 7.29 (m, 1 H), 7.16 (d, J = 1.5 Hz, 2H), 7.10 - 6.94 (m, 2H), 3.00 (p, J = 6.9 Hz, 1 H), 2.68 (pd, J = 6.9, 1.9 Hz, 2H), 1.34 (dd, J = 6.9, 2.3 Hz, 6H), 1.24 - 1.10 (m, 12H).

[0108] Synthesis of BAC2-8, BAC2-11, and BAC-14

[0109] Compound BAC2-8 (5,9,11-tris(3-(trifluoromethyl)phenyl)-2-(2,4,6- triisopropylphenyl)-1 H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione): Compound BAC2-8-1 (8.261 mmol, 6000 mg), ((3-(trifluoromethyl)phenyl)boronic acid (74.35 mmol, 14119 mg), potassium carbonate (82.61 mmol, 11418 mg), and Pd(dppf)Ch (1 .652 mmol, 1209 mg) were stirred in dry THF (150 mL) and water (20 mL) under argon at 80 °C for 90 minutes, then cooled to room temperature. The mixture was diluted with ethyl acetate (up to 500 mL), transferred to a separatory funnel, diluted with water (100 mL), the layers separated, the organic layer washed with brine (100 mL), the organic layer dried over magnesium sulfate, filtered, and evaporated to dryness in vacuo. The residue was evaporated onto ~40g of flash silica gel, packed into a loader, and purified by flash chromatography on silica gel (220g, 0% EtOAc / hexanes (2 CV) 10% (10 CV), stop at 5.0%, isocratic (3+4 elute), then 12.0%, isocratic, 5-isomer elutes. Both sets were evaporated separately. The mixture of 3 and 4 was evaporated onto ~40g of flash silica gel, packed into a loader, and purified by flash chromatography on silica gel (120g, 0% EtOAc / hexanes (2 CV) - 5% (10 CV), stop at 3.2%, isocratic, 3-isomer elutes, - 5.0%, then 8.0% (0 CV), 8.0% isocratic) to finish eluting the 4-isomer. For the 3-isomer, gives a yellow solid, 810 mg (11% yield). MS (APCI): calculated for Chemical Formula: C54H40F9NO3 (M+H) = 922; found: 922.1H NMR (400 MHz, TCE) 5 8.73 (s, 1 H), 8.51 (s, 1 H), 8.12 (d, J = 2.1 Hz, 1 H), 8.07 - 7.97 (m, 1 H), 7.93 - 7.72 (m, 6H), 7.67 (dd, J = 8.6, 2.1 Hz, 1 H), 7.58 (d, J = 7.8 Hz, 1 H), 7.48 (t, J = 7.8 Hz, 1 H), 7.41 - 7.32 (m, 3H), 7.16 (s, 2H), 7.13 (d, J = 2.4 Hz, 1 H), 2.99 (hept, J = 6.9 Hz, 1 H), 2.70 (h, J = 6.8 Hz, 2H), 1.34

[0110] (d, J = 6.9 Hz, 6H), 1.17 (dd, J = 6.8, 2.7 Hz, 12H).

[0111] BAC2-11

[0112] 1814-92 P2 minor Compound BAC2-11 (5,7,9,11-tetrakis(3-(trifluoromethyl)phenyl)-2-(2,4,6- triisopropylphenyl)-1 H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione, major isomer; 5,8,9,11-tetrakis(3-(trifluoromethyl)phenyl)-2-(2,4,6-triisopropylphenyl)-1H- xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione, minor isomer): Gives a yellow solid, 1250 mg (14% yield). NMR too messy. MS (APCI): calculated for Chemical Formula: C65H39F24NO3 (M+H) = 1338; found: 1338.

[0113] Synthesis of BAC2-14

[0114] Compound BAC2-14 (5,9,11-tris(3-(trifluoromethyl)phenyl)-2-(2,4,6- triisopropylphenyl)-1 H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione): Gives a yellow solid, 1030 mg (10% yield). MS (APCI): calculated for Chemical Formula: C68H46F15NO3 (M+H) = 1210; found: 1210.1H NMR (400 MHz, DMSO) 6 8.46 (s, 1 H), 8.41 (s, 1 H), 8.13 (d, J = 7.8 Hz, 1 H), 8.05 (s, 1 H), 7.84 (s, 2H), 7.72 (s, 1 H), 7.57 (d, J = 8.0 Hz, 2H), 7.48 (d, J = 7.9 Hz, 1 H), 7.43 - 7.10 (m, 11 H), 6.90 (d, J = 6.8 Hz, 2H), 2.98 (h, J = 6.9 Hz, 1 H), 2.64 (s, 2H), 1.29 (d, J = 6.9 Hz, 6H), 1.08 (d, J = 6.7 Hz, 12H).

[0115] Procedure to evaluate optical properties and photostability of sharp emitter chromophores

[0116] A glass substrate was prepared in the following manner. A 1.1 mm thick glass substrate was cut to a 1-inch X 1-inch size. The glass substrate was then washed with detergent / soap and rinsed with deionized (DI) water, isopropanol (I PA), and acetone. The cleaned glass substrate was then blown dry with nitrogen gas or air before use.

[0117] A 35 weight% solution of Polyethylene terephthalate glycol (PETG) resin in spectroscopy grade Cyclopentanone was prepared. The prepared PETG polymer solution was stirred at 50 °C until PETG was fully dissolved. [PETG] CAS: 25640-14-6; [Cyclopentanone] CAS: 120-92-3.

[0118] In a 20 mL vial, 2 mg of chromophore was added into the PETG solution to make a 2.0 x 10'3M solution [PETG volume was calculated using the formula: VPETG (mL) = [5000 / 2*mdye], then mixed well by Vortex for about 5 min and sonicated at 70 °C for 60 Mwdyeminutes. The PETG / chromophore solution was then spin coated onto a prepared glass substrate at 1000 RPM for 20s. The spin-coated samples were baked in an oven at 150 °C for 5 minutes to evaporate the remaining solvent.

[0119] The 1-inch X 1-inch sample was inserted into a Shimadzu, UV-3600 UV-VIS-NIR spectrophotometer (Shimadzu Instruments, Inc., Columbia, MD, USA) to measure absorption spectrum.

[0120] The emission spectrum of a 1-inch X 1-inch film sample prepared as described above was measured using a FLS-1000 photoluminescence spectrometer (Edinburgh Instruments, Livingston, United Kingdom). 390 nm wavelength was chosen as the excitation wavelength and the emission spectrum wavelength was scanned from 405 nm to 750 nm.

[0121] The quantum yields of spin-coated samples prepared as described above were determined using a Hamamatsu C11347 Absolute PL quantum yield spectrometer (Hamamatsu Inc., Campbell CA, USA). A 0.5”x 0.5” size film was taken out from glass substrate for QY measurement. Wavelengths were scanned every 30 nm from 390 nm to 450 nm (as excitation wavelengths). The QY at 450 nm are reported in Table 1.

[0122] Photostability Study of sharp emitter chromophores

[0123] Photostability of the chromophores was tested by exposing the 1-inch X 1-inch spin-coated film samples on 150 mW / cm2Blue LEDs (CREE, Durham, North Carolina, USA). The samples were monitored the first 1-2 days, and continued to be monitored weekly if very photostable in the first two days (measured absorbance, emission, and QY for each exposure time being monitored). The chromophore’s durability was quantified by the decrease in the Absorbance% multiplied by QY% for specific exposure time. The photostability study continued until T80 can be identified (when Abs*QY% = 80% or less).

[0124] The optical properties and durability data of the spin-coated films (maximum absorbance peak wavelength, maximum emission peak wavelength & emission FWHM, quantum yield at 450 nm and photostability data (T80@150 mW / cm2) are shown in Tables 1 & 2, below.

[0125] Without intending to be bound by any particular theory, inclusion of at least one trihaloalkyl aryl, such as a trifluoromethyl aryl, on the blue light absorbing compound may lead to increased solubility of the matrix polymer in which the blue light absorbing compound is included to prevent aggregation, which results in significantly improved photostability in comparison to CE-1. Table 1. Optical Properties and Photostability Data of Chromophores in PETG @ 5 mM concentration.

[0126] Table 2. Optical Properties and Photostability Data of Chromophores in PETG @ 5 mM concentration. Table 3. Optical Properties and Photostability Data of Chromophores in PETG @ 5 mM concentration.

[0127] Table 4. Optical Properties and Photostability Data of Chromophores in PETG @ 5 mM concentration. QY% (@450n m) Photosta bility Data (T80% @150m W / cm2)

[0128] As used herein, unless otherwise specified the use of the ordinal adjectives “first” and “second,” to describe a common object, merely indicate that different instances of like objects are being referred to and are not intended to imply that the objects so described 5 must be in a given sequence, either temporally, spatially, in ranking, or in any other manner.

[0129] Use of the term “may” or “may be” or “can” 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 / include scattering centers disposed within the0 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.”

[0130] Unless otherwise indicated, all numbers expressing quantities of ingredients,5 properties, such as, molecular weight, reaction conditions, and so forth used in the specification and embodiments are to be understood as being modified in all instances by the term “about.” The term “about” as used herein, may include any numerical value that may vary without changing the basic function of that value. When used with a range, “about” also discloses the range defined by the absolute values of the two endpoints. The0 term “about” may refer to plus or minus 10% of the indicated number.

[0131] Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and attached embodiments are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, and not as an attempt to limit the application of the doctrine of equivalents. To the scope of the5 embodiments, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. For the processes and / or methods disclosed, the functions performed in the processes and methods may be implemented in differing order, as may be indicated by context. Furthermore, the outlined steps and operations are only provided as examples, and some of the steps and operations may be optional, combined into fewer steps and operations, or expanded into additional steps and operations.

[0132] This disclosure may sometimes illustrate different components contained within, or connected with, different other components. Such depicted architectures are merely examples, and many other architectures may be implemented which achieve the same or similar functionality.

[0133] The terms used in this disclosure, and in the appended embodiments, are generally intended as “open” terms (e.g., the term “including” should be interpreted as “including, but not limited to,” the term “having” should be interpreted as “having at least,” the term “includes” should be interpreted as “includes, but is not limited to,” etc.). In addition, if a specific number of elements is introduced, this may be interpreted to include at least the recited number, as may be indicated by context (e.g., the bare recitation of "two recitations," without other modifiers, includes at least two recitations, or two or more recitations). As used in this disclosure, any disjunctive word and / or phrase presenting two or more alternative terms should be understood to contemplate the possibilities of including one of the terms, either of the terms, or both terms. For example, the phrase “A or B” will be understood to include the possibilities of “A” or “B” or “A and B.”

[0134] The terms and words used are not limited to the bibliographical meanings but are merely used to enable a clear and consistent understanding of the disclosure. The terms “a,” “an,” “the” and similar referents used in the context of describing the present disclosure (especially in the context of the following embodiments) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The use of any and all examples, or representative language (e.g., “such as”) provided herein is intended merely to better illuminate the present disclosure and does not pose a limitation on the scope of any embodiments. No language in the specification should be construed as indicating any non-embodied element essential to the practice of the present disclosure.

[0135] Groupings of alternative elements or embodiments disclosed herein are not to be construed as limitations. Each group member may be referred to and embodied individually or in any combination with other members of the group or other elements found herein. It is anticipated that one or more members of a group may be included in, or deleted from, a group for reasons of convenience and / or patentability. When any such inclusion or deletion occurs, the specification is deemed to contain the group as modified thus fulfilling the written description of all Markush groups used in the appended embodiments.

[0136] Certain embodiments are described herein, including the best mode known to the inventors for carrying out the present disclosure. Of course, variations on these described embodiments, will become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventor expects skilled artisans to employ such variations as appropriate, and the inventors intend for the present disclosure to be practiced otherwise than specifically described herein. Accordingly, the embodiments include all modifications and equivalents of the subject matter recited in the embodiments as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is contemplated unless otherwise indicated herein or otherwise clearly contradicted by context. In closing, it is to be understood that the embodiments disclosed herein are illustrative of the principles of the embodiments. Other modifications that may be employed are within the scope of the embodiments. Thus, by way of example, but not of limitation, alternative embodiments may be utilized in accordance with the teachings herein. Accordingly, the embodiments are not limited to the embodiments precisely as shown and described.

[0137] By the term "substantially" it is meant that the recited characteristic, parameter, or value need not be achieved exactly, but that deviations or variations, including for example, tolerances, measurement error, measurement accuracy limitations and other factors known to those skilled in the art, may occur in amounts that do not preclude the effect the characteristic was intended to provide.

[0138] Aspects of the present disclosure may be embodied in other forms without departing from its spirit or essential characteristics. The described aspects are to be considered in all respects illustrative and not restrictive. The embodied subject matter is indicated by the appended embodiments rather than by the foregoing description. All changes, which come within the meaning and range of equivalency of the embodiments, are to be embraced within their scope.

Claims

CLAIMSWhat is claimed is:1 . A blue light absorbing compound according to the following formula:wherein Ri is a C1-C5 alkyl substituted aryl, and each of R2, R3, R4, Rs and Rs is independently selected from H and an aryl with at least one trihaloalkyl substitution provided that at least one of R2, R3, R4, Rs and Rs is an aryl with at least one trihaloalkyl substitution.

2. The blue light absorbing compound of claim 1 , wherein Ri is according to the following structure:wherein each of R? and Rs is a C1-C5 alkyl.

3. The blue light absorbing compound of claim 1 , wherein Ri is selected from:

4. The blue light absorbing compound of claim 1 , wherein each of R2, R3, R4,Rs and Rs is independently one5. The blue light absorbing compound of claim 1, having one of the following structures:

56. The blue light absorbing compound of any one of claims 1-5, wherein the blue light absorbing compound exhibits at least about 15% durability increase in T80%@150mW / cm2relative to a compound which does not include at least one of R2, R3, R4, Rs and Re as an aryl substituted with at least one trihaloalkyl.

7. A blue light absorption media, comprising a blue light absorbing compound of any one of claims 1-6, and a polymer matrix, wherein the blue light absorbing compound is disposed within the polymer matrix, and wherein light between about 400 nm to about 500 nm is absorbable by the absorption media.

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